HANDBOOK OF ADHESIVES

HANDBOOK OF ADHESIVES
Third Edition
Edited by

lIVing Skeist, Ph. D.

Consultant to the Polymer Industries
Skeist Incorporated
Whippany, New Jersey

CHAPMAN & HALL

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Library of Congress Cataloglng-in-Puhlicatlon Data

Handbook of adhesives / edited by Irving Skeist.-3rd ed.

p. em.
ISBN-13: 978-1-4612-8019-4 e-ISBN-13: 978-1-4613-0671-9
DOl: 10.1007/978-1-4613-0671-9
I. Adhesives. I. Skeist, Irving.
TP968.H35 1989 89-9082
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 Contributors

John S. Autenrieth, Wilmington, Delaware, Research Association, Brickendonbury,

retired Hertford, England
Justin C. Bolger, W. R. Grace & Co., David R. Gehman, Rohm and Haas
Lexington, Massachusetts Company, Springhouse, Pennsylvania
Robert L. Brandis, St. Johnsville, New York A. N. Gent, University of Akron, Ohio
Arnold Brief, Skeist Incorporated, Whippany, Lawrence Gollob, Georgia-Pacific
New Jersey Corporation, Decatur, Georgia
Leonard S. Buchoff, Huntington Valley, M. E. Gross, retired
Pennsylvania Sandra K. Guggenberger, E.1. du Pont de
Carolyn N. Bye, National Casein of New Nemours & Co., Inc., Wilmington,
Jersey, Riverton, New Jersey Delaware
H.W. Coover, Loctite Corporation, G. R. Hamed, University of Akron, Ohio
Newington, Connecticut J. T. Harlan (deceased)
Wiley Daniels, Air Products and Chemicals, Paul M. Hergenrother, National Aeronautics
Inc., Allentown, Pennsylvania and Space Administration, Hampton,
G. A. Davies, Shell Company, Houston, Virginia
Texas J. J. Higgins, Exxon Chemical Company,
John W. Dean, General Electric Company, Florham Park, New Jersey
Waterford, New York Harold Jaffe, Millburn, New Jersey
D. W. Dreifus, Loctite Corporation, Frank C. Jagisch, Exxon Chemical Company,
Newington, Connecticut Baton Rouge, Louisiana
Ernest F. Eastman, E. I. du Pont de Nemours B. A. Jemmott, Monsanto Company,
& Co., Inc., Wilmington, Delaware Springfield, Massachusetts
Michael Elias, Chemark Consulting Group, Harry S. Katz, Utility Development
Inc., Cincinnati, Ohio Corporation, Livingston, New Jersey
E. E. Ewins, Shell Development Company, Harold W. Koehler, Hardman Industries,
Houston, Texas Inc., Belleville, New Jersey
P. H. Farmer, Monsanto Company, Leo Kruger, National Starch and Chemicals
Springfield, Massachusetts Corporation, Bridgewater,
Kendall F. Foley, Hercules Incorporated, New Jersey
Wilmington, Delaware Norman Lacourse, National Starch and
L. A. Fox, The B.F. Goodrich Company, Chemicals Corporation, Bridgewater, New
Akron, Ohio Jersey
Lawrence Fullhart, Jr., retired Donald E. Mackey, The B.F. Goodrich
Anthony C. Gaeta, Carborundum Abrasives Company , Avon Lake, Ohio
Company, Niagara Falls, New York C. Lynn Mahoney, Dexter Corp., Pittsburg,
K. F. Gazeley, Malaysian Rubber Producers' California

v
vi CONTRIBUTORS

Bernard M. Malofsky, Loctite Corporation, Franklin M. Rosenblum, Air Products and

Newington, Connecticut Chemicals, Inc., Allentown, Pennsylvania
James G. Marsden, Union Carbide Conrad Rossitto, Emhart, Middleton,
Corporation, Tarrytown, New York Massachusetts
Allan R. Meath, Dow Chemical USA, Gerald L. Schneberger, Training Resources,
Freeport, Texas Inc., Flint, Michigan
C. A. Midgley, Polysar Limited, Sarnia, Charles S. Schollenberger, Hudson, Ohio
Ontario, Canada Irving Skeist, Skeist Incorporated, Whippany,
Robert S. Miller, Franklin International, New Jersey
Columbus, Ohio Thomas S. Solomon, Brecksville, Ohio
Jerry Miron, Skeist Incorporated, Whippany, N. E. Stucker, Exxon Chemical Company,
New Jersey Baytown, Texas
J. T. O'Connor, Loctite Corporation, Samuel C. Temin, Walpole, Massachusetts
Newington, Connecticut Richard T. Thompson, Loctite Corporation,
Julian R. Panek, Yardley, Pennsylvania Newington, Connecticut
L. A. Petershagen, Shell Chemical Company, Frederick Tobiason, Pacific Lutheran
Houston, Texas University, Tacoma, Washington
Robert E. Politi, American Cyanamid Herb Turner, Nordson Corporation, Amherst,
Company, Havre de Grace, Maryland Ohio
Joseph W. Prane, Elkins Park, Ivor H. Updegraff, Stamford, Connecticut
Pennsylvania W. C. Wake, Clive, Shrewsbury, England
J. B. Rea, Polysar Limited, Sarnia, Ontario, Carl D. Weber, The B.F. Goodrich
Canada Company, Akron, Ohio
Russell Redman, Tremco, Inc., Cleveland, Charles B. Weil, The B.F. Goodrich
Ohio Company, Avon Lake, Ohio
James T. Rice, University of Georgia, J. D. Wellons, Georgia-Pacific Corporation,
Athens, Georgia Decatur, Georgia
John M. Rooney, Sun Chemical Company, William F. Zimmer, Jr., Punta Gorda,
Carlstadt, New Jersey Florida
 Preface

Adhesives are indispensable. They are required pling agents, and other key ingredients. Special
in myriad products-aircraft and abrasives, cars attention is given to such flourishing categories
and cartons, shoes and safety glass, tape and as acrylics, anaerobics, cyanoacrylates, poly-
tires. This Third Edition of Handbook of Ad- urethanes, epoxy resins, polyvinyl acetate, high
hesives, like the 1962 and 1977 editions, seeks temperature adhesives, hot melts, silicones, and
to provide the knowledge needed for optimum silanes.
selection, preparation, and utilization of adhe- The last 14 chapters, on adherends and bond-
sives and sealants. The information is detailed ing technology, involve the auto industry, air-
and explicit, with several hundred illustrative craft, electronics, the bonding of wood,
formulations. textiles, rubber and plastics, construction, ab-
Expert information has been supplied in 47 rasives, pressure-sensitives, nonwovens, and
chapters written by 70 industry specialists, pro- sealants. Mechanical handling of two-compo-
fessors, and consultants. Five chapters on fun- nent systems is examined. The concluding
damentals provide the theoretical and economic chapter highlights the exciting progress that is
underpinnings-why adhesives work, how they being made in the use of robotics to apply ad-
are selected, how the surface is prepared, how hesives, techniques already far advanced in au-
they are applied, how they are set, how the tomotive assembly.
cured joint is tested. The economic importance To Jerry Miron and Arnold Brief of Skeist
of the adhesive-using industries is spelled out, Incorporated, my long time consulting associ-
with specifics on the role of adhesives in con- ates, I express my gratitude and appreciation
struction, packaging, autos, aircraft/aerospace, for their invaluable support.
textiles, footwear, abrasives, electronics, and
in the home. The next 28 chapters cover the
adhesive materials-thermosetting, thermo- IRVING SKEIST
plastic, elastomeric, natural polymers, cou- Whippany, New Jersey

vii
 Contents

Preface / vii 15- Neoprene (Polychloroprene)-Based

Solvent and Latex Adhesives-Sandra
Section A. Fundamentals / ] K. Guggenberger / 284
1- Introduction to Adhesives-Irving Skeist 16- Polysulfide Sealants and Adhesives-
and Jerry Miron / 3 Julian R. Panek / 307
2- The Role of Adhesives in the 17- Phenolic Resin Adhesives-Frederick L.
Economy-Arnold Brief / 21 Tobiason / 316
3- Fundamentals of Adhesion-A. N. Gent 18- Amino Resin Adhesives-Ivor H.
and G. R. Hamed / 39 Updegraff / 341
4- Surface Preparation for Adhesive 19- Epoxy Resin Adhesives-Allan R.
Bonding-C. Lynn Mahoney / 74 Meath / 347
5- Adhesive Selection and Screening 20- Polyurethane- and Isocyanate-Based
Testing-James T. Rice / 94 Adhesives-C. S. Schollenberger /
359
Section B. Adhesive Materials / 121 21- Polyvinyl Acetate Emulsions for
6- Animal Glue-Robert L. Brandis / Adhesives-Harold L. Jaffe, Franklin
'" 123 M. Rosenblum and Wiley Daniels /
7- Casein and Mixed Protein Adhesives- 381
Carolyn N. Bye / 135 22- Polyvinyl Alcohol for Adhesives-
8- Starch Based Adhesives-Leo Kruger Harold L. Jaffe and Franklin M.
and Norman Lacourse / 153 Rosenblum / 401
9- Natural Rubber Adhesives-K. F. 23- Polyolefin and Ethylene Copolymer-
Gazeley and W. C. Wake / 167 based Hot Melt Adhesives-Ernest F.
10- Butyl Rubber and Polyisobutylene-J. J. Eastman and Lawrence Fullhart, Jr. /
Higgins, Frank C. Jagisch, and N. E. 408
Stucker / 185 24- Polyvinyl Acetal Adhesives-P. H.
11- Nitrile Rubber Adhesives-Donald E. Farmer and B. A. Jemmott / 423
Mackey and Charles E. Weil / 206 25- Acrylic Adhesives-David R. Gehman
12- Styrene Butadiene Rubber Adhesives- / 437
C. A. Midgley and J. B. Rea / 227 26- Anaerobic Adhesives-John M. Rooney
13- Thermoplastic Rubber (A-B-A Block and Bernard M. Malofsky / 451
Copolymers) in Adhesives-J. T. 27- Cyanoacrylate Adhesives-H. W.
Harlan, L. A. Petershagen, E. E. Ewins, Coover, D. W. Dreifus, and J. T.
Jr. and G. A. Davies / 239 O'Connor / 463
14- Carboxylic Polymers in Adhesives-C. 28- Polyester and Polyamide High
D. Weber, L. A. Fox and M. E. Gross Performance Hot Melt Adhesives-
/ 270 Conrad Rossitto / 478

ix
x CONTENTS

29· High Temperature Organic Adhesives- 38· Pressure-Sensitive Adhesives for Tapes
Paul M. Hergenrother / 499 and Labels-Samuel C. Temin / 641
30· Silicone Adhesive Sealants and 39· Bonded Abrasives-William F. Zimmer,
Abhesives-John W. Dean / 522 Jr. / 664
31· Organofunctional Silane Coupling 40· Coated Abrasives-Anthony C. Gaeta
Agents-James G. Marsden / 536 / 671
32· Non-Silane Coupling Agents-Harry S. 41· Adhesives for Building Construction-
Katz / 549 Robert S. Miller / 678
33· Resins for Elastomer-Based Adhesives- 42· Adhesives in the Electrical Industry-
John S. Autenrieth and Kendall F. Foley Leonard S. Buchoff / 698
/ 556 43· Conductive Adhesives-Justin C. Bolger
/ 705
Section C. Adherends and Bonding 44· Structural Adhesives in the Aerospace
Technology / 571 Industry-Robert E. Politi / 713
34· Bonding Plastics-Richard T. Thompson 45· Adhesives in the Automobile Industry-
/ 573 Gerald L. Schneberger / 729
35· Bonding Textiles to Rubber-Thomas S. 46· Meter, Mix and Dispensing Equipment:
Solomon / 583 Basic Designs-Harold W. Koehler /
36· Wood Adhesion-Lawrence Gollob and 736
J. D. Wellons / 598 47· Robotic Dispensing of Sealants and
37· Sealants and Caulks-Joseph W. Prane, Adhesives-Herb Turner / 743
Michael Elias and Russell Redman /
611 Index / 757
HANDBOOK OF ADHESIVES
 Section A
Fundamentals
 1
Introduction to
Adhesives
IRVING SKEIST AND JERRY MIRON
Skeist Incorporated
Consultants to the Polymer Industries
Whippany, New Jersey

Adhesives are social substances. They unite (e) Corrugated board, paper bags, labels,
materials, creating a whole that is greater than tapes, stamps, and envelopes.
the sum of its parts. They are small in volume (f) Safety glass.
compared to the metals, glass, wood, paper, (g) Nonwoven fabrics, flocked fabrics, and
fibers, rubber, and plastics that they join to- tufted carpets.
gether; but just as enzymes, hormones, and vi- (h) Clay-coated paper for printing.
tamins are required for individual well-being, (i) Particle board.
the adhesives are recognized as essential to the (j) Veneer furniture.
health of our industrial society.
2. Stresses are distributed over wider areas,
making possible lighter and stronger assem-
ADVANTAGES OF ADHESIVE blies than could be achieved with mechanical
BONDING fastening. For example, airplane wings, tails,
and fuselages may be constructed of sandwich
The rapid growth of the adhesives industry has
panels comprising a honeycomb core bonded to
resulted from its many advantages over other
thin faces of aluminum or magnesium; conse-
methods of joining materials:
quently the possibility of fatigue failure is de-
1. Thin films, fibers and small particles, that creased. Glued floors, wood framing and entire
could not be combined as well, or at all, by room modules, factory-prebuilt for economy,
other techniques, are readily bonded with ad- have the tensile, flexural, and impact strength
hesives. Typical of such uses are: to resist the rigors of transportation and hoist-
ing into place. In reinforced plastics and ad-
(a) Laminates of plastic films, aluminum vanced composites, glass fiber is adhered to the
foil, fabrics, and paper. unsaturated polyester matrix, or graphite fiber
(b) Glass wool insulation and fiber glass mat to epoxy matrix, with the aid of functional si-
composites. lanes and other coupling agents.
(c) Abrasive wheels, sandpaper, emery 3. The strength-to-weight ratios and dimen-
cloth, and brake linings. sional stability of anisotropic materials can be
(d) Tires reinforced with rayon, nylon, poly- improved by cross-bonding. Thus wood, in-
ester, glass fiber, and steel. herently nonuniform and water-sensitive, is

3
4 HANDBOOK OF ADHESIVES

converted into warp-resistant, water-resistant laid at right angles, and the beating was re-
plywoods. Nonwoven fabric having the same peated. The finished papyrus was a luminous
properties in all directions is made by lightly brown. 2
bonding a random web of fiber. We read in Genesis that slime (bitumen) was
4. The glue line provides electrical insula- the preferred mortar of the builders of the
tion in capacitors, printed circuits, motors, pot- Tower of Babel-the first adhesives technolo-
ted resistors, etc. gists to have problems of semantics. Bitumen
5. The glue line can be a moisture barrier, and tree pitches were the sealants for the ves-
sealing window panels in curtain wall construc- sels that plied the Mediterranean. In the days
tion. In laminates for packaging, the glue line of the prophets, as now, the adhesive had to be
adds greatly to the moisture-vapor resistance. specific for the adherend. "He that teacheth a
6. Dissimilar materials can be joined, e.g., fool is like one that glueth potsherds together,"
aluminum-to-paper, iron-to-copper. When two we are advised in the Apocrypha (Jesus ben
metals are bonded, the adhesive separates them Sirach, Ecclesiasticus, Chapter 22). Educators
and prevents corrosion. When the two adher- are still struggling with the first problem, but
ends are markedly different in coefficient of the latter has been solved with epoxy adhe-
thermal expansion, a flexible adhesive lessens sives.
the stress due to temperature change. Lami- According to Pliny, the Romans caulked their
nates of dissimilar materials can give combi- ships with pine wood tar and beeswax. Antic-
nations superior to either adhered alone; for ipating the laminate and the printed circuit,
example, a polyethylene-cellophane composite Pliny described the application of gold leaf to
has the heat-sealability and water-resistance of paper with egg white. We learn also that the
the former plus the grease-resistance and print- Romans, like the ancient Chinese, made bird
ability of the latter. lime, an adhesive from the juice of the mistle-
7. Finally, what is often the key considera- toe, with which they smeared twigs to catch
tion: adhesive bonding may be faster and small birds.
cheaper than the weaving of cloth; soldering, Glues from fish, stag horns, and cheese were
brazing or welding of metals; or mechanical known in the days of Theophilus for fixing to-
fastening of rivets, bolts, or nails. gether wooden objects. Here is his ninth cen-
tury recipe for glutine casei:
HISTORY "Soft cheese is cut very small, and is washed
with warm water in a small mortar with a
Adhesives were utilized in a sophisticated man-
pestle, until, being frequently poured in, the
ner even in ancient times. Carvings in Thebes
water comes away pure. Then this cheese,
dating back 3300 years depict the gluing of a
compressed by the hand, is put into cold
thin piece of veneer to what appears to be a
water until it hardens. After this it is very
plank of sycamore. The glue pot and brush are
finely ground, with another piece of wood,
shown.) Still earlier, in the palace of Knossos
upon a smooth wooden table, and in this state
in Crete, wet lime was the binder for chalk,
it is again placed in the mortar, and is care-
iron ocher, and copper blue frit pigments with
fully ground with the pestle, water mixed
which the walls were painted. 2 The Egyptians
with quick lime being added, until it is made
utilized gum Arabic from the acacia tree, egg,
as thick as lees. The tablets of altars fastened
glue, semiliquid balsams, and resins from trees.
together with this glue, after they are dry, so
Wooden coffins were decorated with pigments
adhere together, that neither heat nor humid-
bonded with "gesso," a mixture of chalk and
ity are able to disjoin them."
glue.
Papyrus was an early nonwoven fabric. Except for the introduction of rubber and py-
Reeds 12 to 20 ft high and 3 in. in diameter roxylin cements a hundred years ago, there was
were cut in thin slices, laid side by side, and little advance in adhesives technology until well
beaten with a mallet. After these were brushed into the twentieth century. In these last few
over with flour paste, fresh slices of reed were decades, the natural adhesives have been im-
 INTRODUCTION TO ADHESIVES 5

proved, and a spate of synthetics has poured from solvent or latex followed by drying
from the laboratories. and cooling.

INFORMATION SOURCES By convention, "hot-melt" often denotes a

lower molecular weight, less viscous material
The second edition (1977) showed some 40 than "thermoplastic."
books on adhesives and adhesion since 1947. If the cooled coating is not tacky, the coated
Another score of more recent volumes are listed substrates can be piled and stored for future use,
in the References to this chapter, 3-21 along with when they will have to be heated to reactivate
eight periodicals from six countries,22-29 of the adhesive. Alternatively, the bond is often
which Adhesives Age24 is the most widely made immediately after application of the hot-
known. . melt, powder, or extruded coating. This pro-
The Gorden Research Conferences, the cedure offers best production rates, since the
American Chemical Society, and many uni- cooling of a hot-melt is faster than evaporation
versities are among the organizations which of solvent or chemical setting.
sponsor symposia on adhesion and adhesives. Paper, paperboard, and cellophane for food
Techno-economic studies of the adhesives packaging present examples of the various
industry are prepared by various consulting modes of applying thermoplastic adhesives.
firms, including ours. The substrate can be protected with a heat-seal-
able moisture barrier by kiss-coating the web
TYPES OF ADHESIVES with molten wax, for bread wraps; by extruder-
coating with polyethylene, for milk cartons and
Adhesives may be classified in many ways,
multiwall bags; or by applying a saran solution
e.g., by mode of application and setting, chem-
or latex and evaporating the solvent or water.
ical composition, cost, and suitability for var-
Where resistance to moisture is not needed, as
ious adherends and end products.
in the sealing of cartons containing cans, a re-
duction in cost is achieved by applying the heat-
Application and Setting
sealable adhesive as a powder rather than a
The adhesive must be applied to the substrate continuous film. Acrylic and vinyl copolymer
in a fluid form to wet the surface completely powdered resins have speeded production of
and leave no voids, even if the surface is rough. some types of nonwovens.
Consequently, the adhesive must be low in vis- Two important determinants of strength in
cosity at the time of application. hot-melts are molecular weight and polarity.
To develop high cohesive strength, however, Thus paraffin wax and polyethylene are both
the adhesive must set. In a completed joint with aliphatic hydrocarbon polymers; but the far
an organic adhesive, the latter layer is either a greater molecular weight of the polyethylene
soluble, usually thermoplastic and fusible ma- results in much higher tensile strength, tear
terial of extremely high viscosity, or a cross- strength, and heat resistance.
linked, infusible thermoset resin or rubber. Several families of hot-melts now offer still
The transition from fluid to solid may be ac- greater strength. The EVA's are ethylene-vinyl
complished in several ways: acetate copolymers which are compounded with
waxes and tackifiers to make adhesives for
1. Cooling of a Thermoplastic. Thermoplas-
packaging, bookbinding, and furniture edge-
tics soften and melt when heated, becoming
banding. Polyamides and polyesters are em-
hard again when cooled. The heating must re-
ployed for the soling of shoes, the edge-banding
sult in sufficiently high fluidity to achieve suc-
of furniture, and the side-seaming of cans.
cessful wetting. The thermoplastic may be
While the rapid setting of hot-melts is usu-
coated on one substrate by various techniques:
ally desirable, there is at least one exception.
from hot-melt, Labels for bottles and cans are sometimes
as a powder, coated with a "delayed tack" adhesive, e.g.,
by extruder, polyvinyl acetate formulated with a plasticizer
6 HANDBOOK OF ADHESIVES

that is solid at room temperature, so that when Therefore, in the manufacture of solvent ce-
activated by heat, the label remains sticky for ments, one employs resins having far lower
as long as a minute, facilitating the operation molecular weights than those preferred for
of a high-speed packaging line. plastics and elastomers. The "half second"
Safety glass for automobiles is a sandwich of cellulose esters and nitrocellulose are examples
highly plasticized polyvinyl butyral, a ther- of short-chain polymers which are adequate as
moplastic, between two sheets of plate glass. adhesives, but might be too weak as plastics.
The compounded PVB must be optically clear, Water is not only the carrier for latexes but
stable to light, and free from volatiles; but is also the most important of the solvents.
above all, it must be tough and a good adhe- Starches and dextrins, protein glues, and poly-
sive, holding glass fragments tenaciously in vinyl alcohol are the more significant water-
case of accident which cracks the glass. soluble organic adhesives. Sodium silicates,
Perhaps the largest volume hot-melt of all is comprising the most important family of inor-
the asphalt which binds aggregate on our road ganic adhesives, are water soluble.
surfaces. To achieve concentrations above 50% it is
2. Release of Solvent or Carrier. Solutions necessary that at least a portion of the polymer
and latexes contain the adhesive composition in be present in agglomerates of greater than col-
admixture with water or organic solvents. loidal size. In a latex, the polymer is present in
These liquids lower the viscosity sufficiently to the form of globules existing as a discrete phase
permit wetting of the substrate. Once this has in an aqueous matrix. Natural and synthetic
been accomplished, however, they must be re- rubbers, vinyl resins, and acrylics are the most
moved. Porous substrates such as paper permit important of the adhesive latexes. The polymer
the liquid to be drawn away from the glue layer. is not limited in molecular weight since the vis-
If both adherends are impermeable, however, cosity does not depend on what is contained
it is necessary to evaporate the water or solvent within the discrete particles. The viscosity of
before mating the two surfaces, thus slowing the latex depends primarily on solids content
down production. This is the great disadvan- and the composition of the aqueous phase. La-
tage of solutions and latexes in adhesive appli- texes are commonly available in concentrations
cations. In addition, organic solvents may be of 35 to 55 %; but it is possible, in some cases,
undesirable because of cost, shortages, flam- to go considerably higher before reaching an
mability, toxicity, or tendency to pollute. In re- excessive consistency.
cent years, regulations such as Los Angeles In many operations, for example the coating
County's Rule 66 have established upper limits of paper on the machine at high speeds, the
on the amounts of various solvents that are per- elimination of water becomes a bottleneck. In
mitted as effluents from industrial applications. choosing a binder for clay and pigment, there
Thus the three E' s-Economy, Energy, and is an increasing tendency to abandon starch so-
Environment-are in opposition to solvent- lutions in favor of combinations of casein or
based adhesives. Nevertheless, their excellent soy protein with synthetic latexes.
wetting characteristics, plus applicability at low Organosols are akin to latexes in being two-
temperatures and high coverage, will enable phase compositions, but with a continuous or-
them to retain an important role. ganic phase instead of water. Organosols are
In a solution, the concentration of "sol- dispersions of vinyl chloride resin in plasticiz-
ids"-Le., material which will remain in the ers and volatile organic solvents. Once again,
final adhesive layer-is usually under 30% for they are sufficiently fluid to promote good wet-
organic solvents but may be higher with water ting of the substrate, which may be paper,
as the solvent, and especially in latexes. For a cloth, or metal. After application to the sub-
solution, too great a solids content results in strate, the coating is heated to flash off the sol-
such high viscosity that the dope has poor wet- vent and fuse the resin.
ting characteristics. The higher the molecular 3. Polymerization in situ. This is the group
weight of the dissolved polymer, the lower is of bonding agents making the most rapid tech-
the maximum permissible concentration. nological progress. All the thermosetting resins
 INTRODUCTION TO ADHESIVES 7

come under this heading, including those which temperature, especially if the adherends are
are first applied to the substrate in solution poor conductors of heat.
form. This category also includes elastomers For some decades, dentists have filled cavi-
that are vulcanized to develop higher cohesive ties with pastes of polymethyl methacrylate in
strength. In addition, some vinyl-type mono- monomeric MMA. Now, adhesives companies
mers, especially methyl methacrylate, cy- are offering similar formulations for industrial
anoacrylate esters, and the dimethacrylates, are applications.
polymerized readily in situ. The anaerobic adhesives, a development of
The main advantage of these materials over recent years, are dimethacrylates which, when
solvent-based adhesives is that strength can be properly compounded, remain liquid so long as
developed in the glue line after the two adher- oxygen is present, but cure rapidly when air is
ends have been brought together. Faster pro- excluded. They have rapidly achieved wide
duction, lower cost, and stronger bonds may usage in metal assembly. They are covered in
result from the elimination of solvents. a separate chapter in this volume.
The reaction-sensitive adhesives fall into two The term aerobic adhesives is being ad-
groups: vanced for a series of two-component structural
acrylic adhesives which have reduced sensitiv-
1. Those formed by condensation, usually
ity to oxygen inhibition. In contrast to the an-
with water as a by-product. This group
aerobic adhesives, they can be applied to
includes the phenolic and amino resins,
porous surfaces and to fill wider gaps, e.g., up
which are the oldest of the all-synthetic
to 60 mils. 60
adhesives.
The radiation-curable adhesives are most
2. Those formed by addition polymerization
commonly either polymers with acrylate side
without by-product formation. Among
chains or unsaturated polyesters. They can be
this group are several of the most inter-
cured by ultraviolet light or by electron beam
esting of the new adhesives, including
radiation, which has greater penetration but is
polyesters, epoxies, urethanes, cyanoac-
more costly. Acrylate-type U. V .-curable coat-
rylates, anaerobics, and radiation-curable
ings have achieved an important place in the
polymers. Conventional acrylics and vul-
coil-coating of steel and aluminum. For adhe-
canizing rubbers are also in this category .
sives, the technique is less useful; but it has
When a composite is made with an adhesive been employed for the sealing of electric light
from group (1), it is necessary to apply pres- bulbs. Also, an ingenious method for making
sure to overcome the deleterious influence of nonwoven webs involves the cryogenic poly-
the water or other volatile by-product. On the merization of frozen monomer with the aid of
other hand, adhesives of group (2) may be U. V. radiation.
cured with only contact pressure. This is es- 4. Pressure-Sensitive Adhesives. 16 These
pecially advantageous in the preparation of adhesives, unlike the other classes, do not
large objects which cannot be conveniently undergo a progressive increase in viscosity. In-
placed in a press. stead, they are permanently in the intermediate
Some of the curing adhesives require heat, tacky stage. One of their chief merits for some
whereas others react at room temperature with applications, in fact, is that they wet so inade-
the help of catalysts, and in some instances with quately that they can be removed from the ad-
activation by light. Again, it is an advantage to herend surface without "mark off," i.e.,
make a bond without the aid of an oven. Among without leaving a residue of adhesive on that
the adhesives which can be processed in the surface. One of the important early advances in
cold, with proper formulation, are resorcinol pressure-sensitive tape technology was the dis-
formaldehyde, unsaturated polyesters, methyl covery that a slightly gelled adhesive layer
methacrylate, cyanoacrylate esters, epoxies, would fulfill this requirement.
and urethanes. The polymerization reaction is While this deficiency in adhesive strength is
usually exothermic, so that the glue line may deliberate, the low cohesive strength of pres-
become somewhat warmer than the ambient sure-sensitive materials is undesirable. Low
8 HANDBOOK OF ADHESIVES

bond strength precludes the pressure-sensitive Cure; Solubility; Crosslinking

tapes from heavy-duty applications. It is inev-
itable that a permanently tacky material will be Alternatively, adhesives may be categorized
easily deformed and ruptured. according to the solubility and fusibility of the
final glue line:
Most pressure-sensitive masscoats contain a
blend of elastomers-natural rubber, reclaim 1. Soluble, including thermoplastic (soluble
and SBR-with tackifiers of low or medium and fusible): starch and derivatives, as-
molecular weight, antioxidants, etc. These are phalts, some proteins, cellulosics, vinyls,
applied to the web-tape or label backing from and some acrylics.
solutions; but the newer "thermoplastic elas- 2. Crosslinked (insoluble and infusible):
tomers" -block copolymers of styrene with is- phenol- and resorcinol-formaldehyde,
oprene or butadiene-can be applied from melt. urea- and melamine-formaldehyde, epox-
Where excellent color and resistance to light ies, polyurethanes, natural and synthetic
and oxidation are needed, the higher priced rubbers if vulcanized, anaerobics, and
acrylic ester copolymers are preferred. Poly- unsaturated polyesters.
isobutylene, also resistant to ultraviolet degra-
dation, is utilized for removable labels. The term "thermosetting" has been used tra-
ditionally for crosslinking compositions, even
Two sided pressure-sensitive tapes, as well
as most PS labels, are interlined with release when they do not require elevated temperature
paper to prevent them from sticking together to initiate the chemical reaction.
prior to use. The abhesive or antistick property Crosslinking may involve the reaction of two
requires that the release web have a surface en- chemically different intermediates, e. g. :
ergy significantly lower than the surface ten- (a) formaldehyde condensed with phenol,
sion of the masscoat. Silicone coatings meet resorcinol;
this criterion. (b) formaldehyde condensed with urea, mel-
amine;
Origin (c) isocyanate reacted with polyol to give
The organic and semiorganic adhesives may be polyurethane;
classified according to origin as: (d) epoxide reacted with primary amine or
polyamide-amine;
1. Natural: starch, dextrins, asphalt, animal (e) unsaturated polyester copolymerized
and vegetable proteins, natural rubber, with styrene;
and shellac. (f) sulfur-vulcanized diene rubbers.
2. Semisynthetic: cellulose nitrate and the
other cellulosics, polyamides derived Crosslinking may also take place among
from dimer acids, and castor-oil based molecules of a single species, for example:
polyurethanes.
(a) epoxide catalyzed by tertiary amine;
3. Synthetics: (b) dimethacrylate compounded anaerobi-
(a) Vinyl-type addition polymers, both cally so that it will polymerize when air
resins and elastomers: polyvinyl ace-
is excluded;
tate, polyvinyl alcohol, acrylics, un-
(c) peroxide-vulcanized rubbers.
saturated polyesters, butadiene-
acrylonitrile, butadiene-styrene, neo- Most adhesives which crosslink at room tem-
prene, butyl rubber, and polyisobu- perature are packaged in two containers, mixed
tylene. just before use. The moisture-curable adhe-
(b) Polymers formed by condensation sives and sealants, however, are single-com-
and other step-wise mechanisms: ponent compositions which have long shelf life
epoxies, poly.urethanes, poly sulfide as long as they are in closed containers, but
rubbers, and the reaction products of react when dispensed and thus exposed to water
formaldehyde with phenol, resorci- vapor in the air. Among the growing roster of
nol, urea, and melamine. moisture-curable systems are three types of
 INTRODUCTION TO ADHESIVES 9

sealants, as well as various adhesives: and compressive strength). The size range of
hybrids is broad:
(a) Isocyanate prepolymers, made, e.g., by
reaction of polyether polyol with an ex- A
cess of aromatic diisocyanate, react with Composites 104 _105 and larger
moisture to yield polyurethane-ureas. Intermolecular 102-103
The concomitant formation of carbon Polymer blends
dioxide gas is a drawback.
(b) Silicones are made moisture-curable by Intramolecular
blocking the end hydroxyls with easily Random copolymers
hydrolyzable acetate groups. Consumer Graft and block
sealants of this type are recognizable by copolymers
the acetic acid odor, when first applied. Other hybrids
(c) Polysulfide sealants can be compounded Among the more significant adhesive hybrids
with calcium peroxide or barium perox-
are:
ide, which reacts with moisture to re-
lease hydrogen peroxide, which cures the 1. Neoprene (polychloroprene)-phenolics:
polysulfide. Cure is slower than with the good "green" strength, adjustable open
lead dioxide cure of two-component sys- times, and high cured strength.
tems. 2. Nitrile-phenolics: excellent strength at
(d) Unsaturated polyesters likewise utilize high temperatures (but requires pressure
barium peroxide, plus a cobalt salt, as a because of evolution of water vapor).
latent catalyst system activated by mois- 3. RFL (resorcinol formaldehyde resin plus
ture. latex): bonding of tire cord to rubber.
(e) Cyanoacrylates polymerize sponta- 4. Epoxy-nitrile: metal bonds with high peel
neously in the presence of basic cata- strength.
lysts, even with very weak bases such as 5. EVA-wax-low molecular weight resin:
water. Setting takes place within a few hot-melts for packaging, bookbinding,
seconds after exposure to atmospheric furniture edge-banding, etc.
moisture. Coupling agents are bifunctional hybrids de-
(f) Epoxy resins can be compounded with
signed to improve the adhesion between phases
ketimines which, on exposure to mois- in composites and blends. Usually the disperse
ture, release amine curing agents. This phase is inorganic, and the coupling agents ac-
technology, already used in coatings, cordingly consist of an organic functional group
may be applicable also to the adhesive and an inorganic residue. The organic active
bonding of porous substrates. site is utilized either to form a true chemical
bond with the organic matrix, or at least to as-
sure strong affinity to it, while the inorganic
Hybrids and Coupling Agents
part reacts with or is absorbed by the reinforce-
Many adhesive-bonded compositions are hy- ment. Currently, the most popular types of
brids, combining two types of groups. An im- coupling agents are of the silane type,
portant benefit of many types of hybrids is a X-R-Si(R')3. The R'-Si bond is hydrolyz-
non-Hookeian (nonlinear) stress-strain curve, able. R' may be alkoxy, chloro, or acetoxy.
with increased area under the curve (work to The organic functional sites "X" are designed
break), hence higher toughness, impact to match the polymer. Among these are amino
strength, and peel strength. Typically they have and epoxide for bonding to epoxy resins as well
at least two Tg's (glass transition tempera- as other polymers, and vinyl for bonding to un-
tures), one below room temperature for the saturated polyester.
elastomeric component (providing good elon- One of the important adhesion problems
gation), the other well above room temperature which has received much attention but still re-
for the rigid component (providing good tensile mains not completely solved is the coupling of
10 HANDBOOK OF ADHESIVES

some reinforcing fibers to thennosetting and mal insulation-also demand binders with good
thennoplastic matrix in advanced composites. heat resistance.
While silanes work well on glass, bonding of Phenolics, the oldest completely synthetic
graphite and aramid fibers could still be im- adhesives, perfonn well at elevated tempera-
proved. Titanate coupling agents seem to work ture, and are available at the low cost that is a
better on aramid then do silanes,58 and graphite necessity in the more mundane applications.
fibers are often sized with uncatalyzed epoxy The aromatic rings, the high crosslink density,
resins when epoxy is used as composite matrix and the resonance-intensifying hydroxyl groups
as well. However, new trends in advanced all contribute to heat resistance as well as high
composites are toward heat-resistant thenno- shear strength. But cured phenolics still contain
plastic matrices which could be even more dif- methylene linkages which provide sites for
ficult to couple with fibers. thennal degradation.
Where still more heat resistance is needed,
Adhesive Films we now have the polyimides, polybenzimida-
zole, polyquinoxalines53 and other linear poly-
Both thennosetting and thennoplastic adhe-
mers in which the methylene content is reduced
sives are available in film fonn. Films offer
or eliminated. Conjugated unsaturation in-
many advantages. They are unifonn in both
creases the thennal stability of these materials.
composition and thickness, convenient to han-
Unfortunately, as the extent of condensation
dle, free from volatiles. But they are difficult
approaches that of the "ladder polymer" pyr-
to make, hence expensive; also, they require
rones which might provide optimum heat resis-
heat and pressure to achieve satisfactory bonds.
tance, the polymers become more intractable.
The largest volume film adhesive, polyvinyl
The type of polymer produced by condensing
butyral for safety glass, has been discussed
aromatic polyacids and polyamines depends on
above under the heading "thennoplastics."
the functionality of the reactants:
Another thennoplastic, pressure-sensItIve
acrylic, is the film material that is growing most
Amine Acid
rapidly. It is used to bond nameplates and trim
Functionality Functionality Polymer
on appliances, metal office furniture, machin-
ery, etc.
2 2 Polyamide (nylon)
The thennosetting films are employed for
2 3 Polyamide-imide
metal-to-metal bonding in aircraft, as well as
2 4 Poly imide
less demanding appliance, electrical, and au-
4 2 Polybenzimidazole
tomotive requirements. These adhesives are
4 4 Pyrrone
hybrids designed to provide an optimum com-
bination of shear strength, elongation, and heat Flame retardancy is a characteristic now re-
resistance. Nitrile-phenolic and epoxy-nitrile quired by the U.S. Government, under the
are the leaders, followed by vinyl butyral-phe- Flammable Fabrics Act, of an increasing num-
nolic, epoxy-nylon, and epoxy-phenolic. The ber of products including carpets, mattresses,
nitrile rubber in the epoxy-nitrile is a carboxyl- automotive upholstery, and children's sleep-
tenninated butadiene-nitrile polymer which wear. The lowest cost flame-retardant organic
reacts with the epoxy at the elevated cure tem- adhesives are vinyl chloride polymers plasti-
perature. cized with phosphate esters, and these are in-
deed being utilized for carpet backing and in
High Temperature Resistance;
the bonding of automotive fabrics. Ironically,
Flame Retardance some of the copolymers which were hailed in
Resistance to prolonged exposure to high tem- the early 1970's as answers to the Govern-
peratures is required of some adhesives for the ment's flame retardance regulations have later
aircraft, aerospace, and electrical industries. been withdrawn because they fail to meet the
Many less glamorous end uses-foundry molds requirements of another Government agency,
and cores, coated and bonded abrasives, brake OSHA, for low content of vinyl chloride
linings and other friction materials, and ther- monomer, now branded a carcinogen.
 INTRODUCTION TO ADHESIVES 11

Other flame-retardant adhesives contain vi- But porous adherends require the appli-
nylidene chloride latexes, halogenated epoxies, cation of sufficient adhesive to avoid a
or additives such as diammonium phosphate or "starved glue line." If the joint is to be
ammonium sulfamate. The epoxy resin derived exposed to considerable shear stress, the
from tetrabromo- or tetrachlorobisphenol A is glue line should be somewhat thicker.
used in special aircraft adhesives. 4. Incorporate inert and preferably inor-
ganic fillers.
MATCHING ADHESIVE TO ADHEREND 5. After applying the adhesive to an imper-
vious substrate, evaporate water or sol-
The adhesive and adherend must be compati-
vents thoroughly before mating with a
ble, if their union is to last.
second impervious adherend.
When two materials are bonded, the resultant
composite has at least five elements: adherent
In Chapter 3 of this Handbook, Gent and
No.1 / interface / adhesive / interface / adherend
Hamed provide a comprehensive presentation
No.2.
of adhesion theory. Surface preparation is dis-
The strength of the adhesive joint will be the
cussed by Mahoney in Chapter 4, and adhe-
strength of its weakest member. If one of the
sives evaluation is examined in Rice's Chapter
adherends is paper, excessive stress will usu-
5.
ally result in a "paper tear." With stronger
In this introductory chapter, we focus on two
substrates, however, the failure will be either
factors relating choice of adhesive to the sub-
adhesive at an interface or cohesive within the
strate: critical surface tension and solubility
glue. Failure will not be at an interface if the parameter.
adherend surface has been properly prepared
Let us examine the types of bonds that may
and the adhesive wets the adherend and is oth-
exist between adhesive and adherend. These
erwise appropriate. In other words, the adhe-
chemical bonds may be either primary or sec-
sion between glue and substrate should be ondary.
greater than the cohesion within the glue line. Primary bonds include electrovalent, cova-
This will occur provided the combining of ad- lent, and metallic bonds. Electrovalent or het-
hesive and adherend has caused a decrease in eropolar bonds may be a factor in protein
free energy, and provided also that excessive adhesives. Covalent or homopolar bonds play
strains are not built up when the adhesive sets. a part in some finishing treatments for fiber
Let us consider the latter requirement first. glass. The metallic bond is formed by welding,
Adhesives usually shrink as they harden. (In- soldering, and brazing. The metals and alloys
organic cements are exceptions.) Polymeriza- involved are essentially high temperature ther-
tion, the loss of solvent, even the cooling of a moplastic adhesives, but are outside the scope
hot-melt may cause the glue line to contract. of this volume.
Strains are set up which induce the adhesive to By far the most important of the adhesive
pull away from the substrate. In addition,
bonds are the secondary or Van der Waals'
strains are produced when the adhesive jointis
bonds that give rise to attraction between mol-
flexed. Various remedies may lessen the dan- ecules. Most significant of these are the Lon-
ger of failure from these causes: don or dispersion forces. They are responsible
1. Choose low-shrinking resins, e.g., epox- for virtually all the molar cohesion of nonpolar
ies rather than unsaturated polyesters. polymers such as polyethylene, natural rubber,
2. Choose adhesives that are less rigid than SBR, and butyl rubber. These forces act at a
the adherends; otherwise flexing will distance of approximately 4 A, and falloff rap-
cause a concentration of stress in the glue idly, as the sixth power of the distance between
line. (However, excessive flexibility in atoms. Consequently, molecules must be in
the adhesive may be accompanied by low close proximity for London forces to be effec-
cohesive strength.) tive. This helps to explain why a very flexible
3. Keep the glue line as thin as possible, molecule such as natural rubber is a better ad-
consistent with the smoothness of the ad- hesive than a moderately flexible molecule such
herends, if the stresses are chiefly tensile. as polystyrene. Low modulus, indicating free-
'2 HANDBOOK OF ADHESIVES

dom of rotation of submolecules that permits critical surface tensions for spreading, with
the adhesive to conform to the adherend, is ad- great precision, for well over one hundred
vantageous to adhesion. polymers, from measurements of the contact
Interaction of permanent dipoles results in angles with a variety of liquids whose surface
strong bonds, especially if the positive dipole tensions had been determined. The critical sur-
is an H-atom. The hydrogen bond, typified by face tension delineates the wettability of a solid
- + - +
surface, indicating the maximum surface ten-
"/N - H ... O=C" / sion desirable
substrate.
in an adhesive for a particular

Zisman showed that comb-shaped polymers

accounts for the excellent success with polar with long fluoroalkyl side chains have the low-
substrates of such diverse adhesives as starch est critical surface energies, while hydrogen
and dextrin, polyvinyl alcohol, polyvinyl ace- bonding polymers such as ureaformaldehyde,
tals, cellulose nitrate, phenolics, and epoxies. proteins and cellulose rank highest. To assure
All of these adhesives contain phenolic or ali- spreading and wetting, the fluid adhesive
phatic hydroxy Is. The carboxyl group, incor- should have a surface tension no higher than
porated in small percentage in many vinyl-type the critical surface tension of the solid adher-
polymers, is an even more powerful aid to end.
adhesion. An entire chapter in this volume is
devoted to carboxyl-containing elastomers.
Solubility Parameter
Among the adherends utilizing H-bond adhe-
sives are wood, paper, leather, glass, and met- When the substrate is organic and not too po-
als. lar, the solubility parameter is useful in helping
Two approaches, ostensibly different but in to select an adhesive.
fact related, facilitate the selection of an appro- If the bond between adhesive and substrate
priate adhesive to bond a specific substrate. In is to be strong, there must be a decrease in free
the Second Edition of this Handbook, 19 Zisman energy as a result of combining the two. The
examines the influence of constitution on adhe- free energy change on mixing two materials is:
sion and demonstrates the usefulness of critical
surface energy in determining which adhesives t:.F = t:.H - T t:. S,
will wet a surface. In the present chapter, sol-
ubility parameter is discussed as a tool for pre-
dicting the compatability of adhesive and where t:. H is the heat of mixing and t:. S is the
adherend. Gardon 34 ,35 has pointed out the cor- entropy change. In general, when two mate-
relation between the two, which is borne out rials are mixed, there is an increase in entropy;
also in Table 1, in which some of the solubility consequently the second term on the right of
parameters collected by Gardon and Burrell are the equation is negative. If we can ignore the
compared with some of the critical surface ten- heat of mixing term, the free energy will also
sions tabulated by Shafrin in the Second Edi- be negative. This tells us that materials will
tion. 19 tend to combine provided the heat of mixing is
Figure 1 shows that, with increasing polarity not too high on the positive side. We see, also,
and hydrogen bonding, the solubility parameter that raising the temperature makes the entropy
rises more sharply than the critical surface ten- term more negative, thus aiding the process of
sion. combination. This is particularly true when at
least one of the materials being mixed or com-
bined is a high polymer.
Critical Surface Tension
The heat of mixing depends on the attractive
In a series of classic investigations over a pe- forces between adhesive and adherend. These
riod of more than 25 years, Zisman and co- forces may be either primary or secondary
workers at Naval Research Laboratory bonds. If the heat of mixing is zero or if it is
examined the relationship between adhesion negative as the result of hydrogen bonding or
and chemical constitution. They determined the other chemical combination of adherend and
 INTRODUCTION TO ADHESIVES 13

Table 1 Solubility Parameter and Critical Surface Tension

Solubility Critical Surface
Parameter, £> Tension, 'Yc
hildebrands (dyn cm- 1 )

Poly(l H, 1 H-pentadecafluoroctyl acrylate) 10.4

Polytetrafluoroethylene 6.2 18.5
Silicone, polydimethyl 7.6 24
Butyl rubber 7.7 27
Polyethylene 7.9 31
Natural rubber 7.9-8.3
Natural rubber-rosin adhesive 36
Polyisoprene, cis 7.9-8.3 31
Polybutadiene, cis 8.1-8.6 32
Butadiene-styrene rubbers 8.1-8.5
Polyisobutylene 8.0
Polystyrene 9.1 32.8
Polysulfide rubber 9.0-9.4
Neoprene (chloroprene) 8.2-9.4 38
Butadiene-acrylonitrile rubbers 9.4-9.5
Poly(vinyl acetate) 9.4
Poly(methyl methacrylate) 9.3 39
Poly(vinyl chloride) 9.5-9.7 39
Urea-formaldehyde resin 9.5-12.7 61
Epoxy 9.7-10.9
Polyamide-epichlorohydrin resin 52
Ethyl cellulose 10.3
Poly(vinyl chloride-acetate) 10.4
Poly(ethylene terephthalate) 10.7 43
Cellulose acetate 10.9 39
Cellulose nitrate 10.6-11.5
Phenolic resin 11.5
Resorcinol adhesives 51
Poly(vinylidene chloride) (saran) 12.2 40
Nylon 6,6 13.6 43
Polyacrylonitrile 15.4 44
Cellulose, from wood pulp 35.5,42
Cellulose, from cotton linters 41.5
Cellulose, regenerated 44
Starch 39
Casein 43
Wool 45

adhesive, then wetting will surely be accom- where t:..E = the energy of vaporization, and
plished. For most nonpolar or moderately polar V = the molar volume.
pairs of materials, however, the heat of mixing
is positive; consequently the free energy will The term, t:..EIV, the energy of vaporization per
decrease only if this positive term is not too cc, is called the internal pressure or cohesive-
high. energy density. Its square root, the solubility
Hildebrand22 and others23 - 3o utilized the con- parameter, is termed the "hildebrand."
cept of solubility parameter, 0, to show why For liquids such as the fluorocarbons and hy-
some pairs of materials mix more readily than drocarbons, this energy is very low; therefore
others. The solubility parameter is related to the low molecular-weight materials of these com-
internal pressure or cohesive-energy density: positions have very low boiling points. The low
molecular-weight fluorocarbons were thus used
in aerosol dispensers, until it was realized that
14 HANDBOOK OF ADHESIVES

16r---------------------------~ coatings; and Skeise3 applied it to the selection

IS of adhesives for plastics. Gardon34 ,35 has pro-
<0 14 vided a comprehensive review of the volumi-

.
~ 13 nous literature. See also Chapters on
Thermoplastic Rubbers, Neoprene, and Bond-

7
~ 12 Poly(vinylidene chloride) 0
ing Plastics.
~ II Cellulose Acetate 0 Burrell attributed some discrepancies be-
~
::!
10 Polys try rene PV tween theory and fact to hydrogen bonding, and
9 Butyl Polybutadiene, 0 0 PMMA Hansen and Crowley added dipole moment as
=
~ 8
Rubbers ~ cis
still a third parameter which should be similar
- Silicone, 0 Neoprene
@ 7 Polydimethyl Polyethylene in the two materials being brought together.
6 Poly(ethylene These two characteristics do not necessarily
Polytetrafluoroethylene tereph thai ate ) operate in parallel. Thus, for example, dioxane
has high hydrogen bonding but almost no di-
CRITICAL SURFACE TENSION he), DYNES/CM. pole moment, while ethylene carbonate com-
Fig. 1. Critical surface tension vs. solubility parameter. bines a more moderate hydrogen bonding with
high dipole moment. 37
they adversely affect the ozone layer; and low
Solubility Hydrogen Dipole
molecular-weight hydrocarbons are the main
Parameter Bonding Moment
constituents of natural gas.
As soon as we incorporate polar groups, we Dioxane (1, 9.9 9.7 0.4
find that it requires more energy to vaporize a 4)
molecule, i.e., to separate it from its compan- Ethylene car- 14.7 4.9 4.9
ions. Thus, acetone has a higher boiling point bonate
than butane, and isopropyl alcohol is still
higher, although all three molecules are ap- The solubility parameter of a polymer cannot
proximately the same size and weight. be measured directly, as polymers are not vol-
Hildebrand indicated that the greater the dif- atile. It can be calculated from Small's molar
ference between the solubility parameters of the attraction constants, but preferably it is inferred
two materials, the greater the (positive and un- from the solubility parameters of solvents hav-
desirable) heat of mixing. ing maximum solubilizing or swelling action.
Table 1 shows good correlation between sol-
Ubility parameter and critical surface tension for
polymers at the low end of both scales. With
where V = the total volume, and cP! and cP2 = increasing values, however, anomalies become
the volume fractions of the respective compo- apparent, e.g., for amino resins and urea for-
nents. Consequently, combination is most maldehyde, poly(ethylene terephthalate), and
likely to take place when adhesive and adher- cellulose from different sources. The discrep-
end are most alike in solubility parameter. Fur- ancies can be attributed at least partly to differ-
thermore, the composite is most likely to resist ences in crystallinity, the presence of
the intrusion of another material (for example, compounding ingredients, and differences in
water) when solubility parameters are close to- chemical composition of the bulk polymer from
gether. the surface. Surface treatment of polyethylene,
Solubility parameter theory was advanced whether by flame, liquid oxidants, electron
first by Hildebrand and Scott. 30 Smale! devel- bombardment, or ionic bombardment, creates
oped a method for calculating the parameters carboxyl groups and other oxygen-containing
from the contributions of groups within the moieties which raise the surface energy, allow-
molecule. Burrell,32 Hansen,36, 38 and Crowley ing the treated polyethylene to accept printing
et al. 37 were especially successful in utilizing inks and polar adhesives which would other-
the concept for the formulation of solvent-based wise not wet the polymer. Where solubility pa-
 INTRODUCTION TO ADHESIVES 15

rameter and contact angle measurements When the adhesives are crosslinked by cur-
disagree, therefore, the latter provide the better ing agents, the design also includes the type of
direction for choosing adhesives, provided they crosslinker, accelerator, etc. Intermolecular re-
have been carried out on the materials as ac- actions between the polymer base and modi-
tually prepared for bonding. fying resins, e.g., neoprene and phenolic resin,
Frequently it is necessary to combine mate- impart stability and non-separation properties
rials having quite dissimilar solubility param- to the adhesives formulae. And, when the com-
eters, and often differing in modulus as well. position includes inorganic fillers or reinforce-
An important example, the manufacture of ment, chemical linkage is constructed through
tires, is discussed in the chapter, "Bonding a coupling agent which ties the matrix polymer
Textiles to Rubber." Use is made of a hybrid to the inorganic surface.
adhesive, RFL, containing heat-resistant resor-
cinol-formaldehyde for good attachment pri- Grafting
marily to the polar, high modulus fiber, plus an
Polar monomers are grafted onto polyolefins in
elastomer of moderate solubility parameter,
order to improve the adhesion properties of the
butadiene-styrene-vinyl pyridine terpolymer la-
latter. This technique is used, for example, with
tex, mainly for the rubber.
polypropylene and polyethylene resins for ex-
Table 2 prepared by Reinhart and Callomon59
trusion coating and hot-melt adhesive applica-
is a succinct tabulation of adhesives suitable for
tions as well as for resin grades reinforced with
combining either similar or different substrates.
glass. The grafted monomers are usually either
acrylic acid or maleic anhydride. Carboxyl
DESIGNING POLYMERS FOR groups introduced in this manner provide in-
ADHESIVES creased adhesion to glass or mineral fillers in
molding resins, as well as better coupling to
Advances in polymer chemistry and technol- aluminum foil, paper, and other substrates in
ogy have led to a variety of new polymers, hy- extrusion-coated products.
brids, copolymers, etc., presenting the adhesive
formulator with a wide choice of materials. Reactive Oligomers and Polymers
Many approaches to synthesis are available:
This approach is already utilized widely in ra-
Grafting diation-cured adhesives, urethane and epoxy
Block copolymerization adhesives, and other areas. Here an oligomer
Reactive oligomers of a particular type, e.g., polyurethane, is ter-
Interpenetrating networks minated with functional groups which are sub-
Copolymerization with functional mono- sequently exploited to extend the polymer chain
mers or to crosslink the system. Examples of com-
mercial materials include:

Polymer Backbone Functional End Groups Use

Urethane Acrylate Radiation cure
Epoxy Acrylate Radiation cure
Silicone Acrylate Radiation cure
Polyether Isocyanate Urethane adhesives
Polyester Isocyanate Urethane adhesives
Polybutadiene Carboxyl Rocket fuel binders
Polyimide Ethynyl Heat resistant adhesives
Polyimide Nadic Heat resistant adhesives
Polybutadiene Hydroxyl Urethane adhesives
Butadiene-acrylonitrile Amine Epoxy adhesive hardeners
Polystyrene ("Macromer") Methacrylate Hot melt pressure-sensitives
 ...
0)

Table 2 Selecting Adhesives. 12 %

J>
Z
Vinyl Phenolic Tile, C
Leather Paper Wood Felt Fabrics Plastics Plastics Rubber etc. Masonite Glass Metals ~
o~
Metals 1,4,21,24, 1,21,22 1,4,11,13, 1,5,22 1,21,22,24 25,36 3,13,21,31, 13,21,22,31, 5,6,13,22, 5,6,13,22 13,32,33, 11,13,31, o."
25 21, 31, 32, 33, 32,33,35,36 32,33,35,36 35,36 34,35 32,33,36
35,36 J>
C
%
Glass, 1,4,13,24 1,21,22 I, 13, 21, 31, 1,5,6, 1,21,22,24 25,36 3,13,21,31, 21,22,31,35, 4,22 4,13,32, C;
ceramics 32, 33, 35, 36 21, 22 35,36 36 35,36 <
C;
Tile, etc. 1,4,21,24 I, 21, 22 1,5,6,21, 5,6,21,22 5,6,21,22, 25,36 3,13,36 21,22,31,35,4,5,6,22 5,8,13
22 24 36
Masonite 1,21,24 1,21,22 1,5,6,21, 5,6, 21,22 5,6,21,22, 25,36 3,13,36 21,22,31,35, 5,6,22
22 24 36
Rubber 21,24 21,22 21, 22, 33, 35, 21,22 21,22,23 25,36 21,22,36 21,22,31,35,
36 36
Phenolic 21,24,25 21,22 11, 13, 21,24, 21,22,25 21,22,24, 36 13,32,33,36
plastics 32, 33, 36 36 25
Vinyl 21 21 21 21 21 25, 36
plastics
Fabrics 21, 22, 23, 21,22,23 21,22,23 5,21,2~23 1,21,22,23
24
Felt 21,22,23, 21,22,23 21,22,23 5,22
24
Wood 21,22,23, 2,21,22 1,11,12,
24 14, 15, 36
Paper 21,22,23, 2,4,21
24
Leather 1,4,21
22,23,24
 INTRODUCTION TO ADHESIVES 17

Copolymerization
A variety of functional monomers can be dis-
tributed throughout the polymer chain, usually
in random fashion, to impact specific proper-
ties at relatively low incorporation level.
Though usually more expensive on a per pound
basis than the monomer which is the major
component of the copolymer, they offer high
cost effectiveness. Many examples can be of-
fered. Allyl ureide56 • 57 monomers have been
incorporated as adhesion-promoting moieties in
architectural latex paints at levels as low as
I % or less to provide wet adhesion to the sub-
strate. Similar benefits were obtained from such
monomers as dimethyl-t-butylaminoethyl-
methacrylate, aminoalkyl methacrylate, and
ethylene imine, though the latter, because of its
carcinogenicity, is no longer produced in the
u. S. Acrylic acid and other organic acids
(methacrylic, fumaric, crotonic) are introduced
during polymerization of ethylene and propyl-
ene to provide adhesion to metal and other
polar substrates.
An interesting modification involves expand-
able monomers. These materials, synthesized
by Dr. William J. Bailey and coworkers at Uni-
versity of Maryland, are spiro monomers, dou-
ble rings which open and expand on
polymerization. 61 • 62 They can be useful in ad-
hesives which are based on polymer/monomer
solution, such as "structural" acrylics, radia-
tion-cured acrylates, etc. These monomers can
counteract shrinkage on curing, which is det-
rimental to adhesion.
Crosslinking is an additional task for co-
monomers. N-methylol acrylamide fulfills this
function in acrylic, vinyl acetate and styrene-
butadiene latexes for textile binding. Glycidyl
methacrylate can crosslink through reaction of
its epoxide moiety with carboxyl or amino
groups. Isocyanatoethyl methacrylate54 con-
tains a reactive isocyanate group; there are
many others.

Block Copolymers

Synthesis of these has led to the development

of thermoplastic elastomers, useful especially
in hot-melt pressure-sensitive adhesives.
Polymers with two glass transition tempera-
tures have been developed which are elasto-
18 HANDBOOK OF ADHESIVES

meric at ambient temperature but become fluid resins, heat-resistant adhesives are in demand
at elevated temperatures. Typical examples are as well.
styrene-isoprene-styrene or styrene-butadiene- Some developments for non-adhesive pur-
styrene block copolymers with their "soft" poses could serve as a starting point to improve
midblocks (low Tg) and "hard" end blocks, adhesives as well. For example, superabsor-
and their hydrogenated modifications, styrene- bents, polymers which soak water avidly, could
ethylene-butylene-styrene. become a basis for adhesives to be applied on
wet surfaces. Other polymers could be devel-
oped to have similar affinity to oil, hence to be
Interpenetrating Polymer Network (lPN) useful for application on oily substrates.
Conductive polymers are the subject of ex-
IPN55 is a new approach to the synthesis of tensive research at many universities and in-
polymers. While still mostly in the investiga-
dustrial research centers. If successfully
tive rather than the commercial stage, IPNs
commercialized, they could become a starting
could become an important tool in designing
point for conductive adhesive formulations and
adhesives. The IPNs are crosslinked or semi-
eliminate the need for the costly silver fillers
crosslinked systems, composed usually of two
used now. These polymers are likely to be
types of three-dimensional polymer networks
based on delocalized electron structures such as
interlocked with each other. This permits the
conjugated double bonds, wholly aromatic
coupling of two dissimilar polymers with
polymers, and the like.
widely disparate glass transition temperatures,
Cross linkers and Accelerators. Besides the
solubility parameters, polarities, etc. A two-
polymers themselves, changes and improve-
glass transition temperature system of that type
ments are taking place in curing agents, hard-
could also be useful in pressure-sensitive ad-
eners, catalysts, and polymer modifiers. For
hesives and other applications where different
example, if epoxy adhesives with improved
elastic properties are needed at ambient and at
heat resistance are needed, the hardeners can
elevated temperatures. The dual glass transi-
be aromatic anhydrides and amines such as
tion pattern also leads to high energy absorp-
benzophenone tetracarboxylic dianhydride, py-
tion characteristics, and adhesives based on
romellitic dianhydride, diaminodiphenyl sul-
polymers of that type could be important in en-
fone. To enhance curing speed, epoxy systems
ergy absorbing devices-acoustical, crash pads,
utilize mercaptan hardeners, while acrylic
etc. Another goal could be improved toughness
monomer/polymer blends avail themselves of
when a high glass transition temperature, high
amine/aldehyde catalysts with benzosulfimide
modulus adhesive with low elongation is
(saccharin) accelerators. Radiation-curing sys-
"married" to a low modulus elastomer such as
tems for today and tomorrow utilize both visi-
a silicone.
ble light and laser beams.
Toxicity. While many new materials are
added to the adhesive chemist's arsenal, some
NEW TRENDS
are being removed as well. Compounds which
Many trends in polymer synthesis generally are cause health and environmental concern in-
being applied, or could be applied in the future, clude ethylenimine, methylene-bis(o-chloroan-
to adhesives. There is a continuous stride to- iline) (MOCA), hexamethylene diisocyanate,
ward polymers with superior heat resistance. formaldehyde. Some systems are no longer in
To achieve this, various heterocyclic and aro- use; in others, modifications have been made.
matic structures are built into polymers, e.g., Thus radiation-curing technology is replacing
by intramolecularcyclization (polyimides, poly- some types of multifunctional acrylate mono-
benzimidazoles), trimerization of terminal mers with alkoxylated compounds, because the
acetylene or nitrile groups, etc. Another route latter are less irritating and less toxic. An ex-
is to introduce highly stable perfiuorinated units ample is trimethylolpropane triethoxy triacry-
into the polymer. While heat-resistant poly- late.
mers find their main applications as laminating Theoretical Developments. Advances in
 INTRODUCTION TO ADHESIVES 19

polymer theory have their applications also in 9. Kinloch, A. J., "Structural Adhesives: Develop-
research on the phenomena of adhesion. Ad- ments in Resins and Primers," New York, Elsevier
Science Publishing Co., 1986.
sorption at the interface, diffusion, and other 10. Lee, Lieng-Huang (Ed.), "Adhesive Chemistry: De-
subjects related to adhesion have been investi- velopments and Trends," New York, Plenum Pub-
gated through a scaling approach which uses lishing Co., 1985.
mathematical models taken from physics (fer- 11. Lees, W. A., "Adhesives in Engineering Design,"
romagnetism theory) to explain the random Deerfield Beach, Florida, Springer-Verlag, 1985.
12. Miller, Robert S., "Energy Conservation with Ad-
walk behavior of polymer molecules. 39-41
hesives and Sealants," Columbus, Ohio, Franklin
Studies of kinetics of wetting include work by International, 1986.
de Gennes42 and Cazabat. 43 Electrostatic adhe- 13. Moskovitin, N. I., "Physiochemical Principles of
sion theory was developed in the 1970s by Der- Gluing and Adhesion Processes," Philadelphia, Co-
yagin.44 ronet Books (for Keter Publishing Co., Jerusalem),
1968.
Analytical methods to probe adhesion have
14. Panek, Julian R., and Cook, John P., "Construction
also advanced. Dynamic mechanical analysis Sealants and Adhesives," 2nd Ed., New York, John
methods have been found especially useful in Wiley and Sons, 1984.
investigating the cure process of epoxy resins 15. Patrick, Robert L., "Treatise on Adhesion and Ad-
and in research on pressure-sensitive formula- hesives," Vol. 5, New York, Marcel Dekker, 1981.
16. Satas, Donastas (ed.), "Handbook of Pressure-Sen-
tions. Widely used is torsional braid analysis sitive Adhesive Technology," New York, Van Nos-
(TBA).48.49 Surface investigation avails itself trand Reinhold, 1982.
of electron spectroscopy for chemical analysis 17. Schneberger, G. L. "Adhesives in Manufacturing,"
(ESCA).5o Other investigative approaches to New York, Marcel Dekker, 1983.
following the cure of epoxies include dielectric 18. Shields, J., "Adhesives Handbook," 3rd Ed., Stone-
ham, Massachusetts, Butterworth, 1984.
spectroscopy51 and viscosity-dependent flu-
19. Skeist, Irving (ed.), "Handbook of Adhesives," 2nd
orescent probe. 52 Ed., New York, Van Nostrand Reinhold, 1977.
20. Wake, William C., "Adhesion and the Formulation
of Adhesives," 2nd Ed., Applied Science Publish-
REFERENCES ers, London and New York, 1982.
21. Weiner, Jack, and Roth, Lillian, "Adhesives," 4
1. Laurie, A. P., "Materials of the Painters Craft," volumes, Appleton, Wisconsin, Institute of Paper
London, Poulis, 1910. Chemistry, 1974.
2. Gettens, R. J., and Stout, G. L., "Painting Mate-
rials," New York, Van Nostrand Reinhold, 1942.
Journals
22. Adhaesion (in German), since 1957, Bertelsmann
Selected Books on Adhesion and Fachzeitschriften GmbH, Postfach 800345, Neu-
markter Str. 18,8000 Munich 80, W. Germany.
Adhesives
23. Adhesion and AdhesiveslSetchaku (Text in Japa-
3. Cagle, Charles V., Lee, Henry, and Neville, Kris, nese), since 1957, High Polymer Publishing Asso-
"Handbook of Adhesive Bonding," New York, ciation, Kobunshi Kankokai, Chiekoin-Sagaru,
McGraw-Hill, 1973. Marutamachi, Kamikyoku, Kyoto 602, Japan.
4. Flick, Ernest W., "Adhesives, Sealants and Coat- 24. Adhesives Age, since 1958, Communications Chan-
ings for the Electronics Industry," Park Ridge, New nels, Inc., 6255 Barfield Road, Atlanta, GA 30328.
Jersey, Noyes Publications, 1986. 25. Assemblages Adhesifs (Text in French), since 1976,
5. Gillespie, Robert H., et aI., "Adhesives in Building EDIREP, 30 rue Turbigo, 75003 Paris, France.
Construction," Washington, D.C., U.S. Govern- 26. Journal of Adhesion, since 1969, Gordon and Breach
ment Printing Office, 1987. Science Publishers Ltd., P.O. Box 197, London
6. Hartshorn, S. R. (ed.), Structural Adhesives: Chem- WC2E 9PX, England.
istry and Technology," New York, Plenum Publish- 27. Journal of Adhesion Science and Technology (Inter-
ing Co., 1986. national), since 1987, VSP, P.O. Box 346,3700 AH
7. Houwink, R. (ed.) "Adhesion and Adhesives, 2nd Zeist, The Netherlands.
Ed., New York, Elsevier Science Publishing Co.; 28. Journal of the Adhesion Society of Japan (Text in
Vol. I, "Adhesives," 1965; Vol. 2, "Applica- Japanese, some English), since 1965, The Adhesion
tions," 1967. Society of Japan, 5-8-29 Nishinakajima, Yodogawa-
8. Kinloch, A. J., "Adhesion and Adhesives: Science ku, Osaka 532, Japan.
and Technology," New York, Methuen, Inc. (for 29. International Journal of Adhesion and Adhesives,
Chapman and Hall), 1987. since 1980, Butterworth Scientific Ltd., Westbury
20 HANDBOOK OF ADHESIVES

House, Bury St., Guildford, Surrey GU2 5BH, En- 45. Papas, S. P., "uv Curing: Science and Technol-
gland. ogy," Technology Marketing Corp., 1978.
46. Hartshorn, S. R., "Structural Adhesive Chemistry
and Technology," New York, Plenum Publishing
Solubility Parameter References
Co., 1986.
30. Hildebrand, J. H., and Scott, R. L., "The Solubility 47. Hauser, M., and Haviland, G. S., "Adhesives in
of Nonelectrolytes," 3rd Ed., New York, Van Nos- Manufacturing," New York, Marcel Dekker, 1983.
trand Reinhold Co., 1950; "Regular Solutions," 48. Lee, W. A., and Oliver, M. J., "Study of Cure of
Prentice-Hall, Inc., Englewood Cliffs, N.J., 1962. Epoxy Resins by Torsional Braid Analysis," Brit.
31. Small, P. A., J. Appl. Chem., 3, 71 (1953). Polym. J., 15,40 (1983).
32. Burrell, H., "Solubility Parameters for Film For- 49a. Gilliam, J. K., A.I.Ch.E. J., 20,1066 (1974).
mers," Federation of Paint and Varnish Production 49b. Hazony, Y., Stadnicki, S. J., and Gilliam, J. K.,
Official Digest, 27, 726 (Oct. 1955); "A Solvent Polymer Preprints, 15(2), 549 (1974).
Fonnulating Chart," Federation of Paint and Var- 50. Briggs, D., "New Applications of ESCA," in "Ad-
nish Production Official Digest, 29, 1973-74 (Nov. hesive Chemistry," L. H. Lee, ed., p. 175, New
1957). York, Plenum Publishing Co., 1983.
33. Skeist, I., "Choosing Adhesives for Plastics," Mod- 51. Hedrig, P., "Dielectric Spectroscopy of Polymers,"
em Plastics" 33, 121, 130 (May 1956). New York, John Wiley and Sons, Inc., 1977.
34. Gardon, J. L., "Relationship between Cohesive En- 52. Levy, R. L., and Ames, D. P., "Monitoring Epoxy
ergy Densities of Polymers and Zisman Critical Sur- Cure Kinetics with a Viscosity-Dependent Fluores-
face Tensions," J. Phys. Chem., 67, 1935 (1963). cent Probe," in "Adhesive Chemistry," L. H. Lee,
35. Gardon, J. L., "Cohesive-Energy Density," in ed., p. 245, New York, Plenum Publishing Co.,
"Encyclopedia of Polymer Science and Technol- 1983.
ogy," N. M. Bikales, Ed., 3, 833, New York, John 53. Hergenrother, P. M., "States of Adhesives," in
Wiley and Sons, 1965. "Adhesive Chemistry," L. H. Lee, ed., p. 447, New
36. Hansen, C. M., "The Three Dimensional Solubility York, Plenum Publishing Co., Inc., 1983.
Parameter-Key to Paint Component Affinities: II and 54. Thomas, M. R., "Isocyanatoethyl Methacrylate: A
ill. II. Dyes, Emulsifiers, Mutual Solubility and Heterofunctional Monomer for Polyurethane and Vi-
Compatibility and Pigments," J. Paint Technol., 39, nyl Polymer Systems," ACS Meeting, Las Vegas,
(511), 505, (Aug. 1967). Nevada, March 1982.
37. Crowley, J. D., Teague, G. S., and Low, J. W., "A 55. Sperling, L. H., "Interpenetrating Polymer Mate-
Three Dimensional Approach to Solubility, " J. Paint rials and Related Materials," New York, Plenum
Technol., 38, (496), 269, (1966) and 39, (504), 19, Publishing Co., 1981.
p. 27, ref. 1 (1967). 56. U.S. Pat. 3,300,429 (1967) Frank J. Glavis, William
38. Hansen, C. M., and Beerbower, A., in "Kirk-Oth- 1. Keighley, and Thomas H. Haag to Rohm and Haas.
mer Encyclopedia of Chemical Technology," Sup- 57. U.S. Pat. 4,111,877 (1978) Dale D. Dixon, and
plementary Vol., 2nd Ed., p. 889, New York, John Frederick L. Hennan to Air Products & Chemicals.
Wiley and Sons, 1971. 58. Monte, S. J., "Titanates," Chapter 4 in "Handbook
of Fillers and Plastics," H. A. Katz and J. V. Mi-
lewski, eds., See also the chapter in this volume,
Recent Developments
"Non-silane Coupling Agents." New York, Van
39. de Gennes, P. G., "Scaling Concepts in Polymer Nostrand Reinhold, 1987.
Physics," Ithaca, New York, Cornell University 59. Reinhart, F. W., and Callomon, I. G., "Survey of
Press, 1975. Adhesion and Adhesives," WADC Technical Re-
40. de Gennes, P. G., Macromolecules, 14, 1637 (1981). port, 58-450, 1959.
41. de Gennes, P. G., Macromolecules, 15,492 (1981). 60. U. S. Pats. 4,348,503 (1982) and 4,429,088 (1984),
42. de Gennes, P. G., Rev. Mod. Phys., 57(3), Part I, Andrew G. Bachmann to American Chemical and
827 (1985). Engineering Co. (later Dymax Corp.).
43. Carzabat, A. M., Contemporary Physics, 28(4), 374 61. U. S. Pat. 4,387,215 (1983), William J. Bailey (later
(1987). assigned to Epolin Inc., Morristown, New Jersey).
44. Deryagin, B. V., Krotova, N. A., and Smilga, V. 62. ACS Symposium Series #59, "Ring Opening Poly-
P .. , "Adhesion of Solids," New York, Consultants merization, •• Takeo Saegusa and Eric Goethals, eds .•
Bureau, 1978. 1977; Paper #4, p. 38, William J. Bailey et al.
 2
The Role of Adhesives
In the Economy
ARNOLD BRIEF
Skeist Incorporated
Consultants to the Polymer Industries
Whippany, New Jersey

In the quarter century between publication of 1975, about 75 % of adhesive tonnage was
the first and third editions of Handbook of Ad- based on synthetic materials; by 1987, the share
hesives, the adhesives industry has shown ex- had climbed to 83 %. Synthetic adhesives pro-
citing development and diversity. It has grown vided improved adhesion to a variety of sub-
from 3 billion pounds worth $650 million in strates, can be applied at faster speeds, exhibit
1962 to over 10 billion pounds valued at $5.5 superior properties and have contributed to
billion in 1987. This chapter will concentrate new, challenging product designs (Tables
on the contributions made by adhesives to in- 2-6).
dustrial growth in the United States since the
second edition of this Handbook, reviewing
both the types of adhesives and applications THE "BIG SEVEN" RAPID GROWTH
employed by the adhesive-using industries. ADHESIVES
In 1975, these industries consumed about 7
billion pounds of compound valued at 2.2 bil- Although overall adhesive volume increased by
lion dollars. A dozen years later, the business 50% in the 1975-87 period, there were seven
had grown to 10.5 billion pounds worth $5.5 adhesive materials that experienced growth of
billion (see Table 1). at least 100%. These high performers are:
While overall adhesive consumption in- acrylics, cyanoacrylates, anaerobics, polyvinyl
creased 250% during the last 25 years, syn- acetate, ethylene-vinyl acetate, styrenic block
thetic compounds (thermoplastic, thermoset, copolymers, and polyurethanes (Tables 7 and
and elastomer) grew by more than 600 %. In 8).

Table 1. Growth of Adhesives.

Average Annual
Growth Rate. %
MM $
Ibs. MM (Ibs.) ($)

1975 7000 2200

1987 10500 5500 3.5 8

21
22 HANDBOOK OF ADHESIVES

Table 2. Market Share by Adhesive Type.

i975 1987
%(Ibs.) %($) %(Ibs.) %($)

Thermoplastic 37 35 44 40
Thermosetting 35 35 33 27
Elastomers 7 IS S 24
Natural and others 21 12 15 9

Table 3. Thermoplastic Adhesives.

Major Markets Key Adhesives Leading Applications
Construction PVAC Gypsum board
Textile C-SB Carpeting backing
Packaging PVAC, EVA Case sealing/assembly, folding carton
sealing/assembly

Table 4. Thermosetting Adhesives.

Major Markets Key Adhesives Leading Applications
Wood bonding UF,PF Particleboard, plywood
Construction PF, VF, Epoxy Glass fiber, asphalt roofing,
concrete
Foundry Phenolics
Auto Aftermarket Unsaturated polyester Body patching

Table 5. Elastomeric Adhesives.

Construction SBR Carpet installation, vinyl flooring
installation, ceramic tile
Pressure-sensitive Natural rubber, SIS block Tapes, labels
copolymer, Butyl

Table 6. Natural and Other Types of Adhesives.

Major Markets Key Adhesives Leading Applications
Construction Starch, Asphalt Gypsum board binders, roofing tiles
Packaging Starch Corrugated board

Table 7. High Achievers.

Table 8. High Achievers as a
% Increase
1975-89 (Ibs.) Percentage of Total.
Acrylics 175 1975 1987
Cyanoacrylates 500 %
Anaerobics 250 (Ibs.) % ($) % (Ibs.) % ($)
Polyvinyl acetate 100
Ethylene-vinyl acetate 150 "Big 7" IS 24 27 33
Styrenic block copolymers SOO
Polyurethanes 450
 THE ROLE OF ADHESIVES IN THE ECONOMY 23

Acrylics Small amounts of acrylic adhesives are uti-

lized by automotive manufacturers, the largest
These are multifaceted polymers that are uti-
application being headliners. This application,
lized in a variety of applications and in many
which consists of polystyrene board bonded
forms: emulsion, solvent solution, 100% re-
with acrylic adhesives, is being replaced by fi-
active, radiation-cured, and film. In the last
berglass headliners bonded with SBR acrylics.
dozen years, consumption of acrylic adhesives
Another outlet for acrylics is bonding vacuum-
jumped 175 %. Construction and pressure-sen-
formed parts.
sitives accounted for most of this increase. In
In the electrical/electronic market, acrylic
the former, acrylic latexes are making inroads
film adhesives are applied to flexible printed
on the territory held by SBR adhesive. In pres-
circuits. Radiation-curable acrylates are em-
sure sensitives, the acrylics (latex, solution, and
ployed as laminating adhesives ( furniture) and
radiation cured) make up one-third of the pol-
binders for coated abrasives (Table 9).
ymer demand. In this segment, acrylic latexes
grew by ten times during the last twelve years.
Cyanoacrylates
Acrylic solutions, used for making tapes and
labels, are usually applied to film substrates. This "miracle glue" was introduced in 1959.
A third major outlet for acrylics is textiles, It took about 10-15 years for the adhesive to
mainly for nonwovens and flocking adhesives. enter the steep growth stage of its life cycle.
Other markets include packaging, automotive, The Consumer Product Safety Commission
electrical/electronic, abrasives, furniture, etc. considered suspending its distribution to the
In construction applications, acrylic adhe- consumer market because of the material's ex-
sives showed a spectacular 15- to-20-fold in- cellent adhesion to skin; but the Commission
crease. In 1975, the predominant outlet was finally decided that a warning label as required
concrete binders; but by 1987 acrylics were under the Hazardous Substances Act would be
being employed in significant quantities for in- sufficient. Since 1975, consumption has jumped
stallation of ceramic tiles, decorative bricks and six-fold, and consumer applications have
stones, carpeting, as a binder for cellulose in- swelled from less than 20 % of the total volume
sulation, and in concrete binders and adhe- to over 40 %. Other major outlets include elec-
sives. These applications account for about tronics, toys and hobbies. Cyanoacrylates are
90% of acrylic adhesives in construction. now reaching maturity, and future growth will
Acrylic textile adhesives are still leaders as be more moderate (Table 10).
binders for nonwovens and fiberfill, but they
have lost much ground to the less expensive Anaerobics
vinyl acetate copolymers. Flocking continues
Initially anaerobic adhesives were used mainly
to be a solid market for acrylics.
for threadlocking of screws, nuts, and bolts.
Pressure-sensitive adhesives based on acrylic
Since 1975, consumption increased 3.5 times;
polymers grew 3.5-fold in the last dozen years.
but as the main applications have matured,
The acrylics are mostly emulsions and solu-
future growth potential is not as great. Auto-
tions, plus small quantities of radiation-curable
motive is the largest outlet for anaerobics; other
systems. In tapes, acrylic adhesives are applied
uses include machine assembly, electrical
mainly to non-paper substrates such as poly-
product assembly, maintenance, repair, etc.
propylene, acetate, cellophane, and polyester.
(Table 11).
In labels, acrylics are used for making perma-
nent paper labels and plastic labels.
Polyvinyl Acetate
In packaging, acrylics have begun to pene-
trate the film laminating field. Water-based PVAC (the term embraces both homopolymer
acrylics are the fastest-growing film-to-film and copolymers) was in the forefront of the
laminating adhesive. However, these water- transition of adhesives from natural to synthetic
based compounds are slower-drying and less adhesives. While overall consumption of ho-
attractive than solvent-based or 100% solids mopolymer plus copolymer doubled in the
systems. 1975-87 period, the copolymer adhesives in-
24 HANDBOOK OF ADHESIVES

Table 9. Acrylic Adhesives.

Application Function/End Use
Construction
Ceramic tile Installation
Decorative brick Installation
Concrete Polymer cements, bond coats, and admix-
ture to concrete
Cellulose insulation Binder for fibers and adhesive to substrate
Carpeting Installation
Core base Installation
Asphalt roofing Additive to urea-formaldehyde resin
Studs and framing Interior
Wall covering Installation
Glass fiber and rockwool insulation Lamination
Ceiling tiles Installation
Textile
Nonwovens Diaper, medical, apparel interlining
Fiberfill Apparel
Flocking Apparel
Laminating Fabric/polyurethane foam
Tie Coats Polyurethane-coated fabric
Pressure Sensitive
Tape Packaging, office, nameplates, medical
Labels and decals Permanent labels, removable labels,
freezer labels, plastic labels
Packaging
Film to film
Film to paper
Foil to paper
Automotive
Headliners
Vacuum-formed parts
Threaded component compounds
Electrical/Electronic
Flexible printed cricuits
Magnet bonding
Die attachment
Abrasives
Coated abrasives
Furniture
Paper or vinyl film lamination Kitchen cabinets, residential furniture

Table 10. Cyanoacrylate Adhesives.

Application Function/End Use
Consumer Fast bonding applications
Electronics Speaker magnet bonding, printed-circuit boards
Automotive Engine rubber mounting, shock absorbers, rubber bonding
Toys and Hobbies Bonding parts of dolls and rubber toys
Cosmetic Con- Lipstick holders, bonding mirrors in compact cases
tainers
Appliances Attaching trim, bonding internal devices
Artificial fingernails Attaching
Maintenance, repair Metal-to-metal, rubber bonding, locking parts
 THE ROLE OF ADHESIVES IN THE ECONOMY 25

Table 11. Anaerobic Adhesives. veneer, and edge bonding. The demand in-
Application Function/End Use creased by 200% in the last dozen years.
In the consumer sector, "white glue" con-
Automotive
Porosity sealants Prevent failure of engine block
tinues to be a staple for both home and shop.
Threaded fittings Consumption of PV AC bookbinding adhe-
Flange sealants Formed-in-place gaskets sive almost doubled during the past 12 years,
Retaining com- mostly for the casing-in step in edition books
pounds and for making continuous business forms
Threadlocking
Rearview mirror Installing (Table 12).
Maintenance, Repair,
Overhaul
Ethylene-Vinyl Acetate Copolymers
Structural Bonding
Consumption of EV A hot melt adhesives in-
creased 150% during the 1975-87 period. More
creased by a dramatic 250 %. The preferred co- than one-half of the EVA adhesive volume goes
monomers are ethylene and acrylate esters. into packaging, and EV A accounts for about
Three outlets for PVAC, packaging, construc- two-thirds of the total demand for hot melt ad-
tion, and textiles, account for 80% of the pol- hesives. Another one-third of the poundage is
ymer and 95 % of the compound. distributed among three applications: textile,
PV AC adhesives are found in a dozen con- disposables, and bookbinding.
struction applications. The largest is ready-mix EVA hot melts are found in some 15 pack-
joint cements for gypsum board. These are aging applications. About 85% of the total is
highly filled formulations with a polymer con- for case and carton sealing. Other markets
tent of only 3 %. Concrete adhesives containing which consume significant amounts of EV A
PV AC serve to bond new concrete to old. Vi- adhesives include: automotive carpeting, as-
nyl acetate-ethylene is the material of choice sembly of disposable diapers, perfect binding
for vinyl and paper lamination to hardboard, (bookbinding), edge banding, film overlay, and
gypsum board, and other substrates. Installa- general assembly of furniture (Table 13).
tion of vinyl flooring may be accomplished with
PV AC adhesives.
Styrenic Block Copolymers
In packaging, PV AC formulations have been
the material of choice for over 25 years, and These thermoplastic elastomers experienced a
they have increased by 140% in the last 12 dramatic nine-fold increase during the 1975-87
years. In spite of its higher cost, PV AC was period, resulting from a veritable explosion in
preferred over starch and dextrin for more de- usage as pressure sensitive adhesives.
manding applications because of its strength, Before the 1970s, the pressure sensitive in-
setting speed, adhesion and ease of compound- dustry was employing solvent-based systems
ing. (Starch retains its huge market in corru- made from SBR or natural rubber. About two
gated board.) PVAC has some 25 packaging decades ago, hot melt pressure sensitive adhe-
applications with the bulk of the tonnage for sives based on styrenic block copolymers
case sealing/assembly, carton sealing/assem- (mainly styrene-isoprene-styrene) and acrylic
bly and envelopes. emulsions were introduced. The reason for
The largest portion of PV AC adhesives in these technological developments was to de-
textiles is a binder for nonwovens and fiberfill. crease the dependency on solvents. Today hot
Here the rise in consumption was more than melts account for about 20 % of the pressure
eight-fold as a result of the successful penetra- sensitive adhesive volume, up from less than
tion of vinyl acetate-ethylene and vinyl acetate- 10% in 1975.
acrylate copolymers. Styrenic block copolymers serve as mass-
As a furniture adhesive, PV AC is used for coats for pressure sensitives, mainly tapes.
general assembly applications, film overlay and They are applied mostly as hot melts but also
high pressure lamination, edge gluing, wood from solution.
26 HANDBOOK OF ADHESIVES

Table 12. Polyvinyl Acetate Adhesives.

Application Function/End Use
Construction
Gypsum board joint cement
Concrete
Paper and film lamination
Vinyl flooring
Wood doors
Glass fiber insulation Bonding facing to fibers
Ceramic tile Installation
Mobile homes Assembly
Packaging
Case Assembly, sealing
Carton Assembly, sealing
Tray forming Assembly
Set-up boxes Assembly
Bags Heavy-duty, specialty, mailer
Envelopes
Gummed products Tape, paper
Laminations Paper-paperboard, film-film, foil-paper,
film-paper
Tubes and cores
Composite cans
Labeling Plastic bottle, can
Paper cups and tubes
Cigarette making
Textile
Nonwovens
Fiberfill
Carpeting
Tie coats
Flocking
Furniture
General purpose
Laminations Film overlay, high pressure
Wood veneer
Edge gluing
Edge bonding
Consumer
General purpose
Bookbinding
Edition books Casing-in
Softcover
Magazines Primers
Business forms
Other
Disposables
Pencils
Paint rolers

Other outlets for styrenic block copolymers plastic beverage bottles (cup and labeling), in-
which were developed during the last decade stalling automotive carpeting, bookbinding
include: assembly of diapers, adhesives for (Table 14).
 THE ROLE OF ADHESIVES IN THE ECONOMY 27

Table 13. Ethylene-Vinyl Acetate Table 14. Styrenic Block Copolymers.

Adhesives. Application Function/End Use
Application Function/End Use Pressure Sensi-
Packaging tive
Case Sealing, assembly Tapes
Carton Sealing, assembly Labels
Tray Assembly Disposables
Labeling Plastic bottle, can, glass bottle Diaper Assembly
Fiber drums Assembly
Composite cans Assembly Packaging
Mailer bags Cup, labeling Plastic beverage bottles
Cigarette making Automotive
Textile Carpeting Installation
Carpeting Automotive Bookbinding
Disposables Edition books Perfect binding
Diapers, others Assembly Magazines

Bookbinding
Edition books Perfect binding, lining
Softcover books Perfect binding consumed in textile applications, mainly car-
Magazines peting. Carpets backed with polyurethane go
Directories into both residential and contract (i.e., com-
Catalogues
mercial) installations.
Furniture Polyurethanes are used in patching com-
Edge banding pounds for softwood plywood. In packaging,
Film overlay
General assembly
polyurethanes are utilized primarily as lami-
nating adhesives, mainly in film-to-film con-
Consumer
structions.
Hobbies
The principal applications for polyurethane
Automotive adhesives in construction include mobile
Sound-deadening Installation
pad
homes, modular homes, thermal sandwich
Sponge-to-metal Bonding panels. In automotive vehicles, polyurethanes
serve to bond FRP (fiber-reinforced plastics)
Filters
Air filters
and vacuum-formed ABS/PVC door panels.
Film overlay laminations (furniture) and sole
Construction
Carpet seaming tape
attaching (footwear) are other applications for
polyurethane adhesives (Table 15).
Footwear
Box toe, counters
Shank attaching THE ADHESIVE-USING INDUSTRIES·
Adhesives form an integral part of myriad fab-
ricated products. The cost contribution of ad-
Polyurethane
hesives is usually small, so that the end user
The major markets for polyurethane adhesives does not pay too much attention to them. But,
are textiles, forest products, and packaging. when they don't work, damages can be severe.
The first two applications were developed only Adhesives serve in the manufacture of motor
during the past decade. Consumption of poly- vehicles, aircraft, appliances, electrical/elec-
urethane adhesives increased by 450 % in the tronic components, homes, bonded wood, fur-
1975-87 timespan. Carpet backing adhesives niture, carpets, books, shoes, and even baby
was the largest segment credited with this re- diapers. Historically, most of the volume has
markable growth. been devoted to the bonding of three porous
Almost one-half of polyurethane adhesives is substrates: wood, paper, and textiles. Future
28 HANDBOOK OF ADHESIVES

Table 15. Polyurethane Adhesives. cially phenol-formaldehyde and urea-

Application Function/End Use formaldehyde (Table 17).

Textile
Furniture
Carpet
Tie coats Adhesives enter into the manufacture of both
Labels and emblems
residential and commerical wood and metal
Forest Products furniture, including office furniture, counter-
Plywood patching
tops, vanities, stereo speakers, TV cabinets,
Packaging kitchen cabinets. More than a dozen types of
Film to film adhesives are employed; PV AC is the largest
Film to foil
(Table 18).
Film to paper
Construction
Mobile homes Installation of gypsum
Automotive
Modular homes board ceilings, thermal Some 25 types of adhesives are utilized in the
Panels sandwich
Glued plywood floors
assembly of cars. The typical vehicle contains
about 20 lbs. of adhesives. About two-thirds of
Automotive the poundage goes into engineering/structural
FRP panel bonding
Vacuum-formed door applications. Among the high-volume uses are
panels the bonding of hood and deck lids (PVC plas-
Furniture
tisol), safety glass (polyvinyl butyral film), and
Vinyl overlay lamina- To boardstock, metal tires (resorcinol-formaldehyde latex.) During
tion the last dozen years, a number of new adhesive
Footwear
applications were developed, and the future for
Sole attaching certain applications such as bonding of FRP
components is bright (Table 19).

growth opportunities, however, are in bonding Aircraft

non-porous substrates, e.g., plastic, metal,
rubber, glass, etc. This industry does not use large quantities of
adhesives. However, the products are expen-
sive, as they are highly specialized and must
Construction
meet strict specifications. The adhesives are
Adhesives are utilized in construction for many utilized for both structural and nonstructural
structural and decorative applications, e.g., for applications. Indeed, aircraft is the single most
installing vinyl flooring, carpeting, ceramic well-defined market for engineering/structural
tile, wallcovering, making doors, gluing floors, adhesives. The most common application is for
etc. The construction industry is one of the epoxy hybrid films to bond metal structures
largest outlets for adhesives, requiring some 40 (Table 20).
types of adhesives in about 30 different appli-
cations. The bulk of the volume consists of Electrical/Electronic
thermoplastic, water-based adhesives (Table
16). A variety of expensive materials are required
in small volumes for electrical/electronic ap-
plications. Their average price is almost 20
Forest Products
times greater than the average for all adhesives.
Wood bonding is one of the largest markets for Conductive adhesives are the most costly.
adhesives. Plywood, particleboard, fiberboard, Electrical/electronic adhesives must exhibit
and other wood products involve mainly ther- good electrical, bonding, and mechanical prop-
mosetting and water-based adhesives, espe- erties (Table 21).
 THE ROLE OF ADHESIVES IN THE ECONOMY 29

Table 16. Construction Adhesives.

Application Adhesive Function/End Use
Gypsum board PVAC Joint cement
Starch Binder
Concrete Epoxy Adhesives
PVAC Adhesives/additives
Acrylic Adhesives/additives
SBR Additive
Carpeting SBR Installation
Acrylic Installation
Neoprene Installation
Natural Rubber Installation
Recreational surfaces PUR Installation
Artificial turf SBR Installation
PVAC Installation
Acrylic Installation
Glass fiber and rock
wool insulation Phenolic Binding glass fiber together
Asphalt Bonding of fibers to facing
Neoprene
PVAC
PVDC
PE
PP
EVA
PVDC Laminating plies of facing
Neoprene
Sodium silicate
Acrylic
PVAC
Roofing Asphalt Installation of vapor barriers and
SBR/asphalt insulation board for roofing
Neoprene Bonding single-ply membranes
Butyl
Ceiling tiles Rosin Installation
Acrylic
Ceramic tile SBR Mortars and Grouts
Acrylic
Epoxy
Furan
Silicone
Ceramic tile SBR Additives to cement
Acrylic
PVAC
PYA
Stud and framing SBR Installing gypsum board, ply-
Neoprene wood, and paneling over wall
Acrylic studs
Wallcovering Dextrin Installation
Starch
Acrylic
Carboxymethyl cellu-
lose

(Continued on page 30)

30 HANDBOOK OF ADHESIVES

Table 16. (Continued)

Application Adhesive Function/End Use

Vinyl flooring Asphalt Installing vinyl tile

PVAC
Epoxy
SBR
SBR Installing viny I sheet
PVAC
Linoleum paste
Epoxy
Pipe-joint cements PVC Joining PVC pipe
ABS Joining ABS pipe
CPVC Joining CPVC pipe
Doors Casein Wood bonding
PVAC
UF
Neoprene Metal bonding
Epoxy
Safety glass PVB Laminated glass
Plywood floors SBR Installing plywood floors
PUR
Asphalt roofing UF Binders used in the manufacture
SB of monomer
Acrylic Glass mat for asphaltic shingle
and roll roofing
Paper and film lamination PV AC Lamination of paper and vinyl
film lamination to hardboard,
plywood, and gypsum board
for paneling
Thermal/sandwich panels Epoxy Interior, exterior partitions and
Neoprene cold-storage thermal-insulating
PUR panels
Phenolic
PVAC
Mobile homes PVAC
PUR
Neoprene
Modular homes PUR Gypsum board to wood joists
SBR plywood to floor joists, gyp-
sum board to studs, insulation
board to exterior studs
Cellulose insulation PVAC Binding fibers and bonding fibers
to the substrate
Parquet floors SBR Installation
Decorative brick Acrylic Installation
SBR Installation
Cove base Acrylic Installation
SBR Installation
Slate tiles SBR Installation
Asphalt tiles Asphalt Installation
SBR
 THE ROLE OF ADHESIVES IN THE ECONOMY 31

Table 17. Adhesives for Forest refrigerators and freezers. Thermal and sound
Products. insulating materials are attached with adhesives
Application Adhesive Function/End Use in washers, driers, dishwashers, ranges, and air
conditioners; cabinet sealing is another major
Plywood PP Manufacture
UP Manufacture
application (Table 22).
PUR Patching
Particleboard UP Manufacture Packaging
PP
One of the visible signs of an affluent society
MOl
is the degree of packaging of consumer goods.
Oriented strandboard PP Manufacture
MOl
In a few countries, e.g., the U.S., most prod-
ucts are wrapped. As packaging becomes more
Medium-density fiberboard UP Manufacture
sophisticated, utilizing coated stocks and high
Waferboard PP Manufacture
speed equipment, the adhesive industry has had
Hardboard PP Manufacture
UP
to develop products which adhere to a variety
of substrates while meeting machine condi-
Lumber laminating RPP
MUP tions.
The packaging industry is one of the largest
outlets for adhesives. About 30 types of adhe-
Appliances sives are employed in 35 different applications.
Segments consuming large quantities of adhe-
Adhesives are present in various large appli- sives include corrugated board, case and carton
ances with the bulk of the volume going into sealing, bags, and tubes and cores (Table 23).

Table 18. Furniture Adhesives.

Application Adhesive Function/End Use
High pressure lamination Neoprene Lamination
Polyamide
PVAC
UP
Pilm overlay PVAC Lamination
PUR
Epoxy
EVA
Neoprene
UP
General assembly PVAC
EVA
Animal
glue
Cabinets, counters EVA
Epoxy
Edge gluing PVAC Bonding strips of lumber stock to
UP make core stock
EVA
Edge banding EVA Attaching strips of veneer or vinyl
PVAC around narrow edges of desks, ta-
UP bles, etc.
Wood veneer PVAC Attaching wood veneer to inexpensive
UP substrates
 Table 19. Automotive Adhesives.
Application Adhesive Function/End Use
Auto-body
Exterior PVC plastisol Hood and deck lids, door-crash bars
SBR FRP bonding, hem flange bonding
Epoxy
PUR
Silicone
Interior SBS Carpet, package trays, vacuum-formed parts,
Polyester headliners, fabric-foam seats
EVA
Polyamide
PUR
SBR
Acrylic
Under the hood Anaerobic Rubber bonding, formed-in-place gaskets, ra-
Halogenated elastomer diator components
Silicone
Epoxy
Polyester
Windshields PVB film Safety glass
Tire adhesives Resorcinol-formalde-
hyde
Natural rubber

Table 20. Aircraft Adhesives.

Application Adhesive Function/End Use
Structural films Epoxy-nitrile Metal-metal bonding, honeycomb structures,
Novolac epoxy composite bonding
Epoxy-nylon
Nitrile-pheno-
lic
Structural liquid Epoxy Assembly
Nonstnlctural liquid Neoprene Interior assembly
Nitrile
Safety glass PVB film Laminated glass

Table 21. Electrical/Electronic Adhesives.

Application Adhesive Function/End Use

Batteries Epoxy Bonding tops and bottoms of battery cases

PP made of rubber
TV tubes Epoxy Implosion proofing
Polyester
Built-up mica Silicone
Epoxy
Shellac
Polyester
Magnet bonding Acrylics Mixers, audio speakers
Epoxy
Cyanoacrylate
Flexible printed circuits Acrylic Lamination of foil-film
Polyester
Epoxy
Conductive Epoxy Die attachment

32
 THE ROLE OF ADHESIVES IN THE ECONOMY 33

Table 22. Appliance Adhesives.

Application Adhesive Function/End Use
Refrigerators and freezers PP Seal, cabinets, seal holes made for
Polybutene refrigeration liners
Epoxy
EVA
Washers and dryers SBR Attaching insulating materials
Cyanoac- Assembling of plastic components
rylate of control panels
Anaerobic Threadlocking
Air conditioners SBR Attaching insulating material
Silicone Bonding aluminum tubes
Dishwashers SBR Attaching insulating material
Silicone Bonding plumbing fixtures
Microwave ovens Silicone Assembly of viewing windows
Ranges SBR Attaching insulating material
Silicone Assembly of viewing windows

Table 23. Packaging Adhesives.

Application Adhesive Function/End Use
Corrugated board Starch Fabrication
Solid fiberboard PVOH Lamination
Can assembly PVAC
EVA
Case sealing EVA
PVAC
Dextrin
Folding carton PVAC Assembly, sealing
EVA
PE
Tray forming EVA
PE
PVAC
Setup boxes Animal glue
PVAC
Bags PE Heavy duty
PP Heavy duty
PVAC Heavy duty, mailer
Starch Heavy duty, grocery
Natural rubber Heavy duty
EVA Mailer
Gummed Tape/Paper Starch
Dextrin
Animal glue
PP
PVAC
SBR
Envelopes Dextrin Front seal, back gum, window patch
PVAC Front seal, back gum, window patch
Natural rubber Front seal
Animal glue Front seal
(Continued on page 34)
34 HANDBOOK OF ADHESIVES

Table 23. (Continued)

Application Adhesive Function/End Use

Paperboard lamination PVOH

PVAC
Dextrin
Cap liner PVAC
PUR
Reinforced web PP
Asphalt
PVAC
Lamination PUR Film-film, film-foil, film-paper, foil-pa-
per
Acrylic Film-film, film-paper, foil-paper
PVAC Film-film, film-paper
Butyl Film-film
Nitrile Film-film
Neoprene Foil-paper
Silicate Foil-paper
Paper tubes and cores Silicate
PVOH
Starch
PVAC
Composite cans PVAC
PYA
Dextrin
Silicate
EVA
PE
Polyamide
Fiber drums Silicate
PVOH
EVA
Labeling Casein Glass
Dextrin Glass, plastic, corrugated
EVA Glass, plastic, can
PVAC Plastic, can, corrugated
S-B-S Plastic
Rosin Can
Starch Can
Paper cups and tubs PVAC
Starch
Cigarette making PVAC
Starch
EVA
Metal can sealing SBR
Neoprene

Bookbinding tributed among several types of publications in-

cluding softcover books, magazines,
Were it not for adhesives, this Handbook could directories, and catalogues.
not be assembled. About one-half of the adhe- "Perfect binding" is a method that has pen-
sive volume in bookbinding goes for binding etrated every type of publication. In this oper-
edition books (hardcover); the balance is dis- ation, the sewing of signatures is eliminated,
 THE ROLE OF ADHESIVES IN THE ECONOMY 35

and the assembling of book sections-trimming acetate, polypropylene, polyethylene, foam,

the back, applying hot melt adhesive, fastening cloth, etc., in order to make tapes, labels and
the cover, and trimming the remaining sides of decals.
the books- requires less than 10 seconds The adhesives are elastomeric. In 1975, al-
(Table 24). most two-thirds of the adhesives were solvent-
based; a dozen years later, their share had de-
clined to about one-third. Besides solvent sys-
Pressure Sensitives
tems, pressure-sensitive adhesives can be 100%
Pressure sensitive masscoats are applied to solids, emulsions, and radiation-curable
backings such as paper, polyester film, PVC, (Table 25).

Table 24. Bookbinding Adhesives.

Application Adhesive Function/End Use
Edition Books
Casemaking Animal Making the cover
glue
Casing-in PVAC Mounting the book in the case by binding end sheets
of the outside pages to the cover
"Perfect bound" EVA
Styrenic
block co-
polymers
Gluing-off PVAC Adhesive placed over signatures
Lining EVA Crash (scrim fabric) is glued to signatures; kraft paper
Animal is bonded to crash
glue
Softcover Books EVA Perfect binding
Magazines EVA Perfect binding
S-B-S
Directories Animal Perfect binding
glue
EVA
Catalogues EVA Perfect binding
Animal
glue
Business Forms PVAC
Dextrin
EVA

Table 25. Pressure-Sensitive Adhesives.

Applications Adhesives Function/End Use
Tapes Natural rubber Retail, commercial, packaging, electrical duct
Butyl pipe wrap, medical, other
Styrenic block copolymer
SBR
Acrylic
Silicone
Labels and decals Styrenic block copoly- Paper
mers Permanent, removable, freezer; plastic labels
SBR and decals
Acrylic
SBR
pm
36 HANDBOOK OF ADHESIVES

Textile to the polyethylene moistureproof shield (Ta-

ble 27).
Adhesives are employed in many textile appli-
cations. In tufted carpeting, they have become
Consumer Adhesives
an integral part of the operation. They provide
added strength and stability to nonwovens and Over a dozen types of adhesives are useful
fiberfill. Flocking adhesives enable fabrics to around the home, office, and shop. The appli-
look like suede (Table 26). cations are diverse. "White glue" continues to
be the indispensable staple for bonding paper,
Assembly of Disposables wood, etc. Epoxy and cyanoacrylates are the
"miracle glues" able to bond more difficult
Several types of adhesives, mainly hot melts,
substrates (Table 28).
are employed in the construction of diapers,
sanitary, medical, and surgical products. In the
Shoes
past, this application was solidly held by poly-
olefin hot melts. However, styrenic block co- About 80% of the shoes sold in the US are now
polymers are rapidly penetrating this market. imported; but domestic shoe production contin-
They are elastomeric, thus have the advantage ues to demand an impressive array of adhe-
of stretchability. The principal bonding opera- sives. These materials are needed to make
tion is adhering the nonwoven absorptive web various shoe components and to attach the

Table 26. Textile Adhesives.

Application Adhesive Function/End Use
Carpeting C-SB Residential, contract, automotive
VDC/SB
PUR
PVC
EVA
PE
PVAC
Nonwoven Acrylic Diapers, sanitary, medical, wipes, towels, ap-
PVAC parel, other
C-SB
PVC
Fiberfill and shoddy pad PVAC Furniture, home furnishings, filter, automo-
Acrylic tive, carpet, other
PVC
C-SB
Flocking Acrylic Home furnishings, apparel, other
Tie coats PUR Footwear, handbags, apparel, upholstery, au-
Acrylic tomotive, other
PVC
Laminating PVC Apparel
Acrylic Automotive tarpaulins, other
Fusible interlinings PA Apparel
PE
Polyester
PVC
Labels and emblems Polyester
PA
PUR
PVC
 THE ROLE OF ADHESIVES IN THE ECONOMY 37

Table 27. Disposable Assembly Adhesives.

Application Adhesive Function/End Use
Assembly compo- EVA Diapers, sanitary, medical, surgical
nents Styrenic block copoly-
mers
PE
PP
PVAC

Table 28. Consumer Adhesives. Table 29. Shoe Adhesives.

Application Adhesive Adhesive Function/End Use
White glue PVAC PUR Sole attaching
Contact cement Neoprene Neoprene Sole attaching
Rubber cement Natural rubber Natural rubber Sole attaching, combining box toe,
Household ce- Cellulose nitrate doubling and box
ment Cyanoacrylate Polyamide Lasting, toe, folding, heel attaching
Epoxy Polyester Lasting
Glue stick Wax EVA Box toe, shank attaching
Hot melts EVA
Library paste Starch
Dextrin Table 30. Binders for Abrasive
Mucilage Starch Materials.
Animal glue
Silicone Application Adhesive Function/End Use
--~-------------------------
Anaerobic Coated abrasives Phenolics Sand paper
------------------- Animal glue
UF
soles, either pennanently (cemented shoes) or Bonded abrasives Phenolics Grinding wheel
temporarily (preparatory to stitching). High Epoxy
perfonnance polyester and polyamide hot melts Alkyd
Natural rubber
have achieved acceptance for many operations
SBR
(Table 29). Shellac
Polyimide

Abrasives
in automotives and construction equipment,
Abrasives are hard, inert particles such as sili-
brakes in elevators and automatic washing ma-
con carbide and aluminum oxide used for cut-
chines, etc. Phenolic and modified phenolic
ting, shaping, polishing, or cleaning. The
resins are the principal binders, followed by
adhesive functions as a binder in the manufac-
oleoresinous and rubber (nitrile and natural),
ture of bonded and coated abrasives. A bonded
which generally have lower heat resistance and
abrasive such as a grinding wheel is a molded
are found mainly in products for the automo-
mixture of abrasive particles and binders. In a
tive aftennarket.
coated abrasive, e.g., sandpaper or emery pa-
Because asbestos is carcinogenic, various
per, a particle layer is glued to a flexible back-
non-asbestos substitutes have been introduced:
ing. The predominant binder is phenolic resin
glass fiber, aramid fiber (Kevlar), carbon fiber,
(Table 30).
etc. A common combination is glass fiber/phe-
nolic (Table 31).
Friction Materials
Foundry Sand Binders
Friction materials have been made mainly from
asbestos or other fiber and an organic binder. Another outlet for binders is to hold together
These materials are used as brakes and clutches the sand in the fabrication of castings. Iron and
38 HANDBOOK OF ADHESIVES

Table 31. Friction Material KEY TO ADHESIVES

Binders.
Adhesive Function/End Use ABS acry lonitrile-butadiene-styrene
CPVC chlorinated polyvinyl chloride
Phenolic Brakes, clutches
Rubber C-SB carboxylated styrene-butadiene
Oleoresinous EVA ethylene-vinyl acetate
MDI methylene-diphenylene isocyanate
MUF melamine-urea-formaldehyde
Table 32. Foundry Sand PE polyethylene
Binders. PF phenol-formaldehyde
Adhesive
PP polypropylene
PUR polyurethane
Phenolic
PVAC polyvinyl acetate
Alkyd-isocyanate
Furan siliceous PVB polyvinyl butyral
Oil-based PVC polyvinyl chloride
PVDC polyvinylidene chloride
PVOH polyvinyl alcohol
steel castings have been declining while non- RPF resorcinol-phenol-formaldehyde
ferrous castings, mainly aluminum base, are SBR styrene-butadiene rubber
gaining. The automotive industry is the major SBS styrene-butadiene block copolymer
user of castings. Phenolic resins are the most SIS styrene-isoprene block copolymer
common type of binder utilized (Table 32). UF urea-formaldehyde
 3
Fundamentals
of Adhesion
A. N. GENT AND G. R. HAMED
Institute of Polymer Science
The University of Akron
Akron, Ohio

INTRODUCTION One method which has been used to charac-

terize interfacial forces is based on specific do-
Adhesion is the interaction that develops be-
nor-acceptor (acid-base) interactions between
tween two dissimilar bodies when they are con-
adhesive and substrate molecules. 1 Here, func-
tacted. Adhesion is thus a multidisciplinary
tional groups in each material are assigned an
science dealing with the chemistry and physics
acid or base strength, which then can be used
of surfaces and interfaces as well as the me-
to calculate expected bond strengths. Further
chanics of deformation and fracture of adhesive
discussion of this approach is delayed to a later
joints. In this overview, these various aspects
section.
of adhesion are discussed. We begin by de-
In some instances, it has been proposed that
scribing the general types of adhesive bonds.
intrinsic adhesion is due to electrostatic forces
This is followed by sections on solid surfaces
developed between materials with different
and their characterization, interfacial proper-
electronic band structures. 2 -4 These forces are
ties, surface treatment, and finally a discussion
attributed to transfer of electrons across the in-
of the mechanics of adhesive joints.
terface, creating positive and negative surface
charges that attract one another. There is seri-
Bond Types
ous disagreement about the magnitude of elec-
Immiscible Planar Substrates. Consider trostatic attractions compared to other physical
the simplest case in which a liquid adhesive is forces. One author' concludes that electrostat-
placed on a molecularly smooth solid substrate ics make a negligible contribution to adhesion;
with which it is totally immiscible. The time- others6 ,7 maintain that these forces are domi-
dependent process whereby the adhesive and nant.
substrate come into intimate contact is called
wetting. The interface is a plane across which Immiscible Substrates with Complex Sur-
molecular forces of attraction, also denoted in- face Topography. As before, the substrate
trinsic adhesion, exist between the liquid and is assumed to be completely immiscible with
solid. These forces range in magnitude from the adhesive, so that adhesive-substrate inter-
strong covalent or ionic chemical bonds to actions are limited to surface sites. However,
weaker physical adsorption, e.g., H-bonding, the substrate surface topography is now com-
dipole-dipole, and van der Waals interactions. plex, as depicted schematically in Fig. 1. Be-

39
40 HANDBOOK OF ADHESIVES

around surface features of the substrate that are

much larger than molecules.
Interdiffusion is important when bonding two
polymers together; if there is a strong affinity
between the different types of molecules, then
the interphase will be relatively thick and the
extent of intrinsic adhesion high.
Fig. 1. Micro-rough solid surface.
In some cases, the contacted materials not
only interdiffuse but also chemically react with
one another. Here, the interphase is not just a
cause of pores, depressions, and asperities,
"physical blend," but becomes a new chemi-
there are many more surface sites available to
cal entity.
interact with an adhesive compared to a planar
substrate. Thus, if the adhesive has sufficient
Immiscible Substrates with Interphase
mobility and the wetting forces are high
Formation via Chemical Reaction. This is
enough, the extent of intrinsic adhesion may be
a rather special case, but is technologically im-
increased by surface roughening. On the other
portant. Here, although the contacting mate-
hand, poorly wetting, viscous. adhesives may
rials are not miscible, each contains a
form relatively few interactions with rough-
component which can diffuse to the interface
ened substrates, especially if the (wetting) time
and chemically react, thereby forming in situ a
from adhesive application to solidification (set-
new interphase which couples the two mate-
ting) is short.
rials together.
Another consequence of the topography
When rubber containing sulfur and curatives
shown in Fig. 1 is mechanical interlocking be-
is pressed into contact with brass (typical alloy
tween the adhesive and substrate. This is de-
-70 % copper, 30 % zinc) and then vulcan-
pendent on the specific shape of the interface.
ized, copper ions diffuse to the brass surface
Good joint strengths can be obtained because
where they combine with sulfur to form a cu-
of this even when the intrinsic interaction is
prous sulfide interphase. 9 Joint strengths are
low. Mechanical interlocking plays an impor-
controlled by the characteristics of this layer.
tant role in bonding wood, textiles, or paper
This bonding is of critical importance in tires
because of their finely divided and porous na-
reinforced with brass-plated steel cords, and has
ture. In addition, many metals and plastics are been extensively studied. 10-12
etched before bonding, so that the adhesive can
penetrate and lock into them. When mechani-
Setting
cal interlocking is substantial, the region around
the interface forms a composite interlayer that After an adhesive wets a solid substrate, it is
can be viewed as an entity coupling the two normally necessary to convert it to a hardened
bulk materials. state (setting) so that the joint will be capable
of supporting stresses. Setting of adhesives can
Partially or Fully Miscible Substrates. occur by physical or chemical means. In order
When the adhering materials are partially or to minimize internal stresses in a joint, there
fully miscible with one another, there will be should not be a large change in volume of the
.formed between them an interphase consisting adhesive during solidification, and the thermal
of interdiffused molecules from each material. 8 expansion coefficients of the adhesive and ad-
The thickness of this interlayer depends on the herends should be similar. This is especially
thermodynamic compatibility of the materials important when the solid adhesive has a high
as well as molecular diffusion rates. Molecular modulus. Furthermore, joints with plane inter-
interdiffusion is quite different from mechani- faces have been suggested 13 to be more sensi-
cal interlocking. The former involves interpen- tive to adhesive shrinkage than are joints made
etration at the molecular level, whereas in the with complex, high surface area adherends.
latter case, the bulk adhesive flows into and Solvent-based adhesives experience the most
 FUNDAMENTALS OF ADHESION 41

shrinkage during setting compared to those fied by adding fillers or tackifiers, and the
which harden by cooling (hot melt) or by modified adhesive gives a higher joint strength
chemical reaction (usually thermosets). The than the unmodified one, it is tempting to con-
fact that epoxy resins shrink only about 3 % clude that the intrinsic strength of adhesion has
upon setting is one reason for their good per- been enhanced. But the bulk properties of the
formance. Another advantage of epoxy solidi- adhesive are also modified by the addition of
fication reactions compared to many other filler and the improved performance may
condensation polymerizations is that no small merely reflect a higher dissipation of mechan-
molecules, e.g., water, which can interfere ical energy within the adhesive layer. To un-
with bonding, are created during setting. Poly- derstand the performance of an adhesive bond
urethane reactions are also favorable in this re- it is therefore essential to recognize the role of
gard. the bulk properties of the bonded members, as
Some inorganic substances adhere exception- well as interfacial energetics, in determining the
ally well because they expand upon freezing. bond strength.
For example, ice will adhere to almost any sur- Fracture analyses and the role of energy dis-
face, even those not wetted well by water. 14 sipation are addressed later after considering
When water freezes in a depression in a solid surface properties.
surface, expansion causes it to lock against the
sides of the depression and form a strong joint.
SURFACES AND THEIR
Attempts l5 •16 have been made to develop or-
CHARACTERIZATION
ganic adhesives, based on ring opening poly-
merizations, that expand upon setting. Solids
With few exceptions (such as carefully cleaved
Adhesive Joint Strengths
mica), all solid surfaces are rough at dimen-
An adhesive joint consists of two or more ad- sions of a few Angstroms. They contain as-
herends held together by adhesion. The strength perities, pores, depressions, projections, etc. of
is assessed by loading it until fracture. Com- one sort or another, depending on their nature
monly determined l7 - 2o are the average fracture and the way in which the solid was processed.
stress and the fracture energy-neither of which For example, the average roughness of a ma-
is readily related to intrinsic adhesion, even if chined metal is about 3-6 JLm. Even after pol-
the locus of failure is fully interfacial. One rea- ishing, surface irregularities in the range of
son is the uncertain contribution to strength 0.02-0.25 JLm remain. 14 At a smaller scale, the
from mechanical interlocking. There is, how- oxide on a metal may have a complex high-
ever, another reason, even when mechanical surface-area structure, which, at an even
interlocking is absent. During fracture of an ad- smaller scale, may itself contain non-uniform-
hesive joint, the adhesive and bonded members ities like growth steps and depressions at grain
are deformed by the applied forces. All mate- boundaries.
rials are imperfectly elastic to some degree,
i.e., they do not return all the energy expended Surface Oxides and Contaminants. All
in deforming them. In general, during fracture, metal surfaces that have been exposed to the
not only is energy expended in cleaving bonds atmosphere have an oxide layer on them. 21 Iron
to create new free surface, but also energy is can have various types of oxide: Fe203' Fe304,
expended away from the interface within the and FeO. With copper, the oxide layer closest
bulk of the bonded members. This causes the to the base metal is CU20, while the outermost
fracture energy from a mechanical test to ex- . layer is CuO. Alloys such as stainless steel and
ceed intrinsic adhesion, which depends only on brass have mixed oxide layers of each compo-
the number and types of bonds disrupted at the nent metal. The thickness of the oxide layer de-
interface. Thus, to judge intrinsic adhesion by pends on the nature of the metal and the
a measured mechanical strength may be mis- environment. Some metals, e.g., aluminum and
leading. For example, if an adhesive is modi- titanium, form thin, tough, tenaciously adher-
42 HANDBOOK OF ADHESIVES

ing oxides, which passivate the surface and its contour. The magnitude of surface irregu-
prevent continued oxidation. Others, like iron, larities are amplified and plotted, giving the
have oxides which continue to grow, especially surface profile. It is possible to profile a solid
in a humid environment. Formation of oxide on surface in severnl directions and genernte a sur-
a metal is thought to involve first chemisorp- face topogrnphical map.28 Although useful,
tion of oxygen on the surface, followed by profilometry has inherent limitations owing to
chemical reaction to form the oxide. The dis- the finite size of the stylus. Thus, it is very dif-
tinction between chemisorption and chemical ficult to follow the true surface profile for
reaction is the retention of chemical identity of sharply varying surfaces. Additionally, surface
the interacting species, which may be re- profiling cannot give information about surface
covered intact by supplying desorption energy roughness at dimensions below about 0.1 I-tm.
in the case of chemisorption, while this is not Microscopy. The best methods to determine
genernlly possible in the case of chemical re- detailed surface topogrnphies are by optical and
action. scanning electron microscopy. The optical mi-
In prnctice, metal oxides are covered with or- croscope is limited by a lack of depth of focus
ganic molecules and water adsorbed from the and a resolution limit of about 2000 A, but
atmosphere. 22 Other common sources of sur- these limitations are overcome in the scanning
face contamination are residual processing oils electron microscope (SEM). The depth of fo-
and lubricants. Whether the interncting species cus is up to 300 times that of the optical micro-
are considered physically adsorbed or chemi- scope and the resolution limit is only a few
sorbed depends on the strength of interaction. Angstroms. 29
Although somewhat arbitrnry, it has been
stated23 that internctions up to 10 kcallmole are Structural and Chemical Analysis. Low
considered physical adsorption, while those Energy Electron Diffraction (LEED). In this
greater than 10 kcal/mole are regarded as technique,30 a low energy electron beam «200
chemisorption. eV) is directed at the surface of a crystalline
Another source of surface contaminants is solid, which serves as a diffraction grating.
from the bulk.21 For example, iron containing Electrons only penetrnte the first few atomic
only 10 parts per million of carbon has been layers and some of them are diffrncted back
shown to form a carbon-rich structure on its onto a fluorescent screen, giving a distinctive
surface upon heating or strnining. In addition pattern charncteristic of the structural arrange-
to carbon, other species, including sulfur, ni- ment of atoms in the outermost atomic layers.
trogen, boron, and oxygen have been shown to LEED is most effective for examining the sur-
diffuse from the interior of metals to their sur- face structure of a single crystal or poly-
faces. A recent pape~4 discusses severnl meth- crystalline sample made up of large grnins so
ods to charncterize metal surfaces. that the primary electron beam can be directed
It is also common for some polymeric com- at a small region within one grain or another.
pounds to form surface regions with composi- In one case,3! this method was used not only
tions different from the bulk material, by to elucidate contaminants on an iron surface,
selective diffusion of components. This process but also to reveal surface strain produced when
is termed blooming when the surface layer is the iron surface was bombarded with an argon
solid, and bleeding if the surface is liquid. Sul- ion beam to remove the contaminants.
fur and fatty acid blooms can inhibit adhesion Attenuated Total Reflectance Spectroscopy
in rubber laminates. 25 Gillberg 26 has published (ATR). ATR, also called internal reflection
an overview on polymer surface analysis. spectroscopy, is a technique used to character-
ize the surface region of a polymeric compo-
Characterization of Surface Topography. sition. 32 A sample is placed on both sides of an
Profilometry. One common method to study appropriate crystal and an infrnred beam within
surface geometry is with an electromechanical the crystal is repeatedly attenuated as it is re-
profilometer. 27 Here a diamond sty Ius passes flected back and forth from one sample surface
across the surface at constant speed and follows to the other. The intensity of the attenuated
 FUNDAMENTALS OF ADHESION 43

beam is monitored for a range of wavelengths. for many materials; metals have the shortest es-
Since ATR has a sampling depth of about 0.3- cape depths, whereas insulators have the great-
3.0 p.m, it is not well suited for characterizing est. Thus, Auger spectroscopy is a technique
surface composition on a molecular scale. that truly characterizes the surface of the irra-
However, it is useful for studying migration or diated specimen. Lateral resolution is ofthe or-
diffusion of compounding ingredients in the der of 1 p.m.
surface region of a polymer sample. 33 ,34 For AES uses a low energy, 1-5 keY, electron
example, ATR analysis has shown 35 that a beam gun to minimize surface heating, which
pressure sensitive adhesive made up of natural could desorb some materials from the surface
rubber and a wood rosin tackifying resin has a or cause decomposition of adsorbed organics.
surface region richer in tackifier than the bulk To enhance the signal, a low angle of incidence
adhesive. is used, which increases the extent of interac-
Electron Microprobe. A common attachment tion with surface atoms. The energy and num-
to the SEM is the electron microprobe. 36 With ber of the emitted Auger electrons are detected
this tool, an electron beam is focused at a sam- by an energy analyzer and counter. The energy
ple surface, causing ionization to a depth of a identifies the element from which the electron
few micrometers. Energies and wavelengths of came and the number is a measure of its abun-
the x-rays emitted during de-excitation are dance.
characteristic of the elements present in the Electron Spectroscopy for Chemical Analysis
solid. Measured intensities of the x-rays can be (ESCA) or X-ray Photoelectron Spectroscopy
compared with intensities of x-rays from a pure (XPS). In XPS, the surface is bombarded with
standard of a given element, to yield an esti- low energy x-rays, resulting in ionization by
mate of the amount of that element in the sam- direct ejection of a core-level electron (a pho-
ple. While the electron microprobe does not toelectron).38,39 The number and energies of
give a strictly surface analysis, it does have the photoelectrons are monitored. The following
desirable capability of determining a "spot by simple relationship holds:
spot" analysis of surface regions.
An advantage of the SEM-electron micro-
Binding of photoelectron
probe combination is the opportunity to exam-
ine the topography of the surface of a sample
= Incident x-ray energy -
Kinetic energy of emitted
by SEM, and then to focus on a small feature
photoelectron +
of interest, e.g., a particle on a fracture sur-
Spectrometer work function (1)
face, and use the electron microprobe to iden-
tify the composition at that specific location.
Auger Electron Spectroscopy (AES). When The last term on the right-hand side can be de-
the surface of a solid is bombarded with elec- termined during spectrometer calibration and is
trons, causing ionization, one way for energy typically about 5 eV. The binding energy of a
to be conserved during de-excitation is by photoelectron is characteristic of the element
emission of electromagnetic radiation (x-rays). from which it came and the way in which that
This is the basis of the previously described element is chemically bonded. Atoms bound to
technique. Alternatively, some of the energy more electronegative species emit photoelec-
released by de-excitation is carried away by trons with higher binding energies. Only hy-
emission of a secondary (Auger) electron, drogen and helium are difficult to detect
whose detection is the basis of AES.37 The because their x-ray absorption cross sections are
emission is a two-step process: an excited elec- very small. The maximum sensitivity for most
tron drops into a core vacancy and an Auger elements with XPS is approximately 0.01
electron escapes. The energy of an Auger elec- atomic layer; the sampling depth is typically in
tron depends on the chemical bonding state of the range of 15-50 A. Although XPS is less
the element from which it escaped. Unlike sensitive than AES, it gives simpler line shapes
x-rays, the maximum depth from which Auger and provides a direct measure of binding ener-
electrons can escape is only about 0.3-0.6 nm gies.
44 HANDBOOK OF ADHESIVES

XPS has been used to characterize polymers tions as low as 10- 3 to 10- 4 monolayer cov-
that have been surface treated prior to adhesive erage.
bonding. 4o It has also been employed to study Secondary Ion Mass Spectroscopy (SIMS).
surface contamination22 and to identify the lo- The incident beam for SIMS is the same as that
cus of failure in adhesive joints. 41 -48 for ISS, but secondary ions from the target are
In a study of aluminum-epoxy adhesive joints, monitored, rather than the back-scattered pri-
Dillingham and Boeri042 used XPS analysis to mary-beam ions. 50,51 These secondary ions are
determine that, after humid aging, the locus of mass analyzed to give an indication of surface
fracture was within the metal oxide. They fur- composition. Like ISS, it is very sensitive-
ther proposed that catalysis during setting by able to detect parts per million quantities of
acidic hydroxyls on the oxide caused the epoxy certain elements. Additionally, hydrogen can
near the oxide to be more crosslinked than the be detected, and, in some cases, chemical
bulk epoxy network. Another researcher48 structure can be determined more directly than
showed that fracture progressed within a weak with XPS or AES. The sampling depth for
boundary layer when a polyvinylidene fluor- SIMS is two to four atomic layers.
ide-nylon bond was ruptured. The spectra consist of plots of the intensity
XPS and AES instruments are often equipped of secondary ions against EIEo. One problem
with an argon ion gun. Ion impingement to with the general application of SIMS is that
sputter away material, and surface analysis, can secondary ion yields may vary by several or-
be alternated to give a composition depth pro- ders of magnitude for different elements and for
file. the same element in different matrices. This
Ion-Scattering Spectroscopy (ISS). ISS uti- often makes quantitative analysis difficult with-
lizes low energy (0.1-3 KeV) inert gas ions as out suitable standards. SIMS is most com-
the incident beam. 49 A fraction of these ions monly used for inorganic surfaces, although
undergo collisions with surface atoms and are Briggs52 has discussed its application to poly-
backscattered with some loss of energy. Back- mers.
scattering will only occur from atoms at the
surface, since ion neutralization occurs for in- Liquids
cident ions that penetrate beyond the first layer.
If the incident ions have energy Eo and mass Consider a liquid which is in contact with am-
M i , then the ions which scatter from a surface bient air. A molecule in the surface does not
atom of mass Ms will have a rebound energy interact with other liquid molecules in the same
E: way as do liquid molecules in the interior. It
experiences instead a different, much weaker
interaction, at the air interface. 53 Thus, surface
molecules experience a net attraction toward the
interior and have an energy exceeding that of
bulk molecules. A drop of liquid in the absence
of any external forces will spontaneously take
where () is the scattering angle and X = MiMi. a spherical shape, thereby minimizing surface
An ISS spectrum consists of the energy distri- area and free energy. It behaves as though it
bution of ions rebounding from a sample, with were covered with an elastic skin, resisting
peaks occurring at specific values of E. Equa- shape changes that would necessitate the move-
tion (2) can be used to calculate the masses of ment of molecules from the bulk to the surface.
the surface atoms. At constant temperature and pressure, the in-
A feature of ISS is that the surface is being crease in Gibbs free energy accompanying a
continuously sputtered away during measure- unit area increase in surface area of a liquid is,
ment, so that the spectra may change if there is by definition, the surface tension 'Y. Alterna-
a composition gradient beneath the surface. tively, 'Y may be viewed as the force per unit
Another feature of the method is that it can be length tending to contract the surface and cause
used to obtain elemental analysis at concentra- a liquid to resist spreading.
 FUNDAMENTALS OF ADHESION 45

INTERFACES tors to promote bonding are: (1) any applied

pressure and (2) intrinsic attractive forces be-
We tum now to the interaction that develops
tween liquid and solid. In principle, it is desir-
when a liquid is placed on a solid. In order for
able for the liquid to possess moieties with
two substances to interact directly, the mole-
strong molecular attraction for the substrate
cules of one must come within a few Ang-
without, at the same time, giving rise to strong
stroms of those of the other, i.e., the liquid
molecular interactions among liquid molecules
must adsorb onto the solid surface. This is an
themselves. For example, a liquid molecule ca-
exothermic process as can be readily shown
pable of H-bondingwith a substrate, but not
from a simple thermodynamic argument. The
with like liquid molecules, would be expected
free energy of adsorption, AGAD , is given by
to wet a substrate well. Ester linkages cannot
the well known equation
form hydrogen bonds with each other but are,
in principle, capable of hydrogen bonding to
surface silanol groups on glass.
The hindrance to wetting imposed by surface
where AHAD and ASAD are the enthalpy and en-
impurities must also be considered. Wetting is
tropy change upon adsorption. If adsorption is
promoted if adsorbed and entrapped gases are
to take place spontaneously, AGAD must be
readily solubilized into the adhesive. Consider
negative. Moreover, since adsorption of a liq-
the microbubble depicted in Fig. 2, containing
uid restricts the freedom of the liquid, ASAD is
entrapped air. At the periphery of the bubble,
always negative. Consequently, AHAD must be
forces between the adhesive and substrate tend
negative.
to increase progressively the area of true inter-
Figure 2 shows a small portion of the inter-
facial contact. As the microbubble is reduced
facial region as a liquid (adhesive) is brought
in size, the pressure within the bubble will in-
into contact with a solid substrate. Certain fac-
crease unless the gas is adsorbed at a suffi-
tors hinder bond formation, whereas others
ciently rapid rate into the adhesive mass. If
promote it. Barriers include: (1) surface rugos-
there is a pressure increase within the bubble,
ity, (2) species adsorbed on the solid before
this would slow the wetting process-in es-
bonding, (3) air entrapped in micropockets be-
sence, the wetting forces are resisted by the
tween the liquid and solid, (4) surface tension
pressure tending to reopen the interface.
of the. liquid and its bulk viscosity arising from
Whether or not this process is important in in-
cohesive forces among liquid molecules. Fac-
fluencing the kinetics of wetting will depend on
the rate at which entrapped impurities are ad-
sorbed into the adhesive.
It is known that many polar substrates such
as glass or metals, which have been exposed to
ambient air, have several molecular layers of
adsorbed moisture on them. Thus, features
within the adhesive that solubilize surface
moisture may be important in speeding up wet-
ting. Perhaps this is one role of polar groups in
a typical adhesive. Certainly an adhesive that
is completely incapable of displacing or solu-
bilizing surface moisture would find it difficult,
if not impossible, to attain rapid molecular con-
Fig. 2. Portion of solid surface soon after contacting with tact with the actual substrate.
a viscous liquid. Some wetting has taken place, but a pocket
of gas has been trapped in a depression. Molecular attrac- Thermodynamics of Adhesion
tion between liquid and solid at the periphery (locations A
and B) of the micro-bubble tend to increase the true contact Contact Angle. The previous discussion of
area. bond formation (wetting) was qualitative in na-
46 HANDBOOK OF ADHESIVES

1.0 , - - r - -....
~-.---~-~-~
", non-H-bonding
" liquids
0.8 ,
,,
,,
Liquid droplet (J) 0.6
e rJ)
o
Solid (.) 0.4

Fig. 3. Contact angle of a liquid droplet on a planar solid H-bonding "

0.2 liquids
surface.

o
ture. Application of thermodynamic principles 30 40 50 6070
to wetting and adhesion is one way to quantify Surface tension (mN/m)
these phenomena. 54 ,55 The extent to which a
Fig. 4. Comparison of Zisrnan plots of H-bonding and
liquid wets a solid is measured by the contact non-H-bonding liquids on polystyrene. (Data taken from
angle, (J. Fig. 3 depicts a liquid droplet on a Ref. 59.)
planar solid surface. When (J is large, the liquid
tends to minimize its area of contact (interac-
tion) with the solid; this indicates·a: preference surface tension "Ie has been taken as an approx-
of liquid molecules to interact among one an- imate measure of the surface free energy "I sv of
other rather than with the solid. On the other a solid. The precise value of "leis dependent on
hand, when (J = 0, the liquid spreads freely the particular series of liquids used to deter-
over the surface and is said to completely wet mine it. A series of polar H-bonding liquids
it. This occurs when the molecular attraction give a lower "Ie than simple hydrocarbons,
between the liquid and solid is greater than that which interact less strongly with the same sur-
between similar liquid molecules. 56 As a re- face. 59
sult, liquid-liquid interactions are disrupted in Polyolefins and fluorocarbon polymers have
favor of creating new liquid-solid interactions. low values of "Ie and are said to have low en-
Stated alternatively, a contact angle of zero is ergy surfaces; these materials are difficult to
a condition where the number of solid-liquid wet and bond. Metals, ceramics and polar pol-
interactions is maximized. ymers have high value of "Ie (high energy sur-
For a liquid droplet on a solid in the presence faces), can be readily wet by many organic
of saturated vapor of the liquid, the relationship adhesives, and exhibit good bondability.
between contact angle and the surface tensions Good proposed another expression that re-
(or free energies) is given by Young's equa- lates interfacial tension "lsi to the individual
tion,57 surface tensions of a liquid and solid: 60
_ (1/2
'Ysv = "lsi + 'Ylv cos (J (4) "lsi - 'Ysv + 'Ylv - 2c/> 'Ysv'Ylv) (5)

where 'Ysv = solid-vapor surface tension; "lsi = The last term represents the reduction in inter-
solid-liquid surface tension; and 'Ylv = liquid- facial tension owing to molecular attraction be-
vapor surface tension. tween the liquid and solid. The term c/> is
A widely used method for approximating the defined by:
surface tension of a solid was developed using
contact angle measurements. 58 A plot of cos (J (6)
against the surface tension "I for a homologous
series of liquids can be extrapolated to give a
critical surface tension of "Ie at which cos (J = where Wei and Wes are the work of cohesion of
1; two such plots are shown in Fig. 4.59 the liquid and solid, respectively, i.e., the ther-
Any liquid with a surface tension less than "Ie modynamically reversible work required to
completely wets the solid surface. The critical create a unit area of new surface in each ma-
 FUNDAMENTALS OF ADHESION 47

terial. Wa is the thennodynamic work of adhe- (10). In the fonner case,

sion (see below). For simple interfaces, ¢ is
approximately unity, but for systems in which Wa = 'Ylv(1 + cos 0), (11 )
there are different types of intennolecular force
in the two substances, ¢ may be appreciably and in the latter,
less than unity.
By combining Eqs. (4) and (5), an expres- ( 12)
sion for 'Ysv can be obtained:
When 'Ysv and 'Ylv are given values appropri-
2
'Ylv( 1 + cos 0) (7)
ate to simple nonpolar substances, about 25
'Ysv = 4¢2 mJ 1m2 , the value obtained for Wa from Eq.
(11) or (12) is only about 50 mJ 1m2 or less.
From the preceding discussion, as 0 -+ 0, then The actual work of detaching one adhering sub-
'Ylv-+ 'Yc (Zisman plot). Substituting this con- stance from another is found to be much larger
dition in Eq. (7), it is found that than this, in the range 1 J 1m2 to 10 kJ 1m2 •
Thus other contributions to the mechanical
(8) strength from dissipative processes within the
adherends greatly outweigh the intrinsic adhe-
Thus, the critical surface tension 'Yc for wetting sion. Nevertheless, these other contributions
is predicted to be approximately equal to the depend upon the existence of the intrinsic adhe-
surface tension or energy 'Ysv of the solid only sion and they seem in some cases to be directly
when ¢ = 1, i.e., for simple interfaces for proportional to its magnitude. 62 ,63 If there is no
which Wa = (WcsWcI)I/2. affinity between the adherends, there is cer-
tainly no mechanical strength of an adhesive
bond.
Work of Adhesion. If a liquid is placed on
a solid surface with which it has no interaction
Acid-Base Considerations
whatsoever,O = 180 0 and Eq. (4) simplifies to
Another approach for describing solid-liquid
'Ysl = 'Ysv + 'Ylv (9) interactions at an interface has been proposed,
based on computations of acid-base interac-
That is, the interfacial tension is simply the sum tions. 64 ,65 An empirical correlation exists for
of surface tensions of the liquid and the solid. the enthalpy of mixing MiAB when an acid, i.e.,
However, in all real systems, there are at least electron pair acceptor, and a base, i.e., elec-
minimal attractions between the molecules of tron pair donor, are mixed: 66 - 68
the liquid and those of the solid. This interac-
tion decreases the interfacial tension, so that 'Ysl
< 'Ylv + 'Ysv' The extent of the decrease is a
direct measure of the strength of the interfacial Drag067 assigned two empirical parameters to
attraction, and is tenned the thennodynamic each acid (CA and E A ) and each base (CB and
work of adhesion Wa: E B ), so that when substituted into Eq. (13) they
give the correct AHAB for the acid-base pair.
Wa = 'Ylv + 'Ysv - 'Ysl (10) Heats of mixing were detennined calorimetri-
cally and could be correlated with infrared
This expression, first given by Dupre ,61 states spectral shifts of groups involved in the acid-
that the reversible work Wa of separating a liq- base interaction. Values of C and E can be used
uid and a solid must be equal to the free energy to predict MiAB for other acid-base pairs. Val-
change upon separation. ues of AHAB calculated in this way for a great
Two different expressions for the thennody- variety of organic liquids agree very well with
namic work of adhesion may be obtained by experimentally detennined ones, usually within
combining Eqs. (4) and (10), or Eqs. (5) and 5 % or less. Upon mixing an acid and a base in
48 HANDBOOK OF ADHESIVES

solution, tUlAB is a direct measure of their mu- Metals

tual interaction.
When a metal is processed, e.g., by a cutting
Fowkes and coworkers extended Drago's
or rolling action, the material near the forming
methods to polymers and solid surfaces and
device, now the surface region, is subjected to
have determined C and E values for them. 69 ,70
high stresses that can cause irregular local
Furthermore, Fowkes suggested that acid-base
yielding and plastic deformation. This leads to
interactions often dominate the attraction that
an oxide which is less stable and less uniform
occurs between a liquid and a solid. He pro-
compared to that which would have formed on
posed, in general, that the thermodynamic work
a strain-free surface. Additionally, the oxide
of adhesion is given by65
layer may be intrinsically weak or it may ad-
here poorly to the underlying metal. These con-
Wa = 2( 'Y~'Y1)!/2 + f( CACB ditions are often associated with an oxide layer
that is too thick.
+ EAEB)x + W~ (14) In order to prepare a metal surface for bond-
ing, techniques have been developed that re-
where the three terms on the right-hand side of move surface contaminants, the existing oxide
Eq. (14) represent (1) nonspecific dispersive layer, and some of the underlying metal as well.
interactions, (2) acid-base or donor-acceptor A new oxide with improved uniformity and
interactions, and (3) a term to account for any strength is then formed under controlled con-
electrostatic interaction not included in the sec- ditions. Fig. 5 shows7 ! an Auger spectrum for
ond term. an "as-received" aluminum alloy (type 6061).
Note the carbon signal indicative of contami-
f = constant close to unity that con- nation by organic species; also, the surface is
verts enthalpy per unit area into rich in magnesium oxide, even though Mg only
surface free energy comprises 1.0% by weight of the alloy. Depth
x = number of moles of acid-base in- profiling71 (Fig. 6) by sputtering reveals that
teraction pairs per unit area of in- the oxide thickness is about 1000 A and or-
terface ganic species are quickly removed during sput-
'Y~, 'Y1 = dispersive components of the sur- tering.
face tensions of the solid and liq- It is important to note that surface contami-
uid respectively. nation is not always detrimental to adhesive
joint strength. In a recent study, 72 aluminum
Fowkes states that the first and last terms are
often negligible.

SURFACE TREATMENT
Solid adherends may have surface characteris-
~N(E) ~ ~fN-o_ _"""''''"'i.~J~..I.''---1
tics that would prevent the formation of a strong dE
S Ca " I,
and durable joint. For this reason, surface ~g AI
treatments have been developed; these alter the
surface region in one or more of the following
ways: modify physical structure, change sur- C o
face topography, change the chemical nature of
surface, or remove a weak boundary layer. 200 600 1000 1400 1800
Two materials which nearly always require Energy (eV)
surface treatment prior to adhesive bonding are Fig, 5. Auger spectrum of aluminum alloy type 6061, "as
metals and low energy polymers. These will be received." (Taken from Ref. 71, published by Plenum
considered in tum. Press.)
 FUNDAMENTALS OF ADHESION 49

100 500

AI
i.€ 450
~
5 400
e350
~
o
o
CD
"t:I
'0 300
iCD
60 80 100 :I: 250
Time (min.)
Fig. 6. Elemental depth profiles of the alloy of Fig. 5, o 2 3 4 5 6
obtained by ion beam sputtering. For each element, the Atoms/mm 2 (x 10- 12)
ordinate is the peak-to-peak magnitude for the sputtered
surface relative to its initial value. (Taken from Ref. 71, Fig. 7. Heat of desorption of sulfur from platinum as a
published by Plenum Press.) function of surface coverage. (Taken from Ref. 73, pub-
lished by Elsevier Science Publishers.)

adherends were purposely contaminated in a

controlled way with either silicone oil or stearic with 40- to 50-mesh Si02 particles clearly show
acid before bonding with an epoxy adhesive. the roughening caused by the latter process. 76
Although joint strengths were reduced with A comparison of the effect of the two treat-
stearic acid contamination, they were influ- ments on butt joint strengths with an epoxy ad-
enced very little by silicone oil. hesive is shown in Fig. 9. For test temperatures
Vapor degreasing in a chlorinated solvent, less than the Tg of the adhesive, joints made
ultrasonic cleaning, and exposure to elevated with grit blasted adherends have higher
temperature have been used to remove surface strengths. Bond strengths with either type of
contaminants, while chemical etching and me- adherend are enhanced if an additional chemi-
chanical abrasion are used to modify the nature cal etching treatment is used (see later).
of the oxide. An important consideration con- Immediately after blasting, the freshly ex-
cerning removal of adsorbed contaminants is posed metal will rapidly oxidize and begin to
that the binding energy is greater at lower sur- adsorb contaminants from the air. For this rea-
face concentrations. 73,74 In consequence, as the son, it is often desirable, especially with sen-
adsorbed species is removed, more energy is sitive metals like steel and copper, to coat the
needed to remove the remaining adsorbate. This adherend immediately with a primer. This pro-
effect is illustrated in Fig. 7, where the heat of tects the surface and allows the item to be stored
desorption of sulfur from a platinum surface is for a period of time before bonding, without
seen to increase as the surface coverage de- sacrificing bond quality. 75 Additionally,
creases. 73 It is often quite difficult to remove
the last traces of a contaminant.
Grit blasting is commonly employed to fur- Polished
0,.~5 "If'l I 0.25 pm
ther modify a metal surface after degreasing. 75
The surface region is removed by the abrasive
action of a stream of high velocity particles,
such as silica or alumina. The resulting surface Sandblasted
topography depends on the size and sharpness
of the grit; high surface areas can result, which
promote mechanical interlocking during bond-
ing. Profilometer traces (Fig. 8) for aluminum Fig. 8. Profilometry traces for an aluminum alloy (6061
(type 6061 T6) adherends that were either pol- T6) after polishing or sand blasting. (Taken from Ref. 76,
ished with diamond-dust paste or grit blasted published by Gordon and Breach Science Publishers.)
50 HANDBOOK OF ADHESIVES

0
80

"iii

t
D. sandblasted
~ 80
&.
'&
c
~ 40 poUshed .Iii

!
II

:!
J
i
~
20

0
0 20 40 80 80
Test temperature ( C)

Fig. 9. Tensile strengths at various test temperatures for

100~--------~----~--~
butt joints made with polished or sandblasted aluminum o 2 4
adherends and an epoxy adhesive. (Taken from Ref. 76, Time (years)
published by Gordon and Breach Science Publishers.)
Fig. 10. Effect of stress during outdoor aging (hot, wet,
tropical climate) on the residual strength of FPL-treated
primers have low viscosities so that they can aluminum/epoxy lap shear joints. Lower curve gives re-
readily fill surface crevices and irregularities. sults for joints which were stressed at 10 % of the original
We now consider some specific examples. breaking load during aging. (Data taken from Ref. 81.)

Aluminum. Aluminum to epoxy bonds have

been studied intensively because of their im- lent ions. AES analysis has shown that the ox-
portance in aircraft structures. 79 A surface ide layer formed after rinsing in deionized water
treatment of vapor degreasing and grit blasting is much thicker than when tap water is
is sufficient to give an aluminum-epoxy lap used. 84,8S
shear joint that fails- cohesively within the During the etching, the original oxide is re-
epoxy layer when stressed. 78 However, upon moved and typically about 1 I'm of underlying
exposure to a moist environment, the joint metal. The new Al20 3 oxide86 ,88 begins to grow
strength declines markedly and failure occurs during etching and then thickens somewhat
in the interfacial region. The strength decreases during rinsing. SEM shows that the oxide con-
more rapidly if the joint is also stressed during sists of a uniform layer ca 50 A thick next to
exposure to humidity. 79 Fig. 10 illustrates this the base metal with oxide spikes ( - 50 A x
effect. 80 In a hot, humid environment alumi- 400 A) protruding outward. 89 ,90 This mor-
num-epoxy lap shear joints fell apart shortly phology provides a high surface area to en-
after three years of exposure when loaded at hance the extent of intrinsic bonding, and also
10% of the original breaking stress, whereas results in mechanical keying of the adherend
unstressed joints did not lose their strength so and adhesive. This gives excellent initial joint
rapidly. Durable bonds with aluminum adher- strengths.
ends require chemical treatments that provide a In order to have a durable joint, it is neces-
stable, high surface area oxide. 81 sary that the interfacial region maintain its me-
A widely used treatment is the Forest Prod- chanical integrity upon exposure to moisture.
ucts Laboratory (FPL) process. 82 This consists Davis and Venables89 have shown that the pri-
of degreasing, alkaline cleaning, and etching in mary mechanism for degradation of strength of
a solution containing Na2Cr207' 2H20, H2S04 , an aluminum-epoxy joint during moisture ag-
and H20 in a 1 : 10: 30 ratio by weight. Speci- ing is the conversion of the oxide to boehmite,
mens are then thoroughly rinsed and air-dried. AlOOH, which apparently is weakly bonded to
The type of water used in the rinse can also the base metal. AES analysis of joints broken
influence bond strength. In one study, 83 deion- after exposure to high humidity has shown that
ized water resulted in decreased bond strengths fracture occurs at or near the boehmite-metal
compared to rinsing in water containing diva- interface. 89
 FUNDAMENTALS OF ADHESION 51

Thus, to increase the durability of aluminum- A new surface treatment93 for aluminum ad-
epoxy bonds, it is necessary to form an oxide herends has been reported to give joints with
with enhanced stability to water. This has been epoxy adhesives that perform better in the
accomplished by phosphoric acid anodization Boeing wedge test than PAA-treated speci-
(PAA). The oxide formed by PAA is much mens. The process involves: degreasing, deter-
thicke~ than that produced by the FPL pro- gent cleaning, alkaline etching, nitric acid
cess. Additionally, the PAA oxide has an open dipping, hard anodizing in 10% sulfuric acid,
cellular structure with a layer of AIP04 on and finally dipping in phosphoric acid.
top.9l The (barrier) phosphate layer is thought
to be responsible for protecting the oxide from Copper. The bonding of polyethylene to
being converted to the hydroxide when a joint copper provides another example of the impor-
is exposed to moisture. Fig. 11 gives XPS re- tance of oxide topography" on joint strength. 94.95
sults comparing the effect of humid aging on If the copper is first cathodically cleaned or
the aluminum 2p peak position for FPL and chemically polished, then polyethylene adheres
PAA treated surfaces. 92 Aging causes the peak rather poorly. However, if the copper is given
to shift to lower binding energies for the FPL a wet oxidation treatment with sodium chlo-
treatment-indicative of the oxide-to-boehmite ride, sodium hydroxide, and sodium phosphate
transformation. Little change is seen with PAA solution before bonding, then polyethylene ad-
samples. The very high surface area of the ox- heres tenaciously. In the former cases, the ox-
ide coupled with its high stability result in alu- ide layer is rather smooth and uniform, whereas
minum-epoxy joints with outstanding strength the last treatment produces a thick, black, den-
and durability. dritic oxide that adheres strongly to polyethyl-
ene by mechanical interlocking. The bond
strength is enhanced by plastic deformation of
FPL the composite interlayer, consisting of the fi-
etch
brous oxide embedded in polyethylene, which
interlinks the bulk copper and polyethylene. 96
,-,, -- 4

\ aged
,--+ -- 3
Steel. Not all metal adherends require chem-
\
ical surface treatments in order to give strong
\ -- 2
\ and durable joints. With mild steel, removal of
,
\
soluble contaminants by vapor degreasing fol-
,, ,, -- 1
/
lowed by grinding or grit blasting is suffi-
cient. 97 However, the freshly created surface of
81 77 73 69
Binding energy (eV)
steel is very reactive and reoxidizes almost in-
stantly. It will continue to oxidize, especially
PAA in the presence of moisture, eventually forming
4 a visible rust. The treated surface must be
coated with a primer or adhesive before the ox-
ide layer becomes too thick, otherwise joint
strength and durability will be poor. 98

Polymers
Low surface energy solids such as polyolefins
81 77 73 69
Binding energy (eV) and fluorocarbon polymers are difficult to bond
with conventional polar adhesives. Various
Fig. II. Comparison of the Al 2p peak from XPS anal-
ysis for (a) FPL-etched and (b) PAA-treated aluminum,
methods have been developed to modify their
both initially and after aging one hour at 60°C and 100% surfaces to overcome this problem. 99 Common
R.H. (Taken from Ref. 92, published by Plenum Press.) to all of them is surface oxidation.
52 HANDBOOK OF ADHESIVES

Corona Discharge. Corona treatment is high temperatures because of enhanced chain

widely used with plastic films. 100,101 Exposure mobility.
to the discharge is usually in air and at atmo-
spheric pressure. Polyethylene treated in this
Acid Etching. Surface groups introduced
way undergoes surface oxidation and some un-
after chromic acid etching 109 of polyolefins are
saturation is introduced. 102 This results in an
similar to those found after corona treatment.
increase in surface energy and wettability by
Surface roughening occurs as well. 110 Add'1-
polar adhesives, such as epoxies. Additionall~,
tionally, a small number of - S03H groups
surface roughening takes place due to nonum-
. 103 Th'IS have been identified. 41 Increasing the etch time
form degradation of the surface regIon.
and temperature for polypropylene does not
is thought to be caused by preferential attack at
significantly change the degree of surface oxi-
the more vulnerable amorphous portions com-
dation, but rather increases the depth to which
pared to the crystalline regions. Enhanced joint
oxidation occurs. In contrast, both the degree
strengths with corona-treated polyethylene are
and depth of surface oxidation increase with
attributed both to increased surface roughness
etch time for polyethylene. 41 Only short etch
and to increased intrinsic adhesion with surface
times are required to obtain polyolefin-epoxy
polar species including,104-106 e.g., hydroxyl,
bond strengths that are comparable to the co-
aldehyde, carbonyl, and carboxyl groups. Fig.
hesive strength of the polyolefin. Extended etch
12 gives XPS spectra for a corona treated sur-
times are detrimental to joint strengths, be-
face of low density polyethylene. 104 The ap-
cause of extensive degradation of the polymer.
pearance of the 0 Is peak indicates the
The relative contribution of surface rough-
formation of surface moieties containing oxy-
ening compared to chemical oxidation on joint
gen. For a typical corona discharge treatment
strengths has not been determined. This is a
of polyethylene, these functional groups range
problem needing further research.
in concentration from 4 X 10- 3 to about 1.4 X
10- 2 groups per surface methy1ene umt. . 104
Upon heating a corona-treated polyethylene Plasma Treatment. A low-pressure acti-
sample to 85°C, it loses wettability and ability vated-gas plasma, produced in an rf field, is
to bond.to7 This is attributed 108 to the polar employed. III When a polymer is exposed, ac-
groups turning inward toward the bulk mate- tive radicals and ions are created in the surface
rial, leaving the surface with more of a hydro- which lead to oxidation. Both inert gas (e.g.,
carbon character. This process is facilitated at argon, helium) and reactive (e.g., oxyge~)
plasmas have been used although the latter IS
generally too active because of rapid and ex-
tensive degradation and ablation. (Oxygen
plasmas are employed to remove organic c~n­
taminants from metals.) Plasma treatment m-
creases the wettability and bondability of
l: nonpolar polyolefins as well as polar plastics
'iii
c
.! such as nylon, although in the latter case the
.5 . . modest . 112,113 An ammon1'a
Improvement IS
plasma treatment of polyethylene enhances
bonding to cellulose (paper).114
There is some controversy regarding the
mechanism of enhanced bondability after
plasma treatment. In one study, 115 suuace ~

eV crosslinking was shown to occur during plasma

treatment of polyethylene. This was proposed
Fig. 12. XPS spectra of low density polyethy~ene before
(lower curve) and after (upper curve) treatment In a corona
to strengthen the surface material, which was
discharge. (Taken from Ref. 104, published by Gordon and hypothesized to consist initially of a weak,.l~w
Breach Science Publishers.) molecular weight fraction. Enhanced Jomt
 FUNDAMENTALS OF ADHESION 53

strengths were attributed to the elimination of

this weak boundary layer. It must be noted,
however, that the existence of a weak: boundary
layer on polyethylene surfaces has not been 2
demonstrated conclusively. Nor has fracture
within such a layer been shown to occur upon
stressing an adhesively bonded polyethylene >-
~
CD
joint. On the contrary, fracture of a bond be- ii 0.8
tween untreated polyethylene and an epoxy ad- CD
5 0.6
hesive occurs cleanly at the interface, and not b
within a polyethylene surface layer. 41 f!
LL. 0.4
Others feel the reason for increased joint ungrafted
strengths after plasma treatment is the intro- ~
duction of polar functionality (oxidation) and
0.2 '-------'--4,--------'-=3-------'
enhanced surface energy. 10- 10-
Peel rate (m/s)

Other Methods. In the three previous meth- Fig. 13. Fracture energies of polyethylene and polyeth-
ods described for treating polymers, surface ylene-g-acrylic acid bonded to an aluminum plate. (Taken
from Ref. 122, published by Butterworth Scientific.)
oxidation took place. Other direct methods of
oxidation have also been used to modify poly-
mer adherends effectively. With flame treat-
ment 1l6 ,ll7 in air, an oxidizing flame briefly Fluorocarbon Polymers. Fluorocarbon
( - 0.01-0.1 sec) impinges on the surface. XPS polymers require treatment with powerful etch-
analysis 118 has shown that amide surface groups ants before they can be strongly bonded. Me-
are generated as well as typical oxidation func- tallic sodium dissolved in either a mixture of
tionality. Treatment by a blast of hot air has naphthalene and tetrahydrofuran, or in liquid
also been used to create surface macro-radicals ammonia is effective. 123,124 These reagents re-
that then combine with oxygen. duce the polymer surface by defluorination. 125
If a sensitizer such as benzophenone is added Initially, the surface is discolored, and it will
to the polymer, sufficient oxidation can occur form a carbonaceous black residue if treatment
simply by exposure to ultraviolet light. In this is continued too long. XPS analyses have
photochemical treatment, creation of poly- shown the presence of unsaturation and car-
meric radicals by proton abstraction occurs bonyl and carboxyl functionality after treat-
readily with the formation of the highly reso- ment. 125 Wettability and joint strengths are
nance-stabilized diphenylhydroxymethyl radi- dramatically improved.
cal. An interesting technique to improve the
Rather than allowing the active species bonding of an epoxy adhesive to polytetrafluo-
formed in a surface to combine with ambient roethylene (PTFE) has been demon-
oxygen, it is possible to have a reactive mon- strated. 126 ,127 Two adherends are abraded in the
omer present and form grafts to a surface. 119,122 presence of liquid adhesive. These are then
In one study, radicals and ions were created in brought into contact and the adhesive allowed
a polyethylene surface by irradiation with 'Y- to set. The shear strength of the joint is about
rays in the presence of vinyl acetate monomer. seven times that obtained if the adherends are
The resulting polyethylene-vinyl acetate graft abraded in air before applying the adhesive.
showed excellent bonding with an epoxy ad- Presumably, when abrasion is carried out in the
hesive. Other researchers 122 have grafted presence of the adhesive, active species are
acrylic acid onto polyethylene using electron created in the PTFE surface due to chain rup-
irradiation. The greatly enhanced adhesion of ture and they react directly with the adhesive.
the modified polymer to aluminum is shown in When abrasion takes place in air, these species
Fig. 13. may decay away before the adhesive is applied.
54 HANDBOOK OF ADHESIVES

MEASUREMENT OF ADHESION But this feature need not extend right up to

the fracture plane itself. If the materials be-
Introduction
come dissipative at high stresses, in the im-
Earlier portions of this review dealt with as- mediate neighborhood of the crack tip; for
pects of making adhesive bonds. We now con- example, if micro-cracking occurred there or if
sider methods of measuring adhesion. Many the yield stress was exceeded locally; then en-
test methods have been developed but not all ergy dissipated around the fracture plane can
of them are amenable to analysis, i.e., to de- still be lumped together with that actually ex-
termining the relation between the breaking pended in molecular fracture as an overallfrac-
load, the dimensions of the components, and ture energy characteristic of the joint. Materials
the properties of the adhesive and adherends. for which these assumptions are valid are
Even for the simplest cases this problem has termed brittle, even though they may be ductile
proved to be quite difficult. Indeed, it is only locally, at the fracture site. Their strength is
recently that general fracture criteria have been characterized by the amount of energy G re-
developed and applied to simple joints. quired to propagate a crack through unit area.
For interfacial failure of an adhesive joint the
Energy Criterion for Failure. It is first nec- corresponding measure is the amount of energy
essary to identify an initial site for separation Ga required to separate the adherends per unit
to begin, usually at a defect or region of high area of interface. Obviously, if the strength Ga
stress at the interface. We then set up an energy of the bond is greater than the strength Gc of
balance, in which changes in strain energy in an adherend, then the bond itself will not fail
the stressed joint, and potential energy in the but the weaker adherend will split apart under
stressing device, are equated to the energy re- sufficiently high stresses. This form of failure
quired for debonding. This equation constitutes is termed cohesive, to distinguish it from sim-
our criterion for fracture: a joint will fail when, ple interfacial failure, termed adhesive.
by growth of an initial defect or debond, Energy considerations were first applied to
enough mechanical energy is released from the the fracture of brittle solids by Griffith 128 and
system to meet, or exceed, the energy require- have since been applied to the adhesion prob-
ments for debonding. The strength of a number lem by Rivlin and many others. 129-145 Notable
of simple adhesive joints is discussed below, recent contributions by Williams 132. 133, 137 and
using this basic concept of fracture mechanics. Kendalll38-14o form the basis for the present
An alternative method of analyzing the discussion.
strength of a bonded assembly is to evaluate the
stresses set up at the site of fracture and assume
Test Methods
that rupture will occur when a critical level of
stress is reached there. In principle, this method General Considerations. Ideally, a test
is equivalent to an energy criterion for fracture method should have the following features.
but energy calculations are often easier to carry First, it should employ simple, easily prepared
out. Energy methods are used here exclusively, specimens. Secondly, the failure force should
for this reason. remain constant, at least in principle, as the line
Notice that an implicit assumption is made of separation is forced to advance over long
that energy is not dissipated in irreversible pro- distances, so that fluctuations in the failure
cesses other than fracture. Whatever energy is force can be attributed to variations in the
applied to deform the components is assumed strength of adhesion. And, finally, the fracture
to be fully regained when the deformation is energy Ga should be obtained directly from the
removed. Although this assumption can be re- dimensions of the specimen, its stiffness during
laxed to take into account some plastic or vis- loading, and the applied force at which failure
cous response, the analysis is simpler and more takes place. No other measurements should be
straightforward if the components are ideally needed to calculate Ga.
elastic. A number of test methods are described here.
 FUNDAMENTALS OF ADHESION 55

Attention is drawn to those that do not confonn

to the above requirements, although they may
well have other advantages that make them
useful tests. As a purely practical matter, some
tests are particularly suitable for soft adhering
layers, such as pressure-sensitive adhesive
tapes, and others are more appropriate for
"rigid," structural adhesives. This aspect
should be obvious from the discussion in each
case.

Peeling. One of the simplest and most widely

used methods of measuring adhesion is by
Fig. 15. Peel mechanics for an extensible adhering layer.
peeling a thin adhering layer away from a rigid
substrate (Fig. 14a) or from an identical layer
(Fig. 14b). The peel force is a direct measure are, respectively, the tensile strain and energy
of fracture energy, at least in the simplest cases, density acquired by the detached strip. Adher-
as the following analysis shows. ing strips are generally thick enough to detach
During steady-state peeling, conservation of without stretching significantly, at least at peel
energy requires that: angles of about 45 0 or more, so that e and tU
are relatively small. In this case, Eq. (16) can
Work done by the peel force = work of de-
be simplified and the peel force becomes
tachment + strain energy imparted to the
newly detached portion. P = Ga /(1 - cos 0). (17)
(15)
One further comment is necessary about Eq.
For peeling apart a unit length of bonded inter- (17). It is based on the assumption that no en-
face, Fig. 15, Eq. (15) becomes136 ergy is expended in bending the strip away.
And yet all materials are imperfectly elastic to
P(1 + e - cosO) = Ga + tU (16) some degree, and some of the work of defonn-
ing the sharply bent portion at the peel front
where P is the peel force per unit width, t is will not be returned as the peel front moves on.
the thickness of the peeled strip and e and U Instead, it will be lumped in with the work of
detachment and lead us to overestimate the true
fracture energy Ga. And this error will be
p greater at larger peel angles, or with particu-
larly dissipative materials, used either as ad-
hesives or as backings.146 It is therefore
advisable to use small peel angles, but not so
small that stretching of the layer becomes sig-
nificant. A peel angle of 45 0 appears to be a
good compromise. 146 With these reservations,
the peel test is a satisfactory method of mea-
suring the fracture energy of adhesion for a
wide variety of flexible layers, tapes and films.
p Of course, the same features that add to the
work of detachment, and lead us to overesti-
(0 ) (b) mate the value of Ga at large angles, can be
Fig. 14. Peel tests: (a) from a rigid base, (b) from a sim- exploited to enhance the resistance of adhering
ilar flexible layer. layers to peeling separation. Indeed, a large
56 HANDBOOK OF ADHESIVES

fraction, over one-half, of the peel strength of hering plates undergo bending as well as
commercial tapes appears to consist of plastic stretching,139 but these are relatively minor.
deformation of the backing material. We shall Moreover, the unexpected dependence of the
find repeatedly that an understanding of the breaking force and stress on the thickness t of
mechanics of adhesive failure gives insights the adhering layer, Eq. (18), is satisfactorily
into possible ways of improving the strength of confirmed by experiment. 139
a joint, even if the true fracture energy of the A further, and convincing, demonstration of
interface is unchanged. the validity of energy considerations is that the
value of fracture energy Ga deduced from lap-
Lap Shear. When a stretchable adhering shear measurements by means of Eq. (18) are
layer is pulled off parallel to the bond plane in good agreement with values obtained from
(Fig. 16) it will become stretched after detach- quite different experiments, for example, from
ment. For a linearly elastic strip the relation for peeling, Eq. (17). Thus, it appears that the en-
the detachment force P per unit width is ob- ergy criterion for fracture is appropriate and ef-
tained from Eq. (16) as fective in accounting for the major factors gov-
erning breaking loads of lap shear joints.
p2 = 2tEGa (18)
Tensile Detachment. We consider first the
where t is the thickness of the strip and E is the detachment of an elastic half-space from a rigid
tensile modulus of elasticity; The product tE plane, Fig. 17. If a circular debond of radius a
thus represents the tensile stiffness of the strip is present at the interface, the tensile stress (fb
per unit width. that will cause it to grow is given by
In terms of the mean shear stress (fs required
to break the joint, Eq. (18) takes the form:

(19) where E is the tensile modulus of the adhering

material. This result is exactly analogous to the
where L is the length of the overlap. It is clear relation for the tensile breaking stress of a bar
that a smaller mean stress will be required to of a solid material containing a small penny-
break a lap-shear joint with a longer overlap. shaped crack of radius a in its interior, 147
Now this prediction is inconsistent with the
idea that joints fail in shear at a critical level of (21)
mean shear stress. It is therefore important to
know whether lap-shear joints do, indeed, fail The same result, Eq. (20), is obtained for
at lower stresses for longer overlaps, because growth of a pressurized debond (a blister) of
this finding would confirm the validity of a radius a at the interface between an elastic half-
fracture energy criterion and disprove the va- space and a rigid plane,137,148 at least for an
lidity of a critical mean shear stress criterion incompressible material. In that case, a tensile
for failure. As engineering designs are based stress (fb acting at infinity is exactly equivalent
on failure criteria, it is important to know which to a pressure of equal magnitude inside the blis-
one is correct. ter.
As far as can be ascertained, the predictions
of Eq. (18) appear to be valid. 142 Corrections
must be made for short overlaps, when the ad-

Fig. 16. Lap shear experiment: detachment of an exten- Fig. 17. Tensile detachment of a thick elastic layer with
sible adhering layer at an angle of peel of 0°. a circular interfacial debond, radius a.
 FUNDAMENTALS OF ADHESION 57

tI
trolled splitting apart of two plates or beams,
bonded together along one edge, by twisting

AdheSiVe~$
them about an axis passing through the adhe-
sive, as proposed by Outwater. 134 This can be
achieved by applying bending loads to one end
of the bonded specimen, as sketched in Fig.
I
19, or by applying a torque with a pulley ar-
~ rangement as sketched in Fig. 20. The latter is
Fig. 18. Tensile detachment of a thin elastic (adhesive) experimentally more convenient,145 but the
layer.
principle is the same. At a critical value of ap-
piied load P, denoted Pc, or torque M, denoted
When the adhering layer is thin, however, Me, an initial crack of length c made between
comparable to the blister radius, then the re- the two adhering plates will advance. At this
sults are quite different because the deforma- point, elastic energy stored in the two twisted
tion is then largely bending and biaxial arms begins to be expended in fracture. If we
stretching. This situation is discussed later. assume that the cleaved arms of the specimen
Another common type oftensile test involves are linearly elastic in torsion, and that their tor-
pulling apart two flat rigid plates with a layer sional stiffness is inversely proportional to the
of adhesive sandwiched between them, Fig. 18.
This experimental arrangement is amenable to
analysis by finite-element methods,149 but the
relation obtained for breaking load as a func-
tion of fracture energy appears to depend
strongly upon the relative thickness (shape fac-
tor) of the adhesive layer as well as upon the
dilatancy of the adhesive under stress. Indeed,
as the thickness is decreased, the location of tp/2
failure initiation changes, first from the edge to Fig. 19. Double-torsion experiment: direct loading for
the center of a bonded interface,149 and sec- small torsions.
ondly, for soft, strongly adhering layers, to the
center of the adhesive itself, where the material
fails cohesively. 150 Thus, although they are
fairly easy to carry out, interpretation of tensile
tests is not a simple matter.
They also suffer from a major scientific Top view
drawback. Because the failure load decreases
as the debond grows in size, failure is autoca-
talytic. Thus, once the conditions are set up for
an initial defect to grow, it will propagate at an
ever increasing rate until the specimen is com-
pletely broken. Experiments at a known and P
controllable speed are thus hardly feasible. Ad-

~--
ditionally, the origin of failure is a chance flaw
or debond of unknown size (unless care is taken
to introduce known, reproducible defects), and 1. L
thus one of the essential parameters in the re- Side view
lation for the failure stress, Eq. (20), is un-
known. Fig. 20. Double-torsion experiment: use of pulley and
beam for large torsional deformations. Torque M = PL.
(Taken from: K. Cho and A.N. Gent, Internatl. 1. Frac-
Torsional Fracture. A particularly attrac- ture, 28, 239 (1985), published by Kluwer Academic Pub-
tive test for structural adhesives is the con- lishers.)
58 HANDBOOK OF ADHESIVES

p
M

p
Fig. 22. Double-cantilever experiment.

e wf / 12 for beams of rectangular cross-section)

Fig.21. Relation between applied torque M and angle of
rotation (J for a double-torsion experiment, Fig. 20. Me de-
and e denotes the distance between the point of
notes the critical value of torque at which fracture propa- application of the load and the crack front, Fig.
gates. (Taken from: K. Cho and A.N. Gent, Intematl. J. 22. In order to obtain a constant failure force,
Fracture, 28, 239 (1985), published by Kluwer Academic at least in principle, as the crack advances, spe-
Publishers.) cially prepared beams can be made with cross-
sections that change in such a way that the
length e of the arms, we can obtain the fracture bending rigidity EI increases appropriately with
energy Ga from an energy balance, in the e.
form l34 ,145
Pull-Off Test. This simple test is shown in
Ga = M~/2kt (22) Fig. 23. An adhering strip is pulled away from
a rigid substrate by a force P per unit width.
where k = Me / () is a constant denoting the tor- Work is expended in stretching the strip as it
sional stiffness of the specimen for a crack of detaches, and in breaking the bond. Assuming
unit length, and t is the thickness of the cleaved again that the strip is linearly elastic and that
bond. The value of k can be obtained from the the angle () at which it detaches is small, the
experimental relation between torque M and relation between P and () is given by
angle () of rotation up to the onset of fracture,
Fig. 21, and the mean value of Me can be mea- (24)
sured thereafter, over long distances for long
test pieces. Thus, the mean fracture energy Ga where E is the tensile modulus of the strip and
can be measured with some confidence, using t is its thickness. In terms of the fracture en-
a single specimen of simple design. ergy,

Cleavage. Another test method used widely p4 = 19.0 EtG~. (25)

for stiff, structural adhesives involves pulling
apart two stiff cantilever beams bonded to- Thus, if only the pull-off force P is measured,
gether with a thin layer of adhesive, Fig. 22. an independent measurement of the stiffness of
In this case, bending energy stored in the bent the strip is needed in order to determine the
arms is released as the crack advances. Again, fracture energy. However, a simple relation is
we can obtain a relationship from energy con- obtained in terms of the product of the pull-off
siderations between the failure force P applied
to cleave apart the specimen, the dimensions
and bending stiffness of the beams, and the
fracture energy Ga :

(23)

In this relationship, I denotes the second mo-

ment of area of a beam cross-section (/ = Fig. 23. Pull-off test.
 FUNDAMENTALS OF ADHESION 59

force P and angle () of detachment, both of

~
which remain constant, at least in principle, as
detachment proceeds: 145
: :
!( 2a ~;
(26) Fig. 24. Blister test.

Thus, continuous measurements of fracture as the blister grows, the pressure at which fur-
energy can be made from simple observations ther debonding takes place is then obtained in
on a single specimen. terms of the fracture energy Ga of the
A notable feature of this experimental ar- interface 152
rangement is the non-linear relationship that
holds between force P and angle (), a measure
of deformation, Eq. (24). Provided that the
Note that the relationship between load and
system is elastic, the principles of fracture me-
deflection is again a cubic one for small deflec-
chanics can be applied to systems that follow
tions of an inflated membrane, Eq. (28), even
nonlinear relations between load and deflec-
though the overlying layer has been assumed to
tion. Another example is given in the next sec-
be linearly-elastic. As a result, Eq. (29) for the
tion.
failure pressure has an unusual three-fourths
power dependence upon fracture energy, as in
Blister Tests. Blister tests are appealing for
Eq. (25). And, again, if we measure simulta-
measuring the adhesion of thin layers or films,
neously the failure pressure II and the deflec-
(for example, of paint), to a rigid substrate, be-
tion y of the blister, then we obtain a
cause they resemble failure processes encoun-
particularly simple relationship for the fracture
tered in service. Also, they can be analyzed
energy Ga l45
theoretically to yield values of the fracture en-
ergy Ga. But they take several different forms.
Ga = 0.65IIy. (30)
When the pressurized debond (blister) is small
in radius compared to the thickness of the over- Thus, even though the blow-off pressure does
lying layer, then the failure criterion is the same not stay constant as the blister grows, Eq. (29),
as that discussed previously under tensile tests, measured values can be employed with corre-
Eq. (20). When the blister radius is comparable sponding values of the blister height to calcu-
to the thickness ofthe overlying layer, then the late the strength of adhesion continuously; no
layer is deformed primarily in bending and the other parameters are needed.
relation for the failure pressure II becomes 133
Pull-Out of Inextensible Rods and Fibers.
The strength of adhesion to the surrounding
material is an important parameter for fibers or
where t is the layer thickness and a is the blister cords used as reinforcing components of com-
radius. posites. One method of measuring this property
A third case, particularly important for thin is by partially embedding the fiber or rod in a
films, is where the blister radius a is larger than block of the matrix material and measuring the
the layer thickness t, Fig. 24. The principal pull-out force P. A sketch of the experimental
mode of deformation of the layer is then biaxial arrangement is shown in Fig. 25. By applying
stretching, and the relationship between inflat- the principle of energy conservation during de-
ing pressure II and height y of the blister before tachment the pull-out force P is obtained in
any further detachment occurs IS . gIven
. by 151
terms of the interfacial fracture energy Ga 153

II = 4.75Etl/a\ (28) (31)

where E is the effective tensile modulus of the where a is the radius of the fiber and A is the
layer. By considering changes in strain energy cross-sectional area of the block in which the
60 HANDBOOK OF ADHESIVES

p p

Area A

p
Fig. 26. Pull-out of n fibers simultaneously from a single
block.
p
Fig. 25. Pull-out of an inextensible rod, radius a, from quired to pull out n fibers simultaneously from
an elastic block, cross-sectional area A. a single elastic block will increase in propor-
tion to n112. This prediction has been verified
fiber is embedded. Experiments to test this re- experimentally for 1-10 cords embedded in a
lation have shown that it is obeyed satisfacto- rubber block, Fig. 27.153 It provides a striking
rily for rods or fibers of small radius, but for example of the success of simple energy cal-
larger radii or for deeply embedded fibers a culations in accounting for important features
large additional term in the energy equation of the strength of bonded joints and structures.
arises from frictional resistance to pull-out. 154
Provided that this term is not a major one, Fiber Fragmentation. An unusual way of
however, there are significant advantages in estimating the strength of interfacial bonding
using a pull-out test to measure the strength of for fine fibers is the single fiber tensile test. 155
adhesion. The pull-out force remains constant, Glass or carbon fibers used as reinforcing com-
at least in principle, as the debond propagates ponents in composites have diameters of only
along the length of the fiber, starting from the a few micrometers and it is difficult (although
embedded tip. Moreover, even for strongly not impossible), to measure pull-out forces'for
bonded fibers, fracture tends to follow the cir- such small fibers. An alternative method is to
cumference of the fiber closely because, as Eq. embed a fiber within a tensile bar of the matrix
(31) indicates, the pull-out force decreases as material, along the axis. On stretching the bar,
the radius a of the circular fracture front de- the fiber, being less extensible, breaks in two.
creases. This test method is therefore particu-
larly helpful when the strength of adhesion
2r-----~----~------~
approaches the cohesive strength of the adher-
ing material and the fracture plane tends to de- p
viate from the interface into the adhesive itself. (kN)
When a number of fibers are embedded in a
single elastic block and are all pulled out to-
gether, Fig. 26, then the work required for de-
tachment is obviously larger than for a single
fiber, by a factor equal to the number of fibers, O~____L -_ _ _ _~_ _ _ _~
n. The strain energy stored within the block
must therefore be larger than before, by a fac-
o 2 3
tor of n, and the total force applied for pull-out n'/2
must be increased, by a factor of n 1l2 • Thus, Fig. 27. Total pull-out force P for n fibers, pulled out
energy considerations lead immediately to the simultaneously from a single block, vs. n l / 2 • (Taken from
surprising conclusion that the total force re- Ref. 153, published by Chapman and Hall.)
 FUNDAMENTALS OF ADHESION 61

Then, as the bar is stretched further the pieces isfactory test method has not yet been devel-
of fiber break again, and so on until the fiber is oped.
fragmented into many small lengths. But, Another urgent requirement is for a nonde-
eventually a limit is reached at which the fiber structive test for adhesion. Although there are
fragments no longer continue to break as the a variety of ways of finding small debonds at
bar is extended further. This state is shown interfaces (for example, by x-ray tomography),
schematically in Fig. 28. as far as the authors are aware there is no
Apparently, when the fiber length is small method presently available that can distinguish
enough, the forces that can be transmitted to it a weak, but defect-free, bond from a strong
by shear stresses from the adhering matrix ma- one, apart from breaking it.
terial are no longer sufficient to break it. A sim-
ple force balance suggests that the strength of Conclusions
the interface, in terms of the maximum shear
What, then, is the best method for measuring
stress (Ja that it can transmit, is given by
adhesion? For flexible materials, it is probably
a peel test at a shallow angle of peel, around
(32)
45 0 , and with the precautions mentioned in the
text. For a structural adhesive, the choice lies
where (Jb denotes the tensile breaking stress for
between a cleavage test and a torsion test, with
the fiber, a is the fiber radius, and Ie is the mean
the latter being slightly preferred. In both cases,
fragmentation length.
it is essential that the adherends be within their
It is thus possible from observations of Ie to
elastic limit. Otherwise, the basic energy bal-
deduce the interfacial bond strength (Ja' Many
ance, on which a quantitative interpretation of
such measurements have been reported.155-15S
the results depends, is invalid.
But this criterion for fracture is not easily trans-
For films and tapes, a pull-off test seems ap-
lated into energy terms. Indeed, it is quite likely
propriate. In this case, a stiff elastic backing
that an energy criterion would take a different
can be applied to reinforce the adhering film,
form from Eq. (32). (We recall the fracture
if it is not stiff enough or too plastic in tension.
analysis of a simple lap shear test, and the fail-
And the same trick can be used with adhering
ure of a shear stress criterion for fracture to hold
paint films, if they would otherwise be too
in that case.) The reader is therefore recom-
plastic to treat as "elastic" layers.
mended to treat Eq. 32 as an interesting cor-
relation between adhesion and observable
features of stiff fibers in a more extensible ma- STRENGTH OF ADHESION
trix, but one that will probably be superseded Introduction
when an energy analysis has been carried out.
Values of the strength of real adhesive bonds,
Needed Test Methods. It is impossible to represented by the fracture energy Ga , can be
list, never mind discuss, all of the other meth- determined by any of the methods described in
ods that have been proposed for measuring the preceding section of this chapter. They are
adhesion. However, there remain serious found to range from a few J 1m2 to 10,000 J 1m2
needs, still unmet. One is for the accurate mea- or more. We must now try to account for these
surement of thin-film adhesion; for example, in differences. Why is a particular value of
microelectronics and biomedical applications. strength obtained with one formulation and not
A detailed review of this subject has been given with another? The answer turns out to involve
by Mittal,159 but it appears that a generally sat- both molecular interactions across the interface
and deformation processes within the adhesive.
Plastic yielding, flow, and other mechanisms
1 : of energy dissipation within the adhesive, near
the failure site, are essential features of strong
adhesives. Far from this region, however, the
Fig. 28. Single-fiber fragmentation experiment. deformations are smaller and may well be vir-
62 HANDBOOK OF ADHESIVES

tually elastic. For example, structural adhe- possible to make measurements of bond
sives are able to carry sizeable loads without strength that approach a lower limit, termed
yielding, and yet there is every indication that threshold strength, that is due solely to molec-
they yield locally, before breaking, at points ular interactions between polymer and sub-
where the bond is highly stressed. strate across the interface. But, as can be readily
We tum now to the separate effects of inter- understood from the stringent conditions that
action at the molecular level and irreversible must be met, the number of adhesive materials
local deformations. that have actually been examined in this way is
still very small.
Molecular Interactions
Threshold Strength. Unfortunately, pub-
It is plausible, but often misleading, to asso-
lished measurements of threshold strength seem
ciate a strong bond with a strong interaction be-
to be inconsistent. In one case, simple, lightly
tween materials on a molecular level. In fact,
crosslinked polymers are reported to adhere un-
rather weak intermolecular bonds, for exam-
der threshold conditions with a strength Ga of
ple, the London-Van der Waals bonds that ex-
about 0.1 J 1m2 , close to the value expected
ist in all substances, are sufficient to make
from London-Van der Waals bond energies. 160
strong materials and joints. The correlation be-
In other cases, the threshold strength for simi-
tween intrinsic strength of chemical bonds and
lar polymers has been reported to be much
mechanical strength of a substance, or of an
larger, about 1 J 1m2 .161 Resolution of this dis-
interface, is often rather poor.
crepancy is clearly desirable. In the meantime,
In order to seek a better correlation, we must
we note only that these values are extremely
first attempt to remove all dissipative mecha-
small, much lower than could be utilized in
nisms from the system. Otherwise, the bond
construction. For example, a strength of 1 J 1m2
will appear to be stronger than it really is, be-
corresponds to a resistance to peeling separa-
cause of energy expended in processes other
tion at an angle of 90° of only 1 Newton (about
than molecular separation or rupture at the in-
4 oz weight) per meter of bond width, and
terfacial plane. So, for soft polymeric adhe-
forces due to gravity would generally exceed
sives, the possibility of viscous flow must be
this. Stronger interactions at the interface are
eliminated. One way of doing this is by lightly
therefore required to create a strong joint under
linking the polymeric molecules together in
threshold conditions.
situ. In this way their characteristic interaction
with the substrate can be preserved, while they
are prevented from flowing apart on separation. Chemical Coupling. Various bifunctional
A second step is necessary. Even crosslinked materials are employed to link two materials
polymers have residual dissipative features due together chemically. Probably the best known
to internal motions of molecular segments, a of these coupling agents are the silanes, de-
type of "internal viscosity." It is therefore signed to react both with OH groups on an in-
necessary to carry out the measurements of organic substrate such as glass or metal and
strength at very low rates of deformation and with reactive groups on the molecules of an ad-
at high temperatures, far above the glass tran- hesive resin. 162 The functional groups on silane
sition temperature, to minimize energy absorp- molecules are chosen to react with the partic-
tion from these processes. ular adhesive. Some examples are given in Ta-
Finally, the adhesive must consist only of the ble 1. Specific coupling agents have been
polymer itself (and possibly some compatible developed for bonding glass fibers to polyester
fluids). If reinforcing solid particles are pres- resins, carbon fibers to epoxy resins, and talc
ent, they may cause energy to be dissipated in particles to Nylon. Virtually all glass fibers
other ways, for example, by internal friction, used in fiber-glass composites are silane-
dewetting of polymer from the particles, or treated, and the resistance to deterioration by
separation of mutually adhering particles. hot water is greatly enhanced in this way.
When all of these precautions are taken, it is A simple example of a coupling agent is tri-
 FUNDAMENTALS OF ADHESION 63

Table 1. Silane Coupling Agents.

Type Formula Used With
Vinyl triethoxysilane crosslinked polyethyl-
ene,
thermosetting polyester,
diene elastomers
-y-glycidoxypropyltrimethoxy sil- CH 20CHC- epoxy, urethane, polyvi-
ane H20(CH 2hSi(OCH 3h nylchloride, phenolic
-y-aminopropyltriethoxysilane NH2CH2CH2CH2Si(OCH2CH3)3 epoxy, melamine, nylon,
polycarbonate, poly i-
mide
-y-mercaptopropyltrimethoxysilane epichlorohydrin, ure-
thane, polyvinylchlor-
ide

ethoxyvinylsilane, Fig. 29. This substance hy- Fig. 29c, and thus introduce chemical bonds
drolyzes to yield silanol groups, and they are between polymer and substrate.
thought to condense with OH groups on a suit- Measurements show that silane interlinking
able substrate, for example, on glass, Fig. 29b, increases the threshold strength enormously,
to form strong chemical bonds. When a poly- Fig. 30, to approach the intrinsic (threshold)
mer having a vinyl group in the molecule is ap- strength of the polymer. But that is only of the
plied to a silane-treated surface, it is then order of 20-100 J /m2.'61 Obviously, the in-
possible to interlink the two vinyl groups, at herent strength of real adhesive bonds must be
least in principle, as shown schematically in further enhanced by dissipative processes.

(a) Hydrolysis

CH -CH -0 HO
3 2 I

CH3 - CH 2 - 0 - Si
I
- CH= CH 2 + 3H 2 0 --+ HO- Si- CH= CH 2 + 3CH3 CH 2 0H
I
CH3 -CH 2 -0 HO

(c) Coupling

Fig. 29. (a) Triethoxyvinylsilane; (b) condensation on glass; (c) reaction with a diene polymer.
64 HANDBOOK OF ADHESIVES

as we move away from threshold conditions to

higher rates and lower temperatures, the mea-
50 sured strength of a bond rises, often by large
factors. This explains how chewing gum, for
example, can adhere strongly, even though it
has little inherent adhesion, because it deforms.
(J!rrf) in a nonequilibrium way under normal circum-
stances.
25 In fact, the same increase in joint strength
that is obtained with a simple viscoelastic ad-
hesive on increasing the rate of debonding, can
be achieved by a suitable reduction in test tem-
perature. This is referred to as the principle of
rate-temperature equivalence. For amorphous
glass-forming liquids above their glass transi-
50 100 tion temperature Tg , Williams, Landel, and
Vinylsilane (%) Ferry (WLF) proposed a universal relationship
Fig. 30. Threshold strength of adhesion for a polybuta- for the ratio aT of corresponding test rates at
diene layer adhering to glass treated with varying propor- temperatures T and Tg : 163
tions of triethoxyvinylsilane. (Taken from Ref. 161,
published by John Wiley & Sons.) loglO aT = 17.4(T - Tg}j(51.6 + T - Tg}

(33)
Rheology of Soft Adhesives
Rate and Temperature Effects. Adhesion The factor aT also represents the ratio of the
of a soft crosslinked polymer to a rigid sub- rates of Brownian motion of molecular seg-
strate is found to increase markedly as the rate ments at T and Tg , and this is the theoretical
of debonding is increased. An example is basis for the WLF relation.
shown in Fig. 31. The strength also increases An example of the utility of this relationship
as the temperature is reduced, Fig. 31. Thus, is given in Fig. 31. The fracture energy Ga is
plotted as a function of peeling rate at several
temperatures, for an elastomeric layer adhering
4.--r-----,.-----.-~ to glass. As can be seen, the results for each
/-aocc temperature give parallel curves when plotted
against the logarithm of peel rate and they can
be shifted along the log rate axis to bring them
into superposition, Fig. 32. 161 The displace-
ments log aT required to do this are found to be
in good accord with Eq. (33), indicating that
the temperature dependence of adhesion re-
2
flects corresponding changes in the rates of mo-
tion of molecular segments. It has nothing to
do with the thermodynamics of wetting and
adhesion, therefore, but is instead related to ki-
I I
netic factors, probably viscous loss processes
-6 -2 as the adhesive layer is pulled away from the
Log,oR (m!s) substrate.
After superposition, the results form a master
Fig. 31. Strength of adhesion of a polybutadiene layer to
glass treated with a silane mixture vs. rate of peeling at
curve, Fig. 32, giving the fracture energy at
various temperatures. (Taken from Ref. 161, published by any desired temperature (in this case Tg) as a
John Wiley & Sons.) function of the equivalent rate of peeling at that
 FUNDAMENTALS OF ADHESION 65

4r-----.-----.-----~ like a mobile fluid, and yet resist detachment

as if they had been transformed rapidly into a
cohesive solid. These apparently contradictory
features can be achieved by careful control of
the physical properties of the adhesive. First,
to secure rapid wetting the adhesive must be
compliant. It is recommended that the com-
pressive compliance after 1 sec under load be
greater than about 10- 6 m2 /N. I64 Then the
2 forces of attraction between molecules of the
adhesive and substrate are sufficient to pull the
adhesive into intimate contact, even when the
I _____ L_ _ _ _ ____
substrate surface is irregular on a microscopic
scale.
~ ~ ~

-20 -10 Secondly, when the adhesive is about to de-

tach, it is subjected to quite high stresses at the
Fig. 32. Master curve relating the strength of adhesion to tip of an interfacial separation. If it is able to
the effective rate of peeling at Tg (-95°C). Results taken flow like a yielding solid, then the separation
from Fig. 31. front is blunted, the stresses are minimized, and
separation is prevented. Moreover, if the ad-
temperature. Thus, it is possible to deduce the hesive also hardens at high strain levels to be-
dependence of the fracture energy upon rate of come a tough solid, the adhesive layer itself
peeling over a wide range, using only limited cannot easily be ruptured. Thus, a substance
data obtained over a narrow range of rates, but which flows readily at low stresses but hardens
at a number of temperatures. at high levels of strain is potentially effective
It must be emphasized that the WLF equation as a pressure-sensitive adhesive. Some elasto-
is only applicable to simple viscoelastic sub- mers are self-strengthening by virtue of the
stances. It does not hold for semicrystalline or steric regularity of their molecules which al-
glassy adhesives. Nevertheless, it reveals the lows them to crystallize rapidly on stretching.
importance of internal dissipative processes in Cis-polyisoprene (natural rubber), trans-poly-
the work of detachment. chloroprene (Neoprene), and polyisobutylene
The mechanical response (elastic modulus all have the property of crystallizing at high
and fracture energy) of certain epoxy and rub- strains, and all of them have been employed in
ber-modified epoxy adhesives as a function of pressure-sensitive adhesive formulations.
test rate and temperature have been shown to Thus, the requirements for a successful pres-
superpose to form single master curves. Here, sure sensitive adhesive formulation are that it
however, the shift factor aT is not a universal must possess little resistance to small strain de-
function of temperature; it must be determined formation, so that rapid wetting takes place,
empirically for each adhesive type. Much re- and yet it must also be able to support large
search is still needed before a good understand- strains without flowing apart easily. These fea-
ing is reached of the rate and temperature de- tures are obtained by a loose network of high-
pendence of the strength of glassy adhesives. molecular-weight entangled molecules, diluted
The effects are generally smaller, however, with special resins (tackifiers).
than for pressure-sensitive adhesives, above
their glass transition temperatures.
Tackifiers. Tackifiers are materials that are
added to elastomers to improve contact adhe-
Adhesion on Contact. Some adhesives sion. They generally have molecular weights in
have the special property (adhesive tack) of the 500-2000 range, with broad molecular
sticking firmly after brief contact under a light weight distributions. Their softening points
pressure. Thus, they wet the surface quickly, vary from 50 to 150°C and they often have
66 HANDBOOK OF ADHESIVES

rather limited compatibility with the elastomer perature, as shown for a simple model system
to which they are added. 165,166 Common tack- in Fig. 34. 168 At low rates the peel force in-
ifiers include rosin derivatives, coumarone-in- creases with rate, and failure takes place en-
dene resins, terpene oligomers, aliphatic petro- tirely within the adhesive layer, which fails by
leum resins and alkyl-modified phenolics. flowing apart. At a critical rate of peel (which
The effect of adding tackifiers on the rheo- depends upon the test temperature) an abrupt
logical properties of elastomers is instructive in transition takes place to interfacial fracture,
understanding how a tackifier functions. Fig. i.e., apparently clean separation of the adhe-
33 shows a plot of the shear storage modulus, sive from the substrate, at much smaller peel
G', of natural rubber with and without a tack- forces. This transition occurs when the rate of
ifying resin. 167 When the resin is present the deformation of the adhesive layer at the peeling
resistance to deformation is reduced (lower G') front becomes so high that the adhesive mole-
at low rates, and hence bond formation is fa- cules are unable to disentangle and flow apart,
cilitated on contact. At the same time, when like a liquid, but remain intertwined as a co-
measuring the strength of the bond at higher herent elastic solid. Although the local stress
rates of deformation, the modulus G' is high required to disentangle the molecules at low
and the material is stronger. This behavior can rates is relatively small, the work expended in
be contrasted with the effects of adding a filler ductile flow is large and the peel force (which
or plasticizer. Fillers cause an increase in elas- measures the work of separation) is corre-
tic modulus, but this is offset by the difficulty spondingly high. In the elastic state, the work
in bond formation. Also, while plasticizers of separation is mainly expended near the in-
promote bond formation, the cohesive strength terface, and is then relatively small.
of the adhesive is lowered. A tackifier is thus The rate of peel and test temperature at which
an appropriate compromise substance that al- the abrupt transition occurs are directly depen-
lows an increase both in the ease of bond for- dent upon the rate of Brownian motion of mo-
mation and in the elastic modulus and hence lecular segments. Simple viscoelastic adhesives
strength during detachment. therefore obey the WLF rate-temperature
equivalence, Eq. (30), as shown in Fig. 35. The
Rate and Temperature Effects for Pres- peel strength above the critical rate depends
sure-Sensitive Adhesives. Pressure-sen- upon factors discussed previously: interfacial
sitive adhesives consist of soft elastomeric attractions and dissipative processes within the
semi-solids. Their peel strength depends adherends. Below the critical rate, the peel
strongly upon the rate of peel and the test tem- strength is primarily a measure of the work of

3
p
2
(kN/m)

-5 -3
Log ,o weT (S-') Log lo R (m/s)
Fig. 33. Effect of a tackifier on the dynamic modulus G' Fig. 34. Peel-force vs. rate of peeling for an elastomer
of natural rubber as a function of reduced deformation fre- layer adhering to Mylar. C and I denote cohesive and in-
quency waT' (Taken from Ref. 167, published by John terfacial failure modes, respectively. (Taken from Ref. 168,
Wiley & Sons.) published by Soc. Francaise de Chimie.)
 FUNDAMENTALS OF ADHESION 67

must come into intimate molecular contact and

4 the materials themselves must be able to resist
high stresses without flowing apart. This latter
property. denoted green strength is an impor-
3
P tant, but little understood, feature of elasto-
(kN/m) meric compounds. It distinguishes a strongly
adhering elastomer from a simple liquid. Both

~)
may attain molecular contact readily, but,
whereas liquids flow apart easily at low
stresses, suitable elastomeric formulations will
undergo large tensile deformations before rup-
o turing. Amorphous elastomers (incapable of
-8 -4 0 4 crystallizing upon stretching) rely on molecular
Log ,o ROT (m/s) entanglements to provide cohesion and green
Fig. 35. Results from Fig. 34 replotted against the effec- strength. When the molecular weight of these
tive rate of peeling at 23°C. (Taken from Ref. 168. pub- elastomers is less than the characteristic value
lished by Soc. Francaise de Chimie.) at which entanglements form, then their green
strength is low. On the other hand, when the
extending a viscous or viscoelastic liquid to the molecular weight is much greater than the en-
point of rupture. tanglement molecular weight, then they cease
These features of soft adhesives can be al- to flow like liquids and do not readily wet on
tered by changes in mix formulation. For ex- contact.
ample, the viscosity of the liquid can be A strain-crystallizing material like NR shows
adjusted by plasticization. The rate of defor- much better autohesion. It can be processed to
mation and temperature at which entangle- a relatively low viscosity for easy wetting on
ments cease to slip free depend upon the contact, and still exhibit green strength due to
molecular weight and glass transition temper- strain-induced crystallization. Several other
ature of the polymer. Thus, increasing the mo- strain-crystallizable elastomers have been
lecular weight, and increasing the glass synthesized 169 ,17o and shown to exhibit autohe-
temperature Tg. will lead to a reduction in the sion and green strength comparable or superior
critical rate. Technically, it is advantageous to to that of NR. These include: trans-polypen-
use carefully selected molecular weight distri- tenamer, trans-butadiene-piperylene elasto-
butions, incorporating a high molecular weight mers, and uranium-catalyzed polybutadiene.
fraction, to add tackifiers and other adhesion- Although crystallization on stretching is ad-
promoting additives, and vacuole initiators, vantageous, it is quite undesirable for an elas-
such as poorly wetted particles, in order to tomer to be partially crystalline in the
maximize adhesion. unstrained state. This would seriously inhibit
But it must be emphasized that a finite level wetting and bond formation on contact. In this
of intrinsic, threshold, adhesion is necessary in regard, partially crystalline EPR and EPDM
order to take advantage of these various have been reported to show very poor autohe-
strengthening mechanisms. If there is no intrin- sion. 171
sic adhesion, then there is no possibility of gen-
erating the deformations and dissipative
Interdiffusion. When two identical layers
processes at the interface that so greatly en-
are brought into contact, molecules from each
hance the intrinsic strength.
surface may diffuse across the interface. This
process is hastened when the molecular weight
Autohesion
is low. It has been proposed 172 as a necessary
For similar layers to adhere well after being condition for strong autohesion, whereas
brought into contact, they must satisfy the basic others 173 consider that intimate molecular con-
criteria outlined previously. The two surfaces tact at the interface is sufficient to give good
68 HANDBOOK OF ADHESIVES

adhesion and that molecular diffusion across the -15

interface is not really necessary. Pressure-sen- SBR
sitive adhesives certainly adhere strongly to
substrates, such as glass, that are quite im-
permeable to polymer molecules. -16
Several investigators have examined the ef- Log D SBR
fect of contact time and pressure on autohe- (m 2 /s) SBR
o
sion. 174-176 In general, the strength of the bond
increases to a plateau value after a sufficient -17
BUTYL EPR
time, Fig. 36. 176 When the plateau is reached, o
NRO
it is assumed that complete contact and inter-
diffusion have occurred. Fig. 37 shows self-dif- -18 L..-_ _--'--_ _ _.l....-_ _--.J
fusion coefficients D measured at room 4.0 4.5 5.0 5.5
temperature for various elastomers as a func- Log M
tion of molecular weight. 177 Although the data
Fig. 37. Self-diffusion coefficients D of various elasto-
are limited, the points fall approximately on a mers as a function of molecular weight M. (Taken from
single line, suggesting that the self-diffusion Ref. 177, published by Rubber Division, American Chem-
rates of NR and SBR are similar for a given ical Society.)
molecular weight. For typical commercial elas-
tomers, of molecular weight 200-300 K, D ""
10- 17 m2 /sec. With this value of D, Skewis 177 later removed at t = t I, the level of tack in-
estimated that one second after contact is creased during the interval 0 < t < t I, but re-
achieved, a typical elastomer molecule would mained constant for t > t I' Since interdiffusion
diffuse about 4.5 nm-enough for substantial is not a function of pressure, and would have
interpenetration. Thus, for elastomers it ap- continued after the pressure had been removed,
pears that the development of good autohesion this observation indicates that the extent of
(tack) is limited principally by the difficulty in contact was the controlling factor.
achieving good contact. This is further con-
firmed in a recent study. 178 When two rubber Effect of Molecular Weight. The effect of
surfaces were brought together under a con- polymer molecular weight on autohesion and
stant pressure at t = 0, and the pressure was strength is shown in Fig. 38 for NR. 179 As the
molecular weight is increased the cohesive
strength rises. On the other hand, the level of
autohesion achieved after a given period in

0.6 BR-51

6.0
BR-36
Green strength, S

BR-25
Log,oS'5.5
Log ,o T
(N/m2)
Tock,T

5.0 5.5 6.0 6.5

Log ,o M
Fig. 36. Development of tensile strength S of autohesion
with time t of contact for different types of poly butadiene. Fig. 38. Tensile strengths of autohesion (tack T) and
(Taken from Ref. 176, published by Rubber Division, cohesion (green strength S) as a function of molecular
American Chemical Society.) weight M. (Data taken from Ref. 179.)
 FUNDAMENTALS OF ADHESION 69

contact passes through a broad maximum with have erroneously drawn conclusions about the
increasing molecular weight. intrinsic strength of interfacial bonds from me-
At sufficiently low molecular weights, con- chanical tests in which the role of energy dis-
tact and diffusion are relatively rapid, but tack sipation within the materials was not included.
is low because of poor cohesive strength (green
strength limited). At high molecular weights, Durability
both contact and diffusion are slow due to re-
stricted molecular mobility, even though there Adhesive bonds are degraded by various chem-
is a substantial increase in green strength. ical reactions, notably hydrolysis, corrosion,
Hence the relative tack is much less than unity and dissolution at the interface. Although
and the absolute level of tack is low (bond for- primers and inhibitors minimize these effects,
mation limited). At intermediate molecular their role is not well understood. It is obvious
weights tack is maximized. that any systematic improvement in our present
From a practical viewpoint, it is fortunate that ability to forecast the service life of bonds will
the relationship between tack and molecular require a greater understanding of the processes
weight shows a rather broad maximum. This involved in bond deterioration.
allows considerable variation in processing·
without great loss of green strength or tack. Nondestructive Evaluation of Bonds

CONCLUDING REMARKS
Perhaps the most serious need at the present
time is for a method to assess the strength of
Although major advances have been made in an adhesive bond without actually breaking it.
our understanding of surfaces, interfaces, Methods exist for detecting defects at .the in-
bonding, and the strength of adhesive joints, as terface, where the materials are not in contact,
described in this chapter, there are still serious and this is an important part of nondestructive
gaps. For example, there is a clear need for fur- testing. But, as far as the authors are aware,
ther application of fracture mechanics to ad- there is no currently available method for as-
hesive joints. Tests in some geometrical sessing by nondestructive means whether a
arrangements cannot be used to predict fracture given bond is weaker than it should be.
behavior in others, and this has led to broad
dissatisfaction with present test methods. A
ACKNOWLEDGMENTS
wider application of the principles of fracture
mechanics will eventually solve this particular This chapter was prepared as part of research
problem, but it may also require the replace- programs in adhesion science supported by the
ment of current test methods by others that are National Science Foundation and the Office of
more directly relevant and more readily ana- Naval Research.
lyzed. For example, there does not appear to
be at present a satisfactory method of measur-
ing the strength of adhesion of thin films in BIBLIOGRAPHY
terms of fundamental parameters.
Detailed stress analysis, including finite ele- Anderson, G. P., Bennett, S. J., and DeVries, K. L.,
ment techniques, should be carried out for in- "Analysis and Testing of Adhesive Bonds," New York,
creasingly complex model systems. Treatments Academic Press, 1977.
Cherry, B. W., "Polymer Surfaces," Cambridge, UK,
need to be developed that properly take into ac- Cambridge Univ. Press, 1981.
count nonlinear, plastic, and viscoelastic re- Kinloch, A. J., "Adhesion and Adhesives: Science and
sponse of both polymeric adhesives and bonded Technology," London, Chapman and Hall, 1987.
structural members. Indeed, recognition and Mittal, K. L. (ed.), "Adhesive Joints," New York, Plenum
Press, 1984.
understanding of the importance of energy dis-
Wake, W. C., "Adhesion and the Formulation of Adhe-
sipation within adhesives and adherends is es- sives," London, Applied Science Publishers, 1976.
sential in order to interpret much of the basic Wu, S., "Polymer Interface and Adhesion," New York,
research in adhesion science. Many authors Marcel Dekker, 1982.
70 HANDBOOK OF ADHESIVES

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131. Malyshev, B. M., and Sagalnik, R. L., Int. J. Frac- 160. Johnson, K. L., Kendall, K., and Roberts, A. D.,
ture Mech., 1, 114, (1965). Proc. Roy. Soc. (London), A324, 301 (1971).
132. Williams, M. L., Proc. 5th U.S. Natl. Congress on 161. Ahagon, A., and Gent, A. N., J. Polym. Sci. Polym.
Appl. Mech., Minneapolis, June, 1966, p. 451, New Phys. Ed., 13, 1285 (1975).
York, ASME, 1966. 162. Plueddemann, E. P., "Silane Coupling Agents,"
133. Williams, M. L., J. Appl. Polym. Sci., 13, 29 New York, Plenum Press, 1982.
(1969). 163. Williams, M. L., Landel, R. F., and Ferry, J. D.,
134. Outwater, J. 0., and Gerry, D. J., J. Adhesion, 1, J. Am. Chem. Soc., 77, 3701, (1955).
290 (1969). 164. Dahlquist, C. A., in "Adhesion Fundamentals and
135. Gent, A. N., and Kinloch, A. 'J., J. Polym. Sci., Practice," p. 143, New York, Gordon and Breach
Part A-2, 9, 659 (1971). Science Publishers, 1969.
165. Hock, C. W., J. Polym. Sci. Part C, 3, 139 (1963).
136. Lindley, P. B., J. Inst. Rubber Industr., 5, 243
(1971). 166. Kamagata, K., Kosaka, H., Hino, K., and Toyama,
M., J. Appl. Polym. Sci, 15,483 (1971).
137. Williams, M. L., J. Adhesion, 4,307 (1972).
167. Aubrey, D. W., and Sherriff, M., J. Polym. Sci.,
138. Kendall, K., Proc. Roy. Soc. (London), A344, 287 Chem. Ed. 16,2631 (1978).
(1975). 168. Gent, A. N., and Petrich, R. P., Proc. Roy. Soc.
139. Kendall, K., J. Phys. D: Appl. Phys., 8, 512 (1975). (London), A310, 433, (1969).
140. Kendall, K., J. Materials Sci., 11, 638 (1976). 169. Bruzzone, M., Carbonaro, A., and Gargani, L.,
141. Maugis, D., Le Vide, No. 186, 1 (1977). Rubber Chem. Technol., 51, 907 (1978).
 FUNDAMENTALS OF ADHESION 73

170. Dall'Asta, G., Rubber Chern. Technol., 47, 511 175. Beckwith, R. K., Welch, L. M., and Nelson, I. F.,
(1974). Rubber Chern. Technol., 23, 933 (1950).
171. Crowther, B. G., and Melley, R. E., J. Inst. Rubber 176. Bothe, L., and Rehage, G., Rubber Chern. Technol.,
Industr., 8, 197 (1974). 55, 1308 (1982).
172. Voyutskii, S. S., "Autohesion and Adhesion of High 177. Skewis, I. D., Rubber Chern. Technol., 39, 217
Polymers," New York, Interscience Publishers, (1966).
1963. 178. Hamed, G. R., Rubber Chern. Technol., 54, 403
173. Anand, I. N., J. Adhesion, 5, 265 (1973). (1981).
174. Skewis, I. D., Rubber Chern. Technol., 38, 689 179. Forbes, W. G., and McLeod, L. A., Trans. Inst.
(1965). Rubber Industr., 30, 154 (1958).
 4
Surface Preparation for
Adhesive Bonding
C. LYNN MAHONEY
Research Fellow
Dexter Adhesives and Structural Materials Division
The Dexter Corporation
Pittsburg, California

INTRODUCTION sion to give reasonable strengths does not occur

unless surfaces are increased in polarity by ox-
Adhesive bonding is unique among structural
idation, plasma treatments, etc.
fabrication methods in having surface and in-
Over the past several decades, much study
terface properties so dominant in controlling
has been focused on surface energetics, wet-
bond formation and bond performance proper-
ting, adhesion, etc., and some generalizations
ties. A single molecular layer of contaminant
have been developed. These can be useful
can prevent proper wetting by the adhesive, or
guides to the adhesive selection and surface
a weak substrate boundary layer can provide
preparation needed to form reliable, strong ad-
the "weak link" for premature failure. For
hesive bonds. Only a brief exposure to some of
these reasons, much adhesive application effort
this valuable information can be presented here,
and technical study has been focused on the ad-
but further reading is available in Chapter 3 and
hesive-substrate interface. With metals, sur-
other chapters of this Handbook, and in listed
face characteristics are largely determined by
references.
the nearly always present oxide layer; this layer
must be strongly adhering and resistant to hu-
TECHNICAL BACKGROUND
midity, etc., or it must be removed or specifi-
cally replaced by a more controlled oxide Many intermolecular material properties, in-
surface. With polymeric surfaces, successful cluding volatility and heat of vaporization, sur-
bonding requires removal of contaminants, face tension, viscosity, solubility relationships,
such as mold release residues, etc. In some etc. are determined by secondary valence
cases, weak, low molecular weight fragments, forces. 1 These same secondary valence forces
which can be pushed to the polymer surface are mainly responsible for critical adhesive
during crystallization processes, etc., must be bond needs, such as wetting and adhesion.
removed. These forces include: (1) London or dispersion
In most practical cases involving metal sur- forces, the net charge separation or dipoles re-
faces, adhesive-substrate energetics are suffi- sulting from the instantaneous imbalance of
cient to cause wetting and adhesion. With many electrons in their orbits, which are relatively
polymers, however, proper wetting and adhe- weak and short range but present in all mate-

74
 SURFACE PREPARATION FOR ADHESIVE BONDING 75

rials; (2) dipole-dipole forces due to the charge hesive energy density which results from the
imbalance in certain covalent bonds because of interaction of the secondary valence forces
the presence of electronegative or electroposi- present. Summaries of such values for a broad
tive elements; and (3) hydrogen bonds, a spe- range of monomeric and polymeric materials
cial class of relatively energetic dipole-dipole are found in a number of books and articles. 2,3
interaction, due to the presence of hydrogen Values for polymers are deduced indirectly
bond donor and acceptor groups. Examples of from their solubility or swelling in selected sol-
such bonds are shown in Table 1. vents. Often single numbers are given, but by
To be effective in promoting interaction be- far the most useful information contains the
tween materials (solvency, wetting, adhesion, separate energy components due to dispersive,
etc.), specific matched secondary forces must polar and hydrogen bonds. Typical values are
be present in both materials or they will prefer shown in Table 2. Such information can pre-
interacting with their own molecules. For ex- dict, directly, solubility and compatibility re-
ample, alcohols, with strong hydrogen bonds, lationships, and indirectly, indicate surface
will not dissolve in a hydrocarbon which has energy and wetting potentials.
only dispersion forces at work. Also, an epox-
ide adhesive, with strong dipoles and hydrogen Contact Angle Measurements
bonding groups, will meet its energy sharing
The angle at the edge of a drop of liquid ap-
needs internally and not wet a polyethylene or
plied to a solid surface reflects the ability of the
polypropylene surface where it can only share
secondary valence forces of the liquid to inter-
the weak dispersion forces that are present in
act with those on the solid surface. This situa-
common. Oxidation or plasma treatment of
tion, shown in Fig. 1, has been developed by
such a low energy polyethylene surface, gen-
Young4 into an equation describing the balance
erating dipolar or hydrogen bonding groups,
of interfacial forces or surface tensions or ener-
now allows such interacting to occur. Such
gies ('Y = surface tensions at solid-vapor, solid-
treated surfaces can now be bonded with polar
liquid, and liquid-vapor interfaces):
epoxide adhesives.
Several methods of quantitatively measuring
'YSV - 'YSL = 'YLV cos ()
the relative energy of materials, both liquids
and solid surfaces, have been developed and
A low liquid contact angle indicates a good af-
can be of major help in predicting wetting char-
finity and a good potential for wetting of the
acteristics or surface modifications needed for
solid.
effective adhesive bonding.
A further extension of these energy relation-
ships, the Young-Dupre equation,S Wa = 'YLV
Solubility Parameter 2
(1 + cos ¢), relates the work of adhesion, or
Based, for liquids, on the heat of evaporation bonding energy, directly to the surface tension
(the energy needed to separate the molecules of the liquid and the contact angle that the liq-
from each other), this reflects the relative co- uid makes with the solid.

Table 1. Intermolecular Forces.

Type Examples Relative Strength
London dispersion Transient displaced electrons Weak, but present in
all materials
Dipole-dipole H-F,-C-Q,-CEN,=C=O Medium
Hydrogen bonds Donors: -O-H, -N-H Strong
/H
Acceptors: O=C=, 0
"R
76 HANDBOOK OF ADHESIVES

Table 2. Critical Surface Tensions and Solubility Parameters of

Polymeric Solids. 2
Solubility
parameter,
Polymer 'Yco dynes !em (cal!em3) 112

Polyhexafluoropropylene 16 6
Polyvinyl fluoride 28
Polyethylene 31 8
Polystyrene 33 8.6-9.1
Polyvinyl alcohol 37
Polyvinyl chloride 39 9.6
Polyethy lene terephthalate 43 10.7
Polyhexamethy lene adipamide 46 13 .6
Metals >500

Critical Surface Tension of Solid surface will occur if the critical surface tension
is higher than the surface tension of the applied
Although the surface tension of solids cannot
adhesive. (Viscosity, time, etc. are also impor-
be measured directly, an empirical method de-
tant variables.) Typical values of high and low
veloped by Zisman6 has allowed a very useful
energy surfaces are included in Table 2.
relative surface energy value to be obtained.
This can be done by measuring the contact an-
Examples of Surface Energy
gle (Fig. 1) made by a homologous series of
Relationships
pure liquids, of known surface tensions, with a
solid surface, and plotting the results as in Fig. Consideration of all the above energy relation-
2. Extrapolating to a zero contact angle (cos () ships and derived values can be of great help
= 1) and extending the intercept to the surface in selecting adhesives and surface preparation
tension axis gives the critical surface tension conditions for attaining predictable, strong ad-
of the solid surface. An extension of this work hesive bonds. Several examples are presented
by Kaelble, 7 taking into account the special in- here.
fluence that polar and especially hydrogen In the bonding of a polyester substrate (sol-
bonding forces can have on such liquid-solid ubility parameter 10.3) with a series of
interactions, has made such determinations adhesives 8 having solubility parameters rang-
even more useful. ing from 8 up to 13, measured peel strengths
These relationships can be of high predictive were greatly increased as the solubility param-
value and indicate that good wetting of a solid eter of the selected adhesive neared a match
with that of the substrate (Fig. 3). When so
matched, the potential for interdiffusion would
'Ys V - 'YS L = 'YL V cos 8 be maximized and the failure location was di-
rected away from the interface.
From Tables 2 and 3, an epoxide adhesive
(surface tension 45 dynes/cm) would not be ex-
pected to wet and effectively bond a low energy
surface such as polyethylene (critical surface
tension 31 dynes/cm). When the polyethylene
surface was etched for increasing times in a
sulfuric acid-dichromate solution, bond
strengths markedly increased and the surface's
contact angle with water (increasing polarity)
Fig . I. Contact angle . similarly decreased (Fig. 4).9
 SURFACE PREPARATION FOR ADHESIVE BONDING 77

(WETTING BY VARIOUS LIQUIDS)

c
g 0.8 .----.---- - ...-- -- -----.-.. -.- -·0 --·-.. -....·_·-·-' --_.- -.-
I
N
E
Q

0.2

oL-~--~--~--4---~~--~--~--~-9L-~

20 28 30 3G 40 46 60 66 80 86 70 76
SURFACE TENSION (mN/m--Dynes/cm)
Fig. 2. Detennination of critical surface tension of solid surfaces.

SURFACE PREPARATION "Standard Recommended Practice for Preparation of Metal

Surfaces for Adhesive Bonding" for general procedures.]
General Considerations To correctly prepare the surface to be joined,
[Based on Dexter Adhesives and Structural Materials Di-
all grease, oil, and foreign particles should be
vision, The Dexter Corporation, Bulletin GI-600 and in- removed. With most high performance adhe-
dicated referenced sources. See also ASTM 02651-79, sives this step is critical, since for good wet-

POLVESTER SUBSTRATE
SOLUBILITY PARAMETER
10
(1750)

I
~
!

,
E
r
Di
5
(875)

8 9 10

SOLUBILITY PARAMETER OF ADHESIVE

Fig. 3. Peel strength of polyester substrate bonded with various adhesives .
78 HANDBOOK OF ADHESIVES

Table 3. Liquid Surface Tension and Solubility Parameter Correlation with

Structure.
Solubility Parameter, (cal/cm3)112
Surface
Tension Hydrogen
Material Intermolecular Forces dynes/cm TotaF Dispersion Polar Bond
n-Hexane Dispersion only 18.4 7.24 7.23 0.0 0.0
Methylene chloride Dispersion plus dipole-dipole 26.5 9.93 8.91 3.1 3.0
Methanol Dispersion plus hydrogen 22.6 14.3 7.4 6.0 10.9
bond
Water Dispersion plus hydrogen 73 23.5 6.0 15.3 16.7
bond
Typical epoxide Dispersion plus hydrogen 45 8-13 (moderate H bonding)
adhesive bond
'Total = vd' + p' + h'

ting, the adherend should have a higher surface ethane, followed by sandblasting or, prefera-
tension than the adhesive. Even a thumbprint bly, by chemical etching. Chemical treatments
on an otherwise clean surface can prevent the may be confined to the bonding areas, but de-
adhesive from spontaneously wetting and greasing should be done to the entire assembly.
spreading. A cleaned assembly should be bonded as soon
Organic contaminants are removed by de- after the cleaning operation as possible, or an
greasing, while loose deposits are dislodged by adhesive primer should be applied. However,
scraping or washing with acids, alkali solu- if storage is necessary, special precautions
tions, or other such chemicals. Metals are best should be taken so that the assembly does not
cleaned by vapor degreasing with trichloro- become contaminated. All parts should be

EPOXY RESIN- - POLYETHYLENE JOINT STRENGTH

(CHROMIC ACID SURFACE TREATMENT)
5
700
F F
A A
I 600 I
4
l l
I I
N 500 N
G G
3
S 400 S
T T
R R
E 2
_ _ _ H ••• _ . _ . _ _ . H _ ' _ _ _
300 E
S S
S S
200
1
M P
P 100 S
a I
0 0
30 40 50 60 70 80 90
CONTACT ANGLE WITH WATER, DEGREES
Fig. 4. Bond strengths between epoxide resin and surface-treated polyethylene.
 SURFACE PREPARATION FOR ADHESIVE BONDING 79

tightly wrapped or placed in airtight and oil- flammable, this solvent is toxic in both liquid
free containers. Etched surfaces must never be and vapor forms, so the working area should
touched with bare hands-even wiping the sur- be well ventilated. Gloves should be worn when
face with a clean cloth can affect the bond. handling this solvent, and smoking should not
Handlers should wear clean cotton gloves· and be allowed.
use clean tools.
Nonmetallic, nonporous materials should be Degreasing Nonmetals
degreased with a detergent solution, rinsed
Solvents or detergent solutions can be used to
thoroughly with clean water, and then dried.
remove mold-release agents or waxes from
Clean solvent may be substituted for detergent.
plastics. Commercial detergents such as Sprex
The surfaces are then hand-sanded or sand-
(DuBois Chemical Co., 1120 West Front, Cin-
blasted to give them a rough texture.
cinnati, Ohio) are suitable. Acetone and methyl
Water is often used to test a metal surface for
alcohol are effective solvents, depending on the
cleanness. A small portion is placed on the sur-
type of plastic to be cleaned. The adverse effect
face. If the water distributes evenly, then the
of solvents on some polymeric materials should
metal should wet well with an adhesive. But if
be checked before their use.
it beads or crawls, then the surface should be
cleaned again and the test repeated.
Surface Abrasion
Bonding should be performed in a room sep-
arate from other manufacturing operations. Smooth surfaces can be improved for bonding
When bonding is done in the same area as plas- by roughening with abrasives such as medium
tic or rubber molding, a physical barrier should grit emery paper. Abrasion should always be
be erected between the two operations to pre- followed by degreasing to remove contami-
vent airborne mold lubricants from depositing nants and loose particles.
on the metal. Similar hazards are presented by Blasting with a fine grit is the best method
spray painting, electroplating, etching, and for removing surface deposits-oxide films,
machining with coolants. Storage and assem- tarnish, rust, mill scale, and other contami-
bly areas should be enclosed, and air to these nants-from metals. This method should be
areas filtered and under slight pressure. used only on structures thick enough to resist
Numerous studies are underway to find sur- distortion. With thinner materials, contami-
face treatment methods that minimize or elim- nants should be removed by vapor honing. This
inate use of toxic materials or polluting method is similar to grit blasting but uses high-
substances. Some progress is being made,13,14 velocity water or steam instead of air. If neither
but replacement of such degreasing solvents as method is appropriate, abrasive disks, belts,
trichloroethane and such toxic materials as the cloth, medium-grit emery paper, or wire
dichromates will take time. For polymeric sur- brushes can be used. Plastics should be rough-
faces, plasma or corona discharge treatments ened with abrasive disks, belts, cloth, or emery
are receiving much attention. paper to remove mold release agents. Medium-
grit emery paper will give the best results.
Surface abrasion can also remove other sur-
Degreasing Metals
face contaminants as well as weak, low molec-
To degrease metal surfaces with a degreasing ular weight components which can be
unit, suspend the metals in a stabilized tri- concentrated at the surface due to their exclu-
chloroethane vapor bath for about 30 seconds. sion during solidification or crystallization of
Check the bath frequently for accumulated con- some polymers. to Also, during solidification of
taminants. If a degreasing unit is not available, both thermoplastic and thermoset materials
clean the surface with a white cotton rag or there is often an orientation of the more polar
pieces of absorbent cotton dampened in tri- groups toward the interior, leaving a concen-
chloroethane. Rags should be changed fre- tration of lower polarity, lower energy groups
quently. Let the surface stand several minutes on the surface. 11 Abrasion can open up access
while the chemical evaporates. Although non- to the more energetic polymer interior.
80 HANDBOOK OF ADHESIVES

Chemical Treatment source to source, and bonding conditions can

vary with location and the experience of the op-
Chemical or electrolytic pretreatments of a
erator. Therefore, all recommendations are
bonding surface can greatly increase the
made without guarantee and those following
strength of the bond. Pretreating can etch the
such listed procedures should become familiar
surface of a metal, and form a highly adherent
with the general requirements of adhesive
oxide. Environmental resistance can often be
bonding and run controls with specific mate-
greatly increased by such treatment. Etching
rials and processes before proceeding with the
solutions should be prep~red in glass, porce-
preparation of critical bonded structures.
lain, polyethylene, polypropylene, or tetrafluo-
roethylen~ fluorocarbon laboratory ware and
Surface Treatment Tables
stirred with rods of the same material. Metals
other than those to be etched should not touch The following tables on surface treatment for
the solutions. For solutions containing hydro- bonding use are based largely on data from
fluoric acid or fluorides, TFE fluorocarbon Dexter Bulletin G 1-600 and indicated refer-
should be used. Solutions in plastic trays can ences. A number of abbreviations have been
be heated by immersion in hot water baths; hot used to reduce their length. These include the
plates or infrared heaters can be used for glass following: Parts by weight-pbw; distilled or
and porcelain trays. See Caution section below deionized water-DI water; minutes-min;
for safe procedures. hours-hr; chemical names-chemical sym-
bols, i.e., hydrofluoric acid-HF, hydrochloric
acid-HCI, sulfuric acid-H2SO4, sodium di-
Caution chromate-Na2Cr207, sodium hydroxide-
The Occupational Safety and Health Adminis- NaOH, etc.
tration of the Department of Labor has defined
some of the following chemicals and substrates REFERENCES
to be hazardous to health in varying degrees.
I. Fowkes, F. M., in "Chemistry and Physics oflnter-
Some are even extremely hazardous. You
faces; A.C.S. Symposium on Interfaces, June 15, 16,
should familiarize yourself with the substrates 1964, "Sydney Ross, Chairman. Washington, D.C.,
and needed chemicals and know the safe han- American Chemical Society Publications.
dling procedures to be used before preparing 2. Burrell, H., in "Polymer Handbook," 2nd Ed., J.
the surfaces for adhesive bonding. Also, many Bandrup and E. H. Immergut, eds., Vol. IV, p. 337,
New York, John Wiley and Sons, 1975.
of the solvents, degreasing solvents and etch
3. Barton, A. F. M., "Handbook of Solubility Parame-
bath chemicals are toxic or can be dangerous if ters and Other Cohesion Parameters," Boca Raton,
not mixed and handled properly. Materials such Florida, CRC Press, 1983.
as hydrofluoric acid and the chromates need 4. Rance, D. G., in "Industrial Adhesion Problems," D.
very careful handling. Care should be taken in M. Brewis and D. Briggs, eds., pp. 49-62, New York,
John Wiley and Sons, 1985.
preparing such chemical solutions, not only be-
5. Rance, D. G., Ref. 4, p. 62.
cause the wrong proportions can seriously 6. Zisman, W. A., in "Handbook of Adhesives," 2nd
weaken a bond but also because the chemicals Ed., Irving Skeist, ed., New York, Van Nostrand
can be harmful to the skin.· Many are strong Reinhold Company, 1977.
acids and bases. Remember that solutions con- 7. Kaelble, D. K., Dynes, P. J., and Cirlin, E. H., J.
Adhesion, 6, 23-48 (1974).
taining concentrated sulfuric acid must be pre- 8. Iyegar, Y., and Erickson, D. E., J. Appl. Poly. Sci.,
pared by adding acid to water with stirring, and 11,2311 (1967).
not vice versa. A violent reaction can occur if 9. DeBruyne, N. A., Nature, 180 (Aug. 10),262 (1957).
this is not observed. Use rubber gloves, aprons, 10. Schonhorn, H., in "Polymer Surfaces," D. T. Clark
face shields, etc. and W. J. Feast, eds., New York, John Wiley and
Sons, 1978.
While the information contained in this arti-
II. Herczeg, A., Ronay, G. S., and Simpson, W. C.,
cle is believed to be reliable, surface treating "National SAMPE Technical Conference Proceed-
methods have been selected from many ings, Azusa, California, 1970," Vol. 2, pp. 221-231,
sources, substrates can vary considerably from 1970.
 Surface Treatment - Metals.
Adherend Material Cleaning Abrasion or Chemical Treatment Method
Aluminum and alloys Degrease in vapor bath of trichlo- (A) Chromic acid etch: (A)
roethane. (See ASTM D265l for DI water I liter • Etch metal in bath for 12-15 min at 150-
general information. See Ref. 12 H 2S04 (conc.) 300 g 160 0P (66-71 0C).
for chromate-free P2 etch.) Na2Cr207' 2H20 60 g • Do not delay rinse! Spray in tap water for 5
2024 bare aluminum 1.5 g min.
Pollow with DI water soak rinse.
Dissolve the 20 mil aluminum sheet to
• Dry thoroughly at 120-140oP max. (49-
"seed" the bath.
60°C).
• Do not touch bonding surface.
(B) Phosphoric acid anodizing (Boeing Co. patent
• Prime or bond within 16 hr.
appl.) (for improved environmental resis-
(B)
tance) (ASTM D3933-S0):
• Prepare etched metal as above in (A).
Prepare anodizing bath: • Anodize at 65-S5°P (lS-30°C).
• Slowly raise voltage to 10-11 V for 20-25 VI
H 3P04 (75% conc.) 454 g C
min. :II
DI water 3.7 I "TI
• Disconnect current, immediately remove »
(")
Add acid to water with stirring. parts and rinse in running water (DI or m
Use titanium racks and a stainless steel cath- < 150 ppm solids tapwater) for 10-15 min. ~
:II
ode. • Dry at 160 0P (71 0c) max. m
• Do not touch surface. ~
• Prime or bond within 16 hr.
~
Aluminum honeycomb core Degrease in vapor bath of trichlo- Not used. • After degreasing, let stand 2 hr at room
oZ
roethane. temp or 15 min at 200 0P (93°C). "TI
o
:II
Bery Ilium (highly toxic) Degrease in vapor bath of trichlo- Dissolve NaOH in equal weight of DI water, then • Immerse in conc. (20%w) NaOH soln. 3 »
roethane. add water to reduce concentration to 20 %w . min at ISOoP (S2°C). C
:I:
• Rinse thoroughly in cold running DI water. m
VI
• Pinally, dry in oven for 10-15 min at 300- ;;:
350 0P (l49-177°C). m
til
o
Cadmium Degrease. Abrade with emery paper. Preferably electroplate • Repeat degreasing step. Z
C
with silver or nickel for bonding. Z
Ci)
(Continued on page 82) til
...
 co
N

:z:
Surface Treatment - Metals (Continued). l>
z
C
Adherend Material Cleaning Abrasion or Chemical Treatment Method
~
o;l1li;
Copper and alloys brass, Degrease in vapor bath of trichlo- (A) For medium strength bonds, abrade with (A)
bronze roethane. (Also see Ref. 12 and emery paper. • Repeat degreasing step. o"TI
ASTM D2651-79.) (B) For high bond strengths etch metal surface (B)
in: • Immerse for 1-2 min at 77°F (25°C). ~
:z:
• Rinse in cold running DI water. m
42 % Aqueous FeCI2 soln. 15 pbw (I)
• Dry immediately with pressurized air at
Conc. HN0 3 (s.g. 1.41) 30pbw <:m
room temp. (77°F, 25°C). (I)
DI water 197 pbw

Gold Degrease with vapor bath or clean None. • Degreasing only treatment.
rag and solvent.

Iron: Degrease in vapor bath of trichlo- Grit blast or abrade with emery paper. • Repeat degreasing step.
Cast iron (alloys under roethane.
steel)

Lead and alloys, pewter Degrease in vapor bath of trichlo- Abrade with medium grit emery paper. • Repeat degreasing step.
roethane.

Magnesium and alloys Wash with liquid trichloroethane, (A) For medium strength bond, abrade with me- (A)
then-Caution-30 seconds only dium-grit emery paper. • Repeat degreasing step.
in trichloroethane vapor bath. (B) For high strength bonds, use etch procedure. • Dry in forced draft oven at 150-200°F (66-
(See ASTM 02651-79.) (ASTM D2651 , Method A) 93°C).
(B)
Bath 1:
• Immerse metal for 10 min in Bath 1 at 140-
Sodium metasilicate 2.5 pbw
160°F (60-71 0C).
Tetrasodium pyrophosphate 1.1 pbw
• Rinse thoroughly in water.
Sodium hydroxide 1.1 pbw
• Immerse metal for 10 min in Bath 2 kept at
Nacconol~ NR (Allied Chern. 0.3 pbw
140-190°F (71-88°C).
Corp.)
• Wash in cold running DI water.
DI water 95 pbw
• Dry in a forced-draft oven at < 140°F
Bath 2: (60°C).
Chromium trioxide 1 pbw • When cool, immediately apply adhesive.
DI water 4pbw
Nickel Degrease. (A) For medium strength bond, abrade with me- (A)
dium-grit emery paper. • Repeat degreasing step.
(B) For higher bond strengths, conc. HN0 3 (s.g. (B)
1.41).12 • For stronger bond, immerse metal for 5 sec-
onds in conc. HN0 3 solution at room temp.
(77°F, 25°C).
• Rinse etched metal thoroughly in cold run-
ning DI water.
• Air dry at 104 of (40°C).

Platinum Degrease. No other treatment needed.

Silver Degrease. U sing fine-grit emery paper, remove any tarnish • Repeat degreasing step.
from bonding area.

Steel and iron alloys (except Degrease in vapor bath of trichlo- (A) Sandblast or abrade with medium-grit emery (A)
stainless steel) roethane. paper. • Repeat degreasing step.
(B) If cannot sandblast or abrade: (B) C/)
• Immerse for 10 min in Acid Bath 1 at c:
Acid Bath 1: ~
140°F (60°C) or 5-10 min in Bath 2 at "T1
Conc. orthophosphoric I pbw l>
68°F (20°C). 0
acid (s.g. 1.73) m
• Remove black residue with stiff brush under
Ethyl alcohol (denatured) 1 pbw "0
running DI water. ~
m
or • Dry at 250°F for I hour. "0
l>
~
Acid Bath 2: If cannot be stored at less than 30% Rela- l>
Conc. HCI 1 pbw tive Humidity, bond prepared surfaces in -t
(5
DI water I pbw short time. Z
"T1
0
Steel, ferrous alloys Degrease in vapor (A) Gritblast if possible. (A) ~
(B) If cannot abrade: • Repeat degreasing step. l>
(B) C
Conc. HCI 1 pt/wt J:
• If cannot abrade immerse for 3-10 min at m
C/)
DI water 1 pt/wt
77°F (25°C) in HCI bath. e::m
• Rinse thoroughly in cold running DI water.
til
• Oven dry at 150°F (66°C) for 10 min. 0
Z
C
:2
C)
(Continued on page 84)
co
w
 Surface Treatment - Metals (Continued).
co
Adherend Material Cleaning Abrasion or Chemical Treatment Method ~

Stainless steel Degrease by washing in trichloro- Remove surface deposits with nonmetallic agent- (A) ,.z:z:
ethane. (See Ref. 14 for alternate alumina grit paper. • Immerse in Bath I for 10 min. at 160- cco
procedures. Also see ASTM (A) General Purpose Treatment: 180°F (71-82°C). 0
026S1.) • Rinse thoroughly in running tapwater then 0
Bath 1: ;1'1:
cold DI water.
See under Magnesium and alloys. 0
• Oven dry at 200°F (93°C) for 10 min. 'TI
• Bond as soon as possible.
,.
C
:z:
(8) For high temperature use, further treat the (B) m
en
metal: 12 • Immerse metal for 10 min in Bath 2 at 18S- <:
m
19soF (8S-90°C). en
Bath 2:
• Under cold running water, scrub away any
Oxalic acid I pbw
black residue with clean, stiff bristle brush.
Conc. H2S04 (s.g. 1.86) I pbw
• Rinse in DI water.
DI water 8 pbw
• Dry in oven at 200°F (93°C) for IO-IS
Dissolve oxalic acid before stirring in the min.
H 2S04 ,

(C) For resistance to high peel stresses, further (C)

treat metal from (A). [Do not combine (B) • Immerse in Bath 3 at 140-160°F (60-71 0C) for
and (C) treatments.] IS min.
• Scrub under cold running water with stiff bristle
Bath 3:
brush.
Na2Cr207' 2H20 3.S pbw
• Rinse in DI water.
DI water 3.S pbw
• Dry in oven at 200°F (93°C) for IO-IS min.
Conc. H2S04 (s.g. 1.86) 200 pbw

Tungsten and alloys Degrease in vapor bath of trichlo- (A) Abrade using medium-grit emery paper. (A)
roethane. (8) For maximum strength, also use a chemical • Repeat degreasing step.
etch: (8)
• Immerse for I-S min at 77°F (2S°C).
Conc. HCI 30pbw
• Rinse thoroughly in cold, running DI water.
DI water IS pbw
• Dry for IO-IS min in a 160-180°F (71-
HF S pbw
82°C) oven.
Conc. H2S04 SOpbw
Hydrogen peroxide few drops
Add HCI and HF to the water, stir in the
H2S04 then add the hydrogen peroxide.

Tin Degrease. Abrade with medium-grit emery paper. • Repeat degreasing.

Titanium and alloys (Many Vapor degrease with trichloro- (A) Bath 1: (A)
procedures in literature. ethane. Remove surface deposits Sodium metasilicate soln. (see Magnesium). • Immerse at 160-180 oP (71-82°C) for 10
Also see ASTM 026SI.) with nonmetallic abrasive. (B) Por stronger bonds: min.
• Rinse in cold, running 01 water.
Bath 2 (polyethylene vessel):
• Dry in oven at IS0-200oP (66-93°C) for
Sodium fluoride lOpbw
lO-IS min.
Chromium trioxide S pbw
(B)
01 water 2S0 pbw
• Immerse in Bath 2 at room temp. for S-10
Conc. H2S04 (add last with
min.
stirring) SOpbw
• Rinse in cold, running 01 water.
• Dry in oven at 160-180 oP (7l-82°C) for
10-IS min.
(C) Alternate Treatment (ASTM 026S1): (C)
• Immerse in Bath 3 for S min at IS00P
Bath 3 (alkaline-clean):
(66°C).
Oakite HO 126 I.S oz
• Rinse in running tapwater at lOsoP (40°C)
01 water to I gal
for 2 min.
Bath 4 (acid pickle): • Immerse in Bath 4 for 2 min at room temp.
HP (70%) 2-3 oz (fl) • Rinse in cold water.
en
Na2S04 (anhyd.) 3.00z c:
HN03 (70%) 4O-S0 oz =
01 water to 1 gal ~
m
Bath 5 (etch bath): • Immerse in Bath S for 2 min at room temp. "II
Trisodium phosphate 6.S-70z • Rinse in DI water at IS00P (66°C) for IS m
=
Potassium fluoride 2.5 oz min. ~
HP (70%) 2.2-2.S oz • Repeat rinse.
01 water to 1 gal • Dry at 140 0P (60°C) for 30 min in air cir- ~
o
culating oven. Z
• Wrap in clean kraft paper. ."
o
(D) Surface treatments with Pasa Jell 107 can =
)l-
also be used (SemCo Div., PRC). e
::z:
Zinc, alloys, galvanized Degrease in vapor bath of trichlo- (A) Abrade using medium-grit emery paper. (A) m
metals roethane. (B) Por maximum strength: • Repeat degreasing step. <:m
(B)
Conc. HCI 20pbw
• Immerse for 2-4 min with the solution at ~
01 water 80 pbw z
77°P (2S°C). e
• Rinse thoroughly in cold, running DI water. Z
G)
• Dry for 20-30 min. in a IS0-I60oP (66-
71°C) oven. co
UI
• Apply adhesive as soon as possible.
 co
al

%
~
C
III
o
o
;III:

o'TI
Surface Treatment- Thermoplastics. ~
%
Adherend m
Material Cleaning Abrasion or Chemical Treatment Method <:
m
UI
ABS (Ref. 12) Degrease in acetone. (Alcohols (A) Abrade with medium-grit sandpaper. (A)
probably better to use.) (B) Etch solution: • Wipe free of dust.
• Prime with Dow Coming A-4094 or G.E.
Conc. H2S04 26pbw
SS-4101.
K2Cr20 1 3 pbw
(B)
DI water 11 pbw
• Etch at room temp. for 20 min .
(Add acid to stirred water) • Rinse in tapwater.
• Rinse in DI water.
• Dry in warm air.

Cellulose plastics Degrease with methyl alcohol or Abrade using fine-grit emery paper or gritblast. • Repeat degreasing step.
isopropyl alcohol. • Heat to 200°F (93°C) for 1 hr and apply
adhesive while hot.

Dially Iphthalate Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step.
Fluorocarbons: Degrease with acetone or MEK. Use chemical etch: • Immerse in the solution for 15 min at 77°F
• Polymonochlorotrifluoro- Also see Ref. 12; flame treatment (25°C).
Sodium metal 23 g
ethylene and corona discharge, etc., also • Wash in acetone or MEK then in cold, DI
Naphthalene 128 g
• Polytetrafluoroethy lene used. water.
Tetrahydrofuran 1I
• Tetrafluoroethylene • Dry thoroughly.
• Polyvinyl fluoride Prepare under anhydrous conditions (dry solvents, • Proprietary solutions may be used:
closed flask, stirrer, drying tube). Add naphtha- Bondaid W.S. Shamband Co.
lene to the THF, carefully add '/4-'h" cubes of Fluorobond Ioclin Mfg. Co.
sodium, one at a time, while stirring. Let soln. Fluoroetch Acton Associates
stand 16 hr at room temp., then stir 2 hr. Store Tetraetch W.L. Gore Assoc.
in bottles with glass stoppers; keep free from air
and moisture. Use near exhaust ventilator.
Nylon Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step.

Polycarbonate, polymethyl- Degrease with methyl alcohol. Abrade using medium-grit emery paper. • Repeat degreasing step.
methacrylate, or polysty-
rene

Polyether (chlorinated), Degrease with acetone or MEK. Chemical pretreatment is necessary: (A)
polyethylene, polypropyl- See Ref. 13 for alternate proce- • Immerse in the chromic acid solution as fol-
K2Cr20 7 75 pbw
ene, or polyformaldehyde dures. Flame or plasma treatment lows:
DI water 120 pbw
may also be used (see Ref. 12).
Conc. H 2S04 1500 pbw Chlorinated polyether 5 min. at 160°F
(71°C)
Dissolve the K2Cr207 in water and stir in the
Polyethylene and 60 min. at 77°F
H 2S04 •
polypropylene (25°C)
Polyformaldehyde 10 sec. at 77°F
(25°C)

• Rinse in cold, running DI water.

• Dry at room temp. en
(B) c:
:II
• Flame or plasma treatments may be used ."
also. l;m
Polyethyleneterephthalate or Degrease with methyl alcohol. See (A) Abrade using medium-grit emery paper. (A) ~
m
linear polyesters Ref. 12; plasma treatments also (B) For a stronger bond use chemical etch: So- • Repeat degreasing step.
used. dium hydroxide solution (20%w) (B)
-:
• Immerse for 2-10 min. at 160-2oo°F (71- ~
93°C). o
Z
• Wash thoroughly in cold, running DI water.
."
• Dry with hot air. o
:II
Polyvinylchloride, rigid Degrease with methanol or trichlo- Abrade using medium-grit emery paper. • Repeat degreasing step.
roethane.
,.o
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m
<:
m
l1li
oZ
o
Z
C)

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.....
 Surface Treatment-Engineering Thermoplastics (Examples of Representative Commercial Materials).
~
Adherend
:z:
Material Cleaning Abrasion or Chemical Treatment Method
~
Polyarylate (Ardelll>, U.C.)12 (A) Ultrasonic clean in alkaline- (A) Using alkaline-etching solution, sandblast (A) C
III
or polyaryl sulfone etching solution. with ISO mesh silica sand. • Water wash. o
(Astrel. 360, 3M)12 (B) Acid etch solution: • Alcohol wash.
o;l1li:
• Dry with dry nitrogen. o"II
Na2Cr207·2H20 3.4%W
Conc. H2S04 96.6%W ,.
(B) C
(C) Corona or Plazma treatment :z:
• Immerse IS min at IS0-I600P (66-71 DC) m
• Cold water wash. en
• Dry at IS00P (66°C) in an air circulating
<:
oven.
m
Polyether-ether-ketone Degrease with trichloroethane or (A) Abrade (A)
(PEEK., ICO l2 isopropyl alcohol. (B) Flame treatment: blue oxidizing flame. • Repeat degrease.
(C) Chromic acid etch (bath composition not (8)
given in Ref. 12). • Abrade.
(D) Corona or Plazma treatment. • Degrease.
• Flame treat (blue oxidizing flame).
(C)
• Abrade.
• Degrease.
• Chromic acid etch.
• Water wash.

Polyphenylene sulfide (A) Degrease with acetone. (A) Sandblast. (A)

Ryton., Phillips)12 (B) Wipe surface with ethyl alco- (B) Sand with 120-grit sandpaper. • Repeat degreasing.
hol soaked paper. (C) Corona or plazma treatment. (B)
• Clean off dust with stiff bristled brush.

Polysulfone (Udelll> U.C.)12 Degrease in alcohol. (A) Grit-blast with 27-S0 /-1m aluminum oxide. (A)
(B) Etch in sodium dichromate-sulfuric acid soln. • Clean in ultrasonic cleaner in Neutra-Clean
(C) Corona or plazma treatment (Shipley Co., Inc.)
• Rinse in tap and then DI water.
• Rinse in IPA for 30 seconds.
• Plush with dry N2.
• Dry in air at IS00P (66°C).
(8) See Polyaryl sulfone treatment.
 Surface Treatment- Thermosets.
Adherend
Material Cleaning Abrasion or Chemical Treatment Method
Epoxy, epoxide resins Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step.

Furane resins Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step.

Melamine fonnaldehyde Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step. en
c:
plastics (Fonnica) ::II
"TI
J>
Phenolics, polyester poly- Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step. n
m
urethane resins ."
::II
m
."
Polyimide (VespelaD (A) Degrease in trichloroethane (A) Abrade with dry or wet abrasive blast. (A) J>
DuPont) 12 (B) Degrease in acetone. (B) Etch solution: • Repeat degreasing.
Sodium hydroxide 5 pbw • Dry.
S
is
(B) z
Water 95 pbw
• Etch for 1 min at 140-194°F (60-90°C). "TI

• Rinse in cold water.

o
::II
• Dry in hot air. J>
c
::z:
m
en
<
m
ID
o
Z
C
Z
Ii)

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CD
 CD
o
::t
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III
o
o~
Surface Treatment-Carbon and Carbon Fiber and Glass Fiber Composites.
o
."
Adherend
Material Cleaning Abrasion or Chemical Treatment Method l>
C
::t
Carbon Degrease with acetone or MEK. Abrade using fine-grit emery paper. • Repeat degreasing step. m
(I)
• Allow solvent to evaporate. <:m
(I)
Glass reinforced laminates Degrease with acetone or MEK. Abrade using medium-grit emery paper. • Repeat degreasing step.

Graphite Degrease with acetone or MEK. Abrade using fine-grit emery paper. • Repeat degreasing step.
• Allow solvent to evaporate.

Carbon fiber-epoxy (A) Solvent wipe (MEK, toluene, (A) Lightly abrade with medium-grit emery pa- (A)
composites 12 trichloroethylene, etc.) per. Avoid exposing the reinforcing fibers. • Wipe with solvent.
(B) Use peel ply during initial cur- • Check surface by water break test. Retreat,
ing. if necessary .
(C) See Ref. 15 for the effect of
abrasion procedures. See also
Refs. 16 and 17.

Carbon fiber-poly ether Solvent wipe with MEK. Abrade lightly with Scotch-brite-Bon Ami. • Rinse in tap water and DI water.
ether-ketone (pEEK(t) Good strengths require (A) or (B) treatment: • Air dry.
(A) Chromic acid etch:
Exact composition of etch solution not de-
(A)
fined in Ref. 18.
• Immerse for 15 min at room temp.
(B) Plasma treatment gave good bond strengths
• Rinse in tap and then DI water.
also.
• Dry at 200 0 P (93°C) for 30 min.
 Surface Treatment-Rubbers.
Adherend
Material Cleaning Abrasion or Chemical Treatment Method

Rubber-natural and syn- Degrease with methyl alcohol. Por maximum strength use: • Immerse for 5-10 min in conc.
thetic chloroprene, neo- • sulfuric acid at 77°P (25°C) (Bath I).
Chemical etch:
prene • Wash thoroughly in cold Dl water.
Bath I, concentrated sulfuric acid.
• Neutralize by immersing for 5-10 min. at
Neutralizing solution: room temp. (Bath 2).
Bath 2, 0.2 % solution of caustic. • Rinse with cold, running DI water.
• Dry.

C/)
C
l:J
."
Surface Treatment-Ceramics, Glass, etc. ~
(")
Adherend m
Material Cleaning Abrasion or Chemical Treatment Method ;g
m
Ceramics, porcelain, glazed Degrease with MEK. Abrade using emery paper or sandblasting. • Repeat degreasing step. ~
l:J
china • Evaporate the solvent. ~
-t
Glass, quartz-nonoptical Degrease with MEK. (A) Abrade using carborundum powder and water (A)
oZ
or fine-grit paper. • Repeat degreasing step. ."
(B) Por maximum strength, continue abrading • Dry for 30 min at 210 0 P (100°C).
ol:J
and use chemical etch: (B) ~
• Immerse for 10-15 min at 77°P (25°C). C
Chromium trioxide 1 pbw J:
Wash well in running water m
C/)
DI water 4pbw
• Dry for 30 min at 210 0 P (lOO°C). <:
m
• Apply adhesive while still hot.
aI
oZ
Glass-optical Degrease in an ultrasonically agi- • Rinse thoroughly. C
tated detergent bath. • Dry < lOOoP (38°C). Z
c;)

Jewels Degrease with MEK. • Dry at room temp. CD

...
 CD
N

:z:
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Z
C
III
o
o
~

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Surface Treatment-Construction Materials.
)I>
Adherend C
:z:
Material Cleaning Abrasion or Chemical Treatment Method
~
Bricks: Degrease in acetone or MEK. Abrade using a wire brush. • Remove all contaminants. <:m
Fired, nonglazed building en
materials

Concrete Decontaminate with a detergent so- Clean by one of these procedures: • Wash thoroughly with water.
lution. • Remove all dust.
(A) Sandblast about '/'6" from bonding surface.
(B) Remove ';' by mechanical scarification.
(C) Chemical etch, hydrochloric acid solution (C)
(15% by wt.). • Spread solution with a stiff bristled broom.
• Remove sludge with water from high pres-
sure hose.
• Check with litmus paper for residual acid.
• If present, rinse with 1% ammonia.
• Flush with water.
• Allow to dry.

Stonework Dry thoroughly. Abrade using a wire brush. • Remove all contaminants.

Wood Dry thoroughly. Decontaminate with a sander, plane, smooth with • Remove all contaminants.
sandpaper.
 SURFACE PREPARATION FOR ADHESIVE BONDING 93

12. Landrock, A. H., "Adhesives Technology Hand- 16. Matienzo, L. J., Venebles, J. D., Fudge, J. D., and
book," Park Ridge, New Jersey, Noyes Publications, Velten, J. J., "30th National SAMPE Symposium,
1985. March 19-21, 1985, p. 302.
13. Rosty, R., Martinelli, D., Devine, A., Bodnar, M. J., 17. Crane, L. W., Hamermesh, C. H., and Maus, L.,
and Beetle, J. SAMPE J., (July/August), 34 (1987). SAMPE J., (March/April), 6, (1976).
14. Tira, J. S., SAMPE J., (July/August), 18 (1987). 18. Wu, Szu-Iy, Schuler, A. M., and Keene, D. V.,
15. Pocius, A. V., and Wenz, R. P., "30th National "SAMPE 19th International Technical Conference,
SAMPE Symposium, March 19-21, 1985," p. 1073. Oct. 13-15, 1987," p. 277.
 5
Adhesive Selection and
Screening Testing
JAMES T. RICE
Chairman of ASTM Committee D-14 on Adhesives (1986-1990) and
Associate Professor of Forest Resources
School of Forest Resources
University of Georgia
Athens, GA

INTRODUCTION 3. If the adhesive's hardening involves sig-

nificant film shrinkage, the system (ad-
Selecting a proper adhesive for a given bonding
hesive and/or adherend) should allow for
application can, at times, appear to be an over-
dissipation of the shrinkage stresses rather
whelming task, but it need not be. The purpose
than locking them in and prestressing the
of this chapter is to help in the selection process
joint.
by:
4. The rheology of the hardened adhesive
1. Listing and briefly describing key mate- film, especially its elastic modulus and
rial and system factors which should be toughness (versus brittleness), should be
considered during adhesive selection. compatible with those of the adherend and
2. Outlining steps in the preliminary adhe- the nature of joint stresses to be applied,
sive selection process. etc.
3. Describing basic test methods which are 5. The adhesive should wet the adherend,
useful in screening the candidate adhe- i.e., be able to establish extensive and in-
sives, once they have been chosen. timate (molecular scale) interfacial con-
tact with the substrate.
GENERAL CONSIDERATIONS IN
ADHESIVE SELECTION The adhesive should work efficiently with the
equipment which will be available for bonding
An adhesive should be compatible with the ma-
(clamps, presses, heaters, etc.) and not have
terials it will join (i.e., its substrates/adher-
pressure, temperature or curing requirements
ends):
which are beyond the limits of that equipment.
1. When a liquid adhesive is involved, the The adhesive must have adequate basic
adherend(s) should allow the carrier (sol- strength for its intended job. This often means
vent or water) to escape as needed for strength as determined under short-term load-
proper film forming and hardening. ing (most standard strength tests are in this cat-
2. The adhesive should not significantly at- egory), but long-term loading (creep tests),
tack or corrode the adherends. shock loading (impact tests), and cyclical load-

94
 ADHESIVE SELECTION AND SCREENING TESTING 95

ing (fatigue tests), or combinations of these, Step 2

may also be needed.
Based on the above determinations and in con-
In addition to adequate basic strength, the
sultation with potential adhesive suppliers, se-
adhesive must be sufficiently durable to pro-
lect, first, the candidate adhesive group(s) and
vide adequate load bearing ability when the
then the specific adhesives which may meet
joint is exposed to hostile elements of the en-
your requirements, i.e., be compatible with
vironment in which it will serve.
your adherends, joint design and stresses, ex-
The physical properties (e.g., color, density,
posure requirements, bonding equipment,
solids or filler content, electrical properties,
physical and working property requirements,
etc.) and working properties (storage life, pot
and cost limitations. This search can be aided
life, viscosity, etc.) often need to be considered
by published articles, books, and catalogings
and subjected to screening testing too.
of adhesives but, most importantly, by adhe-
Last in this list, but often foremost in the
sive supplier recommendations, literature, and
user's mind, is bonding cost. Although many
data sheets. In addition, occasions may arise
factors influence the ultimate bonding cost, the
when the services of an adhesives consultant
price per unit of adhesive is significant and must
may be in order, especially if they are also ca-
be considered early in the selection process.
pable of performing needed screening testing.
A list of general adhesive information sources
is given in Appendix 1 of this chapter. Several
BASIC STEPS IN THE ADHESIVE
of the references cited give specific adhesive
SELECTION PROCESS
supplier names, addresses and phone numbers
and product use listings. These listings can be
Step 1 a good starting point in making initial supplier
Define pertinent material, joint stress, joint ex- contacts and in beginning to generate a list of
posure, processing and service variables relat- candidate adhesives.
ing to adherends, to joint design and loading,
and to available bonding equipment. Of partic- Step 3
ular interest are the following:
Carefully compare your material and system
A. Composition and properties of the sub- characteristics with the relevant properties of
strate or substrates to be bonded. In- selected or recommended adhesives.
cluded are such factors as chemical Your suppliers will have already thought
composition (type of metal, plastic, ce- through the previously listed considerations
ramic or wood, etc.; special surface relative to their products and be glad to discuss
treatments, etc.); porosity and absor- them with you. The adhesive composition and
bency; hygroscopic and/or thermal ex- properties factors of primary interest include the
pansivity; and strength properties. following:
B. Joint design and associated glueline 1. Adhesive form and, if a liquid, the nature
stresses (shear, tension, cleavage, creep, of any solvents or carriers involved. Most ad-
shock, vibration, etc.). hesives are supplied and used as liquids. How-
C. Hostile elements of the joint's service en- ever, they may also be supplied as meltable
vironment (temperature and moisture ex- solids in many forms (e.g., chunk, pellet, rope,
tremes, chemicals, light, etc.). cartridge, etc.) and as flowable or fusible pow-
D. Heating, pumping, and dispensing ca- ders or films. Some liquid adhesives may be
pabilities of adhesive handling and ap- essentially 100 % reactive and contain little or
plication equipment available or no solvent or carrier. However, most liquid ad-
affordable. hesives contain significant portions of carrier
E. Clamping, pressing, and heating capa- (water or other solvents) which normally must
bilities of the available or affordable be largely gotten rid of during hardening.
bonding equipment. 2. The adhesive's hardening mechanism and
96 HANDBOOK OF ADHESIVES

chemistry. During bond fonnation, an adhesive Step 4

must initially be fluid or semi-fluid in order to
Select and perform screening tests on candidate
wet and make good interfacial contact with the
adhesives.
substrate. But then it must harden to develop
When one or more adhesives have been cho-
strength and durability. The hardening process
sen as candidates for a given bonding applica-
is a key property of the adhesive, and the com-
tion, samples should be obtained and joints,
monly encountered mechanisms are generally
representative of intended production, made
as follows:
and tested. Testing will usually be done to
a. Drying. Many liquid adhesives harden measure strength and/or durability. However,
simply by an increase in concentration of testing for physical and working properties may
solids as the solvent or water evaporates also be desirable. Some test procedures call for
into the surrounding atmosphere or is dis- equipment not routinely available in all user
persed into the adherend(s). laboratories. In those cases, the services of an
b. Coalescence. Emulsion adhesives ini- independent testing laboratory should be con-
tially harden by a process of coalescence sidered.
as water in the continuous phase evapo- Selecting appropriate screening tests is not
rates or disperses and the emulsion parti- always easy, but familiarity with the tests
cles make contact. The coalesced film will available and their use will simplify matters.
then harden further as remaining moisture Appendix 2 of this chapter is a complete listing
is dissipated. Chemical reactions may also of standards currently under the jurisdiction of
be involved. ASTM Committee 0-14 on Adhesives (Plus a
c. Chemical Reaction. Many adhesives few adhesive standards from other ASTM com-
harden either totally or in part by chemi- mittees) and should be helpful in looking for
cal reaction (usually polymerization) oc- appropriate screening tests.
curring primarily during bonding. Appendix 2 first lists ASTM's adhesive per-
d. CongealinglJreezing. Some adhesives are formance specifications, most of which are in
applied warm or hot and harden, wholly the area of wood bonding. They are subdivided
or in part, by congealing as they cool off by substrate or application. Whenever a speci-
on the adherends. Hot melt adhesives in fication is available for the adhesive or bonding
particular are applied quite hot and harden application being considered, it should cer-
very quickly as they cool off. Dry film ad- tainly be used in the screening testing if at all
hesives have initially meltable or flow- possible.
able characteristics and may harden ini- The bulk of Appendix 2 is comprised of
tially by cooling off, but with chemical methods of test (as distinct from specifica-
reaction involved too. tions). They are classified first by substrate
(metal, wood, plastics, etc.) and then, within
3. Strength and durability of the adhesive substrate, by primary test objective (strength or
under various stress modes (tension, shear, durability). The strength test listings are further
creep, impact, cyclic, etc.) and stress levels subdivided by stress mode (tension, shear, peel,
(low, medium, high, etc.) in the intended joint etc.) and with separate listings for creep, im-
design and when under the influence of the in- pact, and fatigue tests.
tended service environment. Although we may A number of standard test methods and prac-
speak of the strength and durability of the ad- tices have been developed to measure (a) the
hesive, it must be emphasized that it is the ser- composition of glue mixes (especially polymer
viceability and reliability of the joint or bonded and/or filler/extender content) and (b) the rheo-
assembly that we are ultimately interested in. logical and working properties of adhesives
It is not at all difficult to take an adhesive with (viscosity, density, tack, etc.). They are listed
excellent potential and use it in an improper ap- in Appendix 2 by these property groupings.
plication or with poor bonding technique and Most of the remainder of this chapter is de-
make a very poor joint. voted to a review and discussion of the key
 ADHESIVE SELECTION AND SCREENING TESTING 97

D-14 strength and durability tests as they apply sives Bonding (Phosphoric Acid Anod-
to various adhesives and applications. But first, izing)." Outlines the relatively new
some general precautions on the preparation of phosphoric acid anodizing procedure.
trial joints and their testing are in order. 2. Standards evaluating the effectiveness of
surface treatment of aluminum adherends
by means of resultant bond durability:
GENERAL PRECAUTIONS IN D-3762. "Test Method for Adhesive-
PREPARING AND TESTING ADHESIVE Bonded Surface Durability of Aluminum
BONDED JOINTS (Wedge Test)." Commonly used to mon-
itor the effectiveness of metal surface
Successful adhesive testing depends not only on
treatment in preparation for high durabil-
starting with the right adhesive but also on
ity, high performance adhesive bonds. A
proper (a) preparation of the adherends, (b)
wedge is driven into a prepared opening
mixing and application of the adhesive, (c)
in the glueline and the extent of resultant
clamping of the joint and curing of the adhe-
crack propagation measured.
sive, (d) test specimen preparation, and (e) test
3. Standard relating to the surface treatment
execution. Specific points to be careful about
of plastics in preparation for adhesive
are given below.
bonding:
D-2093. "Practice for Preparation of
Adherend Preparation
Surfaces of Plastics Prior to Adhesive
For best results, the adherends should (1) be Bonding." Suggests sanding, solvent
manufactured and/or machined with dimen- wiping and chemical pretreatments to re-
sional accuracy such that, when clamped or move glossy finishes, dirt, grease, mold
pressed, the joint can be closed uniformly, release compounds, etc. in preparing
bringing the two surfaces into intimate contact, plastics for effective adhesive bonding.
and (2) be cleaned, machined, or treated as
necessary to present a sound, clean bonding
Adhesive Handling, Preparation, and
surface to the adhesive.
Application
For metals and plastics in particular, pre-
bonding chemical treatment of adherend sur- Follow the suppliers' literature, instructions
faces is often necessary. The success of high sheets and precautions, paying close attention
performance metal bonding is so heavily de- to:
pendent on proper surface preparation that sev-
1. Storage temperature extremes or high
eral ASTM standards have been developed
humidity. Very low temperatures can es-
which describe procedures for surface treat-
pecially damage emulsion adhesives, and
ment and for analysis of the chemicals in-
high temperatures will generally cause
volved:
premature polymerization of reactive ad-
1. Standards relating to the surface treat- hesives. High humidity most often cre-
ment of metal adherends: ates problems with adhesives (or their
D-2651. "Practice for Preparation of fillers and extenders) purchased in dry
Metal Surfaces for Adhesive Bonding." form and stored in containers permeable
Includes procedures for washing, steam- to moisture vapor.
ing, solvent cleaning (degreasing), me- 2. Proportioning and mixing procedures.
chanical abrasion and chemical treatment When an adhesive is to be mixed, the
or etching. components should be accurately mea-
D-2674. "Methods of Analysis of Sul- sured, and mixing should be of the rec-
fochromate Etch Solution Used in Sur- ommended type and intensity. The
face Preparation of Aluminum." objective is to achieve a uniform, lump-
D-3933. "Practice for Preparation of free mix without overheating, entraining
Aluminum Surfaces for Structural Adhe- air (unless a foam-type mix is intended)
98 HANDBOOK OF ADHESIVES

or degradation from excessive mlxmg specifications which have been developed and/
shear (a special concern with emulsion or adopted by ASTM.
systems).
3. Proper'application of adhesive to adher-
Construction Adhesives
end. The keys to proper application are
very simply an adequate amount of ad- In recent years the use of adhesives in construc-
hesive, accurately and uniformly applied. tion assembly applications, especially in the
bonding of wood and gypsum panels to joists
Joint Assembly and Handling and studs in floors, walls and ceilings, has in-
creased considerably. Several specifications
The joints to be bonded should be formed and and related test methods have been developed:
clamped or pressed within the allowable as-
sembly times (minimum and maximum, but es- C-0557. "Specification for Adhesives for
pecially maximum) and conditions (especially Fastening Gypsum Wallboard to Wood
temperature). With some chemically curing ad- Framing." Describes test methods and
hesives, prolonged assembly times, especially establishes minimum performance re-
at high ambient or adherend temperatures may quirements for various working and
lead to precure (Le., hardening before the joint performance (strength and durability)
is properly closed), resulting in very poor properties.
bonds. Also, with hot melt adhesives, which D-1779. "Specification for Adhesive for
harden quickly as they cool below their melt Acoustical Materials." Tests primarily
temperature, allowable assembly ("open") for minimum long term gluebond ten-
times are very short and must be very carefully sile strength after exposure to a variety
observed. of simulated average and extreme en-
vironments.
Clamping/Pressing and Curing D-2851. "Specification for Liquid Optical
Bonding pressure should be adequate but not Adhesive." For adhesives used in
excessive. Bondline temperatures and times bonding glass and other transparent ad-
under pressure should be adequate to achieve herends in optical assemblies.
at least nominal cure. D-3498. "Specification for Adhesives for
Field-Gluing Plywood to Lumber
Framing for Floor Systems." Tests
Careful Specimen Preparation and Test
construction assembly adhesives for
Execution
minimum shear strength and perma-
Care must be taken in specimen geometry and nence (including oxygen bomb aging).
machining and in testing and alignment if D-3930. "Specification for Adhesives for
stressing is to be as intended by the test. Wood-Based Materials for Construction
of Manufactured Homes." Tests for
minimum levels of strength and per-
SCREENING ADHESIVES COVERED BY
manence for adhesives used in struc-
STANDARD SPECIFICATIONS
tural and semistructural (mainly panel
Standard specifications (as distinct from stan- to frame) gluing in manufactured hous-
dards which are methods of test only) include ing (modular and mobile homes). Also
(or reference) appropriate test methods and also referenced are standards D-3632,
set forth minimum acceptable performance. "Practice for Accelerated Aging of Ad-
Various industry groups have their own appli- hesive Joints by the Oxygen-Pressure
cation-oriented specifications (e.g., aerospace, Method," and D-3931, "Test Method
automotive, plywood, laminated wooden for Determining Strength of Gap-Fill-
beams, etc.; see documents cited in Appendix ing Adhesive Bonds in Shear by
1). However, discussion here is limited to those Compression Loading."
 ADHESIVE SELECTION AND SCREENING TESTING 99

Wood Bonding Adhesives ments for urea-formaldehyde resin ad-

hesives used in wood gluing.
Standards covering adhesives for various end-
glued (finger-jointed), edge- and face-bonded
Paper Bonding Adhesives
joints.
Most standards in this area have been promul-
gated by T APPI. The few which have been
0-2559. "Specification for Adhesives for
promulgated by ASTM are as follows:
Structural Laminated Wood Products
for Use Under Exterior (Wet Use) Ex- 0-1580. "Specification for Liquid Adhe-
posure Conditions." Sample beams, sives for Automatic Machine Labeling
made under various assembly time ex- of Glass Bottles." For non-pressure-
tremes, are tested for (a) basic dry glue- sensitive adhesives.
line shear strength and wood failure and 0-1874. "Specification for Water- or Sol-
(b) resistance of glueline to delamina- vent-Soluble Liquid Adhesives for Au-
tion after accelerated aging. It also re- tomatic Machine Sealing of Top Flaps
quires testing the adhesive's dry creep of Fiberboard Shipping Cases." For
resistance. Used in qualifying new ad- non-pres sure-sensitive adhesives.
hesives for use in exterior laminated
beams.
TESTING FOR THE STRENGTH OF
0-3024. "Specification for Protein-Base
ADHESIVE BONDED JOINTS
Adhesives for Structural Laminated
Wood Products for Use Under Interior In contrast to the preceding, there are many ad-
(Ory Use) Exposure Conditions." Em- hesives and applications for which we do not
ploys the 0-0905 block shear, 0-0906 have specification documents. However, there
plywood shear, and 0-4300 mold resis- are numerous standards which can be applied
tance tests to evaluate mostly casein- in a general purpose testing manner, and they
base adhesives for use in interior grade are discussed in the following section.
laminated beams.
0- 3110. "Specification for Adhesives Tensile Properties
Used in Nonstructural Glued Lumber
Although shear testing may be more commonly
Products." Employs the 0-0905 block
used, stressing perpendicular to the glueline
shear test and a finger joint test, along
may be called for at times. The following two
with several exposures, to evaluate in-
general-purpose tensile test standards can be
terior and semi-exterior adhesives, in
used with various substrates, including metal,
end, edge and face bonded joints, es-
wood, and plastics:
pecially for the molding and millwork
field. Most of the applicable adhesives 0-0897. "Test Method for Tensile Prop-
are based on polyvinyl acetate. erties of Adhesive Bonds." Fig. 1
0-4317. "Specification for Polyvinyl shows this basic ASTM standard's two
Acetate-Based Emulsion Adhesives." specimen configurations which can be
Somewhat similar in scope to 0-3110, used in the comparative testing of wood-
this standard employs the 0-0905 block and metal-bonding adhesives, respec-
shear and 0-0906 plywood shear tests tively. However, research evidence
in evaluating polyvinyl acetate based suggests that significant stress concen-
adhesives for common wood gluing ap- trations commonly occur in the tensile
plications. testing of butt joints of this type. Ex-
0-4690. "Specification for Urea-Formal- trapolation of stress values derived from
dehyde Resin Adhesives. " Recent stan- this test to different bond areas or con-
dard providing specific test procedures figurations can be very misleading. Re-
and minimum performance require- cent work has shown that much more
100 HANDBOOK OF ADHESIVES

@
D-2095. "Test Method for Tensile
Strength of Adhesives by Means of Bar
and Rod Specimens" (and the compan-
ion standard D-2094: "Practice for
Preparation of Bar and Rod Specimens
l-/ioiom. llt"oiom'1 for Adhesion Tests"). This specimen
''lOI!II~ R UIOIT

I
Diom~---cl
, ±o.OO5'
oiom'$'Om;l
7'0'
(shown, with grips, in Fig. 2) should be
Q798"

r --
:hl
~-r.
1.129"

r--'-cp
I I
I easier to prepare than the preceding one.
.. .
= d.-;- ""Rad
li· .:"",,1 ~
,..~ .-~c:- L1:' I It seems to be in more common use to-
day, and is especially useful with metal
(a) (b)
and plastic substrates. As with D-0897,
Fig. 1. Tension specimens: (a) wood and (b) metal
(0-0897).* significant stress concentrations can de-
velop, and extrapolation of test data to
other joint configurations or bond areas
carefully designed joints and controlled should be approached with care.
stressing are necessary if anything like
, 'pure' , tensile stress data are to be
achieved.
Shear Properties
*All figures in Chapter 5 are reprinted, with permission, Many adhesive bonded assemblies are de-
from the Annual Book of ASTM Standards, copyright, the
American Society for Testing and Materials, 1916 Race signed to take advantage of the generally good
Street, Philadelphia, PA 19103-1187. resistance adhesive joints have to shear stresses.

Attachment Fixture
II II

::~'
L1.,- _Jl
II:
-) ,.
I

4.763 : : ~~~ mm. OIA. Hoi.

(. 1875 ~ : gg~g.,

Test Specimen

4. 699 : . ~~~ mm. OIA. Oow.1

. Pin
(. 185 ~ : gg~.,

Ii ... IZ. 75 ~ : g~~ mm.

1
E"
~ ~_'--+-'
:; ..L..._ _ _
(.50Z::~~~·'
":,+1
<D~
~~.; f==~
Attachment Fixture

II II
II II
II I II
~
I~._.....:...._...+-I__ 31.75 + . U mm. OIA.
(I.Z50-!:. .005"1

Fig. 2. Bar and rod specimen and grips (0-2095).

 ADHESIVE SELECTION AND SCREENING TESTING 101

Shear Load at Rupture. Tests which use 3. Double lap tensile shear for metal adher-
tension loading. ends:
D-3528. "Test Method for Strength
1. Single lap tensile shear tests for metal ad-
Properties of Double Lap Shear Adhe-
herends:
sive Joints by Tension Loading." The
D-l002. "Test Method for Strength
two specimens in this test both use a
Properties of Adhesives in Shear by
~ore balanced, double lap design (see
Tension Loading (Metal-to-Metal)."
Fig. 6 as example), alleviating some of
This is another of D-14's earlier stan-
the distortion and cleavage stressing
dards and may still be the most widely
which easily occurs with standard sin-
used in screening metal bonding adhe-
gle lap shear specimens. However, the
sives. The matter of stress concentra-
problems associated with testing two or
tions (especially edge effects) and
more gluelines at one time now come
associated limitations on interpretation
into play and might complicate com-
and extrapolation of data from this test
parative testing.
have been widely studied and clearly
4. Plywood shear test:
recognized. However, the specimen
D-0906. "Test Method for Strength
(Fig. 3) is relatively easy to prepare,
Properties of Adhesives in Plywood
and the test has still proven useful.
Type Construction in Shear by Tension
Standards D-2295 and D-2557 are the
Loading." Fig. 7 shows the specimen
procedures for running D-l002 at ele-
for this widely used test. In common
vated and reduced temperatures, re-
usage, the main test criterion is a visual
spectively.
estimate of the area percentage of rup-
D-3165. "Test Method for Strength
ture failure which occurs as "wood
Properties of Adhesives in Shear by
failure" (versus "glue failure") and
Tension Loading of Laminated Assem-
not the measured joint strength.
blies." Fig. 4 shows this single lap
5. Testing structural finger joints:
shear specimen which is prepared by
D-4688. "Test Methods for Evaluating
machining notches into strips from
Structural Adhesives for Fingetjointing
laminated metal sheets.
Lumber." A recent standard detailing
2. Single lap tensile shear for wood adher-
the testing of finger joints when used as
ends:
D-2339. "Test Method for Strength end joints in structural glued, lami-
nated timbers (see also D-2559 in wood
Properties of Adhesives in Two-Ply
adhesive specifications).
Wood Construction in Shear by Ten-
sion Loading" (Fig. 5). Useful with Tests where adherends are loaded in compres-
laminations of veneers or other rela- sion:
tively thin sheets of wood. 1. Wood block compression shear:
D-0905. "Test Method for Strength

r
Properties of Adhesive Bonds in shear
(0.064")
LGLUe. LINE by Compression Loading" (Fig. 8). A
Smm basic compression shear test which is
SHEAR widely used in screening wood glues.
AREA
It is also used in specifications D-311 0
(on nonstructural wood laminating ad-
AREA hesives), D-2559 and D-3024 (on ex-
AREA IN
IN TEST terior and interior structural wood
TEST GRIPS
GRIPS laminating adhesives respectively) and
1----177.8 t Lmm---~
D-4317 (on polyvinyl acetate based
Fig. 3. Basic metal lap shear specimen (D-lOO2). wood adhesives).
 S
102 HANDBOOK OF ADHESIVES

OTCH IIIOTH 1.6 mm 10.064in.)

11~..6mm :=BONO LINE

~064in.l ~

.-E============;t~"==~'~==~==3
I . i i

SHEAR AREA

PINNING ALTERNATE 9.53 mm

to.38 in.)

f
25.4mm
1I.00In.l
+

.....- - - - - - 1 2 7 + L mm --------....-j
15.00 + L In. I
.....- - - - - - - - - - 1 7 7 . 8 + Lm m - - - - - - - - - - - - - - t
17.00 + L in. I
AREA IN TEST GRIPS AREA IN TEST GRIPS

NOTE-*L = length of test area. Length of test area can be varied. Recommended length of lap is 0.50 ± 0.01 in.
(12.7 ± 0.3 mm).
Fig. 4. Metal lap shear specimen cut from laminate (0-3165).

~54.~
r 0·'· l 2. Block compression shear:

1
T
2.54 ••
D-4501. "Test Method for Shear Strength
u", of Adhesive Bonds Between Rigid
~J.'" Substrates by the Block-Shear Meth-
------ fT od." Fig. 9 shows the two specimen
O.SZO.'~.~

1
2.54 ••
lOW kerfs II") configurations and the test head for this
I O•.R ••
new, general-purpose, compression
l====t.......LJ{I/a"
T' shear test which should be suitable for
2.54 ...
u", testing adhesives for plastics, metals,
L...-----,---.L glass, wood, and other substrates.
Fig. 5. Basic wood lap shear specimen (0-2339).

/A
fa T'~: I, f' t/ B

1 ~I IJ;"!
J r%£J 25.4 ""'
1.6mm
3.2mm
Test Gluelines
Spacer = T2

-'-31.st= --J 1-.~31.s.;T

-I I-- 63.5 lim
L
63.5 IiID
Area in Test Grips
Shear Area

127 .... L IlIIl

190.6+L1IIIl

Fig. 6. Double lap shear specimen, Type A (0-3528).

 ADHESIVE SELECTION AND SCREENING TESTING 103

f-'''-;

--- p
---- t.1: '~
..... 1<) CUT f THROUGH CORE
~~.l
~ r
,
.....

Fig. 7. Plywood shear specimen (0-0906).

OIL HOLE~~~~~
SELF-AOJUS
BEARING
TEST
SPECIMEN

Fig. 9. New block shear specimens (top) and test head

(bottom) (0-4501).

3. Pin and collar compression shear:

D-4562. "Test Method for Shear Strength
of Adhesives Using Pin-and-Collar
Specimen" (Fig. 10). Designed to
yield data on the shear resistance of ad-
hesive joints where a pin is bonded in-
side a collar. Particularly applicable to
testing adhesives used as retaining
compounds in nut locking and related
applications.
4. Torque strength of UV cured glass/metal
bonds:
D-3658. "Practice for Determining the
Torque Strength of Ultraviolet (UV)
Light-Cured Glass/Metal Adhesive
Joints." Provides a method for mea-
Fig. 8. Wood block shear test head and specimen suring torsional shear strength of glass-
(0-0905). to-metal bonds. The torque needed to
104 HANDBOOK OF ADHESIVES

suPPORT CVL'NDE'"

Fig . 10. Pin and collar shear specimen and test head (0-4562).

shear a metal hex nut off a glass surface surements and oriented more toward
is measured, usually as a function of development of data on basic engineer-
cure time and UV exposure. Often used ing parameters of the adhesive. Origi-
as a "fixturing time" test, i.e., to de- nally developed for use with wood but
termine the minimum amount of time may be applicable to metals as well.
and UV exposure required to develop a E-0229. "Test Method for Shear Strength
"handling" bond with UV cured ad- and Shear Modulus of Structural Ad-
hesives. hesives. " This method employs tor-
sional shearloading on a "napkin ring"
Shear Modulus specimen to determine the shear
strength and shear modulus of structural
D-3983 . "Test Method for Measuring
adhesives in thin gluelines on high
Strength and Shear Modulus of Non-
modulus adherends.
rigid Adhesives by the Thick Adherend
Tensile Lap Specimen" (Fig. 11). For
Rate of Development of Shear Strength.
measuring the properties of lower-mod-
Standard D-l144, "Practice for Determining
ulus, more rubbery adhesive films .
Strength Development of Adhesive Bqnds," is
Glueline thickness is controlled by
based on the D-l002 lap shear specimen.
shims. Developed for wood but appli-
Bonded metal specimens are tested in a cure
cable to metals and other substrates
time sequence.
also.
D-4027 . "Test Method for Measuring
Strength in Bending
Shear Properties of Structural Adhe-
sives by the Modified-Rail Test." A Occasionally, the property of interest may be
rather involved test, especially with re- resistance to bond failure when a laminate is
gard to the system of loading and mea- loaded in bending. D-l184, "Test Method for

Fig. 11. Thick adherend lap shear specimen and grips (0-3983).
 ADHESIVE SELECTION AND SCREENING TESTING 105

Flexural Strength of Adhesive Bonded Lami-

nated Assemblies," is primarily applicable to
wood and metal adherends.

Peel Resistance
The testing of adhesive bonded joints in peel
implies either (a) a flexible adherend being
peeled from a rigid adherend or (b) two at least
semi-flexible adherends being peeled from one
another. Depending on the combination being
dealt with, one or the other of the below-listed
standards should be applicable to a variety of
adherends.
D-0903. "Test Method for Peel or Strip-
ping Strength of Adhesive Bonds. " This
is the standard 180 0 peel test (Fig. 12)
applicable where one of the adherends
is sufficiently flexible to endure the 180 0
fold back. Tests the resistance to peel
separation of flexible foils, films, or
tapes from relatively rigid base adher-
ends (metal, wood, plastic, glass, etc.
of adequate thickness).
D-1781. "Method for Climbing Drum
Peel Test for Adhesives. " Tests the re-
Fig. 13. Climbing drum peel specimen and loading de-
sistance to removal in peel of less flex- vice (D-I781).
ible adherends from relatively rigid
substrates. Fig. 13 shows the test de-
vice, which is a bit complex but useful the severe deformation of other peel
where peel resistance data are needed on tests. Especially intended for measuring
bonds involving adherends too stiff for resistance to peel separation of moder-
ately flexible metal skins from sand-
wich panel cores (e.g., honeycomb).
D-1876. "Test Method for Peel Resis-
tance of Adhesives (T -Peel Test). Tests
resistance to peel separation in joints
between two adherends which are flex-
ible enough to deform into the T config-
uration (Fig. 14) without cracking or
breaking (e.g., thin laminated alumi-
num sheets).
D-3167. "Test Method for Floating Roller
Peel Resistance of Adhesives." Fig. 15
shows this specimen and device. Peel is
achieved at a less-than-90° angle, but
good axis-of-Ioading alignment is main-
tained over a significant bond length.
Useful in peel testing semi-flexible sur-
face adherends bonded to a rigid base
adherends. Particularly applicable in
Fig. 12. 180 0 Peel specimen and grips (D-0903). testing peel resistance of flexible metals
106 HANDBOOK OF ADHESIVES

T-PEEL
TEST PANEL

TEST
SPECIMEN pull
~tETRIC EQUIVALENTS
in. I 3 6 9 12
mrn 25 76 152 229 305
Fig. 14. T-peeJ panel and specimen (D-1876).

1r
I 1/8 IN 1 10.38 -0.39 INl
O.316 CM AlUMINUM 0.95 -0.98 CM
OR STAINLESS STEEL IN DIAMETER

J l.54 CM
11.00 IN 1
L
BEARINGS -
3/ 8 IN - 16 STUD DOUBLE ROLL EXTRA
3/ 8 IN - 16 NUT PRECISION
SYNTHETIC SEAL BALL
BEARING MITH EXffNOrO
INNER RACF

~IGIO AOHf~tNO

FLiXIBL, A8HiW,ND

Fig. 15. Floating roller peel test head and specimen (D-3167).
 ADHESIVE SELECTION AND SCREENING TESTING 107

skins laminated to rigid metal sub-

strates.

Cleavage Strength
From the early days of adhesives testing it has
been recognized that in-service loading on ad-
hesive joints frequently subjects the bondline to
cleavage stresses (more-or-Iess conce:ntrate.d
tensile stresses approximately perpendicular to
the bondline). Thus another of 0-14'rs earlier
standards is 0-1062, "Test Method fOlr Cleav-
age Strength of Metal-to-Metal Adhesive
Bonds." It employs a relatively simple speci-
men (Fig. 16) and loading procedure.

Impact Strength
I
I

t Joints often experience impact or shodk loads,

and their reactions will differ dependin.g on the
A-Upper grip.
rheology of the adherend and the adhesive. An-
S-Pin connecting upper and lower grips. other early standard is 0-0950, "Test Method
C-Lower grip. for Impact Strength of Adhesive Bonds." It in-
D-Pin for attaching grip to specimen.
E-Metal pieces. volves a relatively simple specimen (Fig. 17),
F-Glue line. but a special pendulum device is required for
Fig. 16. Cleavage test specimen and grips (D-I062). application of the impact shear load.

rl",
Adhesive Bond

(a) Metal-to-Metal Specimen

Adhesive Bond

II"i

Directicn of Grein

(b) Wood-to-Wood Specimen

Fig. 17. Impact test specimens for (a) metal and (b) wood (D-0950).
108 HANDBOOK OF ADHESIVES

TEST "RIPS

( I.OOin.1
GLUE LINE
NOTE-Minimum specimen length in the grip 25.4 mm (1 in.).

Fig. 18. Tension shear fatigue specimen and grips (D-3166).

Fatigue Strength this test which also measures creep de-

formation along the bondline edge.
Experience has shown that adhesive bonds can, 0-2294. "Test Method for Creep Prop-
over time, experience gradual deterioration and erties of Adhesives in Shear by Tension
failure from cyclic loading and unloading, even Loading (Metal-to-Metal) (Fig. 21).
when the individual load events are not in the The tensile creep counterpart to 0-2293.
range which would normally produce failure. 0-4680. "Test Method for Creep and
Joints which experience significant vibration in Time to Failure of Adhesives in Static
service are likely to be the most susceptible to Shear by Compression Loading (Wood-
fatigue. In 0-3166, "Test Method for Fatigue to-Wood),' (Fig. 22). A new compres-
Properties of Adhesives in Shear by Tension
Loading (Metal/Metal)," the specimen (Fig.
18) is a relatively simple one. However, load-
ing calls for a tensile tester capable of applying
a sinusoidal cyclic load at rates as high as 1800
cycles/minute or more.

Creep
Long-term, viscoelastic deformation can be a
problem with less rigid adhesives, even under
moderate loads, and may need to be tested for. Three Scribe
Lines on each
Side of Specimen
0-1780. "Practice for Conducting Creep
Tests of Metal-to-Metal Adhesives." A
general procedure for applying a con-
stant tensile load to simple lap shear
specimens (Fig. 19) and monitoring the
scribed glueline edge, by microscope,
for time-dependent deformation. Since
temperature can have a marked affect on
creep, requirements for isothermal test-
ing are emphasized. Metric Equivalents
0-2293. "Test Method for Creep Prop-
erties of Adhesives in Shear by in. 0.030 0.762
mm 0.250 6.350
Compression Loading (Metal-to-
Metal)." Fig. 20 shows the specimen Fig. 19. Tension shear creep specimen for metal bonding
and spring actuated loading device for adhesives (D-1780).
 *
ADHESIVE SELECTION AND SCREENING TESTING 109

+ '
\ -'

A-Slotted bolt
B-Bushing
C- Spring-piano wire cylindrical helical compression spring with six active
coils, eight total coils, wound closed, ground square. and cadmium plated
D-Washer-22.25 mm (,Ie in.) 00. 12.7 mm (V. in.) 10. 1.6 mm ('I,. in.) thick
E- Nut- 12.7 mm ('I. in.}-20 NF
F- Test specimen

Fig. 20. Compression shear creep specimen and soring loading device for metal bonding adhesives (D-2293).

sion shear creep and creep-fail test

which uses a modified D-0905 block
shear specimen to measure creep rate
and time to failure, primarily on adhe-
sives thought to have at least some creep
tendency.

Fracture Strength
Knurl ed Su ppor 11"9
R,nQ As an outgrowth of interest in studying mate-
Lood .nQ Sho ft rial failure via crack propagation, D-3433,
"Practice for Fracture Strength in Cleavage of
Adhesives in Bonded Joints," was developed.
Tes t Spec ime- n It describes specimen fabrication (Fig. 23) and
testing, and calculation of the adhesive's frac-
ture strength in cleavage.

TESTING THE DURABILITY OF

Thi -s pm has a
notch for t he ADHESIVE BONDED JOINTS
specim en

Metal Bonding Adhesives

Joint Strength Retained after Exposure to
Fig. 21. Tension shear creep specimen and spring ac- Hostile Environments. In addition to initial
tuated loading device for metal bonding adhesives strength, adhesive bonded joints should pos-
(D-2294). sess adequate durability and be able to maintain
110 HANDBOOK OF ADHESIVES

LOADING SHAFT

RETAINER SCREWS

LOCKING NUT
LOCK NUT PORTS

LOADING BLOCK

CYLINDER

SPRING-_ _

UPPER BEARING BLOCK

SHEAR SPECIMEN

LOWER BEARING AND

FAILURE PIN RETAINER BLOO<

RETAINER SCREWS

LOWER BAS£.

MICRO SWITCH ----------1aljl1

Fig. 22 . New compression shear creep specimen and spring actuated loading device for wood bonding adhesives
(0-4680) .

needed load resistance over a reasonable ser- sure to selected (generally somewhat harsh)
vice life when exposed to hostile elements of environments, and then measuring resultant
their service environment. Several of the du- strength losses. The following standards de-
rability-related D-14 standards are procedures scribe exposure conditions, both artificial and
for taking one or more of the previously de- natural, general and specific, which could be
scribed strength test specimens, adding expo- used with a variety of the previously described
 ADHESIVE SELECTION AND SCREENING TESTING 111

m=90

_h_ -'-_
0.500 (in.) 1.914 (in.)
0.600 (in.) 2.522 (in.1
0.700 (in.) 3.182 (in.)
0.800 (in.) 3.892 (in.)
0.900 (in.1 4.646 (in.)
90
1.000 (in.1 5.447 (in.)
1.100 (in.) 6.827 (;n.) (Note 41
1.200 lin.) 7.167 (in.)
1.250 (in.) 7.621 (in.) Non Adhering Shim 1

tr=:- '.-
~ r---+----f--- 31.75±0.13mm
(1.250 ± 0.005 in.)

1
Adhesive SIDE

~'2.70±'0.'3mm(0.500 ± 0.005 in.1

635 + 0 05 mm

/
(0.250 ± 0.002 in.)

25.4 ± i/:
,, ,,
O.3mm ,, ,, TOP
(1.00
±O.Ol :, :,
in.) , I

48.62 ±0.13 mm
l-
(1.914 + 0.005 in,) 193.60 ± 0.13 mm
(7.621 ±0.OO5 inJ I
I
241.3 ± 2.5 mm
I (9.5 ±.0.1 in.)

Fig. 23. Double cantilever fracture strength specimen (0-3433).

standard strength specimens to test for various exposes specimens to cycles of temper-
aspects of durability. ature/humidity. Four environments, two
designated as "interior," one as "ex-
D-0896. "Test Method for Resistance of terior, land and air," and one as "ex-
Adhesive Bonds to Chemical Re- terior, marine" are suggested.
agents. ' , Suggests several chemicals D-1828. "Practice for Atmospheric Ex-
which adhesives might be exposed to in posure of Adhesive-Bonded Joints and
testing and references the listings of Structures." Whereas the three preced-
others. ing standards utilize controlled labora-
D-1151. "Test Method for Effect of tory conditions, this standard (a) defines
Moisture and Temperature on Adhesive classes of natural exposure and (b) out-
Bonds." Procedure for taking previ- lines a weathering test practice for mea-
ously described basic tests and measur- suring strength loss as a function of time
ing strength loss as a function of time in those exposures. Several, somewhat
after exposure to defined temperature/ extreme, natural environments and their
humidity combinations. Some 22 sets of associated geographic locations are
exposure conditions, ranging in temper- mentioned.
ature from -70°F to +600°F and var- D-1879. "Practice for Exposure of Ad-
iously including low humidity, high hesive Specimens to High-Energy Ra-
humidity, and water immersion, are diation." Specimens are exposed to
suggested. controlled dosages of high energy radia-
D-1183. "Test Methods for Resistance of tion (x-ray, gamma, electron, or beta
Adhesives to Cyclic Laboratory Aging radiation, etc.) and changes in the be-
Conditions." Whereas D-1151 em- fore-and-after strengths noted.
ploys exposure to constant temperature D-2295 and D-2557. Procedures for mea-
and humidity environments, D-1183 suring shear strength for metal joints at
 112 HANDBOOK OF ADHESIVES

low and high temperatures, respec- for the influence of water immersion on
tively, on adhesive-bonded tensile lap peel resistance. Several other standard
shear specimens. environments are also suggested (i.e.,
0-4299 and 0-4300. Procedures for mea- various relative humidities, tempera-
suring the deteriorating effects of bac- tures, salt spray, etc.).
teria and molds, respectively, on joint 0-2919. "Test Method for Oetermining
strength (see details under durability Ourability of Adhesive Joints Stressed
testing for wood joints). Also useful for in Shear by Tension Loading." Fig. 25
metal bonding adhesives which might shows the lap shear specimen and
be susceptible to molds or bacteria. spring-type loading device used. A
number of standard environments are
Strength Under Exposure to a Hostile En- also suggested for use.
vironment. Ideally, a durability test should
measure an adhesive bond's retention of Wood Bonding Adhesives
strength and bond while exposed to the ele-
Joint Strength Retained after Exposure to
ments of its service environment. However, the
Accelerated Weathering Treatments.
execution of such tests can be physically and
Many of the durability testing concepts sug-
procedurally quite difficult. The following two
gested for metal joints may also be useful with
are 0-14's only durability standards which are
wood. One or more of the basic wood joint-
designed to test strength while joints are under
strength tests (e. g., 0-0897, 0-0905, 0-0906,
exposure.
etc.) could be combined with selected environ-
0-2918. "Practice for Oetermining Ou- mental exposure (0-0896, 0-1151, 0-1183,
rability of Adhesive Joints Stressed in 0-1828,0-4299,0-4300, etc.) to screen wood
Peel" (Fig. 24). A dead load type test bonding adhesives for particular durability re-
quirements.
} - - - - Stationary Object
In 0-3024 (see wood adhesive specifica-
tions), samples of laminated wood and ply-
-~='-r--- String
wood are tested both before and after water
Water exposure and variously evaluated for shear
Unpeeled Portion of strength and/or wood failure. These procedures
1 + - - Peel Joint
could have applications in other wood glue
testing as well.
0-3110 (see wood adhesive specifications),
Pair of Clamps -T-~
Gloss Tube tests for strength retained after exposure and
Peeled Portion
r21~>-li-- Nul and Bolt sets forth minimum performance criteria. Ex-
of the Joint posures include atmospheric water soak, vac-
Pair of Clamps -+--1 uum-pressure water soak, boiling, and exposure
i--+--WIRE
to elevated temperatures in an oven. Whenever
dealing with adhesives falling in the categories
Hose Clomp covered by 0-3110, durability should certainly
be tested that way. However, these procedures
::::2:~ff-- Rubber Stopper almost certainly have other useful wood adhe-
sive testing applications too.
String In addition, 0-3434, "Practice for Multiple-
Cycle Accelerated Aging Test (Automatic Boil
Test) for Exterior Wet Use Wood Adhesives"
is available for those who have access to the
Weight (or beoker rather complex and expensive apparatus in-
containing weighf)
volved. Often abbreviated as the ABT, it has
Fig. 24. Specimen and device for testing peel strength produced very valuable wood adhesive dura-
under environmental exposure (0-2918). bility data.
 ADHESIVE SELECTION AND SCREENING TESTING 113

·- - -
::Si===.!~::~~~~=------- End Plate ShIeld

ID""';~------ Self - AliQninQ Washers

1I~!bd~--------- Lacators

~==r~ r"""'o'fI~~~~~--- Lap Sheor Specimen

~===:!~J--------- Sprin9

f~JlOJ~t-"~~----- Locking Nul

_=~''Y'r_J~--+-------- Chonnel

::d~=l~m~~~~--L------- Grip
I I
i !
--~---- Threaded Rod
\
i ;
: :
I I I.....- - -- Laadinll Bose
! !
i I
!i i i
~j " - "
. I
I: .....
i i
t:==:-.--.... -_".:::::'-"-.. -. ~
H ...... ____
---.- .. -' .. ~

Fig. 25. Specimen and device for testing tension shear strength under environmental exposure (D-2919) .

Delamination of Wood Adhesive Bonds standard includes two delamination test

after Environmental Exposure. Wood procedures which are similar to but
tends to shrink and swell as it is respectively slightly different from the one in D-2559
dried and wetted during environmental expo- (see below). Method A is a 3-day test,
sure. As a result, significant stresses are im- whereas Method B is a 12! hour test
posed on the bonds and can result in used for daily quality control purposes
delamination if the bonds are not properly in evaluating wood laminates.
formed using durable adhesives. Various cycles D-2559 (on adhesives for exterior-use
of wetting, drying, steaming, etc. are used in glued, laminated, wood) uses speci-
the D-14 standards which test for this property, mens cut from small laminated beams
and resultant percentages of glueline delami- and tests for delamination after expo-
nation are measured. Several of these tests are sure to a multi-step accelerated aging
from specifications, where maximum allow- treatment. See earlier listing under
able delamination values are also given. wood adhesive specifications.
D-llOl. "Test Methods for Integrity of Rate Process Assessment of Heat and
Glue Joints in Structural Laminated Moisture Resistance of Wood-Adhesive
Wood Products for Exterior Use." This Joints. D-4502, "Test Method for Heat and
114 HANDBOOK OF ADHESIVES

Moisture Resistance of Wood-Adhesive working properties is also needed. These tests

Joints." This recent standard defines proce- are relatively straight forward and are not dis-
dures where the degrading effects of heat and cussed here but are listed in Appendix 2.
moisture on bond quality are measured in such
a way that the data can be analyzed by means Appendix 1
of classical rate process equations. Results have Selected References of Use in Adhesives
shown that useful, long-term extrapolations of Familiarization, Selection, and Screening
environmental effects can be made. Testing
Plastic and Glass Bonding Adhesives.
Computer Searchable Databases
There are no 0-14 standards specifically de- "Standards and Specifications," prepared by the National
signed to test the durability of plastics or glass Standards Association, Inc., is available on line through
bonding adhesives. However, for screening the Dialog Infonnation Retrieval Service, Palo Alto, CA.
purposes, one or more of the general-purpose It references over 113,000 U.S. and International doc-
uments, including standards from ASTM, ANSI, the
adhesive strength tests could be combined with U.S. Federal Government and Military, and SAE, as
selected exposure and the associated strength well as others. In addition to infonnation on the standard
loss measured. and its acceptance by ANSI and DOD, vendors of prod-
For plastics, we do have the 0-3929, "Prac- ucts and services conforming to the standard are given.
tice for Evaluating the Stress Cracking of Plas- Hard copy of many of the standards is also available
from the National Standards Association.
tics by Adhesives Using the Bent-Beam "Standards Search," prepared by ASTM and SAE, is
Method. " It recognizes that some adhesives available on line through the Orbit Search Service,
may interact with plastic adherends in such a McLean, VA. It contains over 15,000 references (some
way as to induce areas of weakness leading to with abstracts) to the standards included in the ASTM
stress cracking. Book of Standards and in the SAE's Handbook, Aero-
space Index, and Index of Aerospace Materials Specifi-
With glass adherends, we can have the added cations.
problem of light penetrating a more or less "Military and Federal Specifications and Standards," pre-
transparent adherend, possibly having a pho- pared by Infonnation Handling Services, is available on
tochemical effect on the adhesive, its interface, line through BRS Infonnation Technologies, Latham,
etc. Screening for this effect could be accom- NY. Cites over 80,000 nonclassified U.S. Military and
Federal standards and specifications, Joint Army-Navy
plished using a standard specimen (e.g., the specifications, Military Standard Drawings, and Quali-
0-4501 block shear) in combination with ex- fied Product Lists.
posure to sunlight or to artificial light (e. g. , •'Combined Industry Standards and Military Specifica-
0-0904). tions" is also prepared by Information Handling Ser-
vices and available on line through BRS Infonnation
Technologies, Latham, NY. Cites over 150,000 govern-
Paper Bonding Adhesives ment and industry standards. Covers some 50 U.S. and
other national and international standards organizations,
Most standards for paper bonding adhesives are
including the American National Standards Institute
under the jurisdiction of T APPI or related or- (ANSI), the International Standards Organization (ISO),
ganizations. See ASTM's two durability tests and the National Bureau of Standards Voluntary Engi-
for paper bonding adhesives, 0-1581 and neering Standards database, which is based on the stan-
0-1713 in the earlier listing under paper ad- dards of some 400 societies. Also includes the Military
and related standards covered by "Military and Federal
hesive specifications.
Specifications and Standards."

TESTING THE PHYSICAL AND Selected Published References on

WORKING PROPERTIES OF Adhesives and Their Testing
ADHESIVES Adams, R.D., and Wake, W.C., "Structural Adhesive
Joints in Engineering," London, Applied Science Pub-
Although adhesives are screened predomi-
lishers, 1984.
nantly on the basis of their strength and dura- ASTM. "Annual Book of Standards," Part 15.06 on Ad-
bility characteristics, there may be times when hesives. American Society for Testing and Materials,
the testing of their physical, compositional and 1916 Race Street, Philadelphia, PA 19103-1187.
 ADHESIVE SELECTION AND SCREENING TESTING 115

Anonymous. "Adhesives," 4th Ed., Desk-Top Data Bank. Gillespie, R.H. (ed.), "Adhesives for Wood: Research,
San Diego, CA, D.A.T.A., 1986. Applications and Needs, " Park Ridge, NJ, Noyes Pub-
Anonymous. "Adhesives for Industry: Proceedings of a lications, 1984.
Conference." Pasadena, CA, T-C Publications, 1980. Gutcho, Marcia (ed.), "Adhesives Technology Develop-
Anonymous. "Structural Adhesives and Bonding, 1979: ment Since 1979," Park Ridge, NJ, Noyes Publications,
Proceedings of a Special Conference." Pasadena, CA, 1983.
T-C Publications, 1980. Houwink, R., and Salomon, G. "Adhesion and adhe-
Anonymous. "Adhesives Used on Building Materials," sives," 2nd Ed.,vols. I and n, New York, Elsevier Pub-
Pasadena, CA, T-C Publications, 1982. lishing Company, 1965.
Anonymous. "Adhesive Bonding of Composite Mate- Jones, Peter, "Fasteners, Joints and Adhesives: A Guide
rials." Pasadena, CA, T-C Publications, 1983. to Engineering Solid Constructions, " Englewood Cliffs,
Anonymous. "Adhesives-Structural: Formulations and NJ, Prentice-Hall, 1983.
Applications." Pasadena, CA, T-C Publications, 1983. Kinloch, A.J. (ed.), "Durability of Structural Adhe-
Adhesives Age. "Adhesives Age Directory," 21st Ed. At- sives," London, Applied Science Publishers, 1983.
lanta, GA, Communication Channels, Inc., 1989. Kinloch, A.J., "Adhesion and Adhesives: Science and
Adhesives Age. "Consult the Experts. A current list of ad- Technology," London and New York, Chapman and
hesive reference materials." Published each month in Hall, 1987.
Adhesives Age Magazine. Atlanta, GA, Communication Landrock, Arthur H., "Adhesives Technology Hand-
Channels, Inc. book," Park Ridge, NJ, Noyes Publications, 1985.
Anderson, G., et al. "Analysis and Testing of Adhesive Lee, H. (ed.), "Cyanoacrylate Resins: The Instant Adhe-
Bonds." New York, Academic Press, 1977. sives," Pasadena, CA, T-C Publications, 1981.
American Society for Testing and Materials (ASTM). Meese, R. G., "Testing Adhesives," TAPPI Monograph
"Book of Standards," Part 15.06, "Adhesives," Phil- Series No. 35, Atlanta, GA, Technical Association of
adelphia, ASTM, 1985. the Pulp and Paper Industry (TAPPI), 1974.
American Society for Testing and Materials (ASTM). Mittal, K.L., "Adhesive Joints: Formation, Characteris-
"Durability of Adhesive Joints." Special Technical tics and Testing," New York, Plenum Press, 1984.
Publication (STP) No. 401. Philadelphia, ASTM, 1966. Patrick, R.L. (ed.), "Treatise on Adhesion and Adhe-
Bandel, Alberto, "Glues and Gluing Technology for the sives," Vol. 4, "Structural Adhesives With Emphasis
Woodworking Industry," Milan, Italy, Ribera Editore, on Aerospace Applications," New York, Marcel Dek-
1985. ker, 1981.
Bikales, N.M. (ed.), "Adhesion and Bonding," Mel- Patrick, R.L. (ed.), "Treatise on Adhesion and Adhe-
bourne, FL, Robert E. Krieger Publishing Co., 1971. sives," Vol. 5, New York, Marcel Dekker, 1981.
Blomquist, R.F., et al., "Adhesive Bonding of Wood and Pizzi, A., "Wood Adhesives Chemistry and Technol-
Other Structural Materials: Educational Modules for ogy," New York, Marcel Dekker, 1983.
Materials Science and Engineering." University Park, Sadek, M.M., "Industrial Applications of Adhesive Bond-
PA, Materials Research Laboratory, Pennsylvania State ing," London and New York, Elsevier Applied Science,
University, 1983. 1987.
Breitenberg, Maureen A., "Directory of International and Satas, Donatas (ed.), "Handbook of Pressure-Sensitive
Regional Organizations Conducting Standards Related Adhesives Technology," Pasadena, CA, T-C Publica-
Activities," Washington, DC, Supt. of Documents, U.S. tions, 1982.
Government Printing Office, 1983. Schneberger, Gerald L., "Adhesives in Manufacturing,"
Brewis, D., and Comyn, J., "Advances in Adhesives: Ap- New York, Marcel Deker, 1983.
plications, Materials and Safety." Pasadena, CA, T-C Selbo, M.L., "Adhesive Bonding of Wood," Technical
Publications, 1983. Bulletin No. 1512, Forest Products Laboratory, U.S.
Bruno, E.J. (ed), "Adhesives in Modern Manufacturing," Forest Service, U.S. Department of Agriculture, Wash-
Dearborn, MI, Society of Manufacturing Engineers, ington, DC, U.S. Government Printing Office, 1975.
1970. Shields, J., "Adhesives Handbook," 3rd Ed., London,
Cagle, Charles V., et al., "Handbook of Adhesive Bond- Butterworths, 1984.
ing," Pasadena, CA, T-C Publications, 1973 (reprinted Skeist, I. (ed.), "Adhesives Handbook," 2nd Ed., New
in 1982). York, Van Nostrand-Reinhold, 1977.
DeLollis, Nicholas J., "Adhesives for Metals: Theory and Thrall, E.W., and Shannon, R.W. Jr., "Adhesive Bond-
Technology," New York, Industrial Press, Inc., 1970. ing of Aluminum Alloys," New York, Marcel Dekker,
DeLollis, Nicholas J., "Adhesives, Adherends, Adhe- 1985.
sion, " Melbourne, FL, Robert E. Krieger Publishing Toth, Robert B., "Standards Activities of Organizations in
Co., 1980. the United States," Washington, DC, Supt. of Docu-
Department of Defense, "Index of Specifications and ments, U.S. Government Printing Office, 1984.
Standards," Washington, DC, Supt. of Documents, Wake, W.C., "Adhesion and the Formulation of Adhe-
U.S. Government Printing Office, 1984. sives," London, Applied Science Publishers, 1982.
Epstein, George, "Adhesives and Adhesive Bonding: Wake, W.C., "Developments in Adhesives," Vols. 1 and
Theoretical and Practical." Pasadena, CA, T-C Publi- 2, London, Applied Science Publishers, 1977.
cations, 1984. Weiner, J., and Roth, L., "Adhesives," Vol. 1 (with sup-
116 HANDBOOK OF ADHESIVES

plement}, "General Applications, Theory and Testing," panion standard 0-1584, "Test Method for Water
Appleton, WI, Institute of Paper Chemistry, 1974. Absorptiveness of Paper Labels").
Weiner, J., and Roth, L., "Adhesives," Vol. 2 (with sup- 0-1874. "Specification for Water- or Solvent-Soluble Liq-
plement), "Paper," Appleton, WI, Institute of Paper uid Adhesives for Automatic Machine Sealing of Top
Chemistry, 1974. Flaps of Fiberboard Shipping Cases" (and companion
Weiner, 1., and Roth, L., "Adhesives," Vol. 3 (with sup- standard 0-1714, "Test Method for Water Absorptive-
plement), "Board, Plastics, Textiles," Appleton, WI, ness of Fiberboard Specimens for Adhesives").
Institute of Paper Chemistry, 1974.
Pressure-sensitive tape specification.
Weiner, J., and Roth, L., "Adhesives," Vol. 4 (with sup-
0-1000. "Pressure-Sensitive Adhesive Coated Tapes Used
plement), "Tapes and Machinery," Appleton, WI, In-
for Electrical Insulation" (see ASTM Book of Stan-
stitute of Paper Chemistry, 1974.
dards, Part 10.01).
Optical adhesive specification.
0-2851. "Specification for Liquid Optical Adhesive. "
Appendix 2
Use-Oriented Classification of ASTM
Strength Tests for Metal Bonding
Adhesives Standards
Adhesives
Tensile strength of metal bonding adhesives.
0-0897. "Test Method for Tensile Properties of Adhesive
Standard on Terminology of Adhesives Bonds. "
0-2095. "Test Method for Tensile Strength of Adhesives
0-907. "Terminology of Adhesives." by Means of Bar and Rod Specimens" (and companion
0-2094, "Practice for Preparation of Bar and Rod Spec-
imens for Adhesion Tests").
Standard Specifications for Adhesives
Shear strength of metal bonding adhesives.
For adhesives used in construction assembly bonding: pri- 0-1002. "Test Method for Strength Properties of Adhe-
marily adhesives for tile or panel-to-frame bonding appli- sives in Shear by Tension Loading (Metal-to-Metal)."
cations in building construction. 0-2295. "Test Method for Strength Properties of Adhe-
C-557. "Specification for Adhesives for Fastening Gyp- sives in Shear by Tension Loading at Elevated Temper-
sum Wallboard to Wood Framing." atures (Metal-to-Metal}."
0-1779. "Specification for Adhesive for Acoustical Ma- D-2557. "Test Method for Strength Properties of Adhe-
terials. sives in Shear by Tension Loading in the Temperature
0-3498. "Specification for Adhesives for Field-Gluing Range from -267.8 to -55°C (-450 to 67°F).
Plywood to Lumber Framing for Floor Systems" (ref- D-3165. "Test Method for Strength Properties of Adhe-
erence 0-3632, "Practice for Accelerated Aging of Ad- sives in Shear by Tension Loading of Laminated Assem-
hesive Joints by the Oxygen-Pressure Method" and blies. "
0-3931, "Test Method for Oetermining Strength of Gap- 0-3528. "Test Method for Strength Properties of Oouble
Filling Adhesive Bonds in Shear by Compression Load- Lap Shear Adhesive Joints by Tension Loading."
ing"). 0-3983. "Test Method for Measuring Strength and Shear
0-3930. "Specification for Adhesives for Wood-Based Modulus of Nonrigid Adhesives by the Thick Adherend
Materials for Construction of Manufactured Homes." Tensile Lap Specimen."
For primary wood bonding adhesives. 0-4027. "Test Method for Measuring Shear Properties of
Structural Adhesives by the Modified-Rail Test."
0-2559. "Specification for Adhesives for Structural Lam-
0-4501. "Test Method for Shear Strength of Adhesive
inated Wood Products for Use Under Exterior (Wet Use)
Bonds Between Rigid Substrates by the Block-Shear
Exposure Conditions. "
Method. "
0-3024. "Specification for Protein-Base Adhesives for
0-4562. "Test Method for Shear Strength of Adhesives
Structural Laminated Wood Products for Use Under In-
Using Pin-and-Collar Specimen. "
terior (Ory Use) Exposure Conditions."
E-0229. "Test Method for Shear Strength and Shear Mod-
0-3110. "Specification for Adhesives Used in Nonstruc-
ulus of Structural Adhesives."
tural Glued Lumber Products."
0-4317. "Specification for Polyvinyl Acetate-Based Bending strength of metal bonding adhesives.
Emulsion Adhesives." 0-1184. "Test Method for Flexural Strength of Adhesive
0-4689. "Specification for Adhesives, Casein-Type." Bonded Laminated Assemblies. "
0-4690. "Specification for Urea-Formaldehyde Resin Ad-
Peel strength of metal bonding adhesives.
hesives. "
0-0903. "Test Method for Peel or Stripping Strength of
For paper bonding adhesives. Adhesive Bonds. "
0-1580. "Specification for Liquid Adhesives for Auto- 0-1781. "Method for Climbing Orum Peel Test for Ad-
matic Machine Labeling of Glass Bottles" (and com- hesives. "
 ADHESIVE SELECTION AND SCREENING TESTING 117

0-1876. "Test Method for Peel Resistance of Adhesives 0-2674. "Methods of Analysis of Sulfochromate Etch So-
(T-Peel Test)." lution Used in Surface Prepamtion of Aluminum."
0-3167. "Test Method for Floating Roller Peel Resistance 0-3933. "Practice for Prepamtion of Aluminum Surfaces
of Adhesives." for Structural Adhesives Bonding (Phosphoric Acid An-
odizing). "
Cleavage strength of metal bonding adhesives.
0-1062. "Test Method for Cleavage Strength of Metal-to-
Metal Adhesive Bonds." Strength Tests for Wood Bonding
Impact strength of metal bonding adhesives. Adhesives
0-0950. "Test Method for Impact Strength of Adhesive Tensile strength tests for wood bonding adhesives.
Bonds. " 0-0897 and 0-1344 (See metal, strength, tensile.)
Fatigue strength of metal bonding adhesives. Shear strength tests for woad bonding adhesives.
0-3166. "Test Method for Fatigue Properties of Adhe- 0-0905. "Test Method for Strength Properties of Adhe-
sives in Shear by Tension Loading (Metal/Metal)." sive Bonds in Shear by Compression Loading."
0-0906. "Test Method for Strength Properties of Adhe-
Creep of metal bonding adhesives.
sives in Plywood Type Construction in Shear by Tension
0-1780. "Practice for Conducting Creep Tests of Metal-
to-Metal Adhesives." Loading. "
0-1002. (See metal, strength, shear.)
0-2293. "Test Method for Creep Properties of Adhesives
0-2339. "Test Method for Strength Properties of Adhe-
in Shear by Compression Loading (Metal-to-Metal)."
sives in Two-Ply Wood Construction in Shear by Ten-
0-2294. "Test Method for Creep Properties of Adhesives
sion Loading."
in Shear by Tension Loading (Metal-to-Metal)."
0-3528, 0-4027, and E-0229. (See metal, strength, shear.)
Fracture strength of metal bonding adhesives. 0-4688. "Test Methods for Evaluating Structural Adhe-
0-3433. "Practice for Fmcture Strength in Cleavage of sives for FingeIjointing Lumber."
Adhesives in Bonded Joints."
Bending strength test for wood bonding adhesives.
Rate of strength development for metal bonding adhesives. Not often used with wood adhesives, but 0-1184 (see
0-1144. "Practice for Oetermining Strength Oevelopment metal, strength, bending) should be applicable.
of Adhesive Bonds."
Peel strength tests for wood bonding adhesives.
Not often used for wood but these standards should be ap-
Durability Tests for Metal Bonding plicable with wood as the rigid substmte: 0-903, 180·
peel; 0-1781, climbing drum peel; and 0-3167, floating
Adhesives
roller peel (see metal, strength, peel).
0-0896. "Test Method for Resistance of Adhesive Bonds
Cleavage strength test for wood bonding adhesives.
to Chemical Reagents."
Not commonly done with wood adhesives but 0-1062 (see
0-0904. Light aging (see glass, dumbility).
metal, strength, cleavage) should be applicable with
0-1151. "Test Method for Effect of Moisture and Tem-
possible modifications to assure stressing the glueline.
pemture on Adhesive Bonds."
0-1183. "Test Methods for Resistance of Adhesives to Impact test for wood bonding adhesives.
Cyclic Labomtory Aging Conditions." 0-0950, "Test Method for Impact Strength of Adhesive
0-1828. "Practice for Atmospheric Exposure of Adhe- Bonds. "
sive-Bonded Joints and Structures."
Fatigue strength test for wood bonding adhesives.
0-1879. "Practice for Exposure of Adhesive Specimens to
High-Energy Radiation. ,. Not clearly applicable to wooden joints. but cyclic tension
shear (e.g., 0-1002) or bending (e.g., 0-1184) test could
0-2295 and 0-2557. Extreme tempemture shear testing
be tried and strength examined as a function of number
(see metal, strength, shear).
of cycles, percent of maximum load, etc.
0-2918. "Practice for Oetermining Dumbility of Adhesive
Joints Stressed in Peel. " Creep tests for wood bonding adhesives.
0-2919. "Test Method for Oetermining Oumbility of Ad- 0-3535. "Test Method for Resistance to Oeformation Un-
hesive Joints Stressed in Shear by Tension Loading." der Static Loading for Structural Wood Laminating Ad-
0-3762. "Test Method for Adhesive-Bonded Surface Ou- hesives Used Under Exterior (Wet Use) Exposure
mbility of Aluminum (Wedge Test)." Conditions. "
0-4299 and 0-4300. Mold and bacteria tests (see wood, 0-4680. "Test Method for Creep and Time to Failure of
dumbility). Adhesives in Static Shear by Compression Loading
(Wood-to-Wood). "
See also the creep test in 0-3930 on adhesives for wood
Standards on Preparation of Metal bonding in mobile homes.
Surfaces for Adhesive Bonding
Rate of strength development for wood bonding adhesives.
0-2651. "Practice for Prepamtion of Metal Surfaces for 0-1144. Procedure for mte of joint strength development
Adhesive Bonding." (see metal, strength, miscellaneous).
118 HANDBOOK OF ADHESIVES

Durability Tests for Wood Bonding Creep tests for plastics bonding adhesives.
Adhesives Where applicable, perhaps use long term loading with the
new block-shear test (0-4501) or consider the creep test
0-0896, 0-1151, 0-1183, 0-1828, 0-2919. (See metal, methods now used for construction adhesives in the
durability. ) specification for adhesives used in bonding wood in mo-
0-1101. "Test Methods for Integrity of Glue Joints in bile homes (0-3930).
Structural Laminated Wood Products for Exterior Use"
Miscellaneous tests for strength of plastics bonding adhe-
(previously in ASTM Book of Standards, Part 4.09 on
sives.
WOod but now to be in Part 15.06 on Adhesives).
0-1144. Rate of joint strength development (see metal,
0-2559. "Specification for Adhesives for Structural Lam-
strength, miscellaneous).
inated Wood Products for Use Under Exterior (Wet Use)
0-3808. "Practice for Qualitative Determination of Adhe-
Exposure Conditions."
sion of Adhesives to Substrates by Spot Adhesion Test
0-3110. "Specification for Adhesives Used in Nonstruc-
Method." .
tural Glued Lumber Products."
0-3434. "Practice for Multiple-Cycle Accelerated Aging
Test (Automatic Boil Test) for Exterior Wet Use Wood
Durability Tests for Plastics Bonding
Adhesives. " Adhesives
0-4299. "Test Methods for Effect of Bacterial Contami- 0-0896, 0-1151, 0-1183, 0-1828, 0-1879, 0-2295,
nation on Permanence of Adhesive Preparations and Ad- 0-2557,0-2918 and 0-2919. (See metal, durability.)
hesive Films." 0-4299 and 0-4300. Mold and bacteria tests (see wood,
0-4300. "Test Methods for Effect of Mold Contamination durability).
on Permanence of Adhesive Preparations and Adhesive 0-904. Light aging test (see glass, durability).
Films. " 0-3929. "Practice for Evaluating the Stress Cracking of
0-4502. "Test Method for Heat and Moisture Resistance Plastics by Adhesives Using the Bent-Beam Method."
of Wood-Adhesive Joints."
Standard on Surface Preparation of
Strength Tests Applicable to Plastics Plastics for Adhesive Bonding
Bonding Adhesives
0-2093. "Practice for Preparation of Surfaces of Plastics
Tensile strength tests for plastics bonding adhesives.
. Prior to Adhesive Bonding. "
0-1344 and 0-2095. (See metal, strength, tensile.)
Shear strength tests for plastics bonding adhesives. Strength Tests for Glass Bonding
0-3163. "Test Method for Oetermining the Strength of Adhesives
Adhesively Bonded Rigid Plastic Lap-Shear Joints in
Shear by Tension Loading." Tensile strength tests for glass bonding adhesives.
0-3164. "Test Method for Determining the Strength of 0-0897 and 0-1344. (See metal, strength, tensile.)
Adhesively Bonded Plastic Lap-Shear Sandwich Joints Shear strength tests for glass bonding adhesives.
in Shear by Tension Loading." 0-3164. (See plastics, strength, shear.)
0-3983. (See metal, strength, shear.) 0-3658. "Practice for Determining the Torque Strength of
0-4501. "Test Method for Shear Strength of Adhesive Ultraviolet (UV) Light-Cured Glass/Metal Adhesive
Bonds Between Rigid Substrates by the Block-Shear Joints. "
Method." 0-4501. (See plastics, strength, shear.)
Bending strength test for plastics bonding adhesives.
Bending strength test for glass bonding adhesives.
0-1184. (See metal, strength, bending.)
Probably not applicable.
Peel strength tests for plastics bonding adhesives.
Plastic films and rigid plastics could variously use the 180· Peel strength tests for glass bonding adhesives.
peel (0-0903), climbing drum peel (0-1781) or floating To test peel adhesion to glass as a rigid substrate, one could
roller peel (0-3167) (see metal, strength, peel). use the 180· peel (0-0903), climbing drum peel
(0-1781) or floating roller peel (0-3167) tests.
Cleavage strength test for plastics bonding adhesives.
0-3807. "Test Method for Strength Properties of Adhe- Cleavage strength test for glass bonding adhesives.
sives in Cleavage Peel by Tension Loading (Engineering Where applicable, perhaps use 0-1062 with sandwich con-
Plastics-to-Engineering Plastics)." struction (see metal, strength, cleavage).

Impact strength test for plastics bonding adhesives. Impact strength test for glass bonding adhesives.
Where applicable, perhaps use 0-0950, the basic impact Where applicable perhaps use 0-0950, the basic impact
test. test method (see metal, strength, impact).
Fatigue strength test for plastics bonding adhesives. Fatigue strength test for glass bonding adhesives.
Where applicable, perhaps use a cyclic shear or bending Where applicable, perhaps try 0-3164 (tensile shear test
test as suggested previously for fatigue testing of wood for adhesively bonded plastic lap joints) with cyclic
substrates. stressing.
 ADHESIVE SELECTION AND SCREENING TESTING 119

Creep test for glass bonding adhesives. 0-0899. "Test Method for Applied Weight per Unit Area
Perhaps use 0-2293 (see metals, strength, creep). of Liquid Adhesive."
Miscellaneous tests for glass bonding adhesives.
Tests for rheological and tack propenies of adhesives.
0-1144. On rate of joint strength development (see metal,
0-1084. "Test Methods for Viscosity of Adhesives."
strength, miscellaneous).
0-3808. (See plastics, miscellaneous.) Spot adhesion test 0-1146. "Test Method for Blocking Point of Potentially
developed for plastics but may be usable with glass. Adhesive Layers. "
0-1875. "Test Method for Oensity of Adhesives in Fluid
Form."
Durability Tests for Glass Bonding 0-1916. "Test Method for Penetration of Adhesives."
Adhesives 0-2183. "Test Method for Flow Properties of Adhe-
0-0904. "Practice for Exposure of Adhesive Specimens to sives. "
Artificial Light (Carbon-Arc Type) and Natural Light." 0-2556. "Test Method for Apparent Viscosity of Adhe-
0-0896, 0-1151, 0-1183, 0-1828, 0-1879, 0-2918, sives Having Shear-Rate-Oependent Flow Properties."
0-4299 and 0-4300 (see metal, durability). 0-2979. "Test Method for Pressure-Sensitive Tack of Ad-
hesives Using an Inverted Probe Machine."
0-3121. "Test Method for Tack of Pressure-Sensitive Ad-
Tests for Paper Bonding Adhesives hesives by Rolling Ball."
Most tests for paper bonding adhesives have been devel- 0-4338. "Test Method for Flexibility Determination of
oped by TAPPI and published by them in "Testing Ad- Supported Adhesive Films by Mandrel Bend Test
hesives," by R. G. Meese (see Appendix 1). Method."
ASTM tests for strength of paper bonding adhesives. Tests for propenies of hot melt adhesives.
See tests in specifications 0-1580 and 0-1874 (under spec- 0-3111. "Practice for Flexibility Oetermination of Hot
ifications, paper). Melt Adhesives by Mandrel Bend Test Method. "
ASTM tests for durability of paper bonding adhesives. 0-3932. "Practice for the Control of the Application of
0-1581. "Test Method for Bonding Permanency of Water- Structural Fasteners when Attached by Hot Melt Adhe-
or Solvent-Soluble Liquid Adhesives for Labeling Glass sives. "
Bottles. " 0-4497. "Test Method for Oetermining the Open Time of
0-1713. "Test Method for Bonding Permanency of Water- Hot Melt Adhesives (Manual Method).
or Solvent-Soluble Liquid Adhesives for Automatic Ma- 0-4498. "Test Method for Heat-Fail Temperature in Shear
chine Sealing Top Flaps of Fiberboard Specimens. " of Hot Melt Adhesives."
0-4499. "Test Method for Heat Stability of Hot-Melt Ad-
hesives. "
Tests Relating to Other Specific
Adhesives and Applications Tests for electrical propenies of adhesives.
0-0816. "Methods of Testing Rubber Cements" (see 0-1304. "Methods of Testing Adhesives Relative to Their
ASTM Book of Standards, Part 09.01). Use As Electrical Insulation. "
0-2558. "Test Method for Evaluating Peel Strength of 0-2739. "Test Method for Volume Resistivity of Conduc-
Shoe Sole-Attaching Adhesives." tive Adhesives."
0-3482. "Practice for Oetermining Electrolytic Corrosion
of Copper by Adhesives."
Tests Related to the Physical and
Working Properties of Adhesives Tests for working and storage life properties of adhesives.
0-1337. "Test Method for Storage Life of Adhesives by
Tests for adhesive composition and chemical properties.
Consistency and Bond Strength."
0-1488. "Test Method for Amylaceous Matter in Adhe-
0-1338. "Test Method for Working Life of Liquid or Paste
sives. "
Adhesives by Consistency and Bond Strength."
0-1489. "Test Method for Nonvolatile Content of Aqueous
0-1382. "Test Method for Susceptibility of Ory Adhesive
Adhesives."
Films to Attack by Roaches. "
0-1490. "Test Method for Nonvolatile Content of Urea-
0-1383. "Test Method for Susceptibility of Ory Adhesive
Formaldehyde Resin Solutions. "
Films to Attack by Laboratory Rats."
0-1579. "Test Method for Filler Content of Phenol, Re-
sorcinol, and Melamine Adhesives."
Miscellaneous adhesive propenies tests.
0-1582. "Test Method for Nonvolatile Content of Phenol,
0-1916. "Test Method for Penetration of Adhesives."
Resorcinol, and Melamine Adhesives."
0-3310. "Practice for Oetermining Corrosivity of Adhe-
0-1583. "Test Method for Hydrogen Ion Concentration of
sive Materials. "
Ory Adhesive Films."
0-4339. "Test Method for Determination of the Odor of
Tests for applied adhesive weight. Adhesives."
0-0898. "Test Method for Applied Weight per Unit Area 0-4500. "Test Method for Determining Grit, Lumps, or
of Oried Adhesive Solids." Undissolved Matter in Water-Borne Adhesives."
 Section B
Adhesive Materials
 6
Animal Glue
ROBERT L. BRANDIS
St. Johnsville, New York

Animal glue has been used as an aqueous ad- Technical gelatin and animal glue, on the
hesive and size for thousands of years, and in other hand, have seen their market share con-
more recent times has also found acceptance as siderably eroded in the last 25 years. This de-
a protective colloid, flocculant, and adhesive cline has been brought about by the advent of
composition. synthetic polymers, which have taken over the
Commercial manufacture dates back to 1690 sizing of synthetic fibers and the binding of pa-
in Holland, 1700 in England, and the early 19th perback books. (But telephone books and cat-
Century in the United States.) By 1900 there alogs have stayed with animal glue because of
were at least 60 producers of animal glue in the its superior durability and flexibility as well as
United States; now there are only two. lower cost.)
Glue is derived from collagen, the major pro- Because of the recent demise of a number of
teinaceous component of animal and fish skins, glue factories in the western world, there is
as well as tendons and the proteinaceous matrix currently a worldwide shortage of glue, partic-
of bones. In recent times the important com- ularly in the higher test grades. At this time
mercial raw materials for making animal glue there are only two manufacturers in the United
come from tanneries, which supply limed splits States: Milligan & Higgins Division, Hudson
and chrome tanned pieces, and from slaughter Industries Corp., of Johnstown, New York,_
houses, which furnish fleshings, hide pieces who make hide glue; and Swift Adhesives (Div.
and bones. of Reichhold Chemicals), St. Joseph, Mis-
The terms gelatin, technical gelatin, and an- souri, who make bone glue. Cattle are the ma-
imal glue refer to similar materials obtained jor source, with rabbits and sheep contributing
from approximately the same stock but through to a much lesser degree. A substantial amount
different treatments. Edible gelatin and photo- of hide and bone glue is imported from Brazil,
graphic gelatin are produced under more strin- Chile, China, and other countries, and finds its
gent conditions, producing a product of way primarily into compounded adhesives and
excellent color and clarity, low ash and low protective colloids. Leading importers of ani-
grease, combined with a very low bacteria mal glue are Hudson Industries Corp., Olym-
count. These gelatins, because of manufactur- pic Adhesives, Inc., Nicholson & Co.,
ing costs, sell for considerably more than tech- Transatlantic By-Products Corp., and Swift
nical gelatin and animal glues. Edible and Adhesives (Div. of Reichhold Chemicals).
photographic gelatins have tended to keep mar- It is estimated that domestic consumption of
ket share and have been the subject of contin- technical gelatin and animal glue is 25-30 mil-
uing research. lion pounds per year. 2

123
124 HANDBOOK OF ADHESIVES

CHEMISTRY hydrolysis, yielding tightly coiled lateral ag-

gregates of peptide chains. Alkali and heat
Animal glue is essentially the hydrolytic prod-
bring about a much more complete cross-link-
uct of collagen, the main protein in animal skins
age breakdown, resulting in randomly coiled
and bones. Collagen as its exists in its natural
peptide chains.
state is water-insoluble and resistant to mild
Veis 3 .4 describes the collagen-gelatin transi-
acids and alkalies as well as proteolytic en-
tion as a stepwise process involving the melting
zymes other than the collagenases. Veis and
of a trihelical network to an amorphous form,
Cohen discuss the structure of collagen:
followed by the sequential hydrolysis of var-
ious types of covalent bonds.
A collagen fibril may thus be pictured as ...
Collagen from different species and even dif-
segments varying in length and cross-section
ferent parts of the same species varies in sta-
area due to differences in the cross-link distri-
bution and the lateral ordering of the polypep- bility to acids, alkalies and heat because of
tide chains ... The segments are chain differences in intramolecular and intermolecu-
networks held together by sets of the acid-sta- lar organization. Glue molecules may be con-
ble or B bonds. These segments contain and are sidered to be polypeptide chains containing
held in the gross structure by the acid-labile A amino acid sequences of varying lengths de-
bonds and physical forces. 3 pending upon the treatment. 5 The amino acid
analysis done by Eastoe, and corroborated by
The conversion of collagen to soluble poly- others, on an ox hide gelatin indicated that there
peptides involves the breaking of covalent are 18 separate amino acids present in varying
bonds and the disruption of physical forces amounts. 6
through the use of either acid and heat or alkali Table 1 agrees within tolerable limits with
and heat. Acid and heat cause selective disrup- that of Eastoe but also characterizes the ionic
tion of some bonds plus selective peptide bond nature of the R-radicals on each amino acid.

Table 1. Amino Acids in Animal Glue. 5

Residues Per
Character of R-Radical
J()OO Total of
Amino Acid All Residues Distinctive Groups Ionic Character
Glycine 335.0 Neutral
Proline 128.0 Pyrrolidine in the chain Neutral
Alanine 113.0 Neutral
Hydroxyproline 94.5 Hydroxypyrrolidine in the chain Neutral
Glutamic acid 72.0 Carboxyl Acid
Arginine 47.0 Guanido Basic
Aspartic acid 46.5 Carboxyl Acid
Serine 35.0 Hydroxyl Neutral
Lysine 27.0 Amine Basic
Leucine 23.0 Neutral
Valine 20.0 Neutral
Threonine 18.0 Hydroxyl Neutral
Phenylalanine 13.0 Phenyl Neutral
Isoleucine 12.0 Neutral
Methionine 5.0 Thiomethyl Neutral
Hydroxylysine 5.0 Amine, Hydroxyl Basic
Histidine 4.5 Imidazole Basic
Tyrosine 4.4 p-Phenylene, Hydroxyl Very weakly
acid

Additional amino acids:?

Glutamine 20 Primary Amide Neutral
Asparagine 20 Primary Amide Neutral
 ANIMAL GLUE 125

Later analyses of calfskin collagen7 show two The intrinsic viscosity is a measure of the av-
additional amino acid residues, glutamine and erage volume occupied by the individual poly-
asparagine, each present in about 2 % concen- mers molecules in dilute solution, where they
tration (by number of residues). The distinctive are in their most random configuration. 11
groups have been added to the table. Stainsby l2 examined the viscosities of mol-
Amino acid residues are amphoteric, con- ecules of an alkali-processed gelatin at various
taining both amine and carboxyl groups that are pH's. At the isoionic point in the absence of
reactive and ionizable. salt, the net charge on a glue molecule is zero
Amide groups may be hydrolyzed to car- and the molecule is in a compact fonn corre-
boxyl and amine by either alkaline treatment sponding to its lowest viscosity in nonnal pH
(leading to Type B gelatin) or extended acid ranges. Alteration of the pH through the use of
degradation (Type A). This loss of amide acid or base results in a net charge that will
groups and its relation to the isoionic point has make the molecule either anionic or cationic.
been studied by Eastoe with the results shown The ionic repulsive charges at these pH values
in Table 2. prevent the chain from assuming a compact
Because glues are amphoteric, they may react shape, thus causing higher viscosity. Subse-
as cations or as anions depending upon the pH quent additions of acid or alkali produce enough
of the medium and the isoionic point of the counter-ions to eventually neutralize the mo-
glue. Prepared by the alkaline process, glues lecular repulsive charges, and the viscosity be-
have a pI close to pH 4.8, while those pro- gins to collapse below pH 3 or above pH 10.
cessed in acid will have apI nearpH 9.0. The
fonner react as cations, the latter as anions. MANUFACTURING
Gelation involves both intramolecular and
intennolecular reorientation upon cooling the Animal glue is the water-soluble product of the
system. Veis,9 among others, concludes that the hydrolytic degradation of water-insoluble col-
collagen fold stability is influenced by solvent lagen fibers. The products of hydrolysis vary
hydrogen bonding. A crystalloid structure is in- greatly in molecular weight (approx. 10,000 to
dicated. Gel fonnation involves the creation of over 250,000), and measurements of viscosity
random primary and secondary bonding; but and gel strength are necessarily average.
intennolecular organization or network fonna- The approximate chemical composition of
tions of gels is stabilized by secondary forces glue is:
such as hydrogen bonding rather than primary
covalent bonding. These bonds show a strong Carbon 50.7%
dependence upon solvent and temperature. Hy- Hydrogen 6.5%
drogen bonding results in a sharp melting tem- Oxygen 24.9%
perature whose value depends upon the number Nitrogen 17.9%
of these bonds that have fonned. 10
Only minor variations on the above composi-
tion are found in glues extracted from dissimi-
Table 2. Relation Between pi and lar stocks and different methods of
Amide Nitrogen. manufacture. 13
Amide Glues in aqueous wann solutions undergo
Material Treatment pI Nitrogen" hydrolysis to lower molecular weights. The rate
Calfskin Unknown- 4.82 1.3 is dependent upon the pH and the temperature.
Eastman Kodak The further the pH is from 7.0 in either direc-
Hide Lime 4.9 6.8 tion, the more rapid will be the hydrolytic ac-
Hide Lime 4.94 7.9 tivity. Glue manufacturers recommend that
Calfskin Lime and caustic 5.15 14.3
Ossein Acid 7.8 35.6 dissolved glue solutions not be kept at temper-
Pigskin Acid 9.4 43.7 atures above l40-l50 o P for extended periods,
Pigskin Acid 9.4 42.9 as this would cause thennal degradation.
'mmolel I 00 g protein Glues are subject to enzymatic as well as
126 HANDBOOK OF ADHESIVES

bacterial attack. Particular care must be taken as hydrochloric, sulfuric, or phosphoric, which
in manufacturing to reduce these effects through should completely permeate the swollen hide.
good manufacturing procedures and the use of The stock is next backwashed with water until
preservatives. The preservatives currently pre- the desired pH is reached. This could be 5-5.5
ferred in the industry are phenols and phenol in order to obtain a pH of 6-7 in the finished
derivatives, zinc sulfate, and other types as in- product. Then the stock is transferred to cook-
dicated by particular industries. ing tubs containing perforated steam coils and
The two categories of animal glue are hide water. The cook involves usually four extrac-
glue and bone glue. Hide glue raw materials tions of approximately four hours each, at pro-
may include fleshings, limed or pickled splits, gressively higher temperatures. Drawdowns
cattle pieces, and chrome-tanned hides and ranging from 2 % to 9% glue solids are ex-
pieces. The producer of either hide glue or bone tracted and filtered. Finally, the glue liquor is
glue strives for greatest yield and cost effi- evaporated to 20-50% solids, depending upon
ciency, resulting in optimum test properties, its viscosity.
including viscosity, gram strength (jelly), pH, In some countries glue continues to be dried
moisture, foam, grease, ash, color, clarity, and in tunnel driers using heat and air which is
odor. passed over jelled sheets, stacked on wire nets
Until very recently a high percentage of hide with air spaces between. Modem driers feed
glue was derived from chrome-tanned skins. jelled noodles, chips or beads on a continuous
Reductions became necessary due to EPA con- traveling screen through heat staged, filtered
straints on chrome eftluent. The tanning agent and conditioned hot air, until the moisture con-
is largely removed by the application of caustic tent is approximately 10-15 %.
and then acid, after which the stock is washed. Limed splits may be placed in soaking vats
This process generally takes 24 hours. The directly for additional liming time, or pro-
stock is then soaked for a number of days in cessed as received depending upon the eco-
magnesium hydroxide and again washed, nomics involved. It is cheapest to cook
maintaining a slightly alkaline pH. The reten- immediately, but the product has lower gram
tion of a slight excess of magnesium hydroxide strength.
during the cook causes any remaining tanning Fleshings, which contain as much grease as
agent in the skin to be precipitated as an insol- glue, are not a significant factor in domestic
uble hydroxide. The resulting glue is very light glue manufacturing at this time.
in color, almost transparent, with a grease con- Bone glues are extracted from the collage-
tent well below 1 %. nous matrix which is the chief organic constit-
A shorter method of chrome glue production uent of all bone. Bone glues fall into two cat-
uses much less water and greatly reduces the egories, extracted bone and green bone.
chemical eftluent. Even though glue yields and Extracted bone glues are prepared from bones
tests are lower, this method tends to be cost- that have been solvent-extracted to remove by-
efficient in areas of high sewage rates. The product grease. Green bones are processed as
method involves starting with a magnesium hy- received from slaughter houses. The bones are
droxide soak as discussed and then cooking in crushed, washed and processed in mild acid in
the usual manner (in four steps as described be- pressure vessels. A series of extractions, alter-
low). The final product is similar to that ob- nating steam pressure in the jacket and sparg-
tained by the previous method, except for ing with hot water, removes the dilute glue
higher ash content (4! % versus 3 %) . liquor, which is then filtered or centrifuged to
Hide pieces and pickled splits as received remove by-product grease. The glue is finally
must be thoroughly washed in cold water over concentrated and dried. The residual bones are
a number of hours to remove salts, acids, offal, utilized as an additional by-product to produce
blood, etc. The stock is then soaked in cold bonemeal fertilizer, which contains approxi-
milk of lime for a number of days or weeks, mately 85% calcium phosphate. Bone china
after which the lime is washed out. The pH is derives its name from the fact that purified bone
then adjusted with a small quantity of acid such residue is incorporated into its manufacture.
 ANIMAL GLUE 127

PROPERTIES Glue can be modified by a variety of chemi-

cal reactions, including acetylation of the hy-
Dry animal glues are hard, nearly odorless ma-
droxyl groups, alcoholysis to yield amino acid
terials ranging from pale yellow to dark amber.
At approximately 260-270°C glue begins to esters, and aryl sulfonation to give complexes
decompose with swelling and charring, evolv- insoluble in water but soluble in organic sol-
vent. Reaction with fatty amines improves
ing dense smoke. Glue retains its characteris-
water resistance. Quatemization yields cationic
tics unaltered if kept dry. Films heated above
molecules. The literature abounds with ideas
100°C for relatively short periods becoine
for modification. 15
water resistant. Normal unmodified dry glue
will absorb 6-8 times its weight of cold water, Animal glue has been compounded with
many materials, e.g., starches, dextrins, sug-
remaining in a jelled form until heated. The
ars, various salts, sulfonated oils, emulsions of
higher the test (viscosity/grams) the higher the
melting point. An extremely useful property of oils, polyvinyl alcohol, polyvinyl acetate; plas-
ticizers such as glycols, glycerine, and sorbi-
aqueous glue solution is its ability to form a
tol; as well as some water-soluble organic
reversible gel upon cooling. This property can
solvents such as butylcarbitol acetate. Viscos-
be modified to advantage by altering concen-
ities can be modified by compounding with
trations and/or adding modifiers.
compatible natural gums, alginates, and syn-
The approximate specific gravity of glue is
1.27. The moisture content is normally 10- thetic thickeners such as carboxymethylcellu-
IS%, ash 2.0-S.0%, pH S.S-8.0, grease con- lose.
Glue manufactured by an acid process, whose
tent 0.2%-3.0%.
pI is approximately 9.0, possesses a jelly
Glues are soluble in water and insoluble in
strength-to-viscosity ratio of 4-S: 1; while al-
oils, waxes, organic solvents and absolute al-
cohol, but emulsification can be achieved in kaline-treated glue whose pI is approximately
both water-oil and oil-water systems. Glue 4.8 has a ratio of 2!-3 : 1.
emulsions serve as encapsulating agents. The melting point of glue and glue compo-
sitions can be varied from below room temper-
Glues can be precipitated in the laboratory by
ature to over 120°F by altering the test of the
absolute alcohol, tannic acid, picric acid, phos-
glue, changing the glue-water ratio, and the ad-
photungstic acid, or a saturated solution of zinc
dition of specific chemicals. Viscosities are
sulfate. Aluminum, ferric, chromic, and mag-
nesium sulfate thicken, coagulate, or precipi- controlled by glue strength, glue-water ratio,
tate glue from solution; mild tannage and total solids, and temperature; glues have good
working characteristics from water-thin to ap-
melting point increases can be achieved with
proximately 70,000 cps.
the proper use of these compounds.
Numerous patents have been granted for sys-
tems involving the insolubilization (cross-link-
TEST GRADES
ing, tanning) of glue. Formaldehyde and
aldehyde donors are effective. Animal glue manufacturers grade their produc-
Glue gives a positive reaction to the biuret tion according to gram strength or jelly
test and also Molisch's test. In the absence of strength, which increases with viscosity. Peter
other nitrogen containing materials, the per- Cooper Corp., one of the earliest and largest
centage of glue is, by commercial agreement, manufacturers of animal glue and gelatin in the
the Kjeldahl nitrogen multiplied by the factor United States, developed the grading system
6.2S. about 1844. Procedures and equipment evolved
Dried films deposited from solutions are con- over the years and did not become standardized
tinuous, resilient, and noncrystalline, and de- until well into the 20th Century.
velop shear tensile strength in excess of 3000 Table 3 cross references the now closed Peter
psi on glue-bonded wooden blocks; indeed, Cooper's code designation with that of Milli-
tensile strengths as high as 10,000 psi have gan & Higgins. This table takes into consider-
been reported for glue films. 14 ation only alkaline-extracted glue, which
128 HANDBOOK OF ADHESIVES

Table 3. Glue Test Grades (Hide Glues).

Bloom Grams
Peter Cooper Milligan & Higgins Millipoise Value
Standard Grade Standard Grade Range Mid-Point (Minimum)
5A Extra 8A 495-529 512 191
4A Extra 6A 461-494 477 175
3A Extra 5A 428-460 444 157
2A Extra 4A 395-427 411 145
A Extra 2A 363-394 379 131
#1 Extra A 331-362 347 121
# 1 Extra Special X 299-330 315 111
#1 2XA 267-298 283 101
lXM 2X 237-266 251 92
IX 3XA 207-236 222 82
I! 3X 178-206 192 72
Ii 4X 150-177 164 62
g 5X 122-149 135 57
1~ 6X 95-121 108 52
Ii 7X 70-94 82 42

accounts for the greatest proportion of hide glue ture content, relative foam value, ash content,
production. and grease content are also of concern.
Bone glues differ from hide glues in method
of extraction, and have smaller ranges of jell
strength and viscosity. The gram strength-vis- CUSTOMER PREPARATION OF GLUE
cosity ratio is quite different, particularly in the SOLUTIONS
medium to high test range where bone glues
The glue manufacturer often feels frustrated
tend to have higher ratios of gram strength-to-
because some customers have inadequate mix-
viscosity, on the order of 4 : 1. (Swift bone glue
ing equipment and/or housekeeping problems.
seems to be an exception, with ratios closer to
Although glues contain bacterial inhibitors the
those of hide glue.) In addition, bone glues tend
situation can get out of control if the equipment
to have slightly lower pH values (5.5) than hide
is not clean, and fresh glue solution is contin-
glue (6.3).
ually run in on the remains of older batches.
The price of glue increases with test grade.
Glues are available in to, 20, or 30 mesh
The higher the test grade, the higher the glue's
granulation. The glue is dissolved in water pre-
viscosity, water absorption, and melting point,
heated to ISO-170°F, in an agitated stainless
the faster it sets to a gel, the more aggressive
steel vessel which has been cleaned to avoid
the tack, and the stronger the dried film.
bacterial contamination from earlier batches.
Concentration ranges from 5 % to 50 %. Large
TESTING
batches are usually processed in jacketed ves-
The viscosity in millipoise is determined by the sels either using electrically heated oil jackets
flow time in seconds through a standard pipette or vented water jackets with low pressure steam
of a 12.5% solution of the glue at 60°C. injection. Smaller vessels usually have electri-
To determine the jelly value, the 12.5 % so- cally heated oil jackets or low wattage electri-
lution is first chilled at to ° C for 16-18 hours. cal elements placed directly on the vessel
Then the gram strength is obtained by the use surface. Agitation is important for rapid and
of a Bloom Gelometer or comparable instru- uniform dissolving of animal glue and its com-
mentation which measures the force necessary pounded forms. Agitators of various types and
to move a 0.5 inch diameter plunger (resting speeds are used depending upon the type of in-
on the surface of the jell) a distance of 4 mm dustry, the viscosity of the solution, and the
at prefixed speed. need to keep foam levels within required lim-
The solution pH is measured at 40°C. Mois- its.
 ANIMAL GLUE 129

LIQUID ANIMAL GLUES Glue test can vary from 135 to 450 gram
strength.
Liquid animal glues are glues modified by gel
Non-warp glues do not have good flexibility ,
depressants so that they remain fluid somewhat
but can possess fairly good "lay flat" charac-
below room temperature. Urea, thiourea, and
teristics through the addition of sugars. They
ammonium thiocyanate are the usual gel de-
can be compounded to yield very strong dry
pressants, incorporated at approximately 8-
films. The major areas of use are in the paper
20% by weight of the total fonnula. The ability
box trade in hand fed, semiautomatic and au-
of this product to stay fluid with nonnal tem-
tomatic covering machines, in the application
perature reduction allows for very slow assem-
of cover stock in the book manufacturing in-
bly time, an important characteristic in the
dustry, in hard notebook binders, phonograph
furniture industry. The final bond is achieved
record covers, hard luggage, etc.
as the water is slowly removed from the glue,
Dry non-warp glues are very similar to non-
increasing its concentration and tack, thus
warp cake glue except that the manufacturer
overcoming the gel depressant effect, then set-
supplies this product as a dry fine mesh mate-
ting and finally drying. The resulting film has
rial which the customer must dissolve in hot
high tensile strength. Further modifications can
water prior to use. Advantages are indefinite
be obtained by the addition of materials such
shelf life and lower shipping cost because of
as clay, calcium carbonate, plasticizers, wet-
the absence of water.
ting agents, etc. Fonnulations may range be-
A dry, moderately flexible glue, patented by
tween 35 % and 65 % solids with viscosities of
M. Konigsberg, contains 8-20% glycerine but
3000-5000 cps at room temperature.
remains free-flowing indefinitely. The method
utilizes the absorptive properties of synthetic
FLEXIBLE AND NON-WARP GLUES alkaline earth metal silicates such as hydrous
calcium silicates (e. g., Micro-cel, J ohns-Man-
Flexible and non-warp glues are compounded ville) and other specially prepared synthetic sil-
animal glues containing modifiers such as su- icas. 16 It has met with considerable success in
crose, corn syrup, dextrin, clay, acid, salt, the bookbinding industry.
magnesium sulfate, glycerine, glycols, sorbi- Viscosity measurements are made by Brook-
tol, water soluble organic solvents, surfactants, field viscosimeter or Zahn cup. Readings of
perfume, and preservatives; in the case of cake solids content, as a means of monitoring vis-
glue, water is added. cosity and water loss, can be made by refrac-
Because of differences in equipment, appli- tometer. Manufacturers of glues and
cation, and end product, the cake glue is tai- compounds can supply customers with viscos-
lored for each user, and further alterations to ity/solids and viscosity/temperature graphs.
the fonnula may even be made to compensate
for seasonal changes in temperature and hu-
GLUE APPLICATION
midity. Properties of importance include vis-
cosity at a particular running temperature (e. g. , Cake glue, compounded dry glue, and straight
135-155°F), speed and degree of tack, and dry glue are utilized at temperatures between
bonding characteristics. Glues supplied as 135 and 155°F (57 and 68°C). Too Iowa tem-
cakes have the advantage of easy meltdown and perature does not allow for good wetting and
may be added directly to the applicator pans. filling of the pores of the substrate before the
Flexible glues are used primarily in book glue sets, resulting in bond failure. Tempera-
binding, including telephone directories, also tures that are too high create prolonged open
in soft luggage and other products where a per- time, with resultant slower productivity. Ele-
manently flexible, strong, resilient adhesive vated temperatures also result in high moisture
film is desired. A good flex product contains loss in the reservoir and heat hydrolysis, re-
approximately two parts glue to one part plas- sulting in weaker glue strength. Dry glues are
ticizer. The higher test glues employ more usually prepared at 25-55 % solids, depending
plasticizer to maintain a desired flexibility. upon the test glue used, the speed of production
130 HANDBOOK OF ADHESIVES

necessary and the type of material to be bonded. of wood products and the fine finishes essential
It is bad practice to dilute high test glue in order to machinery, automobiles, household equip-
to retard gelation. This practice can result in a ment, and appliances.
"starved" glue bond or insufficient dry glue to There are two principal classifications of
perform the job. Instead, gel depressants can coated abrasives:
be added. The materials to be glued must be
1. Sandpapers and sand cloths in rolls,
neither too hot nor too cold. Additional heat to
sheets, bolts, disks, cones, and other spe-
the system can slow adhesion, while a cold
cialties.
substrate can cause premature gelling with poor
2. Set up abrasive wheels, belts, disks,
bonding.
cones, and bobs, generally prepared in the
The woodworking industry observes four
user's own plant for grinding and buffing
time-honored steps:
of metal, plastic, and wooden items.
1. Deposit a thin continuous glue film on the
In the production of coated abrasives there
surface to be bonded.
are five basic steps:
2. Permit the glue film to become slightly
tacky before mating surfaces and apply- 1. The backing material is presized, if nec-
ing pressure. essary, with low test glue or glue/starch
3. Apply uniform pressure. blends. This loading at approximately 35-
4. Continue pressure to insure initial bond 40% solids imparts body and strength.
strength. 2. The presized cloth or paper is fed through
a glue applicator which deposits the mak-
Since it is applied from aqueous solutions,
ing coat in the film thickness dictated by
animal glue is not a filler, and only performs
grit size. The larger the grit size, the
well as an intimate thin film in combining. The
thicker the glue laid down. The making
relationship of viscosity to concentration and
coat takes full advantage of the jelling
test value is shown in Table 4.
characteristic of glue. The glue concen-
Mating porous surfaces requires a heavier
tration can be 25-45 % and may be loaded
bodied (higher solids) glue, while thinner bod-
with extenders such as calcium carbon-
ied glue is indicated for dense, nonporous sur-
ate. The glue grades vary with the appli-
faces.
cation and the type of grit. The higher
grade glues are used for silicon carbide
COATED ABRASIVES
and aluminum oxide, the medium grades
At the present time the largest consumer of an- for emery and garnet, the lower grades
imal hide glue is the abrasives industry. Abra- for flint.
sives are involved in the enormous production 3. The grit is uniformly dispersed upon the

Table 4. Viscosity in Centipoises at 140°F for Dry Glues of Given Grade Test and
Millipoise Value.17
Glue High Test Medium High Test Medium Test Low Test
% Concentration (155 m.p.) (102 m.p.) (63 m.p.) (32 m.p.)

5 3.0 2.4 2.0 1.6

10 8.8 5.6 3.6 2.6
12.5 15.5 10.2 6.3 3.2
15 28.0 17.2 8.4 5.0
20 79.2 46.0 22.4 10.0
25 196 112 49.6 19.6
30 524 264 108 37.6
35 1360 612 224 72.0
40 3216 1320 476 133
50 16320 7240 2400 566
 ANIMAL GLUE 131

unjelled glue film through a gravity feed to lower cost. Glue is ideal for gummed tape
hopper. The grit can be electrostatically because of its fast, aggressive tack, rapid set,
oriented in the vertical position until the permanent bond and excellent machinability.
glue is jelled, by which time the product The open time, tack, set time, wetability, and
is partially dried. strength of bond are often altered, depending
4. A thin film of animal glue, and in some upon the end use, by varying the glue test or
cases a resin, is laid down over the grit, adding modifiers such as dextrin, wetting
further locking it into the adhesive ma- agents, jell depressants, and plasticizers.
trix. Formulations usually have around 50% sol-
5. The abrasive cloth or paper is fed to a ids. The adhesive weight per square foot varies
carefully controlled hot air drier. It is then over a wide range, but typically the dry glue
wound into jumbo rolls for storage and solids amount to 25 % of the weight of the pa-
later cut into various shapes. per.
In the manufacture of gummed tape, large
SET-UP WHEELS rolls of paper are fed through a glue applicator,
where the adhesive at a temperature of 140-
Under the heading of set-up polishing wheels 145°F is applied by the use of pick-up rolls.
are abrasive wheels, belts, disks, and bobs. The The tape is passed under tension over drying
user prepares these on site by laying down a rolls or through a drying tunnel, then stored as
making coat and applying a particular grit. In jumbo rolls until slit and cut into standard sizes
some instances the grit is top coated with a for the trade.
more dilute glue and then carefully dried. Glues
of various test values are utilized as dictated by
GLASS CHIPPING
the severity of the end use. Applications in-
clude metal finishing, glass grinding, granite A unique application of glue has been perfected
finishing, and grinding in the leather industry. in the process of glass chipping. This proce-
dure involves pouring warm glue solutions onto
clean glass and allowing the glue to dry. As the
GREASELESS BUFFING COMPOUNDS
film dries it shrinks and has a predisposition to
Greaseless abrasive compositions are manufac- curl. Since the dry glue is stronger than the
tured as sticks, finding a considerable market glass and the bond formed with the glass is te-
as abrasive compounds for recoating cloth buff- nacious, the glass chips, leaving a rather uni-
ing wheels used for metal finishing. The stick form, floral like design. Lower test glue leads
is held against a revolving wheel where the heat to a finer, more evenly chipped texture. Pat-
of friction melts the compound, transferring it terns and lettering can be formed by appropri-
to the wheel. A layer of grit compound is de- ately covering areas of the glass with metal foil
posited which contains approximately 6-8 % prior to introducing the glue.
high test glue, 24% water, and the remainder,
abrasive grains. SIZING AND COATING
Of particular importance in these sticks is
shelf life. Considerable attention must be paid Glue as a size has been used to advantage for
to chemical preservation, guarding against bac- many years in the textile industry, particularly
terial breakdown which would lead to soft, non- on cotton, rayon, acetate and viscose. The
performing sticks. newer man-made fibers such as nylon, orlon,
and Dynel have in some instances been suc-
cessfully warp sized with animal glue. Com-
GUMMED TAPE
positions containing 2.5-8% glue solids are
Both low test hide glue and bone glue have suitable. Various test grades of glue are utilized
played an important role in the manufacture of depending upon the application. For maximum
gummed tape. Glue has to a certain extent been stiffness, unmodified glues are used. Usually,
replaced by dextrin or combined with dextrin however, the glue is modified with plasticizers
132 HANDBOOK OF ADHESIVES

and softening agents such as glycerine, sorbi- amounts of glue or glue combinations are in-
tol, sugars, sulfonated oils, and wax emul- corporated into the wet paper stock, creating a
sions. The size composition usually contains very slightly tacky film at the drier surface
20-45% lubricants and softening agents. which prevents blowing or lifting to the doctor
In the process of weaving crepe the yams blade as it is peeled off the drum.
used are held in a tight twist by glue while being The process of making paper with the Four-
woven into fabric. Later the glue is washed out drinier machine or paper board with cylinder
during boil-off, thus releasing the twist and cre- machines involves the use of modified animal
ating a creping or pebbled effect. glue as a colloidal flocculant. Incorporated with
Another use is in warp sizing, where the ob- the fine cellulose fibers may be fillers, pig-
jective is to strengthen and coat the yam to be ments, colors, and rosin. By adjustment of the
woven. The glue composition acts as a lubri- pH of the system with acids, alkalies or salts,
cant and a protective coating on the yam to pre- the amphoteric nature of the glue may be
vent breakage and chafing. The composition is changed to a highly charged negative or posi-
later washed out preparatory to finishing and tive colloid. The effective reaction of 0.5-1.0%
dyeing. glue solution on the system is that of floccula-
tion, resulting in enhanced water drainage and
PAPER paper formation. Normal usage rates are ap-
proximately two pounds of glue per ton of pa-
Animal glue has played an important role in the
per.
manufacture of papers and paper products. The
The same type of glue solutions are also em-
important attributes of glue, including film for-
ployed in the Saveall process for recovery of
mation, colloidal properties, and amphoteric
solids by agglomeration in the effluent white
nature, have led to its being used as a sizing
waters of paper mills.
agent, protective colloid, colloidal reagent, and
adhesive.
Glue is a protective colloid for rosin particles COMPOUNDED RUBBER
during beater sizing, particularly when hard Relatively large amounts of glue form the basis
water is encountered. In practice the glue is for the successful use of compounded synthetic
added near the end of the beater operation. The rubber in textile mills. The accepted practice of
paper fiber, with a pH of 4.5 or less, is posi- maintaining heat and humidity in textile mills
tively charged in relation to the glue, whose creates problems of fiber lapping, i.e., winding
charge is negative. The glue/rosin is therefore around the drafting roll during operation. The
attracted to and held by the paper fiber. The addition of approximately 25-50% glue by
addition of small quantities of glue improves weight to compounded synthetic rubber pro-
the internal sizing, toughness, density, forma- duces cots and aprons with a very significantly
tion erasability, and resistance to scuffing of the diminished tendency to lap as long as humidity
final product. is present. This reaction is explained by the re-
Glue improves the wet strength of paper and duction of the electrokinetic or zeta potential
can later be insolubilized, or it may be incor- between the rubber and moisture to near zero
porated with resins that are aldehyde donors by the incorporation of an electrolyte such as
under certain conditions, rendering the glue glue. The zeta potential of approximately zero
water resistant. Glue as a surface size on papers at the rubber-moisture interface of the system
such as fine writing paper, currency, and blue- (fiber-moisture-moisture-rubber) effectively
print stock imparts strength, tear resistance, prevents lapping. 18
folding qualities, moisture resistance, and soil
resistance and prevents feathering of inks.
GASKET MANUFACTURING
For tissue paper made with a Yankee drier,
glue or a combination of glue and polyvinyl al- Gaskets have long been made from selected pa-
cohol is well established as an aid. Small per products of various thickness and density
 ANIMAL GLUE 133

impregnated with animal glue. The object is to a blanket of foam on the bath suppressing the
produce a gasket that is water and solvent re- evolution of fumes.
sistant, flexible, compressible, resistant to dis-
tortion, and easily cut, one that provides a tight OTHER APPLICATIONS FOR ANIMAL
seal and will not fuse to the body. GLUE
The process involves the saturation of the pa-
Technical gelatin (high quality animal glue) of
per stock by floating it across a tank containing
relatively low test is being used successfully in
a glue/plasticizer solution, then passing through
microencapsulation. The gelatin can be used to
squeeze-rolls to remove excess liquid. In a sec-
encapsulate many materials as long as the latter
ond pass, the wet impregnated paper is moved
do not react with or invade the thin film of gel-
through a bath of curing agent and (optional)
atin surrounding them.
plasticizer. The paper is then dried and later cut
CarbonIess paper uses the technique of gel-
into shapes. The final product is flexible,
atin encapsulation of ink, whereby the appli-
waterproof, etc. Variables include paper type
cation of pressure ruptures the gelatin
and thickness, glue test, and formula modi-
microspheres, releasing ink to a copy.
fiers.
In the manufacture of printer's rollers, glue
is compounded with glycerine/sorbitol, water,
MATCHES and a curing agent such as hexamine to produce
The match industry consumes animal glue in a tough, flexible, resilient, water resistant,
the manufacturing of "strike-anywhere, " book smooth roller with a long life. The roller is used
matches, and wooden safety matches. Glues of in the printing industry to transfer ink to the
various tests and foam characteristics are spe- impression plate. Glues for this purpose are in
cially formulated. The glue acts as a binder for the 350-450 gram range.
the ignition chemicals, combustible fillers, and Medium-to-Iow test undefoamed glue is uti-
inert materials and is also an important contrib- lized in the production of strong, cellular, light-
uting factor in the formation of a head of cor- weight concrete.
rect density, form, and strength. Technical gelatins are also employed in the
Match glues possess rigidly controlled grease manufacture of protein hydrolysates, an ingre-
content, usually below 0.3% on dry weight of dient in personal care items such as skin
glue. By careful blending, specific foam char- creams, hair shampoos, and cosmetics. Gen-
acteristics can be obtained. These are described erally the gelatin is reduced to a molecular
as foam height, in mm, and foam half-life, or weight under 2000 by the use of enzymes or
the time in minutes for half the foam to dissi- caustic and further combined chemically at re-
pate. The foam creates a uniform porous head active sites to form modified proteins of inter-
which contains oxygen to promote the ignition est to the industry.
and combustion.
REFERENCES
METAL REFINING
1. Bogue, Robert H., "The Chemistry and Technology
Electrolytic metal refining for gold, silver, of Gelatine and Glue," pp. 1-5, New York, McGraw
copper, antimony, and lead is improved with Hill, 1922.
2. Palmer, Arnold (President, Hudson Industries Corp.),
animal glue. Without glue as a modifier in the Interview, December, 1985.
electrolytic bath, the disposition of the metal at 3. Veis, Arthur, and Cohen, Jerome, "A Non-random
the cathode becomes coarse, with the forma- Disaggregation of Intact Skin Collagen," J. Arner.
tion of nodules. These can be eliminated by in- Chern. Soc. 78,244 (1956).
cluson of 0.03-0.15 % glue in the bath, 4. Veis, Arthur, "The Macromolecular Chemistry of
Gelatin," p. 171, New York, Academic Press, 1964.
resulting in a finer particle disposition with the 5. Hubbard, John R., "Animal Glues," in "Handbook
absence of nodules. Some refiners request that of Adhesives." 2nd Ed .• I. Skeist, ed., p. 140, New
the glue not be defoamed so that it can create York, Van Nostrand Reinhold, 1977.
134 HANDBOOK OF ADHESIVES

6. Ward, A.G., "The Present Position in Gelatin and 15. Lower, Edgar S., "Utilizing Gelatine: Some Appli-
Glue Research," J. Photog. Sci. 9,57 (1961). cations in the Coatings, Adhesives and Allied Indus-
7. Piez, K.A., "Collagen," in "Encyclopedia of Poly- tries," Pigment and Resin Technol. pp. 9-14, July
mer Science and Engineering," 2nd Ed., 3, 699, New 1983, and pp. 9-15, August 1983.
York, John Wiley and Sons, 1985. 16. Konigsberg, Moses, to Hudson Industries Corp., "Dry
8. Ward, Ref. 6, p. 58. Flexible Glue Composition and Method of Making
9, Veis, Ref. 4, pp. 304, 305-312, 349. Same," U.S. Patent 4,095,990 (June 20, 1978).
10. Veis, Ref. 4, p. 349.
11. Veis, Ref. 4, p. 72. 17. Hubbard, Ref. 5, p. 146.
12. Ward, Ref. 6, pp. 62, 63. 18. Bayrniller, John W., to Armstrong Cork Co., "Roll
13. Bogue, Ref. 1, pp. 49-50. Cover for Textile Fiber Drafting," U.S. Patent
14. Hubbard, Ref. 5, pp. 141-142. 2,450,409 (October 5, 1948).
 7
Casein and Mixed Protein Adhesives
CAROLYN N. BYE
National Casein of New Jersey
Riverton, New Jersey

The casein, soy protein, and blood adhesives less paintings of the Renaissance. Early use re-
are often considered as a family of adhesives quired only mixing of the wet curd with lime.
because they have some properties in common. Casein was supplied for glue in Switzerland and
Although similar, the chemical structures of Germany in the early 1800s. A century later
these three proteins are different enough to give mixtures of dry casein, lime, and sodium salts
unique properties to the adhesives which are were patented, the first of the convenient com-
made from each. This chapter will primarily mercial dry mixed casein glues, which are
cover the casein adhesives, but will touch also added to water at the time of use. For several
on some of the properties common to the three decades casein was the preferred wood glue for
protein sources and the use of combinations of furniture and plywood-wherever a measure of
casein-soy, casein-blood, and casein-soy-blood water resistance was needed. But casein gave
in the same adhesive. In the matter of termi- way to phenolic resin adhesives (1931-1935),
nology, casein adhesive will be used as a broad urea formaldehyde resin adhesives (1937), re-
term embracing all the adhesives based on cas- sorcinol resin adhesives (1943), and water re-
ein; but for the casein-lime-sodium salt wood sistant polyvinyl acetate copolymers (in the
glue, the colloquial term casein glue will be 1970s). Polyvinyl acetate emulsion adhesives
used. (in the 1960s) became a popular choice where
water resistance was not important. Despite this
strong competition, there is still a steady and
HISTORY
substantial market for casein, as wood glue,
The use of casein and animal blood as adhe- protective colloid, paper pigment binder, foil
sives goes back over many centuries, while the laminating agent, label paste adhesive, etc.
use of soybean flour and other soy products for Animal blood also has old credentials. Ac-
adhesives and binders is a recent development cording to Lambuth, 2 there is evidence that the
in view of its long history as a food. Both cas- Aztec Indians, the ancient people of the Med-
ein and animal blood owe their place in adhe- iterranean, and the people of the Baltic used
sive history to the water-resistant formulations blood as a water resistant structural adhesive.
which have been made from them. There was an increase in the use of blood as an
Casein is the main protein of milk. Salzbergl adhesive in the period from 1910 to 1925, fol-
notes that the adhesive nature of the casein curd lowing the discovery of a method for producing
was recognized in ancient Egypt. It has been dried soluble blood. This use coincided with
identified as the glue in ancient museum pieces the need for water-resistant plywood for the
and in wood backs and frames holding price- airplane industry in World War I. Heat-cured

135
136 HANDBOOK OF ADHESIVES

blood glues were the most water-resistant ply- 1985 to as high as $2.50-2.75 per pound in late
wood adhesives available at that time and re- 1988, with a premium for casein meeting spe-
mained so until the development of phenol- cial specifications. The cost abated somewhat
formaldehyde resin film glues in the early by the second quarter of 1989.
1930s. Blood glues are covered in detail by
Lambuth in Chapter 11 of the second edition of Manufacture of Casein
this Handbook. 2
Commercial casein is obtained from cow's
Soybean flour first came into use as an ad-
milk, in which it is the main protein at about
hesive in the 1920s, when a method was de-
3 % concentration. Most of the casein for ad-
veloped for extracting the oil from the soybean
hesives is obtained by acid precipitation; how-
meal without altering the solubility of the pro-
ever, some is precipitated from milk by rennet,
tein. Soybean flour was widely used as a wood
a preparation made from the stomach of young
adhesive before World War II. It is still an im-
calves. Only the use of acid casein is covered
portant adhesive in many phases of the wood
here, since a very limited amount of rennet cas-
utilization industry, with much of its use in
ein is used for adhesives.
combination with casein or blood or both (see
Acid casein is manufactured by a selective
Lambuth3 in Chapter 10 of the second edition
precipitation process. Skim milk is prewarmed
of this Handbook).
to 42-45°C and acidified with dilute acid. The
acid may be hydrochloric or sulfuric, or it may
CASEIN AS A RAW MATERIAL
be provided by the addition to the milk of a
Current Market Position of Casein bacterial culture which produces lactic acid
from the lactose. According to Spellacy,6 in
All of the casein used in the United States is
some parts of the world sour whey which has
imported. This product has not been manufac-
been permitted to obtain an acidity of approx-
tured in this country since the early 1950s when
imately 1-2% lactic acid by natural fermenta-
the U. S. dairy producers switched production
tion is used as the precipitating agent. After
to non-fat dry milk. This followed the passage
precipitation, the steps followed in the manu-
of the dairy price support program in 1949,
facturing process are: draining off the whey,
whereby the price of non-fat dry milk was sup-
washing and pressing the curd, and finally,
ported while that of casein was not. In the
drying and grinding the casein. 7 Historically,
1980s industrial users in the United States have
lactic casein has been the type used for adhe-
been working with the Committee to Assure the
sives. However, the purity and quality of the
Availability of Casein (C.A.A.C.)4 to inform
product depend more on the structure of the
Congress of the significant contribution of cas-
curd and the thoroughness with which it is
ein to this country's economy, in an attempt to
washed than on the type of acid used. In the
counter the drive by the dairy lobby to impose
last decade all three types of casein-lactic,
tariffs and restrictions on the importation of
sulfuric, and hydrochloric-have been avail-
casein. The industrial users of casein have
able for adhesives.
shown that their use of casein in no way in-
fringes on the sale of dairy products.
Specifications and Typical Analyses for
In 1985 and 1986 the casein sources which
Casein
played a significant role in the adhesive indus-
tries were New Zealand, Australia, France, There are no universal specifications for' casein
Ireland, Uruguay, Russia, and Poland. Argen- as a raw material. Each manufacturing country
tina, one of the major suppliers to the adhesive has its own way of grading its product, usually
industry in the 1960s and 1970s, has cut its cas- based on purity, cleanliness, and solubility. A
ein production to the point that Argentine cas- high quality casein is one which has a high pro-
ein comprised less than 1 % of the casein tein, and a low free acidity, total acidity, ash,
imports in 1985, and none in 1986 and 1987. 5 fat, and lactose, indicating a product prepared
The recent cost of casein to the consumer has under closely controlled conditions. It is low in
risen from an average of 90 cents per pound in insoluble material such as overdried casein par-
 CASEIN AND MIXED PROTEIN ADHESIVES 137

Table 1. Typical Analyses, Industrial Casein Used in the United States. 8

Medium Low
High Grade Grade Grade
Moisture, % 9-13 8-12 8-12
Ash (unfixed), % 0.75-1.8 1.2-2.0 2.0-2.7
Protein (N x 6.38), % 83-88 83-86 82-84
Free acidity, (as % lactic acid) 0.1, max. 0.2-0.7 0.9-1.8
pH value 4.0-5.5 4.0-5.0 4.0-5.0
Dirt content (mg per 100 grams) 0.5-3.0 2-7 8-14
Insolubles (ml per 100 grams) 0.1-0.6 1-2 2-20
Viscosity (15% solids, NH.OH solution), cp 900-1200 800-1200 700-1000

ticles or other protein fractions of the milk. It tle 21, Part 175.105, April 1, 1977, covering
is clean and free of dirt or other extraneous ma- adhesives regulated by the Food and Drug
terial which can contaminate the casein during Administration, states that these regulated ad-
the manufacturing, grinding, or packaging pro- hesives may contain substances classified as
cess. It has a creamy white appearance, the GRAS, subject to the stated limitations of
clean odor of fresh milk, and a low bacterial 175.105. 11
and fungal count.
The high quality casein described above is CHEMISTRY AND PHYSICAL
not necessary for all industrial adhesives. The PROPERTIES OF GLOBULAR PROTEINS
important features for many adhesives are min-
imal viscosity variations and predictable per- Casein, soy, and blood are globular proteins,
formance in a formula. For some applications soluble in water or aqueous acids, bases, or
the particle size is important, and either the salts. The molecules are spherical in shape and
normal 30 mesh casein is specified, or for many made up of heavily coiled (folded) chains of
processes not using heat for solubility, a 60 or amino acids, whose side chains are cross-
an 80 mesh. Tables 1 and 2 give typical anal- linked. 13 Because of hydrogen bonding with
yses for the industrial casein currently in use in each other, the highly polar reactive groups of
this country. 8 Standard methods for testing cas- the amino acids are not available until after a
ein appear in the "Encyclopedia of Industrial dispersion process, which is usually an alkaline
Chemical Analysis," Vol. 9, 1970,9 and in treatment. The usefulness of this group of pro-
TAPPI Monograph 35,1974. 10 teins as adhesives is based on their high degree
Casein is listed as "generally recognized as of polarity in the dispersed state.
safe" (GRAS) in the Code of Federal Regula- Proteins are amphoteric. In neutral solution
tions (CFR), Title 21, Part 182.90, April 1, both the basic and carboxyl groups are gener-
1979, covering substances migrating to food ally charged, corresponding to the dipolar ions
from paper and paperboard products. CFR, Ti- ofthe amino acids. At the isoelectric point dis-
sociation as an acid is equal to that as a base,
so that solubility and rate of migration in an
Table 2. Typical Sieve Analyses on
electric field is at a minimum. 14
Casein,12 Percent (Cumulative)
Proteins are also extremely prone to undergo
30M some form of alteration, described as denatur-
(all in) 30M 60M 80M
ation. Lambuth has described in some depth the
On 20 Mesh 0.1 0 effect of denaturing agents on blood and soy
On 30 Mesh 0.5 6.0 0
protein in Refs. 2 and 3. Many of his expla-
On 50 Mesh 60.0 72.0 10.0 0
On 70 Mesh 1.5 nations apply to casein as well, and will be
On 80 Mesh 86.0 92.0 73.2 8.9 covered in the section on formulation of casein
On 100 Mesh 91.0 95.0 87.2 30.9 glues.
On 200 Mesh 97.0 98.0 98.0 80.4 Soy protein differs from casein in structure,
Passing 200 Mesh 3.0 2.0 2.0 19.6
as shown by Coco and Scacciaferro. 15 In the
138 HANDBOOK OF ADHESIVES

soy molecule, much of the hydrophobic region Table 3. Amino Acid Composition of
is enclosed within the hydrophilic region, so Casein. Wt. %.18.19
that many of the polar groups are unavailable. Hydrophilic, ionizable, acidic
In casein, the hydrophobic and the hydrophilic glutamic acid 22.4
regions are at opposite ends of the coiled chain, aspartic acid 7.1
and the polar groups are more accessible. Coco tyrosine 6.3
and Scacciaferro have been able to restructure Hydrophilic, ionizable, basic
the soy molecule by thermochemical means to lysine 8.2
arginine 4.1
make more polar groups available. They
histidine 3.1
showed that casein can be 90% solubilized at a
pH of 6.5 but this solubility remains unchanged Hydrophilic, non-ionizable
proline 10.6
even if the pH is increased to 12. With the un- serine 6.3
modified soy protein, on the other hand, the threonine 4.9
solubility shows a gradual climb, from 60% at methionine 2.8
pH 6 to 88% at pH 11.5. tryptophan 1.2
The dried blood product which is used for the Hydrophobic
protein blend adhesives is the soluble blood leucine 9.2
valine 7.2
type, which is 80-95 % soluble in water. This
isoleucine 6.1
product becomes strongly adhesive in alkaline phenylalanine 5.0
dispersed form at a lower pH than the soy prod- alanine 3.2
uct. Sulfur bridge
cystine 0.34
CHEMICAL PROPERTIES OF CASEIN Unclassified
Casein exists in milk as the calcium salt, and glycine 2.0
is classified as a phosphoprotein. It is thought
that the phosphoric acid is esterified with the
hydroxyl groups of the lysine chains of the pro- heavy metal ions, such as calcium, aluminum,
tein. Precipitation of casein by the enzyme ren- or zinc. The chelating mechanism is pH depen-
net leaves organically bound phosphate, while dent-the higher the pH, the greater the che-
acid precipitation causes the casein to split off lating capacity. Reaction with metals whose
the calcium phosphate. The ash content of ren- salts are relatively insoluble gives water resis-
net casein is high, about 7 %, reflecting the tance to the casein.
presence of the calcium salt, while that of acid The amino acid composition of casein is
casein is relatively low, about 2 %, with a small shown in Table 3. This breakdown was re-
amount of calcium phosphate as an impurity. 16 ported in 1949 and 1950 by Gordon and co-
The protein structure of the casein molecule workers. ls The classification of the amino acids
was described by Salzberg et al. 17 to consist of into the hydrophilic and hydrophobic groups
chainlike compounds united through the pep- and subgroups was taken from a visual repre-
tide linkage where R may be -H, -CH3 , sentation of the amino acids and side groups of
-C6Hs, -(CH2)4NH2, -CH2COOH, etc.: the casein molecule by N. King. 19

I I PHYSICAL PROPERTIES OF
RCO-I-NH-CHCO-I-NH-CH-COOH
I I I I CASEIN 2o •21
R R
Casein is a granular solid, varying in color from
Ref. 17. Reprinted with pennission.
cream to light yellow, typically having a sweet
Casein will dissolve in basic solutions. These and milky odor. Poorly prepared casein may
solutions can be dried down yielding a soluble have a deeper yellow color and at times a ran-
salt, e.g., sodium, potassium, or ammonium cid or musty odor. The moisture content of cas-
caseinate. The caseinate in solution will chelate ein usually falls between 8 and 11 %, but it is
 CASEIN AND MIXED PROTEIN ADHESIVES 139

not unusual to see ranges from 7 to 13 %. Cas- additional water, while urea-cut solutions have
ein is insoluble in water and most non-aqueous minimal water acceptance. Dried films of basic
media, but it forms colloidal dispersions in solutions are soluble in water, but the dried
aqueous solutions of acids, bases, and some films of urea solutions will not dissolve easily
salts. Some organic substances can also dis- unless the pH is raised by addition of a base.
perse casein. The ones having practical appli- Addition of aldehydes and heavy metal ions in-
cations are urea and the thiocyanates. creases the viscosity and water resistance of
(Although the term dispersion is technically the casein solutions. Dicyandiamide, used in a
correct one when referring to casein treated in basic solution, is a very effective viscosity re-
a manner to break the internal hydrogen bond- ducer, and generally reduces the water resis-
ing, uncoiling the molecule, the term solution tance. The viscosity-temperature and viscosity-
is more frequently used. The two terms will be concentration relationships are exponential.
employed interchangeably in this discussion.) Salzberg22 reported this relationship between
Casein is insoluble at its isoelectric point, pH viscosity and concentration, showing values in
4.6. Although it has minimal solubility around centipoises of 1080, 26,000, and 160,000 for
this point, any success preparing solutions at 15, 20, and 25 % concentrations, respectively.
pH's close to the isoelectric point require very At 25°C a 20% concentration solution may
careful control of conditions. There is a marked hardly flow, but it will be free-flowing at 60°C.
increase in solubility below pH 3 and above pH The variables which affect the apparent viscos-
6. There is little application for acidic casein ity of casein solutions are: concentration, tem-
solutions (those prepared at pH's below 3.0) perature, pH, type of cation, age, and method
and they are seldom used for industrial pur- of preparation-especially the time, tempera-
poses. Basic solutions are typically prepared in ture, and order-of-addition factors. The com-
the 7-9 pH range at concentrations of from 10 plex relationship of the viscosity, type of
to 20%, and show Newtonian properties. At cation, and pH factors was reported by Salz-
concentrations greater than 18 % most solutions berg et al. 23 and is shown in Table 4.
are too viscous to be handled conveniently at
25°C. Casein solutions at 25% solids, prepared
with most bases, are jellies at 25°C. Other Viscosity Factors
Urea can be used to disperse casein at a pH The viscosity of the raw casein and its reactive
of 5.5 to 6.0. It can also be used to obtain a potential upon exposure to metal ions directly
higher solids content, since it has a thinning affect the viscosity of casein adhesives and so-
effect. Basic solutions are highly receptive to lutions. The inherent viscosity depends on sev-

Table 4. Viscosity of Casein Solutions Prepared with Different Alkalies at

Varying pH's. a.b.25
pH
Alkali Added 6 7 8 9 10 11 12
Sodium hydroxide 300 700 900 1000 900 300 100
(NaOH)
Ammonium hydroxide 900 1000 1300 1000 1000
(28.6% N~OH)
Sodium carbonate 1400 1700 2400 3600
(Na2C03)
Trisodium phosphate 800 1200 3200 5700 8000 10300
(Na3P04 . 12H2O)
Borax 700 800 1300 3700
(Na2B407 . 1OH2O)
Source: Ref. 10. Reprinted with pennission.
'In centipoises measured at room temperature.
·Casein concentration 14% by weight.
 140 HANDBOOK OF ADHESIVES

eral factors: the season of the year as it relates are prepared with heat because of many advan-
to the lactational cycle of the herd, the genetic tages, the most important of these being the
makeup of the herd, and the protein content and ability to speed up and control the process, and
the purity of the casein. The casein produced to result in a uniform and stable product. Urea
from milk obtained early season, shortly after has widespread use as a dispersant for casein
the calving, will be twice as high in viscosity and is discussed in the section on label paste
as that produced in late season. Creamer4 de- adhesives. Selection of one or a combination of
termined that in a controlled test, high pH and two or more dispersants, is determined by many
high calcium content of the casein will result factors relating to the intended use of the so-
in a higher viscosity product. Countries which lution, pH range desired, and other agents used
have poor manufacturing facilities frequently in the system. Table 526 shows the percent of
lack control over the temperature and pH of various alkalies needed to solubilize casein.
precipitation, and have inadequate washing Ammonium hydroxide is the most commonly
cycles. This results in a high ash, high acidity, used alkali. It is generally added in excess of
low protein casein, containing a higher per- the amount necessary for solubilization, be-
centage of milk by-products. These caseins are cause frequently some of the ammonia volatil-
lower in viscosity and less reactive in formu- izes in the cooking process; also, excess
lations which use metal ions for added water ammonia has a preserving effect. Frequently
resistance. The viscosity difference between ammonia is used in combination with borax,
these poorer quality caseins and those manu- improving the preserving properties of each.
factured under modern and controlled condi- Studies have shown that although a casein so-
tions shows up more sharply when they are lution made with borax has good biocidal prop-
tested in a higher solids urea solution at a pH erties, at a pH of 6.9 it does not equal the
below 7. It is essential, when testing a casein adhesive and viscosity properties in storage of
lot for suitability, that the viscosity be deter- a solution made with 5 % borax plus 10% am-
mined by running the test within the structure monium hydroxide, which has apH of 9_10. 27
of the formula which is to be used, and with Ammonium hydroxide has also proven useful
the intended dispersant and crosslinking chem- for pH adjustment at the end of the cooking
icals. period. Except for sodium hydroxide, ammo-
nia-cut casein solutions are lower in viscosity
LIME-FREE CASEIN ADHESIVES than those cut with other alkalies. Borax im-
parts a very high viscosity to a casein solution,
Casein is utilized in diverse ways, as an adhe-
and when it is used alone at 12 % on the casein
sive, as a binder, and as a protective colloid
weight, most of the caseins on today's market
and stabilizer for emulsified adhesive systems.
will dissolve at a pH of about 7.0.
Casein is sold as a raw material, and casein ad-
Sodium hydroxide is a strong base and should
hesives are sold in both the dry and liquid
be used in small amounts, just enough to
forms. The useful wood adhesive known as
achieve solubility, the amount needed varying
casein glue, which is formulated with lime and
with different caseins. Generally 2.0-2.5% will
sodium salts, will be addressed later. This sec-
be sufficient to solubilize the casein and will
tion will cover other uses of casein, for which
result in a pH of 7. The amount of alkali needed
the solubilization of the casein is generally ac-
varies with different caseins, so should be
complished with the use of heat, and at lower
worked out in each instance. Table 4 28 shows
pH's than for the lime-containing glues.
the effect of pH on the viscosity of casein so-
lutions prepared with several alkalies. Note that
Preparation of Casein Solutions. General
atpH 9, sodium hydroxide and ammonium hy-
When given sufficient time, casein can be sol- droxide cut solutions are at their peak viscos-
ubilized cold with most alkalies and alkaline ity, but when alkaline salts are used, the
salts, but cold solubilization usually results in viscosity increases continuously as the percent
a lower viscosity product with very little sta- salt increases. The sharp drop-off in viscosity
bility. Most of the lime-free casein adhesives of the solutions cut with sodium hydroxide at
 CASEIN AND MIXED PROTEIN ADHESIVES 141

Table 5. Typical Alkalies Needed to Dissolve Casein, and pH Values of Casein

Solutions. a.26
Alkali, Pans per 100 parts of Casein, by WI.
Alkali Added 2.5 5.0 7.5 10 12.5 15 17.5 20
NaOH 7.0 11.0 12.6
NH40H (26°Be) 7.7 9.2 10.0 10.3 10.6 10.7 10.8
Na2C03 6.7 7.4 8.3 9.1 9.7 10.0 10.2
Na3P04' 12H2O 6.8 7.2 7.4 7.7 7.9
Na2B407' lOH2O 6.8 7.3 7.7 7.9 8.1
Source: Ref. 10, Reprinted with pennission.
"In centipoises measured at room temperature.

pH's above 10 is also of special interest. Po- below:

tassium hydroxide behaves in a similar man-
Parts by weight
ner, with the sharp drop in viscosity coming
between pH 10.8 and 11. Casein 100
H20 555
NH4 0H (26°Be) 9
Preservatives
Biocide *
Casein, as a milk product, is susceptible to mi- *Follow the manufacturer's recommen-
dation for level of selected biocide and
crobial attack, and requires protection with an guidelines on point and method of intro-
appropriate biocide when the product contain- duction.
ing it is to be kept in the liquid form more than
a day. The level of biocide should not be based (1) Using continuous agitation during the
only on the casein present, but should be cal- preparation, charge the water into a jacketed
culated to be effective in the total system of kettle. Add the casein and allow to soak for 10
which the casein is a part. Sodium orthophen- minutes to wet the grains of casein thoroughly.
ylphenate and sodium pentachlorophenate have (2) Warm the casein-water slurry to approxi-
a long history as effective preservatives for cas- mately 43-49°C. (3) Add the NH4 0H and con-
ein products. Less harsh preservatives are the tinue heating until reaching 60°C, holding at
esters of p-hydroxybenzoic acid. Other useful this temperature for 20 minutes or until solu-
ones are chlorinated methylisothiazolin, tribu- bilization is achieved. (4) Cool to 49°C. Most
tyltin oxide, and chlorinated xylenols. Formal- biocides are added at this point. If the aim is to
dehyde is effective, but its use is a concern for prepare a solution with long term stability, ex-
OSHA, and it also causes viscosity increases tend the solubilization period from 20 minutes
because of its strong crosslinking tendency with to 30, and increase the temperature during so-
casein. It must be handled very carefully when lubilization to 71°C. (The extra time and tem-
used with casein. Many new biocides are now perature is necessary to destroy the proteolytic
available due to recent advances in biological enzymes, which could cause viscosity to drift
protection. An appropriate one should be se- down, or sometimes up, during the storage life
lected after considering the use of the end prod- of a casein solution. Enzymatic breakdown of
uct, the environmental impact of disposal of casein can occur in solutions which are ade-
waste, and applicable governmental regula- quately protected with biocide, so this is an ad-
tions. ditional problem to be addressed.)

Preparation of an Alkaline Casein Additives for Casein Solutions 29

Solution
For many purposes the formula and procedure
A formula and the steps in the preparation of a would be modified. A casein solution quite
15 % alkaline dispersed casein solution is given often is high in viscosity and foamy. A casein
142 HANDBOOK OF ADHESIVES

film is brittle and adsorbs water easily. A num- emulsion must be balanced against the unde-
ber of additives have been used. Anti/oams and sired loss in water resistance and tack when too
defoamers include amyl alcohol, silicone oils much casein is used. These applications are
and emulsions, octyl alcohol, tributyl citrate, covered in further detail elsewhere in this vol-
pine oil, and tributyl phosphate. Frequently ume, particularly in the chapter on tackifying
used viscosity reducers are urea, dicyandiam- resins and natural and synthetic rubbers.
ide, and ammonium thiocyanate. The plasticiz- Success in stabilizing a resin with casein is
ers may be divided into true plasticizers, which dependent on following the proper procedure
dissolve in the polymer, and flexibilizing when combining the materials. Levels of var-
agents, such as the resins and latexes which do ious components are given in parts by weight.
not dissolve, but merely form a blend of the The resin (40-43) is dissolved in toluene (10-
two components, acting as a softening agent. 14) in the presence of oleic acid (0.25-0.75).
Plasticizers used for casein are glycerol, sor- Resins can be blended, or toluene may be in-
bitol, latex, glycols, urea, sulfonated oils, creased to achieve the desired viscosity of 25-
water, and resin emulsions. The hardeners to 30 poises and an optimum particle size. The
increase moisture resistance are formaldehyde, potassium oleate plus the caseinate provide a
urea-formaldehyde resin, aluminum formate, versatile emulsifier system which delays the
hexamethylenetetramine, melamine-formalde- break of the emulsion. Then, potassium hy-
hyde resin, lime, glyoxal, zinc salts and ox- droxide (0.15-0.2) in a 2.0-2.5% solution is
ides, and alum. added slowly to form potassium oleate in situ,
followed by ammonium caseinate (1.3-1.5),
added as a 10-15% caseinate solution. When
APPLICATIONS USING CASEIN an ester type resin is used, the caseinate is pre-
SOLUTIONS AND ADHESIVES pared with a low level of ammonium hydrox-
Casein as a Protective Colloid30,31 ,32 ide. To this point there is a high viscosity
water-in-oil emulsion. Then, there is a second
Casein is used widely as a stabilizer and pro- addition of potassium hydroxide (a diluted
tective colloid in latex systems. Ref. 31 gives KOH/water premix) equal to the first, trigger-
formulas for use of ammonium caseinate as a ing an inversion to a low viscosity oil-in-water
stabilizer in a number of latex dipping opera- emulsion, which has a small particle size and
tions-with neoprene latex to make neoprene is very stable. The resin emulsion may then be
gloves and a metal coating compound; with compounded with a latex to produce an emul-
natural latex to make toy balloons, footwear, sion adhesive. When the resin is a hydrocarbon
canvas work gloves, high modulus drug sun- type, the total solids are generally 45.7-50.0%,
dries, and flexible squeeze toys; and with nat- and the pH is 10.3-10.7.
ural latex to make latex molded products.
Ammonium caseinate is used with styrene bu-
Paper Coatings
tadiene (SBR) to make a dry combining adhe-
sive, tile adhesive, and rug, upholstery and Casein and isolated soy protein are the two pro-
linoleum backing; and with natural latex to tein binders used by the paper coating industry.
make shoe adhesives. Potassium and sodium They are normally used in combination with
caseinates are also sometimes employed. When one of the latexes, styrene-butadiene, buta-
used to stabilize latex, the percent caseinate diene-acrylonitrile, or acrylic emulsions. Cas-
solids needed will vary with different latexes, ein and isolated soy dispersions are usually
but in all instances caseinate will increase the compatible with each other; however, in prac-
viscosity. tice, they are not generally combined in the
Casein is also suitable as a stabilizer in resin same formula. The casein coatings show a bet-
emulsions, and as a thickener for anionic emul- ter gloss and strength than the soy coatings. A
sions. On occasion, the resin emulsions are soy protein coating is thixotropic, and a casein
used as tackifiers for the latex systems. The coating Newtonian, although these properties
amount of casein needed for stabilizing a resin may be affected by the use of latex and the
 CASEIN AND MIXED PROTEIN ADHESIVES 143

preparation process. The thixotropy of the soy Table 6. Casein/Latex Paper Coating. 35
coatings gives them the advantage of running Parts by Wt
better on high speed coaters. Because of diffi-
Dry Wet
culties in completely dispersing the isolated soy
protein at a low p H, the preparation of a casein Pigment
cook is simpler than that of a soy protein cook. Coating grade clay 94.0 134.2
TiOz (rutile type) 6.0 8.6
Due to the high pH necessary for dispersion, Binder
frequently, the soy protein cooks must be acid- SBR latex 8.0 16.7
ified after solubilization to bring the p H down. Casein 8.0 53.3
For prevention of flocculation of the pigment Water (Sufficient to yield de-
when the casein or protein solution is added, sired % solids)
the pigment is generally alkalized first, and the Source: Ref. 33. reprinted with pennission.
first portion of the solution is added slowly.
Sometimes casein is combined with starch as a coater, solids would be adjusted to 40-45 %,
binder for coatings for paper board and carton yielding a coating weight of 2-3 Ib per sq ft.
stock. When starch is cooked with casein, the A typical formula for a casein cook is shown
temperature of the cook must be high enough in Table 736 , with choices of alkalies given.
to cook the starch. Generally 71°C is adequate, Due to the volatility of ammonia and in order
and this temperature is acceptable for casein. to assure complete solubilization of the casein
The amount of binder (casein, soy protein, when ammonia is used, Salzberg et al. recom-
or latex) for a paper coating is given in dry parts mended dissolving casein to a predetermined
of binder per 100 dry parts of clay. Usually 16- pH value. The preparation steps are the same
20% binder is used, and the ratio of casein (or as given earlier for an alkaline casein solution,
soy protein) to latex is varied to give desired except that the 60°C temperature is recom-
properties to the coating. Since excessive shear mended for solubilization. The practice of
on the latex results in foam and possible phys- dropping the casein solution into a clean stor-
ical breakdown, the latex should be added after age tank and rinsing out the kettle between
the casein. When the latex is styrene-butadiene batches or at least once a day should be fol-
(SBR), an increase in casein and a decrease in lowed.
SBR results in a higher viscosity at a lower sol-
ids. The reverse effect is used to advantage in Foil-to-Paper Laminating Adhesives
preparing coatings: the latex-to-casein ratio is One of the better known uses of casein is the
increased in order to accommodate a higher manufacture of foil-to-paper laminating adhe-
percent solids. At higher solids, heavier coat- sives. Because of its listing as GRAS by the
ing weights may be applied. The use of differ- FDA, casein is used for much of the packaging
ent latexes and different latex/casein ratios will in the food and cigarette industries.
result in different viscosities, rheology, and
tack. SBR latex adds desirable properties to
Table 7. Typical Mill Formula, Low
pigmented coatings bound with casein, im-
Solids Casein Solution. 36
proving the gloss, the varnish holdout, and the
water resistance. 33 Water 365 gal in clean jacketed kettle
Casein 500lb
A comprehensive discussion of the use of NaOH 16.25 lb, or ]
casein and isolated soy protein in paper coat- N140H(26°Be) 5 gal, or
ings may be found in Tappi Monograph Series NazC03 60 lb, or
No. 22.34 Borax 75lb
Table 635 shows typical paper coating for-
Yield 414.25 gal
mulations with a 50 : 50 SBR-to-casein ratio, Casein solids 14 %, air dry basis
for use on two types of coaters. For a multiple Casein per gal 1.2 lb.
roll coater, water would be added to adjust to Viscosity at 80°F l000-3000cp
a percent total solids of 50-55, giving a coating pH 8.0-8.4
weight of 3-4 Ib per 1000 sq ft. For an air knife Source: Ref. 17. Reprinted with pennission.
 144 HANDBOOK OF ADHESIVES

A typical foil adhesive is made by first pre- Table 8. Typical Label Paste Formula.
paring an ammonium caseinate solution with a Parts by weight
low level of ammonium hydroxide, and then
Water 47-50
combining it with a styrene-butadiene (SBR) Preservative 0.3-0.5
latex with a pH of about 7.0. The pH of the Defoamer 0.5
resulting adhesive should be close to neutral Starch 1.5-3
because of the tendency of high pH adhesives Zinc acetate 0.3-0.5
to slowly eat through the foil. Some proprietary Zinc oxide" 0.5-0.75
Urea (microprilled) 21-23
fonnulations at pH's below 7 contain additives Casein 20-25
to increase water resistance. To make a simple Ammonium hydroxide 1.0-1.6
casein-latex foil laminating adhesive: (1) Dis- (26°Be)
solve 20 parts of casein in 78.75 parts of water, 'Zinc oxide is usually added as a 50 % dispersion
using 1.25 parts of NH40H (26°Be) as the dis-
persant. (2) Combine 16 parts of this 20% am-
monium caseinate solution with 52 parts of SBR
points of introduction of the various raw ma-
latex. (3) Add two parts of defoamer as needed,
terials and the heat-up, cook, and cool-down
one of a sulfonated wetting agent, and 0.5 of
periods. A recommended order of addition for
preservative. (4) Add water to a total fonnula
the fonnula given is: H20, zinc oxide, zinc
weight of 100. The SBR should be non-carbox-
acetate, preservative, defoamer, starch, urea,
ylated with 25-50% styrene, with rosin acid as
casein, and ammonium hydroxide. It has been
the protective colloid.
established that for the primary components,
use of the order: ammonium hydroxide, urea,
Ice Water Label Paste Adhesives
and casein, gives a very unstable product,
Ice water label paste is a very specialized water- which tends to increase in viscosity sharply for
based casein adhesive which is used primarily several days, and then to drop off just as
to adhere paper labels to beer bottles. The la- sharply. The typical cook temperature is 77-
bels must remain attached if the bottles are 80 a C. This temperature is held for 15-20 min-
chilled in ice or otherwise subjected to wet con- utes before initiating the cool-down period.
ditions, but they must wash off reusable bottles A small fonnula change can make a large
easily with hot water. Casein is dispersed with change in properties. Increased zinc oxide will
urea at an approximate 50 : 50 ratio in the give faster drying, but will shorten shelf life.
presence of ammonium hydroxide as an addi- Usually, to get a faster drying time, the gel de-
tional dispersant. The high percent casein sol- pressant is decreased and the casein is in-
ids in this type fonnulation is possible because creased, but a shift in this direction will shorten
of the urea, which acts as a viscosity reducer. the shelf life. A very short shelf life is known
The urea, sometimes along with ammonium in the industry as setback, and is a major prob-
thiocyanate, functions also as a gel depressant. lem when it occurs. The experienced fonnula-
Zinc oxide and zinc acetate are used to cross- tor balances the fonnula to gain the best
link and provide water resistance. A defoamer compromise in properties. A successful label
and a preservative are always included. Starch paste must also meet the special running con-
is one of several agents incorporated to shorten ditions of the machines which apply the labels
the thread of the adhesive to improve its per- at a fast speed. Various grades of casein, and
fonnance on high speed labelling machines. even different lots within a grade, may perfonn
Because the fonnulas in commercial use are differently. It is helpful to use a test for the se-
proprietary, the one given in Table 8 gives typ- lection of casein which relates to the fonnula
ical ranges, not specific percentages. The com- in which it is to be used.
pounding of the components is of equal Specifications for viscosity, speed of set, and
importance to the fonnula. A successful order water resistance vary with the consumer. Table
of addition must be established, along with a 9 gives the typical ranges for the properties de-
time-temperature log which relates to both the sired in a label paste.
 CASEIN AND MIXED PROTEIN ADHESIVES 145

Table 9. Typical Specifications for Ice Chemistry of Protein Blend Glues

Water Label Paste.
The key to formulating protein adhesives is un-
Viscosity 4S,000-7S,000 cp @ 80°F (27°C) derstanding what happens to the protein under
Solids 48-S0% the influence of alkaline dispersion and in the
pH 7.S-8.S
Setting time Fiber tear in 30 seconds
presence of denaturing chemicals and condi-
Water resistance Pass 24 hr soak in water @3soF tions. Lambuth 38 discusses the complex chem-
(20C)a ical process. At a p H of 11-12 the protein
Shelf life 3-6 monthsb molecules are almost completely and irrever-
'Label is adhered to bottle and is dried for 24 hours before soaking. sibly uncoiled, freeing their reactive and polar
Label must not flag off the bottle following 24 hr soak. groups for adhesive bonding. Hydrolysis into
"The shelf life must hold at a stable viscosity with no sharp climb
or drop for this period of time. peptones, peptides, and amino acids further en-
hances the adhesive potential, but with loss of
water resistance and bond strength, unless the
Miscellaneous Uses for Casein Adhesives formulator intervenes. Alkaline dispersion pro-
ceeds rapidly, hydrolysis more gradually. Thus,
A casein-lime adhesive and other casein based viscosity rises quickly from a low to a high pla-
adhesives are involved in a cone winding pro-
teau from which it will subside to a low value
cess bonding paper to paper. The cones are
again over several hours. It is up to the for-
used by the textile mills as yam carriers. There mulator to build into the formula a few hours
are some specialty manufacturers of stable cas- of relatively level viscosity. This is much eas-
ein solutions who sell their products for varied ier with casein than with soy flour and blood,
applications. because the casein glues do not demonstrate a
A casein coating on steel is one step in the rise in viscosity as rapid as that shown by the
manufacture of aperture masks for color TV other two protein sources. With proper formu-
tubes. 37 Casein is also used as a partial binder lation, it is possible to obtain several hours of
in some types of caulking adhesives. fairly level viscosity with casein, before hy-
drolysis takes over, or before certain formula-
tions carry the casein glue to a gel. Casein
CASEIN AND PROTEIN BLEND GLUES makes an excellent contribution to the water re-
AS WOOD ADHESIVES sistance. Addition of blood increases the water
The wood adhesives discussed here will be the resistance even more, but soy flour causes a de-
casein-lime-sodium salt glues and similar glues crease.
formulated with combinations of casein with Proteins are extremely prone to undergo a
soy flour, blood, or both. The pH of these ad- form of alteration described as denaturation.
hesives is 11-12, due to the lime, sodium hy- The elements which cause denaturation may be
droxide, and sodium salts used for dispersion. chemical or physical. The chemical agents of
Casein can be dispersed with a number of al- importance are: (1) the agents used for adding
kalies at pH's of 7 and above, and with urea, water resistance-lime, metal salts and oxides,
an amide, at about pH 6. Isolated soy protein formaldehyde and formaldehyde donors-and
can be dispersed at a slightly higher pH. How- (2) organic chemicals such as alcohols and ke-
ever, soy bean flour, the product used in the tones which block the action of the crosslinkers
protein blend glues, requires a highly alkaline by reducing the polarity of the solvent. The
treatment in the pH range of 11-12. Animal physical agent which is of importance is heat
blood can be dispersed in water to a certain de- or any mechanical situation such as grinding or
gree, but for complete dispersion, alkaline friction which develops heat. 38
treatment is also required. The use of the high
pH alkalies has proven to be the successful Formulation and Chemistry of Casein-
route with this group of wood adhesives, be- Lime Glues
cause in addition to the dispersion factor, the The simplest formula for casein glue includes
lime provides water resistance. casein, light mineral oil, lime, and sodium
146 HANDBOOK OF ADHESIVES

salts. The choice of sodium salts is restricted dium salts increases, the level of water resis-
to salts of acids whose calcium salts are rela- tance will increase. Formula 1 in Table 10 has
tively insoluble. The sodium salts also cannot water resistance, while Formula 2 has none.
be hygroscopic and must not be capable of re- It is the balance between the equivalents of
acting with the casein, lime, or other chemicals sodium salts and lime that controls whether or
in the dry state. The addition of oil retards the not a glue gels. Within a given formula, when
interaction of the casein particles with the using the same glue powder-to-water ratio and
chemicals until they can be completely wet out the same casein content, incremental increases
and also reduces the dustiness of the powdered in sodium salts, lime, or both, can carry the
casein glue. Upon addition of the dry glue glue from a gel to a nongelling glue. The vis-
powder to water, the lime (calcium hydroxide) cosity of a gel glue increases rapidly, so most
and the sodium salts dissolve, yielding a highly casein glues that gel have limited pot lives, an
basic solution. The sodium hydroxide, which undesirable feature. Formerly some casein glue
is more reactive than the calcium hydroxide, specifications required a gel glue to assure that
disperses the casein, yielding essentially an the glue had water resistance, and to prevent
ionized sodium caseinate. There is a slow re- use of the glue after hydrolysis set in. The gell-
action between the sodium caseinate and the ing carried the glue through an unusable stage
excess lime, and the sodium caseinate slowly before the glue hydrolyzed.
converts to the insoluble calcium caseinate. A In the earlier classification of casein glues by
simultaneous reaction is the hydrolysis of the water resistance, a gel glue was the only ex-
casein molecule, a process which continues at ample given for a glue which had water resis-
an even slower rate. tance. A glue which gelled only by the loss of
The typical sodium salts include sodium water was described as non-water-resistant. 4o
fluoride, trisodium phosphate, soda ash, so- However, very water resistant casein glues
dium bicarbonate, sodium sulfite, and others. which do not progress to a gel are available to-
The lime and sodium fluoride are essential for day. With these glues the excess lime is the
ready liquefaction of the glue. Casein may be primary key to the water resistance. Also, the
dissolved with only lime, but this type of ad- mix ratio of water to dry powder influences
hesive remains fluid only a short time before whether the mixed glue demonstrates the gel
gelling. Additives, including defoamers and tendency.
zinc compounds, and extenders, such as clays, Some of the older literature speaks of a cas-
wood flour, and shell flour, are frequently used. ein glue going through a very heavy stage be-
The experienced formulator can customize a fore breaking down to a usable glue. current
glue to perform specific jobs. At times a fast formulations may be slightly heavier during the
setting glue is important, but under other con- first 10 to 20 minutes after mixing with water,
ditions, the glue must allow longer assembly but the bodying up described for earlier for-
time under warm conditions. The most suc- mulations is not evident. This might be due to
cessful formulas are closely guarded propri- the better quality of the casein available today
etary information. By finding the optimum bal- or to advances in formulating.
anced levels of sodium salts and lime, it is pos- Casein from different countries of origin and
sible to control the viscosity of the wet glue in even different lots from the same country can
a manner which will provide a reasonable affect the viscosity pattern of casein glue. To
working life at a fairly level viscosity, and at maintain a predictable performance, minor for-
the same time provide a glue with good dry and mula adjustments must be made routinely.
wet strength over the usable life of the wet mix. These highly alkaline glues are not as sus-
The formulation of casein glues was de- ceptible to microbial attack as are the lower p H
scribed by Brown and Brouse. 39 Using 100 casein adhesives; however, addition of a fungal
parts of casein as a constant, when the gram inhibitor is recommended for a glue to be used
equivalents of lime and sodium salts are equal, for a structural application. Salzberg warns that
the casein glue will have no water resistance. it should be clearly understood that fungal in-
As the excess equivalents of lime over the so- hibitors protect only the glue line and the ad-
 CASEIN AND MIXED PROTEIN ADHESIVES 147

Table 10. Formulas for Casein and Casein-Blend Glues (Dry Mix Type).42.43
Formula
Formula Formula No. 3 Formula
No. 1 No. 2 Casein-Soy No. 4
Materials Casein Casein Blood Casein-Soy
Casein 59.1 70.8 36.0 15.0
Light mineral oil 3.6 3.6 2.6 3.0
Lime, hydrated 17.7 9.4 18.0 12.0
Sodium fluoride 2.5 2.8 2.5 3.0
Trisodium phosphate 11.2 9.0 7.6
Sodium carbonate 3.8 5.0
Sodium sulfite 3.7 4.4
Soluble Blood 2.0
Soy flour 24.0 57.0
Wood flour 1.0 5.0
Bentonite 1.2 3.5
Total Dry Parts by 100.0 100.0 100.0 100.0
Weight
Water 165.0 200.0 200.0 250.0

jacent wood, not the bulk of the glued struc- or sodium silicate solution was added, liquids
ture, which can support fungal growth unless which could not be incorporated into the dry
separately protected. Because of leaching, a mixes. Also, the components could be added
gradual loss of fungal protection may be ex- in the most advantageous sequence. The dry
pected when water soluble biocides are used. 41 mixes, however, had the strong advantage of
Sodium pentachlorophenate is the fungicide convenience, and replaced the wet mixes over
with the longest history of successful use with the years. Formulas for preparing wet mixes are
casein glue, typically at 3 % on the dry powder. given in the second edition of this Handbook,
In recent years only the glues that had to meet Chapter 10, Soybean Glues, and Chapter 11,
government specifications requiring a fungal Blood Glues.
inhibitor have been protected, because of in- The usual mix ratio for casein glue is 2 parts
creased concern about environmental impact of of water to one of dry glue powder; however,
this type biocide in waste. Since recent Envi- some casein-soy glues need a mix ratio as high
ronmental Protection Agency (EPA) regula- as 2.5 : 1. Two kinds of mixers are used: a high
tions, no biocide is being used in casein glue. speed double propeller type and a slower pad-
See the Adhesive Specifications section of this dle type. With the preferred high speed type,
chapter and Ref. 45. Use of other, safer fun- the water is charged and the powder is added
gicides is being investigated. In addition, other as fast as the mixer can introduce the material.
means, such as paint and epoxy coatings, plus With the low speed mixer, frequently a portion
protection from humid conditions, are being of the water is withheld, the lumps are rubbed
used to protect most casein-glued laminations out by agitation of the heavy mix, the remain-
from biological attack. der of the water is added, and the glue is mixed
to uniformity. For both types of mixers, the
glue is allowed to stand 10 to 15 minutes to
Mixing Casein Glue
allow time for the casein to dissolve, and is
The formulas given in Table 10 are for the dry mixed again for several minutes before using.
mix type of casein and protein blend glues Casein glue develops an exothermic reaction
which are currently in use in the United States. when added to water, so the temperature of the
Several decades ago, the practice of formulat- water used should be about 5-6°C cooler than
ing these glues as wet mixes was widespread, the desired temperature of the wet mix. Typi-
an approach which made a wider range of ad- cally, 18°C water is used to give 24 °C glue.
ditives available. Frequently a phenolic resin Hot water should not be used.
148 HANDBOOK OF ADHESIVES

Additives for Casein and Protein Blend glues. A level of 30% furfuryl alcohol, based
Glues on the dry casein glue, has been found to be
effective, although lower levels will also ex-
Latex. The bonds achieved with these glues
tend the assembly time of the glue to a lesser
may be improved with two classes of additives.
degree. There is some use of diacetone alcohol
Latex is used widely to improve the bonding of
for this purpose, but it is less effective than fur-
difficult-to-glue skins. The problems with these
furyl alcohol. These additives are sold under
skins are manyfold, usually caused by high
the trade names assigned by the adhesive com-
density wood, by extractive heartwood, by
resin which has been brought to the surface panies promoting them.
when the plywood has been manufactured in
hot press, or by glazed surfaces caused by dull Uses of Casein Glues
knives used to cut the veneer. Latex is fre- The casein wood glues have a long history of
quently added to the casein-soy blend glues to use as interior structural adhesives, assembly
improve the bond. It gives a plasticity to the adhesives, and panel-to-frame adhesives. A
glue line, a feature which reduces the brittle- limited but important use is as a nonconductive
ness of the cured casein or protein glue line, adhesive in the construction of spacers for the
helping, as the lamination ages, to retain the large transformer boards for the electrical in-
normally high early (green) strength of the dustry. The most popular use of casein and pro-
glueline. tein blend glues is in the production of hollow
The recommended latex for use with both and solid core flush doors, an operation for
casein and protein blend glues is a carboxy- which these glues are ideally suited. Most of
lated styrene-butadiene, with a styrene content the doors in this country are made with this type
of 60 to 65 %. When this latex has a pH of 7.5- of glue.
8.5, it will increase the viscosity of the base Flush doors are produced by bonding
glue and sometimes will require a higher dilu- "skins" of plywood, hardboard, or particle
tion of water. When the latex has a pH of 9.0- board to the vertical and horizontal frames (the
9.6, the effect on viscosity will be minimal. The stiles and rails), which are usually either a soft
latex must be added to the mixed casein or pro- wood such as fir or a man-made product com-
tein blend glue, not to the water. The typical prising layers of pressed board. Hollow core
addition is one gallon of latex for one 50 lb bag doors utilize an accordion-type paper core,
of glue. while a solid core door is constructed with a
core of pieces of scrap wood edge-glued with
Furfuryl Alcohol. The use of furfuryl alco- an inexpensive casein-soy glue. Some of these
hol is recommended to counter the effect of cer- cores are held to shape by corrugated card-
tain acid-treated fire retardant woods and is board, which is bonded to their surfaces with
covered by U.S.A. and Canadian patents. 42 the same type of protein blend glue.
This type additive extends the allowable as- Fire doors are usually constructed by bond-
sembly time by delaying the gelling action of ing plywood to a frame of fire-retardant-treated
the acid salts on the alkaline casein glue. The stiles and rails, made with either hard maple or
alcohol retards the reaction of the acid salts in a man-made hardboard, this frame having been
the fire-retardant-treated lumber with the alka- fastened around a fire-resistant mineral core.
line casein glue, and at the same time slows Casein and casein-soy blend glues with and
down the formation of calcium caseinate, which without the furfuryl alcohol additive are the
has a viscosity-building effect. Use of furfuryl primary adhesives currently selected for use in
alcohol reduces the ratio of water to dry pow- these operations.
der needed to mix the casein glue. Furfuryl al-
cohol is recommended for use with casein glues
Specifications Applying to Casein Glue
or with casein-soy flour blend glues where soy
flour is only a minor fraction of the protein. It The specifications most frequently used for
is not recommended for the high soy content casein glue are of two types: those specifically
 CASEIN AND MIXED PROTEIN ADHESIVES 149

written to apply to the generic adhesive, and sociation. (A copy of Series 8, "Wood Doors,"
industry specifications which control the end may be obtained from NWWDA, 20S W.
products for which casein glue is normally Tough Ave., Park Ridge, IL 60068.) The glue
used. lines of a finished door are tested for compli-
ance with either: Type I, "Exterior Use," a
Adhesive Specifications. There are two two-cycle boil test, or Type II, "Interior Use,"
ASTM specifications covering casein glues: 44 a three-cycle soak test. Casein glue is used to
(1) ASTM D 3024-84, "Standard Specifi- bond the skin (frequently plywood) and the
cation for Protein-Base Adhesives for Struc- frame, while other adhesives are used between
tural Laminated Wood Products for Use Under the plies of the plywood, so if delamination oc-
Interior (Dry Use) Exposure Conditions." A curs, it is important to pinpoint the location.
request to drop this specification is currently in Casein glue easily passes the Type II speci-
the balloting process. No conforming glue is fication. Casein-soy blend glues pass Type II if
currently being manufactured commercially for the percentage of soy flour is not too high.
several reasons: a decreased demand for casein There are some highly water resistant casein
glue for structural purposes, availability of so- glues that pass the Type I specification. Some
dium pentachlorophenate only in the dusty of these glues are currently being used for ex-
powdered form (beads no longer available), and terior doors, although it is recognized that the
a recent EPA withdrawal of the registration of doors must be painted or coated with a material
sodium pentachlorophenate for this application which is impervious to water or humidity. It is
and others. 45 important not to equate the NWWDA Type I
(2) ASTM D 4689-87, "Standard Specifi- bond with other much more highly water re-
cation for Adhesive, Casein-Type" - This sistant Type 1 adhesives, such as the cross-
specification is a replacement for Federal Spec- linked polyvinyls, resorcinols and melamines.
ification MMM-A-12S-D, "Adhesive, Casein
Type, Water and Mold Resistant. " 46 Upon ac- Canadian Specifications. In Canada, CSA
ceptance by the government, ASTM D 4689- Standard for Wood Adhesives No. 0112.3-M
87 will be the designated specification regulat- 1977 covers the specifications for casein glue.
ing the testing of casein glues for purchase by Glue line requirements for wood doors are cov-
the Federal government, or for use by agencies ered in CSA Standard 0132.2-M 1977. (Copies
filling government contracts. The new specifi- may be obtained from Canadian Standards As-
cation covers three categories: Class A, Water sociation, 178 Rexdale Blvd., Rexdale, On-
and Fungal Resistant; Class B, Water Resist- tario, Canada, M9W lR3.
ant; and Class C, Dry Use (a new classification
which will not require a test for water resis- Viscosity and Pot Life
tance). No conforming glue is currently being In addition to the bonding properties, casein
manufactured to meet Class A, but ASTM D glue manufacturers pay close attention to the
4300-88, "Standard Test Methods for Ability viscosity and pot life of their products, when
of Adhesive Films to Support or Resist the mixed using the recommended ratio of water to
Growth of Fungi", may be used to test new dry powder. A glue with a four hour pot life
biocides for compliance with the fungal resis- when tested under laboratory conditions will
tance requirements. To meet the ASTM last approximately two hours in a plant situa-
strength specifications, casein glue is tested tion, when subjected to the agitation of a
with laboratory prepared birch plywood (ASTM spreader. Because the glues containing soy flour
D 906) and maple block (ASTM D 90S) spec- are more thixotropic, they are made in a slightly
imens. higher viscosity range; see Table 11.
Industry Specifications. The manufacture
Certification of Fire Doors
of doors in the United States is controlled by
NWWDA Industry Standard, IS 1-86., written Adhesives for use in making fire doors must be
by the National Wood Window and Door As- tested and certified within a licensed construc-
150 HANDBOOK OF ADHESIVES

Table 11. Viscosity Pattern of Casein and Casein-Soy

Glues. 47
Viscosity. cp @ 25°C'
Hours Minutes b Casein Glue Casein-Soy Glue
20 4500 6500
1 3800 5000
2 3600 4800
3 4000 5500
4 6000 8000
"Tested with a Brookfield rotational viscometer.
"Timed from the introduction of the glue powder to the water.

tion system, currently available from four com- a few hours later. Low temperature bonding re-
panies: Weyerhaueser, Georgia Pacific, Cal- quires a longer press time because of slower
Wood, and Masonite. The two certifying agen- curing time.
cies for fire doors in the United States, War- Some of the earlier work of Browne and
nock Hersey (W-H) and Underwriter's Brouse was reported in Ref. 1 by Salzberg. 48 •
Laboratories (U.L.), have lists of approved ad- 49 Joints bonded with casein glue will average
hesives for each licensee's fire door construc- better than 90% wood failure when the follow-
tion, for 20, 45, 60, and 90 minute fire doors. ing softer wood species are used: redwood,
The 20 minute fire doors are solid core doors, western red cedar, white fir, Sitka spruce,
and do not require the special frames and min- southern cypress, western hemlock, eastern red
eral cores of the other fire doors; but they still cedar, chestnut, red alder, and northern white
require W-H or U.L. approval. pine. With the harder woods-red oak, maple,
white ash, yellow birch, and persimmon-the
Properties of Casein Glues joints will show 30-50% wood failure.
The highly alkaline casein-lime-sodium salt
Casein glue is known as a very forgiving glue.
glues have a tendency to stain oak, maple, and
It can be used under warm conditions at am-
some other species, a problem especially con-
bient temperatures as high as 100°F and under
spicuous in thin veneer. Discolored wood may
cold conditions, at temperatures in the range of
be treated with sodium perborate and stained
40°F. Because improved water resistance is re-
glue lines may be bleached with a dilute solu-
lated to a faster curing cycle, bonds developed
tion of oxalic acid. It is better, however, to
at lower temperatures will show less water re-
avoid staining by preventing bleed-through.
sistance than bonds developed at the optimum
This may be accomplished by using drier stock,
60-80°F. It has also been demonstrated that
thicker glue, by releasing pressure sooner, and
with even warmer ambient temperatures, in the
by drying the assembly immediately after
90-l00°F range, the water resistance will in- pressing. 50
crease as the speed of cure is increased. 56 How-
ever, because of more rapid loss of moisture in
Durability of Casein Glues
the glue line under warm conditions, allowable
assembly time is shorter. Casein glue works In studies by Selbo and Johnson for Forest
well with an assembly time which can vary Products Laboratory, six types of joint designs,
from less than 10 minutes to over 30 minutes, prepared with ten different adhesives, were
a feature which is used to advantage in the door subjected to three different humidity cycles over
industry, where a stack of 40 to 50 doors is a period of three years. In maple wood joints
built before applying pressure. At temperatures bonded with casein glue containing preserva-
of 65-80°F, sufficient strength will develop so tive, the side grain-to-side grain joints retained
that the stack may be removed from pressure the highest strength. 5 1.52
after only 25 minutes, and may be trimmed only Although the dried casein glue l~ne is hard
 CASEIN AND MIXED PROTEIN ADHESIVES 151

and brittle, high frequency vibration of lap 172-173, New York, Van Nostrand Reinhold Co.,
joints for 40 hours did not affect their strength. 1977.
4. C.A.A.C., 214 Massachusetts Ave., NE, Suite 520,
Glue lines 0.02 in. thick held up better than Washington, DC 20002.
glue lines 0.002 in. thick, although initial shear 5. Special Foreign Trade Statistics Report, U. S. General
strength was higher for the thinner glue lines. 53 Imports, 1985, TSUSA Commodity Number
Casein glue has a history of use as an adhe- 493.1200, "Casein."
sive for interior structural laminated products, 6. Spellacy, John R., "Casein, Dried and Condensed
Whey, p. 402, San Francisco, Lithotype Process Co.,
beams, trusses, girders, and columns. As evi-
1953.
dence of the durability of the bond, there are 7. Bye, C. N., Casein, in "Encyclopedia of Industrial
structures laminated with casein glue which Chemical Analysis,"·F. D. Snell and L. Ettre, eds.,
have been standing since the 1930s. The du- Vo!. 9, p. 1., New York, Interscience Publishers, Div.
rability of the casein bond on wood increases of John Wiley and Sons, 1970.
when the preservative sodium pentachloro- 8. Data supplied by the laboratory of National Casein of
New Jersey, using test methods developed by ASTM
phenate is used to protect the glue line from the Committee D 25, and appearing in ASTM Standards,
growth of fungi, a problem in the presence of Part 15,1970, now out of print. Summaries of the test
conditions of heat and moisture. Selb054 found methods appear in Ref. 7.
that Douglas fir beams far outlasted Southern 9. Ref. 7, pp. 8-14.
10. Salzberg, H. K., Britton, R. K., and Bye, C. N., Cas-
pine beams, both bonded with casein glue
ein Adhesives, in "Testing of Adhesives," G. Meese,
without preservative, perhaps because of the ed., Tappi Monograph No. 35, Chapter 2, pp. 31-39,
lower moisture content of the fir at the time of Atlanta, GA, Technical Association of the Pulp and
gluing. Paper Industry, 1974.
At the Department of Forestry in Canada, it 11. The Code of Federal Regulations, Title 21, Parts 100-
was determined that when a lamination bonded 199, "Food and Drugs," may be obtained from the
U. S. Government Printing Office, Washington, D. C.
with casein glue is stored at an eqUilibrium 12. Ref.8.
moisture content of 15% or less there is an 13. Fieser, Louis F., and Fieser, Mary, "Advanced Or-
equal rate of loss of the strength of the glue line ganic Chemistry," p. 1035, New York, Reinhold
and the wood substance. At higher moisture Publishing Corp., 1961.
contents the glue line failed sooner than the 14. Ref. 13, p. 1047.
15. Coco, C. E., and Scacciaferro, L. M. (for Ralston
wood. This study resulted in the requirement Purina), "Soy Polymer Technology as it Applies to
by the Canadian Specifications Administration the Adhesive Industry," paper presented at the 1984
that structural laminates bonded with casein Spring Seminar, Philadelphia, PA, for The Adhesive
glue shall not be used for installations where and Sealant Council, Arlington, VA 22209.
atmospheric conditions produce a wood mois- 16. Ref. 7, p. 4.
17. Salzberg, H. K., Georgivits, L. E., and Cobb, R. M.
ture content of more than 15 %.55 Bergin56 has K., Casein in Paper Coating, in "Synthetic and Pro-
shown that for a casein glue line in yellow tein Adhesives for Paper Coating," R. G. Jahn and
birch, the dry strength is not affected by a wide H. R. Hall, eds., Tappi Monograph Series No. 22,
variation in temperature, but the ultimate wet Chapter VII, pp. 106-107, New York, Technical As-
sociation of the Pulp and Paper Industry, 1961.
strength is higher as the storage temperature is (TAPPI is now located in Atlanta, GA.) •
increased. 18. Gordon, W. G., eta!., J. Amer. Chern. Soc., 71, 3293
(1949); 72, 4282 (1950).
19. King, N., Austral. J. Dairy Techno\., ll(3), p. 3
REFERENCES (1956).
20. Ref. 7, pp. 3-4.
1. Salzberg, H. K., Casein Glues and Adhesives, in 21. Ref. 10, pp. 40-42.
"Handbook of Adhesives," 2nd Ed., I. Skeist, ed., 22. Ref. 10, p. 41.
Chapter 9, p. 159, New York, Van Nostrand Reinhold 23. Ref. 10, p. 42.
Co., 1977. 24. Personal communication, L. K. Creamer, New Zea-
2. Lambuth, Alan, Blood Glues, in "Handbook of Ad- land Dairy Research Institute, Palmerston North, New
hesives," 2nd Edition, I. Skeist, ed., Chapter 11, p. Zealand.
181, New York, Van Nostrand Reinhold Co., 1977. 25. Ref. 10, p. 42.
3. Lambuth, Alan, Soybean Glues, in "Handbook of 26. Ref. 10, p. 41.
Adhesives," 2nd Ed., I. Skeist, ed., Chapter 10, pp. 27. Ref. 17, p. 127.
152 HANDBOOK OF ADHESIVES

28. Ref. 10, p. 42. 43. Fonnula No.4 taken from Lambuth, Soybean Glues,
29. Taken in part from Ref. 10, p. 43, with pennission. in "Handbook of Adhesives," 2nd Ed., I. Skeist, ed.,
30. Some of the infonnation on the use of casein as a pro- Chapter 10, p. 176, New York, Van Nostrand Rein-
tective colloid was obtained as a personal communi- holds Co., 1977.
cation from colleagues, who requested no credit be 44. Copies of the ASTM test methods and specifications
given. appear in the "ASTM Book of Standards," Vol.
31. Vanderbilt News, Latex and Latex Products, Vol. 34, 15.06, "Adhesives," and may be obtained from the
No.2,1972. American Society of Testing and Materials, 1916 Race
32. Hercules Resins for Adhesives in "Say Something in St., Philadelphia, PA 19103.
Adhesives," Publication OR-175B, Hercules Co., 45. Federal Register, Jan. 21, 1987, "Final Detennina-
Wilmington, Del., pp. 15-17 (no date). tion and Intent to Cancel and Deny Applications for
33. Jahn, R. G., and Hall, H. R., Styrene-Butadiene Lat- Registrations of Pesticide Products Containing Pen-
ices for Paper Coatings, in "Synthetic and Protein Ad- tachlorophenol (Including, but not Limited to its Salts
hesives," L. H. Silvernail and W. M. Bain, eds., and Esters) for Non-Wood Uses"; and Federal Reg-
Tappi Monograph 22, Chapter IV, pp. 49-50, 69-70, ister, Feb. 24, 1988, Pentachlorophenol Products;
New York, Technical Association of the Pulp and Pa- "Amendment of Notice to Cancel Registration of
per Industry, 1961. (TAPPI is now located in Atlanta, Products for Non-Wood Use."
GA.) 46. A copy of MMM-A-125-D is available from General
34. Silvernail, L. H., and Bain, W. M. (ed.), "Synthetic Services Administration Regional Offices in Boston,
and Protein Adhesives," Tappi Monograph Series No. New York, Washington, D. C., Atlanta, Chicago,
22, New York, Technical Association of the Pulp and Kansas City, MO, Fort Worth, Denver, San Fran-
Paper Industry, 1961. (This publication is out of print. cisco, Los Angeles, and Seattle, WA.
TAPPI is now located in Atlanta, GA.) 47. Data supplied by National Casein of N. J., Riverton,
35. Ref. 33. p. 70, Table XV. NJ 08077.
36. Ref. 17, p. 128. 48. Ref 1, p. 163.
37. Infonnation from sales literature of Buckbee-Mears 49. Ref. 39, Chapter 8, pp. 272-274.
Company, St. Paul, MN 55101, 1976. 50. Ref. 1, p. 163.
38. Lambuth, Alan, Blood Glues, in "Handbook of Ad- 51. Ref. 1, p. 166. [From Selbo and Olson, J. Forest
hesives," 2nd Edition, I. Skeist, ed., Chapter 11, p. Products Res. Soc., 3(5), 50 (1953).]
173, New York, Van Nostrand Reinhold Co., 1977. 52. Selbo, M. L. "Adhesive Bonding of Wood," Tech-
39. Browne, F. L., and Brouse, D., Casein Glue, in nical Bulletin No. 1512, pp. 72-74. Washington, DC,
"Casein and Its Industrial Applications," 2nd Ed., E. Forest Products Laboratory, USDA, August, 1975.
Sutenneister and F. L. Brown, eds., Chapter 8, New 53. Ref. 1, p. 166. [From Olsen, W. Z., et aI., U. S.
York, Reinhold Publishing Corp., 1939. Forest Products Lab. Bull. 1539, (1946).]
40. Ref. 39, p. 234. 54. Ref. 1, p. 164. [From Selbo, M. L., J. Forest Prod-
41. Ref. 2, p. 175. ucts Res. Soc., 3, 361 (1949).]
42. Bye, Carolyn N., to National Casein of N. J., "Pro- 55. Ref. 1, p. 164. [From Peterson, R. W., "How Mois-
teinaceous Adhesive Composition," U.S. patents ture Affects Strength of Casein Bonds," Forest Prod-
4,046,955, (Sept. 6, 1977) and 4,141,745 (1978); and ucts Research Branch, Canada, Contribution P-40,
Canadian Patent 1,043,052 (Nov. 28, 1978). (For- 1964.]
mulas 1, 2, and 3 in Table 10 were taken in part from 56. Ref. 1, p. 164. [From Bergin, E. G., Forest Products,
examples in these patents.) J., April, 1965].
 8
Starch Based Adhesives
LEO KRUGER AND NORMAN LACOURSE
National Starch and Chemical Corporation
Bridgewater, NJ

Starch is a natural polymer, available in very starch, potato starch, tapioca starch, wheat
large quantities and at relatively low and stable starch, rice starch, and sago starch. The term
prices. It consists of glucose units chemically sago was originally applied to starch from the
bound together so as to form a nonreducing stem of Metroxylon-type palm trees, but is often
polyhydroxy material. Because ofthe many hy- used to describe starches from other palm trees,
droxyl groups, starch has a high affinity for po- or even applied to some varieties of tapioca
lar substances such as water or cellulose. Starch starch. Some characteristics of several com-
can be reduced to low molecular weight sugars mercially available starches are shown in Table
by enzymes called amylases, or by acid hy- 1.
drolysis. Regular com starch consists of two major
Some major changes in starch usage in ad- fractions that can be separated by precipitation
hesives and related fields are the large increase with butanol under appropriate conditions. The
of cationic and amphoteric starches in paper fraction that precipitates out is called amylose.
manufacture and the increased use of high Amylose is essentially linear in form, stains
amylose starches in the corrugating industry. blue with iodine solutions, tends to form a rigid
The increased emphasis on recycling makes gel from concentrated solutions or to precipi-
the use of starch desirable because amylases are tate from dilute solutions, and is about 95 % di-
able to degrade the starch with essentially no gested by beta amylase (a test for strict linearity
effect on the major part of the adherent matrix. or lack of branching) when very carefully iso-
There is a patent on the use of amylase as a lated. Amylose forms strong, water-resistant
release agent in starch glued materials recy- films when a solution is evaporated.
cling. 1 The other main fraction is called amylopec-
Most of the starch used in adhesives in the tin. Amylopectin is highly branched (one
United States is produced from com or maize. branch every 14 to 27 glucose units), stains
There are four commercially available starch brown to purplish with iodine solutions, tends
types that are used in adhesives. These are waxy to remain in solution at room temperature, and
com starch, regular com starch, high amylose is digested to about 55 % by beta amylase.
type V com starch, and high amylose type VII Amylopectin forms weak, water sensitive films.
com starch. The major difference between Regular com starch (when carefully fraction-
these starches is in the amount of amylose con- ated) contains an additional intermediate frac-
tained in them-approximately 0, 28, 55, and tion. This fraction is precipitated out of the
70%, respectively, by iodine titration. Other original com starch solution by butanol, but is
starches usable in adhesives include sorghum not reprecipitated when water and butanol are

153
154 HANDBOOK OF ADHESIVES

Table 1. Commercial starches. Approximate Data and Ranges. 4

Starch Corn Wheat Rice Tapioca Potato Sago

Source Seed Seed Seed Root Root Pith

Granule size in diameter microns 5-26 3-35 3-8 5-35 15-100 10-70
Gelatinization
Temp. ("C) 62-72 58-64 68-78 49-70 59-68 60-67
Amylose (%) 28 25 19 20 25 26
Amylose (DP) 480 1050 850
Amylopectin (DP) 1450 1300 2000

added to the amylose fraction dissolved in di- molecular weights as the methods of isolating
methylsulfoxide. The intennediate fraction is the fractions of starch and the methods of de-
precipitated by iodine from the various solu- tennining molecular weight have improved.
tions, and is 5-7 % ofthe starch in regular corn Most literature indicates that amylose has a
starch. The full analysis for regular corn starch molecular weight of about 1,000,000 to
is 25-27% fractionated amylose, 68% amylo- 2,000,000 depending on its source, and amy-
pectin, and 5-7 % intennediate fraction. lopectin has a molecular weight of about
When waxy corn starch is carefully fraction- 400,000,000. These are weight average molec-
ated, 2 % intennediate fraction is found. The ular weights detennined by light scattering ex-
remainder is amylopectin. periments of the fractions with the starch
High amylose corn starches differ from reg- dissolved in dimethylsulfoxide. Commercially
ular corn starch in that the high amylose corn used starches probably have much lower mo-
starches contain more amylose, much more in- lecular weights. For example, the amylopectin
tennediate fraction and much less amylopectin of one cultivar of potato starch was consistently
than regular corn starch. For example, a high detennined to be 65,000,000, while the amy-
amylose type VII starch having 70% amylose lopectin from a second cultivar was just as con-
by iodine titration contained 63 % recrystallized sistently detennined to be 440,000,000. A
butanol complex (standard amylose), 31 % in- sample of waxy maize starch had a molecular
tennediate fraction, and only 5 % amylopectin. weight of 400,000,000 but after shearing a 15 %
About half of the intennediate fraction is prob- solution in boiling water the amylopectin mo-
ably low molecular weight amylose (19,000 lecular weight was detennined to be
daltons). This low molecular weight amylose 10,000,000. 2 At high molecular weights the er-
fraction may be responsible for some of the ror of measurement becomes quite large. The
rapid bond fonnation noted in corrugating ad- error at 100,000,000 is ± 10%, and at
hesives using high amylose starches. The stan- 500,000,000 the error is ±20%. The amylo-
dard amylose detennination (70 %) is not fully pectin from pea starch appears to be the highest
indicative of possible perfonnance. A better recorded, being 1,500,000,000 in one case. 3
analysis would be: nonnal amylopectin 5 %; The tenns linear and branched were used in
low molecular weight, less branched amylo- the preceding discussion in describing amylose
pectin about 16%; low molecular weight amy- and amylopectin. Fig. 1 illustrates the way in
lose about 16%; high molecular weight which glucose units are linked together to fonn
amylose 63 %. Total amylose is about 79 %, and starch. Most of the glucose units in starch are
total amylopectin is about 21 %. linked in a (1-4)-alpha-D-linkage. All of the
Some of the true solution properties of starch linkages are of this type in amylose (theoreti-
appear to be related to the molecular weight of cally at least). This is called the linear poly-
the amylose or amylopectin fractions. For ex- mer. Amylopectin contains, in addition to the
ample, the viscosity of jelly gums probably de- above linkage, a (l-6)-alpha-D-linkage once in
pends on the amylopectin molecular weight. about 25 glucose units. 4 The 1-6 linkage is
The literature has tended to show increased called a branch point and the linear extension
 STARCH BASED ADHESIVES 155

& 9H • OH polarizing microscope, showing a "polariza-

5/~--\~ tion cross." These disappear at or near the ge-
\, 4/\9H ~/~\ latinization temperature when heated in water,
o c--c b indicating a loss of crystallinity. With further
'H heating the granules tend to swell a little fur-
c--o
20H &\CH.
s
IA \~
& CH .OH
fA
s ,1.--0
\~ ther, collapse to a degree, and fragment if
\, ~\OH ~/~\ 1~\9H ~l\'/ sheared to any extent. Although some starches
o ~--c 0 c--c;: 0 such as waxy starch, potato starch, tapioca
'Ii 26H 'Ii 20H
starch, and sago starch cook to an almost clear
suspension, the starch is not in solution. This
s can be seen by examining the starch cook with
x-O-x-O-xO-x-o a phase contrast or interference contrast micro-
----x-o-x-O-x-o-x-b-Xo-\o-S-""'\ scope, where the swollen granules or granule
fragments are evident. Most starches start to
-----x-o-x-chbxo~iO-xOxO swell at about 140-170°F (60-70°C), and ap-
L _____ j
pear to be reasonably dispersed at 203 OF
Fig. 1. Schematic representation of a segment of amylo- (95°C). In order to completely solubilize the
pectin molecule. 4
starch a much higher temperature of 300-320°F
(150-160°C) is required. Some granules in the
of this branch point is called a branch. Amy- high amylose starches tend to retain their po-
lopectin is therefore called a branched poly- larization crosses above 212°F (l00°C), but at
mer. Many amylases are able to hydrolyze at the 300-320°F range these granules are also
both the 1-4 and the 1-6 linkages, but beta am- completely dissolved.
ylase hydrolyzes only at the 1-4 linkage. Fur- The cook texture of many starches can be ex-
ther, beta amylase is able to attack only at the plained by their composition. Waxy corn
nonreducing end of the starch molecule, and starch, which is all amylopectin, when heated
hydrolyzes off one two-glucose unit at a time at 8 % starch solids in water becomes very
only if that unit is linked 1-4 (maltose). Hence, heavy and cohesive as the granules swell. With
the low digestion by beta amylase (65 % in continued heating, the viscosity decreases as
some commercial amylose) suggests an occa- the granules are broken up. On cooling, the
sional short branch in all except the most highly viscosity increases. The texture remains cohe-
purified samples. 5 sive, and the solution retains its clarity. This
When starch is suspended in water it tends to behavior is typical when the amylopectin frac-
increase in volume and to absorb about its tion dominates the cook characteristics. Regu-
weight of water. If the temperature is slowly lar corn starch, at the same solids, is much
increased there is a point at which water ab- thinner, behaves like a short paste, and is quite
sorption increases dramatically. The starch cloudy when hot. On cooling, the cook be-
granule expands 10-100 times in volume de- comes an opaque, rigid gel. In this case the
pending on the type of starch. If the amount of amylose has modified the hot cook character-
starch present is greater than required to absorb istics of the amylopectin, and completely dom-
all of the water available, then the viscosity of inates the characteristics of the cooled cooked
the starch dispersion becomes very heavy. The suspension. If the amylose has too high a mo-
swollen granules can be partially destroyed by lecular weight, then the gelling on cooling may
mechanical agitation, and the viscosity will de- not take place. Tapioca, potato, and sago
crease, depending on the type of starch. The starches behave more like waxy corn than corn,
temperature at which the starch suddenly swells even though these are amylose containing
when heated in water is called the gelatiniza- starches. 6 These amylose containing starches
tion temperature. will set to firm gels if the starch is degraded
The unswollen starch granule is in a crystal- with acid (see fluidity starches). Many of the
line state and as such is anisotropic. Most of characteristics of common starches after cook-
the starch granules are birefringent under the ing are given in Table 2.
156 HANDBOOK OF ADHESIVES

Table 2. Cook Characteristics of Native Starches (cooked 1 part in 15 parts water

at neutral pH).4
Viscosity Gel
Hot Cook Hot Cook on Prolonged Formation Oarity
Starch Body Viscosity Cooking on Cooling (cold)

Corn Short Medium Stable Very high Opaque

Wheat Short Relatively low Stable Very high Opaque
Amioca Stringy-cohesive Moderately high Thinning None Fairly clear
Tapioca Stringy-cohesive High Thinning Very low Quite clear
Sago Stringy-cohesive Moderately high Thinning Moderate Fairly clear
Potato Gummy, very cohesive Very high Thinning Very low Very clear

Likewise, many of the adhesive properties Oxidized Starches

can be explained by reference to the amylose
A second modification to reduce viscosity is to
and amylopectin properties of the starch used.
treat the starch with chlorine under alkaline
Jelly gums are usually made from waxy starches
conditions. Lightly chlorinated starches use the
(100% amylopectin) and are stable at room
water fluidity method of viscosity designation,
temperature for many months, as would be ex-
but more heavily chlorinated products use a
pected from the slow retrogradation rate of this
borax fluidity procedure. Chlorinated starches
starch. A corrugating formulation must set to
are generally called oxidized starches. They are
form a bond and become water resistant in a
anionic, in that they contain negative charges.
short period of time. The low molecular weight
This can be verified by staining with cationic
portion of the amylose would be expected to
dyes. Methylene Blue is a typical cationic dye.
come out of solution fairly rapidly to make a
temporary bond, and the high molecular weight Dextrinization
portion would more slowly tend to create water
resistance. A third method of reducing viscosity is by the
use of dry heat, usually in the presence of
MODIFICATION OF STARCHES 70
aD
The previous discussion was concerned almost 50

exclusively with the use of native starches dis- co

persed in water. The properties· of the disper- _30
sions can be changed considerably by additives, "#.
or by modifying the starch. The principal mod- I/)
C 20

ification in the adhesive industry is to decrease :::::i

0
the molecular weight of the starch components I/)
:z:
so as to permit a higher solids content in the u
II:
10

formulation. The starch is usually treated in cC

l-
I/)
granular form.

Fluidity Starches
Fluidity starches are made by hydrolyzing the eo .0
starch in dilute acid below the gelatinization
4,,0 r..:f t
4.~: ~ a
, 20
WF
40
.,
,f ..~ THill 8011.1110 TYI'S DEXTRINS:
temperature of the starch. The range of fluidi- NATIVE STARCHES .. IRITlSII OUIU

-
ties is 20-90, with a 90 fluidity starch being STARCH TYPE .. WHITE
• CONVERSION:
very much thinner than a 20 fluidity. Fig. 2 _ YELLOW

gives an indication of the concentrations re- Fig. 2. Approximate concentrations of starch in thin
quired to produce a given hot viscosity. flowing cooks (l40°F).4
 STARCH BASED ADHESIVES 157

2000

10DD
en
W
:..:::
500 0
300 Ii; 1000
j:::
200 Z500
W
'" 0300
~
100
I 200
e;... 50
>-
'-' t: 100
3D en
~ 0
v; 20 0
50
en
C>
'-'
'"
;:
10
:;: 30
'-' 20

iII!!
0
j:::
C 10
;< ~
W 5
Z
i2 3

1~--~----~----~----~--~
10 20 3D 40 50 60

I CONCENTRATION (SOLIDS) (lO'F., (13O'F.' (11O'F.)

3400 3200 3000
Fig. 3. Viscosity-concentration relationship of corn dex- 1
trins at 80°F.4 - X 106
K
Fig. 4. Viscosity-temperature relationship of corn dex-
trins at 25 % solids. 4
acids. This process produces dextrins. Their
viscosity is also measured by using the BF or
Cationic Starches
borax fluidity method. Dextrin viscosities are
illustrated in Figs. 2, 3,4. Other dextrin prop- Starch is reacted with tertiary or quaternary
erties are given in Table 3. amine halides or epoxides under alkaline con-
ditions. g The cationic starches improve sheet
Hydroxyethylation strength, possibly through ionic bonding with
slightly anionic paper. The cationic starches are
Starch is treated with ethylene oxide under al-
also used in bottle-labeling adhesives and in
kaline conditions. The major purpose is to slow
paperboard.
down retrogradation, or precipitation of amy-
lose from solutions of starch. This is effective Amphoteric Starches
because the amylose tends to be uniformly sub-
stituted, whereas amylopectin is substituted Cationic starches are phosphated by heating
mainly near branch points. 7 with orthophosphate to produce a starch with

Table 3. Comparison of Dextrins. 4

Dry-roasting Process Dextrin Properties
Degree of
Polymerization Cold water
Dextrin Acidity Moisture Temperature (DPn) Color Swelling Stability

White High High Low 20 White Partial Limited

Yellow or
canary Low Low Moderately high 20-50 Light High Good

British Very low Moderately high Yellow to Partial to

gums -none Very low to high Very wide range dark brown complete Good
158 HANDBOOK OF ADHESIVES

amphoteric (both cationic and anionic) prop- tends to prevent crystalization of the starch or
erties. These starches offer improved pigment dextrin when a film is dried. It is used at
retention and dry strength over a wide pH 1-10% based on starch present. Other chemi-
range. s cals with similar effects are sodium nitrate, di-
cyanamide, salicyclic acid, thiocyanates,
Miscellaneous Derivatives iodides, guanidinium salts, andformaldehyde.
(Formaldehyde can also crosslink under acid
These include cross linked or inhibited starches,
conditions or be used as a preservative).
hydroxypropylated starches, phosphorylated
starches, starch succinates, grafted starches,
Glycerol
and carboxymethyl starch. 9
Most of the formulations using starch adhe- Glycerol acts as a plasticizer by slowing drying
sives appear to be obtained by trial and error. time, preventing excessive drying of a film. In
The preceding listing of modifications and ref- this capacity it is a humectant. Other humec-
erences is intended to enlarge the scope of pos- tants are ethylene glycol, invert sugars, d-glu-
sibilities for adhesive development. The cose, and sorbitol.
discussion of the effects of amylose and amy-
lopectin on starch dispersions serves a similar Soluble Soaps
purpose.
These are used as lubricants to impart flexibil-
ity regardless of atmospheric conditions. Too
EFFECT OF ADDITIVES
much lubricant will weaken adhesive bonds.
Sodium Hydroxide Other lubricants are sulfonated castor oil and
sulfated alcohols.
Sodium hydroxide (also called caustic soda)
will increase tack, tend to solubilize the starch
Urea-Formaldehyde Resin
to a greater degree, increase viscosity, increase
cohesiveness, and also increase color. It is usu- This resin is added to give water resistance.
ally added after cooking in water, usually to the Resorcinol-formaldehyde, poly(vinyl acetate),
extent of about 0.5 % based on total solids. The acrylics, and poly(vinyl alcohol) are also used
increase in pH tends to place negative charges to increase water resistance.
on the starch, which tends to explain dispersion
and higher viscosity. Miscellaneous Additives
Clays and bentonites are used as fillers in ad-
Borax
hesives. Sodium bisulfite, hydrogen peroxide,
Borax (sodium tetraborate decahydrate) and so- sodium perborate serve as bleaches. Solvents
dium metaborate (essentially a mixture of borax are added to help wet water-repellent surfaces.
and sodium hydroxide) change the properties Preservatives prevent microbial growth. De-
of cooked starch dramatically. There is a large foamers prevent foam during cooking. Colloid
viscosity increase with increasing borax addi- stabilizers such as soaps and sodium chloride
tion to about 15 % (based on starch present); are often added. 10,11
tack and cohesiveness are also increased
greatly. Borax is used up to 10% based on STARCH ADHESIVES
starch and is usually added before cooking the
To be useful as an adhesive, starch must be dis-
starch. It acts by complexing with the starch to
persed in water, usually hot water, and a num-
produce negative charges, and in addition tends
ber of chemicals are added to modify the
to crosslink the starch. It is the crosslinking that
properties of the starch dispersion. The disper-
causes the large increases in solution viscosity.
sion and formulation can be done by the user
from the different types of starches or modifi-
Urea
cations of starches previously described, Or the
Urea is a plasticizer that acts by forming solid user may purchase formulated adhesives from
solutions with starch and dextrins. The urea adhesives manufacturers.
 STARCH BASED ADHESIVES 159

Jelly Gums white to cream, and their solubility and viscos-

ity varies from low to high. They are used in
These are used for bottle labeling. They are
bag-seam, tube winding, case and carton seal-
prepared by treating waxy starch or waxy flu-
ing, laminating, gummed sheets, label, and en-
idity starch with caustic under high shear. The
velope back seam adhesives.
starch swells in the caustic, and most of the
caustic is neutralized with nitric acid. One for-
Canary Dextrins
mulation yields a final composition of 39 %
starch (40 fluidity waxy), 3% urea (an addi- Canary dextrins are prepared by heating dry
tive), 3% sodium nitrate (from the sodium hy- starch containing a moderate amount of acid at
droxide and nitric acid used), and 56% water moderate temperatures (3oo°F, 149°C) for a
(Ref. 10, p. 605). The viscosity as used is about moderate time (11 hours). They are very light
100,000 cPo The labels are cold water resis- to dark tan in color, have a high cold water sol-
tant. ubility, a low stable viscosity, and excellent re-
moistening ability. They are used in gummed
Other Liquid Formulations tape, envelope front seals, stamps, case and
carton sealing, laminating and tube winding.
Alkaline starch formulations (prepared by add-
ing enough caustic to gelatinize the starch) are
British Gums
used as carriers in corrugating, infoil-to-paper
adhesives, and in carton or case sealing adhe- British gums are prepared by heating dry starch
sives. If the caustic used to gelatinize the starch with a low amount of acid at high temperature
is neutralized, the adhesives at 18-25% starch (330°F, 166°C) for a long time (17 hours).
solids are usable for wall paper printing or foil- They have low to high solubilities and low to
to-paper lamination. Combinations of starches high stable viscosities, dark color, and fast
and water with added salts are the simplest ad- tack. They are used in solid fiber laminating,
hesives, and can be used in bill posting, bag bag-seam pastes, and tube winding adhesive.
making, and tobacco seam gluing.
Waxy Starch Dextrins
Pastes
Waxy starch dextrins are similar to dextrins
Short, soft, nonstringy adhesives formulated made from non-waxy starch, but have a greater
from heavy bodied starches or dextrins are viscosity stability than the corresponding reg-
called pastes. A typical formulation for library ular dextrin. Envelope front seals, stamps, and
paste is to cook a mixture of 45 % low-soluble gummed sheets are some uses.
white dextrin, 5 % com starch, 5 % glycerol,
and 45% water. 4 • IO Dextrin/Silicate Blends
Fast tack, rigid films, low viscosity, and very
Borated Dextrins
good adhesion are obtained from this combi-
Dextrins are frequently formulated with borax, nation. High speed case sealing and fiber foil
sodium metaborate, boric acid, or caustic in dif- cans are some uses.
ferent proportions to give good tack and higher
stable viscosities at moderate concentrations. Pregelatinized Starches
The pH ofthe formulations is about 9.0 in most
Pregelatinized starches are prepared by heat
cases. Borated dextrins find use in case sealing,
swelling a starch-water slurry, drying, and
carton sealing, tube winding, and laminating.
grinding the dry powder. The starch at 40%
solids is fed to a steam-heated drum where it is
White Dextrins
gelatinized and dried, and finally scraped off
White dextrins are prepared by heating dry the drum with a blade. These starches are used
starch containing relatively large amounts of in some one-tank corrugating applications,
acid at low temperatures (258°F, 120°C) for multiwall paper bags, wallpaper, and bill post-
rather short times (3-7 hours). Their color is ing.
160 HANDBOOK OF ADHESIVES

APPLICATION AREAS cled may cause pigment and fines retention

problems in the wet end. Cationic starch which
Papermaking
has been preconverted to a low viscosity ap-
Cationic, anionic, and amphoteric starch de- pears to have advantages in physical properties
rivatives are cooked and added at the wet end of the paper and in retention of the surface sized
of the papermaking machine at 5-20 pounds per broke.
ton of paper. The starch flocculates pigments Starch is added at the calender stack for curl
and fine pulp particles, improves retention of control, surface strength, laying of surface
fines, helps drainage, and increases internal fuzz, clay coating holdout, printing character-
(Scott bond) and burst (Mullen) strengths. The istics, and grease or oil resistance. Solids vary
starches are retained by the pulp because the from 2 to 24 %, depending on the starch type
pulp has a slight negative charge, which holds used and on the paper requirements. Low vis-
the positively charged starch. The positive cosity starches, hydroxyethylated converted
charge is present directly in the cationic and starches, and oxidized starches are used in this
amphoteric starches, and is formed by com- application.
plexing with alum in the case of anionic Similar starches to those used on the size
starches. press can be used in pigment binding applica-
Unmodified starch is also used at 20-40 tions, but the viscosity of the starch should be
pounds per ton of pulp. It is retained mainly by lower. A possible formulation for a 59 % solids
entrapment. coating is 0.2 % sodium hexametaphosphate,
Although starch is largely added at the wet 10.1% calcium carbonate, 40.5% clay, 8.1%
end of the paper machine, it can be placed di- low viscosity starch, 0.05 % pine oil, and
rectly on the formed sheet. The starch can be 0.21 % soap.4 Thin boiling cationic starch has
sprayed onto the fibers, applied as foam di- also been recommended for this application. 12
rectly on the wet web, or applied as a thin cur- The same starches as are used above can be
tain to the wet web. 12 These alternative used when starch is added with pigment at the
methods have certain advantages, but they lose size press. Solids are generally 30-40%, and
the flocculating ability of cationic or ampho- the starch to pigment ratio can be as high as 1
teric starches. to 1. The viscosity is usually below 300 cP.

Paper Coating Corrugating

In addition to adding starch at the wet end to Most of the corrugated board is made using the
hold the fibers together, starch can be added at Stein Hall system, which consists of a mixture
the size press, at the size press with a pigment, of gelatinized starch (called the carrier starch)
at the calender stack, or as a pigmented coating and ungelatinized starch. Flat corrugating me-
as a separate operation. In all of the above ap- dium is fluted, starch is applied to the fluted
plications, starch acts to bind the paper fibers tips, and a heated liner is brought in contact
together or to bind the pigment particles to- with the fluted tips under heat and pressure to
gether or to bind the pigment to the fiber. The produce a single facer. Adhesive is applied to
paper has been partially dried at the size press. the fluted tips on the other side of the corru-
The viscosity ofthe starch solution must be rel- gating medium and a flat liner called a double
atively low (50 cP) at the size press. The backer liner is applied. When the facers are
2-12 % solids used in coatings would have too brought in contact with the flutes containing the
high a viscosity. Therefore a viscosity reduc- adhesive, the ungelatinized starch gelatinizes.
tion is usually necessary. This can be accom- This creates an extremely high viscosity at the
plished by enzymes or heat treatment in the case flute-liner interface. The applied heat also
of regular starches, or oxidized, hydroxyethy- evaporates water and further increases the flute-
lated, acid fluidity, or acetylated acid fluidity liner bond, so that the corrugated board can be
starches can be used. cut without delaminating. The formulation in-
Oxidized starches are anionic, and if recy- cludes sodium hydroxide and borax to decrease
 STARCH BASED ADHESIVES 161

the gelatinization temperature of the raw starch 424 parts high amylose starch, 6 parts borax;
and to increase viscosity at the flute after ge- bring to 130°F (54°C) and add with stirring a
latinization. mixture of 36.6 parts caustic in 47.5 parts
A typical old formulation is: put 13 parts water. The raw starch portion is made by mix-
water, 3.2 parts starch, 0.54 parts caustic dis- ing 3480 parts water, 1600 parts com starch,
solved in 0.8 parts water into a tank (called tank 28 parts borax and 91.2 parts thermosetting
1, or the upper tank), heat with steam to 160°F, resin. Mix the carrier into the raw starch. 15
agitate 15 minutes, and then add 16 parts cold It appears, at least in the case of high amy-
water. This gelatinizes the starch present and lose carrier starch, that the carrier starch is the
makes the carrier starch portion of the adhe- principal adhesive. 16 The raw starch, when ge-
sive. In another tank (called tank 2, or the lower latinized, absorbs water to concentrate the dis-
tank) 49 parts cold water is mixed with 0.54 persed high amylose starch on the flutes. Older
parts borax and 18 parts starch is added. The ideas of the mechanism were that the carrier
contents of tank 1 are slowly added to tank 2 starch was simply a suspending agent for the
with efficient mixing.4 It is possible to carry the raw starch, which was the principal adhesive.
entire operation out in tank 2, but control is One suggestion was that amylose migrating out
more difficult. of the granules caused at least the initial tack. 12
So called no-carrier or single-component There are many publications on the use of
systems depend on careful control to gelatinize high amylose starches. High amylose starch is
the correct proportion of the granules present. esterified with acetic anhydride or succinic an-
One formulation, which increases water resis- hydride to improve stability. 17 Another patent
tance by adding urea-formaldehyde, is: mix 20 concerns the addition of dihydroxyethyleneurea
parts starch, 77 parts water, 0.8 parts 50% together with acetone-formaldehyde to im-
caustic, and stir at 101°F until the viscosity prove water resistance. 18
reaches 25 Stein Hall seconds. Then add 0.04 The use of high amylose starches in the pro-
parts alum, 0.4 parts boric acid, and 3 parts duction of cold corrugating adhesives (not re-
60% urea-formaldehyde resin. 4 Other ways to quiring extensive heating) has been published.
make "no-carrier" systems are to add exactly A mixture of oxidized and hydrolyzed 70%
the correct amount of caustic and stop the amylose containing starches is dispersed as a
swelling by addition of boric acid; control the 35% starch suspension, gelatinized at 140°C,
swelling by carefully injecting steam into the and used in corrugating without steam. The
mixture; or partially swell the granules by mill- high amylose starch was treated with 4 % so-
ing a 10-40% moisture starch to damage gran- dium hypochlorite at an initial pH 11 to make
ules before suspending in water. 12 A chemical- part A of the degraded mixture. Part B was
mechanical method of producing the carrier made by hydrolyzing high amylose starch for
starch is to introduce a mixture of 12 % starch 12 hours at 50°C (122°F) with 6% of 35%
and 30% caustic into a centrifugal pump. Final hydrochloric acid. Both A and B were neutral-
alkalinity was 14.4% and the viscosity was ized to pH 5, washed, filtered, and dried. Then
4200 cP. at 76 of. 13 The use of starches having 70 % A and 30 % B were mixed to a 35 % sus-
different gelatinization temperatures is given in pension and cooked at 140°C. The use of the
Ref. 14. Here 350 parts tapioca starch and 3000 B portion is claimed to improve speed from 90
parts com starch are suspended in 9000 parts m/min to 230 m/min. 19
water and treated with 500 parts 20 % caustic Mixtures of waxy, regular, and high amylose
at 38°C. (100°F). Then 55 parts of borax are starches are degraded with a mixture of sodium
added. The Stein Hall viscosity is 52 seconds, persulfate, sodium sulfite, boric acid, and caus-
and the gel point is 63°C (145°F). The tapioca tic, and cooked at 90°C (194°F) and about
starch swells before the com starch, and essen- 33 % solids to form a starch adhesive that hard-
tially produces the two-component system. ens on cooling. 28 The cold corrugating process
High amylose starches improve water resis- is described in other references. 26-28
tance and increase speed of corrugation. A for- Other claims for improving corrugating for-
mula for the carrier starch is: 1192 parts water, mulations include increasing the carrier starch
162 HANDBOOK OF ADHESIVES

solids,21 addition of urea,22 using crosslinked ing paperboard to paperboard, or rotary lami-
starch in the carrier,23 and using cationic starch nation. Lay-ftat, or noncurling, is an important
as the carrier starch. 24,25 attribute of these adhesives. High tack and low
penetration are also required. One formulation
Bag Adhesives is water 43 %, high soluble white dextrin 21 %,
corn starch 4 %, sodium nitrate 32 %; heat to
Three adhesives are used in paper bag manu- 200°F (93°C), hold 20 minutes, add preserv-
facture: side seam adhesives, bottom paste ad- ative. 4 Another formulation is high soluble
hesives, and cross pastes. The side seam white dextrin 20%, clay 13.5%, urea 6.7%,
adhesive is used to form a cylinder from a flat borax 5 %, water 55 %.10
sheet of paper. This adhesive must develop a Foil laminations usually call for resins, but
strong bond quickly, so the tube can be cut for even here a small amount of starch is often
further operation. The viscosity should be about added for its smoothing properties. One ex-
3,000 cPo and solids about 25%. One formu- ample is: poly(vinylalcohol) 3, starch 3, water
lation is: water 68%, dextrin 28%; heat to 49, potassium persulfate O. 1; add dropwise a
160°F (71°C), add 3% borax, heat to 190°F mixture of 5 dibutyl phthalate and 39 vinyl ace-
(88° C), add 3% preservative. 4 A water-re- tate at 70°C (158°F), dilute to 25% solids. 3o
sistant formulation is: water 1700 pounds, Starch at 3-15 % is claimed to prevent coarse
white dextrin 700, soap 2, urea-formaldehyde particle formation in the following formula-
70, heat to 200°F (93°C), dilute with cold tion: 45 % aqueous emulsion containing 1: 99
water to 260 gal volume, and add 14 pounds acrylic acid: vinyl acetate copolymer 100, corn
ammonium chloride. This formulation should starch 4, poly(vinylalcohol) 5, dibutyl phthal-
be used immediately. Its pH is about 6. 4 ate 15. Aluminum foil was coated on paper at
Bottom paste adhesives are applied to one end 300 m/min (meters per minute) without coarse
of the tube formed above to close that end to particle formation, while a similar formulation
form a bag bottom. These pastes are usually omitting the starch formed coarse particles at
made from unconverted starches. Soap and/or 90 m/min. 31
salt may be added to produce a thixotropic paste
(flows under shear but sets up if left undis-
Tube Winding
turbed).l1 A water-resistant formulation is corn
starch 13 %, poly(vinylalcohol) 4.5 %, Tube winding is either spiral (a continuous
poly(vinylacetate) 1 %, soap 0.1 %, water 81 %, winding where adhesive is applied to outer plies
heat to 90°C (194°F), cool to room tempera- as they are wrapped on a cylindrical mandrel),
ture. 10 or convolute (where the sheet is as wide as the
Cross paste is used for multiwall bags to glue mandrel is long, and the mandrel wraps the
the plies together before forming a tube. This sheet over itself). The tube is removed from
is similar to seam paste, but should not pene- the mandrel by a pusher arm. Convolute ad-
trate the ply. Clay or poly(vinylacetate) is hesives are usually used cold, while spiral ad-
added to prevent penetration. 10,11 The seam ad- hesives may be used at 131°F (55°C). Many
hesive for multiwall bags can be somewhat starch products may be used, but 50% solids
heavier than given above, and higher molecular borated dextrins are common, as seen in Table
weight white dextrins can be employed. The 4.
bottom adhesive is usually a fluidity starch. 11
A mechanical way of converting potato starch Corrugated Boxes
for use in paper bags is also described. 29
The tops and bottoms of corrugated boxes are
closed with case sealing adhesive. Although
Laminating Adhesives
liquid glues and hot melts are preferred, carton
The requirements of the particular equipment adhesives are used, sometimes with added
must be met for bonding paper to paper or to caustic. Carton sealing involves bonding the
paperboard, for making poster displays, bond- bottom and top flaps of folded paper boxes. A
 Table 4. Adhesives in Packaging Applications. 4
Viscosity
Acceptable Approximate Requirement
Use, Function Major Adhesives Solids (cps) (Brookfield
Type of Adhesive Requirements Base (%) Spindle/RPMf F)

Bag Adhesives:
Cross pasting Tacky and Starch-dextrin-
quick setting mineral filler 25-30
Seam adhesives Well machining Starch or
slower borated dextrin 5-39 2800 (RV 4/20/80)
Bag bottom pastes Heavy, short Raw starches
or converted
borax 15-30
Laminating:
Mounting Rapid tack, Dextrin and low
good open time, viscosity starches
nonwarp 50 3800 (RV 4/20/75)
Rotary laminating High tack White dextrin with
urea or sodium
nitrate 55 4000 (VR 4/20/80)
Foil laminating Adhesion to foil Alkaline glues
resins (PVAC)8 60 2700 (RV 4/20/75)
Tube winding Tough, fast bond Borated dextrin 48 2500 (RV 4/20/80)

Corrugated Box:
Manufacturer's Rapid tack, PVAca, Hot-melt
joint adhesive good open time PVOHb 60 2000 (RV 4/20/75)
Built-up pad Nonwarp Dextrin
adhesives borated dextrin 35-36 1000 (RV 3/20/75)
Case seal adhesive Very fast, nonwarp Canary dextrin
borated white
dextrin resin 40-50
Tray maker adhesive Rapid setting PVAC8 Hot-melt 59 800/1000 (RV 4/20/80)
Set-up Box:
Machine laminating Quick setting, Animal glue
nonwarping and sugar,
canary dextrin 70
Hand laminating Lay flat Borated, white
dextrin 48
Ender pastes Good flow and tack Borated dextrin 50 400 (RV 3/20/80)
Label Adhesives:
Porous substrate Thin white Borated dextrin
adhesives 30 350 (RV 4/70/80)
Plastic container Adhesion and PVAca
high tack (Highly modified
starch) 52 4000 (RV 4/20/80)
Can labeling Tack and adhesion Converted starch 33 4000 (RV 6/20/72)
Glass bottle High tack Jelly gums dextrin 40-50
Notes: a PV AC =polyvinylacetate
b PVOH =polyvinyl alcohol

163
164 HANDBOOK OF ADHESIVES

top and bottom carton sealing adhesive is water ner with viscosities close to 1000 cP, and 40-
51 %, white dextrin 37%, preservative 1 %, 50% solids.
borax 6%, antifoam 0.06%; cook to 185°F Discrete particle, flat gumming, solvent-
(85°C) for 20 minutes, cool to 120°F (49°C), based adhesives are another method of making
add 5 water and 0.6 of 50% caustic. 4 remoistenable adhesives. The cold-water-solu-
ble material (usually a dextrin) is suspended in
Gummed Tapes a solvent and applied to the paper and dried.
Since the dextrin is not soluble in the solvent,
The types of remoistenable tapes are regular
it is deposited in discrete particles. On contact
sealing tapes, reinforced sealing tapes, and box
with water, the dextrin swells and will glue two
tapes. A regular sealing tape formulation is:
pieces of paper together. The dextrin is usually
thin boiling waxy starch 44, urea 6, water 50.10
used at 40 % solids and a viscosity of 1000
For reinforced tape, thin boiling waxy starch Cp. 4 •10
39.5, canary dextrin 17, polyacrylamide 2, dis-
persing agent 0.4, water 41.1 is suggested. 1O
Box tape is usually made from animal glue, but Paper Box
one patent claims performance superior to an-
Paper box manufacture involves the operations
imal glue from a starch acrylamide graft co-
of ending (box body formation), stripping
polymer prepared as follows: water 51 %,
(coating the box walls with precut wrap and
sodium nitrate 7 %, waxy corn starch 33 %,
smoothing), tight wrap (machine wrapping a
copper sulfate 0.03%, acrylamide 10%; mix,
box with glue on most of the wrap), and loose
then add 0.05 % ammonium persulfate and
wrapping (adhesive only on border of the
0.03 % sodium metabisulfate; heat rapidly to
wrap). Borated dextrins containing 10-15%
200°F (93°C) and maintain for 15 minutes.
borax and cooked at 30-50% solids are usually
Add sodium tartrate to adjust pH to 5.5. 32
used. See Table 4 for more information.
The use of an oxidized starch acetate 180,
urea 20, and water 200 as a gummed tape ad-
Textiles
hesive has been patented. 33 The formulation of
an acrylamide starch graft polymer is also Starch is used predominantly in warp sizing in
claimed: hydrolyzed low viscosity acrylamide- the textile field. The purpose is to strengthen
starch graft copolymer 67, canary dextrin 20, the yarns for weaving operations. A typical for-
animal glue 10, urea 10, petrolatum 0.25, and mulation is corn starch 8.5 %, softener (tallow
sodium hexametaphosphate 0.1, are heated for or sulfonated oil) 1.5 %, kerosene 0.2 %, cook
30 minutes at 185-205°F (85-96 o C).34 to 190°F (88°C), and homogenize at 2000 psi.4
Oxidized starches are used in finishing and
Label and Envelope Adhesives printing, and low treatment starch acetates,
starch monophosphate blended with poly(vinyl
The general adhesives for these uses can be
alcohol), cationic and amphoteric starches, as
found in Table 4. Dextrins, enzyme-converted
well as fluidity starches are used in finishing
starches, or mechanically degraded starches are
and warp sizing. 35 ,36
suitable, with white or canary dextrins made
from tapioca, waxy corn, and regular corn
Wall Covering Adhesives
starches the most used. The envelope front
seam is remoistenable and can have 55-65 % These require good wet tack and good slip.
solids with a viscosity of 2,000-10,000 cPo Plasticizers give slip (the ability to move the
After drying the adhesive should be non-block- paper around to obtain a good fit), borax gives
ing at high humidity. This requires a nonhy- tack, and clay allows easier removal of the pa-
groscopic plasticizer. One formulation per later. A formulation consists of acid mod-
containing poly (ethylene glycol) is high solu- ified pregelled starch 25, clay 20, urea 3.75,
ble waxy corn dextrin 63, sodium bisulfite 1, sodium metaborate 1.25, and water 50.10 A re-
Carbowax 4,000 (Union Carbide) 0.5, water moistenable composition containing other
35.5.10 Backseam adhesives can be a little thin- polymers is: dry blend carboxymethyl cellulose
 STARCH BASED ADHESIVES 165

25, hydroxyethyl cellulose 8.5, sodium algin- Stanley, Eds., pp. 427-444, Westport, Conn., AVI
ate 0.5, anionic polyacrylamide 0.3, urea 30, Publishing Co., 1976.
7. French, D., Organization of Starch Granules, in Ref.
potato starch 27, colloidal silica 1, sodium
2, p. 227.
stearate 2.5, sodium soap 3.5, sodium fluoride 8. Solarek, D. B., Cationic Starches, in "Modified
0.5, and 4-chloro-meta-cresol 1. The mixture Starches: Properties and Uses," pp. 114, 116, 120,
is suspended in 3 parts water, coated on paper 124, O. B. Wurzburg, ed., Boca Raton, Florida, CRC
and dried. 37 A second formulation is: starch Press, Inc., 1986.
9. Wurzburg, O. B., Crosslinked Starches, p. 41; Jar-
375, carboxymethyl cellulose 400, urea 200, awenko, W., Acetylated Starch and Miscellaneous
polyacrylamide 5, colloidal silica 5, para- Organic Esters, p. 55; Moser, K. B., Hydroxyethy-
chloro-meta-cresol10, sodium fluoride 5. 38 An lated Starches, p. 79; Tuschhoff, J. V., Hydroxypro-
inverted emulsion formulation containing a pylated Starches, p. 89; Solarek, D. B.,
starch graft copolymer has also been suggested Phosphorylated Starches and Miscellaneous Inorganic
Esters, p. 113; Trubiano, P. C., Succinate and Sub-
for wallpaper adhesives. 39
stituted Succinate Derivatives of Starch, p.131; Fanta,
G. F., and Doane, W. M., Grafted Starches, p. 149;
Miscellaneous Uses Hofreiter, B. T., Miscellaneous Modifications, p. 179;
all in Ref. 8.
Gelatinized starch 100, dextrin 100 is used to 10. Kennedy, H. M., and Fischer, A. C., Starch andDex-
make fish food stable in water. 40 AI: 1 mixture trins in Prepared Adhesives, in Ref. 2, pp. 593-610.
of starch and polyacrylamide was used to make II. Williams, R. H., Corrugating and Adhesive Indus-
an adhesive for high voltage transformers. 41 A tries, in ref. 8, pp. 255, 256.
12. Mentzer, M. J., Starch in the Paper Industry, in Ref.
mixture of poly(vinyl acetate) emulsion 100, 2, pp. 543-574.
plasticizer 20, and starch 20 has been used in 13. Harvey, R. D., et aI., Eur. Pat. Appl. EP 8241 to
book binding. 42 Grain Processing Corp., (1980), CA92(26):217034y.
14. Allen, L. A., U.S. Pat. 4359341, to Harper-Love Ad-
GOVERNMENTAL REGULATIONS: hesives Corp. (1982), CA98(6):36434g.
15. Ray-Chaudhuri, D. K., Schoenberg, J. E., and Sick-
ADDITIVES
afoose, K. E., US Pat. 3,728,141 1973 to National
The Food and Drug Administration (FDA) of Starch and Chemical Corp., from Ref. 4.
16. Sickafoose, K. E., A New View of the Functionality
the U. S. Department of Health, Education and
of Starch Based Corrugated Combining Adhesive,
Welfare (HEW) has issued a series of regula- Lecture presented to the National Corrugated Case
tions concerning the use of potentially toxic Association of Japan, November 4, 1974, from Ref.
substances in packaging materials contacting 4.
food. Most of the regulations may be found in 17. Chui, C. W., and Krieg, W. J., German disclosure
DE 3134336 to National Starch and Chemical Corp.
the Code of Federal Regulations, Title 21, re- (1982), CA96(24):201564t.
vised annually (21 CFR 121.2520, "Adhe- 18. Silano, M. A., and Featherston, R. D., European pat.
sives"). appl. EP 66056 Al To National Starch and Chemical
Corp. (1982), CA98(1O):74181e.
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Ltd. (1985), CAI03(4):24041k.
1. Patent Japan 59/24770, to Yayoi Kagaku Kogyo K.K. 20. Patents Japan A2 (82/131274) (1982),
(1984). CAI01(4):2532x. CA98(6):36432e; A2 (82/121074) (1982),
2. Young, A. H., Fractionation of Starch, in R. L. Whis- CA98(4):18406v; A2 (82/117576) (1982),
tler, J. N. Bemiller, and E. F. Pashall, eds. "Starch: CA98(4): 18408x; A2 (82/115469) (1982),
Chemistry and Technology," 2nd Ed., especially pp. CA98(4):18407w; A2 (82/131273) (1982),
261-263, New York, Academic Press Inc., 1984. CA98(4): 18409y; (81132570) (1981), CA(95):64125p;
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Staerke, 26, 289 (1974). Oil Co., Ltd.
4. Jarawenko, W., Starch Based Adhesives, in "Hand- 21. Durinda, J., et aI., Czech. pat. CS 221869 B (1985),
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211, New York, Van Nostrand Reinhold Co., 1977. 22. DiDominicis, A. J., UK Pat. Appl. GB 2026001, To
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"Rheology and Texture in Food Quality," J. M. 24. Japan Pat. JP (80/89369) to Hohnen Oil Co., Ltd.
DeMan, P. W. Voisey, V. F. Rasper, and D. W. (1980), CA93(22):206476p.
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25. Mochizuki, K., and Yamazaki, T., Japan Pat. JP (871 33. Bovier, E. M., and Carter, J. A., US Patent 4231803
209180), to Japan Maize Products Co., Ltd. (1987), to Anheuser-Busch, Inc. (1980), CA94(4): 17392t.
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27. Touzinsky, G. F., and Sprague, C. H., "Fundamen- 35. Rutenberg, M. W., and Solarek, D. S., Starch Deriv-
tals of the Cold Corrugating Process: Adhesives and atives, in Ref. 2, pp. 323, 339, 353, 363.
Bonding," Annual Meeting-TAPPI, 427-432 (1982). 36. Rohwer, R. G., and Klem, R. E., Acid Modified
28. Touzinsky, G. F., Sprague, C. H., and Kloth, G. R., Starch: Production and Uses, in Ref. 2, pp. 537, 538.
"Fundamentals of the Cold Corrugating Process: Ad- 37. Gruenberger, E., and Mueller, R. German Patent DE
hesives and Bonding," TAPPI J., 65(10), 86-88 3018764 to Henkel K. (1981), CA96(8):53459v.
(1982). 38. Gruenberger, E., and Mueller, R. German Patent DE
29. Kamminga, 1., VanderWerff, H. G. A., Eur. Pat. 3112180 to Henkel K. (1982), CA98(4):17789k.
Appl. EP 96935 AI, to Avebe B. A. (1983), 39. Japan Patent, A2 (87/53366) to National Starch and
CAl00(16): 123122g. Chemical Corp. (1987), CA107(12):98532a.
30. Japan Pat. JP A2(82/165472), to Daicel Chemical In- 40. Japan Patent JP A2 (85112939) to Kanegafuchi Chem-
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31. Japan Pat. A2 (84/142269), to Hoechst Gosei Co. Ltd. 41. Japan Patent JP A2 (821202362), to Hohnen Oil Co.
(1984), CAI0l(24):212374d. Ltd., (1982), CA98(24)200152m.
32. Kaspar, M. L., and Lowey, 1. F., US Patent 4322472 42. Japan Patent JP A2 (82/198771), to Saiden Chemical
to Alco Standard Corp., (1982), CA96(24)201015q. Industry Co., Ltd. (1982), CA98(24):200146n.
 9
Natural Rubber Adhesives
K. F. GAZE LEY
Malaysian Rubber Producers' Research Association,
Hertford, England. SG13 8NL
and

W. C. WAKE
Clive, Shrewsbury, Shropshire, England. SY43LL

INTRODUCTION vidual trees is transferred to collecting tanks,

and from this stage its treatment is determined
This chapter reflects the changes in the tech-
by its destination. If it is to be marketed as la-
nology of one of the natural materials which
tex, it is converted to concentrate; otherwise it
was used as an adhesive long before modem
is coagulated, sheeted or crumbed, dried, and
synthetic polymers and which still maintains an
baled for use as dry rubber. Natural rubber la-
important place. The chapter includes a few
tex grades are described by the method of con-
formulations from the first edition of this Hand-
centration and the type of preservative system
book,l others have been revised. More impor-
used. Three methods of concentration are used:
tantly, over the second and the present editions
evaporation, creaming, and centrifuging, and a
the introduction of natural rubber grafted with
combination may be used in some special
methyl methacrylate has been accompanied by
grades.
greatly improved grading systems for the more
Evaporated latex is produced by heating at a
simple product as well as chemically stabilized
reduced pressure, the ammonia usually being
and chemically depolymerized products. Re-
replaced by potassium hydroxide with the ad-
claimed rubber must now be regarded as ob-
dition of a small amount of soap to assist sta-
solescent in the adhesives industries of
bilization. It has a solids content of about 73 %.
advanced countries, partly because of its un-
Also available is an ammonia preserved grade
certain composition but partly on economic
with 62 % solids content. Retention of the pro-
grounds; it may still have a place in autarchic
teinaceous and other non-rubber components
economies.
during concentration results in greater colloidal
stability than other types exhibit, and improved
RAW MATERIALS resistance to aging, but discoloration and mois-
ture absorption are greater. The stability of
Natural Rubber Latex
evaporated latex is useful in some applications
Latex is tapped from the tree Hevea brasilien- involving addition of a high level of filler.
sis and contains about 35 % solids. It is imme- Creamed latex is prepared by adding fatty
diately ammoniated to prevent bacterial attack acid soap and a creaming agent such as an al-
and coagulation. The field latex from the indi- ginate, after which it is stored in large tanks

167
168 HANDBOOK OF ADHESIVES

until separation of the creamed layer from the the most important grade commercially is LA-
serum is complete. Total solids content is 66- TZ latex. Natural rubber latex is sold to spec-
69 %. Preservation is by ammonia, normally ification, ISO 2004:1979 for creamed and cen-
0.70-0.76% wt/wt, although low ammonia la- trifuged latex and ISO 2027:1978 for
tex is available with secondary preservatives. evaporated latex.
Creamed latex has no special properties of in-
terest to adhesives manufacturers and is not Dry Natural Rubber
normally used by them.
Centrifuged latex is by far the most impor- Eight basic natural rubber types are recognized
tant type, accounting for about 95% of latex internationally by appearance and description
production. A significant proportion of the only. These are:
water soluble non-rubber components is re- 1. Ribbed smoked sheets
moved by centrifuging or creaming. It is usu- 2. Pale crepes
ally safe to assume that natural rubber latex 3. Estate brown crepes
formulations will be based on centrifuged latex 4. Compo crepes
unless otherwise specified. 5. Thin brown crepes (remills)
Double centrifuged latex is made by diluting 6. Thick brown crepes (ambers)
centrifuged latex and recentrifuging. As a re- 7. Flat bark crepes
sult of this, the non-rubber content (TSC - 8. Pure smoked blanket crepes
DRC: total solids content minus dry rubber
content) is reduced significantly. This is of in- The definition of these grades is described in
terest mainly in medical applications. the so-called Green Book2 and summarized
Sub-stage centrifuged latex is produced by elsewhere. 3 Only the first two grades are pro-
creaming to about 50 % solids content and then duced by deliberate coagulation of field latex,
centrifuging. This enables a higher solids although grade 8 is prepared by reworking
(67%) to be achieved. smoked sheet. The other types are derived from
CV latex is a grade which is treated at an early various adventitious forms of scrap which have
stage with a small amount of hydroxylamine to been subjected to a cleaning process. In this
inhibit storage hardening. system, the rubbers normally used for prepar-
ing adhesive solutions are type 1 (e.g., RSS1)
Preservation or type 2 grades (pale crepe).
In 1965 a system based upon technical spec-
A number of preservative systems are in use ification was introduced under the description
(Table 1). Evaporated latex may be preserved Standard Malaysian Rubber (SMR). This is
by ammonia or potassium hydroxide. Centri- sold in the form of crumb compressed into
fuged latex is always preserved by ammonia, 33~ kg bales wrapped in polythene. The bale
either on its own as in high ammonia (HA) la- carries a standard mark which identifies source,
tex or at a lower level in combination with a weight, grade and also the viscosity number if
secondary preservative as in grades of low am- it is a viscosity-stabilized rubber. This is illus-
monia (LA) latex. The LA grades are typified trated in Fig. 1. Similar schemes are operated
by the type of secondary preservative, of which by some other producing countries. The SMR
scheme was revised in 1979. 4 Some require-
Table 1. Preservatives. ments for the main grades are given in Table 2.
Latex Type Preservative System CV and L grades are "latex" grades, that is,
prepared by direct coagulation of whole field
Heat conc. Ammonia, alkali
Centrifuged latex. SMR5 is restricted to rubber derived from
HA 0.7% ammonia sheet material, such as RSS, which is pro-
LA-BA 0.2% ammonia + 0.2% boric acid cessed and presented in the SMR block form.
LA-TZ 0.2% ammonia + 0.05% TMTD The lower grades SMRI0, SMR20, and
+ 0.05% ZnO SMR50 originate from field grades of rubber,
 NATURAL RUBBER ADHESIVES 169

of such materials in the rubber. The better

grades of rubber have the higher PRJ .
Users of natural rubber will be familiar with
the increase in viscosity and gel content which
can occur during storage, an effect not surpris-
ingly called storage hardening. This is partic-
ularly obvious in latex grade rubbers. The
evidence suggests that the hardening is due to
crosslinking associated with the presence of al-
dehyde groups on the rubber chain, and it can
be inhibited by adding a small quantity of a
monofunctional reactant for the aldehyde
groups. CV rubbers are grades in which the
viscosity is stabilized by the addition of about
0.15 % of a hydroxylamine salt to the latex be-
fore coagulation. The hydroxylamine is not de-
tectable in the finished rubber. In the revised
SMR scheme the number of viscosity-stabi-
lized grades has been reduced to three plus an
Fig. 1. A bale of standard Malaysian rubber.
LV grade in which the viscosity is reduced by
addition of a small quantity of light mineral oil.
the number referring to the dirt content allowed For use in solution adhesives, natural rubber
in the specification. SMR GP is a general pur- must be masticated sufficiently to break down
pose viscosity-stabilized grade prepared from a gel and reduce the viscosity to the required de-
blend of latex grade rubber, sheet material, and gree for dissolution in suitable solvents. As a
field coagulum rubber. result of their very low gel contents, viscosity
The plasticity retention index (PRJ) is a mea- stabilized rubbers dissolve without the need for
sure of the susceptibility of the raw rubber to mastication, although some milling may be re-
oxidative degradation. Oxidation is catalyzed quired for other reasons . It is usual to form the
by some metals such as copper, so that the PRJ rubber into a thin sheet to present a large sur-
test gives an indirect indication of the presence face to the solvent for rapid swelling. The most

Table 2. Mandatory Specifications for SMR Graded Natural Rubber. 3

SMR5. SMRGP.
SMR 10 SMR20
SMR CV, From Blend
Viscosity SMRL, sheet viscosity Field grade
stabilized Latex material stabilized material
Dirt retained on 44 I'm 0.03 0.03 0.05 0.10 0. 10 0.20
aperture (max % wt)
Ash content (max % 0.50 0.50 0.60 0.75 0.75 1.00
wt)
Nitrogen content (max 0 .60 0.60 0.60 0.60 0.60 0.60
% wt)
Volatile matter (max 0.80 0.80 0.80 0.80 0.80 0.80
% wt)
Wallace rapid plastic- 30 30 30 30
ity, minimum initial
value (Po)
Plasticity retention in- 60 60 60 50 50 40
dex (PRJ) (min %)
170 HANDBOOK OF ADHESIVES

Table 3. Granulated Natural Rubber- dent on the temperature of mastication. 5 Gen-

Effect of Particle size on the Rate of erally, the lower the temperature of mastication
Dissolution. to a given Mooney, the higher the viscosity of
Particle size, expressed as a resulting solution (Fig. 2).
Time to reach 0.8%
diameter, mm
rubber concentration,
mean range h Natural Rubber Grafted with Methyl
6.8 5.6-8.0 18 Methacrylate (Heveaplus MG)
4.8 4.0-5.6 11
2.4 2.0-2.8 6 A grafted copolymer (Heveaplus MG) based on
1.2 1.0-1.4 4 natural rubber has been available for many
0.9 0.7-1.0 2.5 years. In distinction to the synthetic block co-
'For a nominal I % solution in toluene. polymers which have been introduced into ad-
hesive technology, Heveaplus MG is a comb-
convenient way to achieve faster dissolution is type material having a natural rubber backbone
to use one of the particulate fonns now avail- and polymethyl methacrylate side chains.
able which are produced by mechanical com- MG 30 and MG 49 are graft copolymers con-
minution and grinding of dry rubber. taining the percentage amounts of methyl
The effect of mean particle size on the rate methacrylate indicated by the numbers. They
of dissolution is illustrated in Table 3 for frac- are available either as latices or as solid rubbers
tions sieved from granulated SMR-5 bale rub- from suppliers in Malaysia. Alternative sup-
ber. Particles having a mean diameter of 1 mm plies are often available from specialist manu-
are taken up by solvent 5-10 times faster than facturers in consuming countries. Although
particles having a mean diameter of 7 mm. A there is always present some methyl methac-
rubber powder prepared from spray dried latex rylate homopolymer, at least 50% is grafted.
was marketed but proved difficult to produce. The latex contains 50 % total solids and is eas-
A small level of anti-tack agent such as calcium ily manufactured in an adhesives factory. Table
stearate is commonly used to minimize ag- 5 gives the recipe for preparation of the latex. 7
glomeration during manufacture, and this can The latex fonn of Heveaplus is compounded
usually be ignored. in the usual way with dispersions of required
The advantages of CV rubbers in facilitating additives to fonnulations as exemplified in a
the preparation of rubber solutions are clear; latter section. Solid Heveaplus MG is best
but it should be appreciated that for a given milled on a two-roll mill to bring about some
concentration, a solution prepared from an un- breakdown and elimination of gel material be-
masticated rubber such as a CV grade will be fore dissolving in solvent. The degree of mill-
more viscous than when prepared from a harder ing should be carefully controlled, as excessive
rubber masticated to the same rubber viscosity milling will lead to the elimination of grafted
(Table 4). The relationship between Mooney material and increase the amount of homo-
viscosity and solution viscosity is very depen- polymer. A recommended solvent is made of

Table 4. Concentrations of Various Rubber Types

to Give Solution Viscosity of 105 Brookfield LVT
units.
Mooney viscosity, Concentration
Rubber type ML (1 + 4) 100°C required, %
SMR L, masticated 45 17.5
SMR L, masticated 70 11.5
SMR L, unmasticated 95 7
SMR CV, unmasti- 65 9
cated
 NATURAL RUBBER ADHESIVES 171

Mooney viscosity
70~

60

50

40

30~l'-----'--'~,
200 500 1000 2000 5000
----L...-.----.'

10000
Solution viscosity (60 rpm) cP
Fig. 2. Effect of mastication temperature on the solution viscosity of natural
rubber (SMR5 grade, 7% solution in toluene).s

equal parts of toluene and methyl ethyl ketone. Depolymerized Rubber

The hardness of the film deposited from solu-
tion may be varied according to the balance be- This material has been available for many years
tween nonpolar solvent favoring rubber solution in the United States8 and in the UK. 9 It is a
and polar solvent favoring polymethyl meth- liquid rubber prepared by extensive mastication
acrylate solubility. Solution polymerized Hev- at high temperature (250°C) in the presence of
eaplus MG is made from SMR or masticated air and a peptizing agent. A range of viscosity
pale crepe rubber, and a method suitable for a grades can be produced by varying the time of
laboratory scale preparation was described in treatment. This material is soluble in many or-
the second edition of this Handbook. ganic solvents but not alcohols and ketones, and
is compatible with many drying oils and ester-
Table 5. Manufacturing Recipe for type plasticizers. More recently, French work-
Heveaplus MG 49. ers have developed a method for preparing liq-
uid natural rubber from chemically treated
Pans by wt.,
wet latex. 1O Although this particular method has
some disadvantages, a pilot plant has been
Natura! rubber latex concentrate
erected in the Ivory Coast to develop the pro-
(high ammonia, 60% rubber
content) 1000 cess technology. Possible markets include use
Ammonia solution (2% by wt.) 735 as a tack builder in the manufacture of tires.
Methyl methacrylate monomer Experimental work has shown that a chemi-
(stabilizer, less than 0.02 % cally depolymerized latex exhibits the charac-
hydroquinone) 610
teristics of a pressure-sensitive adhesive. II
t-butyl hydroperoxide (minimum
65% active) 2.0 Good peel strength was found without the ad-
Oleic acid 3.0 dition of resin, and as the low glass transition
Tetraethylene pentamine temperature of natural rubber was not affected
aqueous solution (10% by by the reaction, these materials may be of in-
wt.) . 8.5
terest in low temperature applications. Blends
172 HANDBOOK OF ADHESIVES

with normal latex and resins gave good bonds the reader together with underlying scientific
to polythene. phenomena such as thermodynamic wetting and
diffusion.
Synthetic Polyisoprene Natural latex is polydisperse, i.e., the size of
the individual particles varies considerably
There is no reason in principle why synthetic
(Fig. 3) from as little as 0.01 p.m up to about
polyisoprene should not replace natural rubber
5 p.m. This is in contrast to most synthetic latex
in many of the recipes discussed later. How-
in which the range of part~cle size for a partic-
ever, there are some differences in behavior
ular latex is quite narrow. In natural latex the
mainly associated with the differences in mo:
greatest proportion of the particles in number
lecular weight and gel, the higher content of
terms has a diameter less than 0.5 p.m but most
trans isomer in synthetic polyisoprene, and the
of the mass of the rubber is in particles greater
naturally occurring materials in the natural rub-
than 0.6 p.m in diameter. As a result of the wide
ber.
particle size distribution, NR latex has a very
On the advantageous side the gel-free nature
good relationship between rubber content and
of the synthetic material gives solubility in sol-
viscosity, so that the viscosity at a given rubber
vents without preliminary mastication. Set
content is relatively low in comparison with
against this is the relatively poorer tack and
synthetic latex.
poor green strength. For unvulcanized adhe-
In common with other high polymers natural
sives, therefore, the poorer performance must
rubber is heterogeneous with regard to molec-
be set against greater ease of preparation and
ular weight, so that any particular sample con-
possibly less tendency to gel in storage.
tains a range of molecular weights (Fig. 4). The
Vulcanizing adhesives need some small
average molecular weight is usually taken to be
changes in the recipe to allow for the fact that
about one million. However, the picture is
synthetic polyisoprene does not contain lauric
complicated by the presence of gel, the portion
acid, so that the minimum loading of stearic
of the rubber which does not dissolve in a good
acid must be watched. It is also free of nitrogen
solvent.
compounds, so that for a given level of sulfur
In fresh ammoniated latex the gel content is
and accelerator a slightly softer compound is
usually low, e.g., about 2 % at 14 days after
obtained, which also cures rather more slowly.
tapping. This may rise to about 30% by 2
Should the bond be under some stress before
months and 40-50% by 4 months. The latter
curing starts, tackifiers could usefully be added
figure would be typical of commercial latex by
or increased to ensure holding the bond until
the time it is delivered to the consumer in most
vulcanization is under way. There is no reason
countries. Atypical molecular weight distri-
why, in a vulcanized adhesive, fully equal per-
bution plot for commercial concentrate is
formance should not be obtained.
shown in Fig. 4. The formation of gel is greatly
A liquid synthetic poly isoprene is marketed
inhibited in CV latex (Fig. 4), resulting in a
by the Japanese company Kuraray. 12 This
product, which is made by the polymerization
of isoprene monomer, is available in a wide Weight fraction
rang~ of different viscosity and chemically
0.2
modlfied grades. Because of its high purity,
there is a significant market in surgical adhe-
sives. 0.1

FORMULATION OF LATEX ADHESIVES

200 500 1000 2000 5000
The general principles governing the formula- Equivalent particle diameter (nm)
tion of adhesives have been discussed Fig. 3. Particle size distribution (weight) of a sample of
elsewhere 13 and it will be assumed that the NR latex obtained by Proton correlation spectroscopy
property of tack or tackiness is understood by (Malvern 4600 instrument).
 NATURAL RUBBER ADHESIVES 173

40 Dry bonding adhesives are used to form

I gel
I bonds after the water has evaporated. They may
I
30 I
I also be classed as pressure-sensitive adhesives,
wi'" I
I because pressure is needed to achieve contact
between the joining surfaces. The most simple
case is the dried natural rubber latex film which
will stick only to itself and requires that both
surfaces be coated. At the other extreme is the
material normally associated with the term
4 5 6 7 pressure-sensitive adhesive, which will stick to
Log MW
a variety of surfaces.
Fig. 4. Molecular weight distribution in samples of nat- In some cases bonding is carried out with the
ura! rubber latex: (1) HA latex; (2) CV latex; (3) depoly- adhesive in a part dried condition, as natural
merized latex.
rubber latex films combine very easily in this
state. Further reduction in water content at the
lower gel content (5-10%) and average molec- combination stage may be allowed if small
ular weight (Mw :::::; 600,000). quantities of a tackifying resin are added.
The main characteristics of normal NR latex In many cases it will be necessary to increase
are as follows: the viscosity of the adhesive with thickener.
1. High gel content Examples of this are thick bed or gap filling
2. High molecular weight adhesives, or adhesives for use on porous sub-
3. High cohesive strength strates. Naturally occurring materials are
4. Low intrinsic tack sometimes used, such as karaya gum; casein
5. High self tack also tends to increase viscosity as well as be-
6. Low content of soap and other non-rub- having as a stabilizer. However, it is now more
ber materials usual to use synthetic polymers such as methyl
7. High rubber content cellulose and similar derivatives, and polyacry-
lates.
The relative importance of these factors varies
with the application. In some cases the appli-
Quick-Grab Adhesive
cation may be critically dependent on one or
two properties. These adhesives are used in the shoe industry
Latex adhesives may conveniently be di- for bonding insoles and labels into shoes. The
vided into two types, wet bonding and dry adhesive is applied wet, must allow adequate
bonding. Wet bonding adhesives are applied to time for positioning, and should then set within
the joining surfaces in the fluid state, the bond a few seconds under finger pressure. On sub-
being formed by drying. An important feature strates which are reasonably porous, a natural
of these adhesives is that there is an important latex with high rubber content (ca 65 %) has
mechanical component in the bonding process. suitable properties. 14 Water absorption into the
Therefore bulk properties, such as modulus, are substrate reduces the colloidal stability so that
significant and filler addition is often used to it becomes sensitive to the rubbing action of the
stiffen the adhesive with a useful reduction in finger. The time required for this can be con-
cost. It is essential for the development of the trolled by adjusting the viscosity of the aqueous
bond that water should be removed from the phase with small additions of thickener or
adhesive, and wet bonding adhesives are only water.
suitable for situations in which at least one sur- Although the film is still wet at this stage,
face is water-porous, e.g., paper, leather, con- the gel has sufficient strength to hold the insole
crete, and textiles. Typical instances of this in place until full strength is reached through
type are anchor coats for tufted carpets, ce- drying. Soap addition, even at low level, tends
ramic tile adhesives, and the quick-grab adhe- to destroy the quick-grab action by making the
sive described later. latex too stable. The best material for this ap-
174 HANDBOOK OF ADHESIVES

plication is high solids centrifuged latex; Latex Pressure-Sensitive Adhesives

creamed latex, although of high solids content,
Although natural rubber has good self tack, in
does not behave in the same way, possibly due
adhesive terms its intrinsic tack is low. How-
to residual creaming agent.
ever, it is well known that the good tack prop-
Normal concentrate can be made to behave
erties required for pressure-sensitive adhesives
in a similar fashion by the addition of 3-5 pphr
can be obtained by compounding with tacki-
of a swelling solvent such as toluene. This ef-
fying resins. This technology is well estab-
fectively increases the nonaqueous volume
lished in solution adhesives based on solid
fraction, simulating a high solids latex. As an
rubber, and usually requires that the gel frac-
alternative, the stability of the latex can be re-
tion be eliminated and the molecular weight be
duced by treatment with a proteolytic enzyme,
reduced to faciliate solution and for other rea-
with very small addition of soap to adjust sta-
sons. This is done by mastication, but masti-
bility if this is found to be too low.
cation is not possible with latex. From the
compounding viewpoint this does not matter,
Self-Adhesive Envelopes
as components are added as dispersions; but it
When natural rubber latex dries, some of the does have some effect on the resulting adhe-
soluble non-rubber components are brought to sive.
the surface by water transport and are left as a In general, for a given composition the latex
thin film when drying is complete. This tends adhesive will tend to have higher cohesive
to reduce the surface tack of the rubber so that strength. It will also have lower tack and will
raw latex films are generally nonadherent when require a higher contact pressure or longer con-
pressed on to other surfaces. When the film is tact time to achieve the same bond strength.
pressed against a similar surface, however, it This is because the high molecular weight and
is thought that the thin non-rubber layer is dis- gel phase impart a higher modulus and resili-
placed, allowing the two natural rubber sur- ence to the adhesive, so that the adhesive is less
faces to achieve contact and form a bond, compliant and it is more difficult to achieve
accounting for the good self tack of films from good contact with a surface. Thus the latex ad-
natural latex. This characteristic has led to the hesive will require the use of softer resins and/
development of the self-adhesive envelope. The or higher levels of resin than for comparable
high cohesive strength of the rubber provides a solution adhesives prepared from solid rubber.
security aspect by ensuring that the envelope The lower gel content and molecular weight of
cannot be opened without the fact being ob- CV latex rubber is reflected in an increase in
vious through damage to the seal. tack measured under low contact pressure, as
Formulation I at the end of this chapter is a shown for probe tack and the quick-stick test
suitable base. Preservation against bacterial at- in Table 6. 15
tack is necessary, as also is a fungicide, as the This trend can be developed further by chem-
dried film is open to the atmosphere. Zinc di- ical modification. l1 Fig. 4 shows the changes
ethyldithiocarbamate performs both functions. in molecular weight distribution which can be
It is sometimes found that an occasional batch obtained by controlled oxidative depolymeri-
of latex does not display a sufficient degree of zation of the latex rubber. These materials are
self adhesion, and this may be overcome by particularly interesting as they have intrinsic
adding a small amount of a high molecular
weight plasticizer. A liquid polybutene added
Table 6. Effect of Rubber Plasticity on
up to 10 pphr as a 50% emulsion is suitable. In
Tack.
some cases it may be necessary to improve the
bond to the paper so that the envelope may not HA latex CV latex
be opened without tearing the paper; a polyvi- Wallace plasticity 95 50
nyl acetate latex added at about 10 pphr has Probe tack (N) 5.4 7.3
been found to achieve this without noticeable Quick-stick (N/cm) 2.9 4.3
90° Peel (N/cm) 5.4 5.2
loss of self tack.
 NATURAL RUBBER ADHESIVES 175

tack, i.e., they possess pressure-sensitive ad- required. Generally it will be necessary to add
hesive properties without addition of tackifying a surfactant to maintain colloidal stability, and
resin (see Fig. 5). They can be blended with this requires careful consideration, as such ma-
nonnallatex to improve cohesive strength (Fig. terials can affect tack by migrating to the sur-
5), with resin to improve tack or peel strength face. This and other matters have been
(Fig. 6), or with both as necessary. discussed elsewhere. 16
Tackifying resins must be added to latex in
the fonn of an aqueous dispersion. These are Tile Adhesives
available commercially, although at present the
choice is not as wide as with solid resins. Con- The major part of the market for ceramic tile
siderable expertise is required to fonnulate resin adhesives is held by fonnulations based on a
dispersions, as it is important that the particle filled polyvinyl acetate latex, but natural rubber
size be small, preferably less than 1 ILm in di- latex is still used as a base, particularly where
ameter. Large particle dispersions may result in the adhesive is to perfonn under damp condi-
reduced tack and delay in attaining equilibrium tions. Fonnulations II and III give examples.
between rubber and resin in the adhesive film. Tile adhesives need to be stiffer than most other
The most popular resins for natural rubber are applications, and this effect is provided by the
based on rosin esters, and these may be ex- clay filler, which also reduces material costs
tended with cheaper synthetic hydrocarbon res- and imparts gap filling properties. Cost may be
ins depending on the adhesive properties further reduced by increasing the level of clay
to 250 pphr, although perfonnance will be re-
duced. The resin serves to improve bond
Peel strength, N.cm- 1 Shear time, hrs
I strength and water resistance.
12 A suitable latex stabilizer is essential in view
80 of the high filler content. The cellulose thick-
ener aids spreading by retarding loss of water
8
into concrete or other porous substrates. Zinc
40 diethyldithiocarbamate serves the dual function
4
of antioxidant and fungicide/bactericide, but
additional biocide is advisable for use under
o adverse conditions.
10 20 30 40 50 The ingredients should be mixed in the order
Rubber from LA latex, %
given. Resin and oleic acid are dissolved in the
Fig. 5. Blends of depolymerized latex with nonnal NR
solvent and then allowed to cool. Then the al-
latex. Mw = 160,000. (1) 180 0 Peel strength on glass; (2)
hold time, PSTC7, 500 g; (3) Mw = 80,000, 180 0 peel kali and casein solution is added, followed by
strength. the clay slurry, latex, and other ingredients. A
water-in-solvent dispersion of the clay slurry
Peel strength, N.cm- 1 fonns initially, which inverts during the later
stages of adding the slurry or latex. Thickener
12 is added to give the required viscosity. It should
be noted that the conventional technique by
8 which resin and filler are added to a stabilized
latex gives a lower bond strength, and inferior
4
spreading characteristics. This fonnulation in a
50 X 50 mm lap bond between tile and con-
crete gave a shear force of 440 N when tested
o wet after 7 days immersion in water. In a sim-
10 20 30 40 50 60
Resin content, % ilar test using a commercial PYA-based adhe-
Fig. 6. Blends of depolymerized latex (Mw = 160,000) sive, the tile fell off on removal from the water.
with alphatic hydrocarbon resin. 180 0 Peel strength tested A cheaper, solvent-free mix is given in for-
against (1) glass, (2) polythene. mulation III; it uses a liquid coumarone resin
176 HANDBOOK OF ADHESIVES

which disperses directly into the clay slurry base. The pile is locked into position by apply-
with stirring. ing a coat of adhesive, called the anchor coat
A similar style of adhesive is shown in For- or primary backing, to the back of the carpet.
mulation IV for wet bonding vinyl tiles to con- In carpets with a secondary backing this adhe-
crete, etc. In this case a softer adhesive with sive is also used to laminate a layer of textile
greater peel resistance is required. To this end such as hessian to improve the structural sta-
the amount of filler is reduced and the resin is bility of the carpet. Modem practice is to use a
increased, which also improves tack. Addi- non-vulcanizing compound for these adhe-
tional softening comes from the oil. Some filler sives; Formulation VI is suitable for use with
is retained to give some gap-filling ability for natural rubber latex. As the action of the ad-
minor variations in substrate level. The prepa- hesive is essentially mechanical, a high mod-
ration is broadly similar to Formulation II. ulus is required and this is provided by the
Resins, oil, and oleic acid are dissolved in the stiffening effect of a high filler loading. Further
solvent with heating and allowed to cool. The stiffening giving improVed bond strength can be
alkali and half of the casein are added to the obtained by adding 30 pphr MG49 latex. In
solution with stirring, followed by the water. some cases a soft "hand" is required, and this
The remaining casein is added to the latex be- can be met by reducing the filler content to
fore adding this to the mix. The clay may be about 100 pphr.
added dry or slurried first with some of the Low ammonia latex (LA-TZ) is preferred be-
water. Vinyl-to-vinyl adhesion for a 75 x 35 cause of its higher inherent mechanical stabil-
mm overlap joint tested in shear was 300 N for ity. The preferred surfactant is a salt of an
a 7-day-old bond, and the peel force was 19 N. alkylarylpolyether sulfate with a polyether
chain length of 8-10 ether units, which is re-
Reseal Adhesives sistant to the multivalent cations sometimes
found in association with fillers. Good protec-
This is a type of envelope adhesive which has
tion against aging is given by the combination
characteristics enabling the flap to be sealed and
of thiourea and conventional antioxidant. For
unsealed several times. The main requirements
specifications which require a temperature
are the ability to make a good bond to the paper
above 100°C for an aging test, the conven-
or other substrate and good cohesive strength
tional antioxidant should be of the p-phenyl-
so that the adhesive is not distorted during the
enediamine type, e.g., UOP26. Tetrasodium
unsealing action. As the adhesive is applied to
pyrophosphate aids dispersion of the filler and
each joining surface only a limited degree of
also has a beneficial effect on mechanical sta-
tack is necessary. Formulation V has these
bility.
characteristics. The resin suggested, which has
The components of the mix should be added
a high degree of aromatic structure, promotes
in the order given, the filler being added slowly
the bond to difficult substrates without impart-
with stirring to avoid localized dehydration of
ing too much tack. The clay and prevulcanized
the latex resulting in the formation of coa-
latex improve cohesive strength and also con-
gulum. Thickener is added to adjust the vis-
trol surface tack.
cosity as required and to avoid inconsistency
The balance between tack and cohesive
due to entrained air; this is best done after the
strength may be varied by the balance between
air has been allowed to come out. Anchor coats
unvulcanized and prevulcanized latex. The pre-
of this type give a face pull tuft bond strength
vulcanized latex should be clarified after pre-
of 60 N or more.
vulcanization, i.e., centrifuged to remove
excess vulcanizing components. This is to pre-
vent post-cure in the adhesive, which may re- Other Nonvulcanizing Latex Adhesives
duce tack too much.
Latex adhesives are widely used in the shoe in-
dustry; one instance, the quick-grab adhesive,
Anchor Coat for Tufted Carpets
has already been described. Another example
Tufted carpets are manufactured by looping the is found in the manufacture of canvas shoes.
yam, which forms the pile through a textile The base of the canvas upper is dipped into a
 NATURAL RUBBER ADHESIVES 177

bath of natural latex to a depth of about two used for this purpose. It is free from fillers but
centimetres and dried. The resulting film of contains preservatives; for, although it is not in
rubber, having impregnated the canvas, forms direct contact with biologically active liquid,
a mechanical bond and provides a surface with mold growth could develor.
good green tack to which a rubber sole may be
attached and bonded in a subsequent oven cure.
Vulcanizing Latex Adhesives
Formulation VII is suitable. It is not necessary
to add vulcanizing ingredients, as these diffuse The major use of vulcanizing latex adhesives is
across the interface from the sole compound. in the manufacture of textiles, rugs and carpets,
Another use of latex in shoe manufacture is and closely allied products such as rubberized
leather bonding, where there is often a need for hair. As in many other latex applications, ultra-
a temporary support to assist positioning while accelerators are used to effect vulcanization.
the leather shapes are stitched together. An ad- The materials used must be stable in alkaline
hesive with good self tack is required. As some dispersions, although they need not be active,
leathers contain heavy metals, particularly since if the alkali is ammonia it will normally
chromium, adequate protection is necessary be removed early in the drying/vulcanization
against their effect in promoting oxidation; this process. The vulcanization ingredients, sulfur,
could cause undue softening of the rubber and zinc oxide, and the insoluble accelerators must
result in defacement of the leather by bleed- be added as dispersions in water, and these are
through. For unvulcanized rubber adhesives the conveniently prepared at 50% solids and sta-
best protective systems are based on metal bilized by an anionic surfactant. Such disper-
complexing agents usch as EDT A and zinc di- sions may be made by ball-milling or may be
ethyldithiocarbamate. For more sensitive ap- easily purchased premade from specialist sup-
plications involving larger areas, as in ladies pliers. Soluble accelerators can be added as so-
fashion boots, a prevulcanized latex is pre- lutions directly to stabilized latex, but the
ferred (Formulation VIII). solutions have a much more limited life than
Internal trim for automobiles may be conve- do dispersions.
niently secured by a latex adhesive which must To obtain vulcanization at room temperature,
be light colored and protected against oxidation combinations of accelerators are often used.
by a nonstaining antioxidant. Some thickener The most effective for general use is zinc di-
and tackifier is desirable, as much of the trim butyldithiocarbamate (ZBUD) and a thiazole
is fabric and penetration through this would such as zinc mercaptobenzthiazole (ZMBT).
constitute a serious fault. Formulation IX aims Typical levels are I pphr together with 1-1. 5
at meeting these properties. pphr sulfur. The use of the sodium salt of the
Latex compounds are used as sealants in var- dithiocarbamate should give some increase in
ious types of metal containers, including ordi- activity. Several manufacturers supply low
nary cans, drums, and pressurized aerosol cans. temperature accelerators based on activated di-
The latex is applied as a wet layer to the end- thiocarbamates in which the zinc is complexed
plates and dried and cured. When the plate is by an organic amine. In most instances room
seamed to the body of the can the latex deposit temperature curing systems are not required, as
acts as a seal. As cans are commonly used in temperatures suitable for normal curing sys-
food contact applications, the formulation must tems are used in the drying oven; cure takes
be chosen with care and be based on HA latex. place during and as an extension of the drying
Formulation X is an example. It should be en- stage. For these cases a conventional system of
sured that in food contact applications the com- dithiocarbamate, zinc oxide, and sulfur is sat-
pound complies with local regulations, which isfactory, e.g., I pphr of each. Modulus can be
vary from country to country. boosted by 1 pphr 2MBT if required.
Similar comments apply to crown cork ad- It should be realized that many latex vulcan-
hesives. These are used in crown cork closures izing systems are more active in wet latex than
to secure the thin layer of cork to the waxed in the dry film, and will prevulcanize the latex
paper in contact with the liquid or the metal over a period of one to two weeks, particularly
cap. Formulation XI is typical of the material in regions having high ambient temperatures.
178 HANDBOOK OF ADHESIVES

This may alter the characteristics of the adhe- portant. Formulations XIV and XV differ only
sive; for example tack will be lower even if in the sulfur level. Some sulfur combines with
tackifying resin is present. Where prolonged animal hair and extra is needed to give the de-
storage is envisaged a two-part compound may gree of vulcanization required for low
be necessary, with the accelerator and sulfur compression set and good resilience. Interme-
separated. As an altemative, an accelerator diate levels should be used for hair/coir blends.
system based upon zinc dibenzyldithiocarba- Application rates may vary from 10 to 100%
mate may be used, as this is much less active of the weight of the fiber depending on the end
in ammoniated latex. use. The sprayed fiber pads should be dried at
The increase in modulus produced by vul- 6O-70 o e and cured 30 min at l00 0 e in hot air.
canization is useful where the adhesive bond Low ammonia (LA-TZ) latex is preferred for
has an important mechanical component, as the its better mechanical stability. An efficient an-
need to add filler for stiffness is reduced. Filler tioxidant is needed to protect the thin films of
is sometimes included to reduce cost, but the rubber which bind the intersections of the fiber.
amount may be limited by the higher perfor- An unfilled gum adhesive is also suggested
mance requirements of those applications in for bonding the two-part fabric covers to the
which vulcanizing adhesives are often used. An inner core of tennis balls. In common practice
example of this is Formulation XII for anchor a solution adhesive has been used, but a switch
coat backing of washable rugs and bathroom to natural rubber latex can avoid the problems
mats. 17 The highly filled unvulcanized adhe- arising from the use of solvents. A simple com-
sives of Formulation VI would not stand up to pound based on a stabilized latex with vulcan-
the repeated washing to which such articles are izing system can be used but tends to be
subjected. In this compound choice of antiox- sensitive to the degree of drying given before
idant is particularly important for adequate ag- bonding, i.e., poor bonding may occur if drying
ing/washing resistance. IS This formulation is taken too far. The addition of a minor pro-
requires drying/curing conditions of about 15 portion of tackifying resin as in Formulation
mins at 130 o e. XVI eliminates this problem without the coated
Nonwoven fabrics are usually prepared by surfaces becoming difficult to handle. The ball
forming a uniform web of fibers to which a and the covers are coated with adhesive and
bonding agent is applied by spray or impreg- dried for about ten minutes at 70 o e, when the
nation. Natural rubber latex has been displaced covers can be applied. A dry rubber type of
from much of this market by special purpose curing system is used to prevent the latex pre-
synthetic polymer dispersions but is still pre- vulcanizing and to be compatible with the
ferred where mechanical properties, particu- higher temperatures used for vulcanizing the
larly resilience, are important. Examples are core.
carpet-underlay felts and low density shoe in- The final example is a flocking adhesive for
soling felts. A general purpose formulation for latex rubber gloves (Formulation XVII). Latex
this purpose is shown in Formulation xm. A gloves are manufactured by the coagulant dip-
suitable stabilizer is a sulfated alkylaryl poly- ping process in which a layer of coagulant is
ether surfactant. As waste fibers are often in- left on the former when it is immersed in a so-
cluded in nonwoven fabrics, the antioxidant lution of calcium nitrate. When the former is
should give good protection in the presence of dipped into a suitable latex compound, a layer
copper. of latex gel forms, which is removed after
A preservative such as lauryl pentachlor- drying and vulcanizing. Domestic gloves are
phenate may also be included, and a deodorant frequently made with a flocked inner surface to
for insoling. A cure of 3-8 minutes at 120 0 e produce a soft, warm feel, at the same time
in hot air is suggested. making the glove easier to put on the hand. The
Natural rubber latex is also the preferred flock cannot be applied to the latex gel, so an
binder for rubberized hair/coir products. In intermediate layer of wet latex is used. For the
these materials, which are used for packaging flock to bond, the adhesive must be fluid, and
and upholstery, resilience is particularly im- a nonionic surfactant is used to stabilize the ad-
 NATURAL RUBBER ADHESIVES 179

hesive against the gelling action of calcium ions these produce a degree of crosslinking, it would
which diffuse through the gel deposit. The vis- be more logical to include adhesives using them
cosity is increased to 200-300 cp (Brookfield in the section on vulcanizable solution adhe-
LVT Viscometer, spindle 2,60 rpm, 23°C) by sives. However, there are differences which af-
the addition of a thickener so that sufficient ad- fect their formulation as well as their properties.
hesive is picked up on the gel to anchor the Like vulcanizing solution adhesives, those
flock. reinforced by isocyanates must be supplied as
two-part compounds mixed immediately before
SOLUTION ADHESIVES FROM use. However, in the present case, one part is
NATURAL RUBBER identical in composition with a typical nonvul-
canizing solution adhesive and the other is a
Nonvulcanizing Adhesives
simple solution of the polyisocyanate. More-
For many purposes a simple solution of rubber over, curing is always at room temperature. As
in a solvent gives a useful adhesive. This is is well known, isocyanates react readily with
particularly so for natural rubber, which is water and other compounds with active hydro-
tacky without the need for tackifying resins. gen. Hence special care must be taken to use
However, the adhesives of commerce are much dry solvents and in particular to avoid the use
more sophisticated and achieve their superior of the tailings from tanks of hydrocarbon sol-
results by the careful matching of additives and vents. When mixed solvents are used, alcohols
solvents to intended applications. The principal must be absent. The crosslinking of natural
additives in use today are described here. rubber by isocyanate occurs at the few hy-
Tackifying Resins. These are advantageous droxyl groups introduced adventitiously during
when the dried surface of the adhesive is in- preparation or mastication of the rubber. Iso-
tended to be permanently tacky, as with a pres- cyanate may also react with the substrate on
sure-sensitive tape, or at least to remain tacky which the adhesive is spread.
for a long while after removal of solvent. Var- Chlorinated rubber is also a valued reinforce-
ious naturally occuring resins and their deriv- ment agent for natural rubber adhesives, im-
atives are used, such as rosin and rosin esters, proving the cohesive strength of all adhesives
terpene, and coumarone and coumarone-in- formulations and the adhesive strength to many
dene. Resins synthesized from petroleum are substrates.
widely used, often in combination with those Antioxidants. The use of an antioxidant at
from biological sources. about I phr or as recommended by the supplier
Softeners. Unless excessively masticated, the is always to be recommended with natural rub-
rubber may be too hard for the application, so ber except for surgical applications. Care must
softeners are employed. Examples are lanolin, be taken with the choice, bearing in mind the
used for surgical plasters, and liquid polybu- possibility of migration to the substrate.
tenes. Fillers. Apart from carbon black, fillers do
Reinforcing Agents. To increase the cohesive not play a large part in the formulation of so-
strength of an unsaturated rubber adhesive, car- lution adhesives. Small additions of clay or
bon black is the material of choice. It must be whiting are sometimes used to control viscos-
added to the rubber in an internal mixer or on ity, but usually this is achieved by solvent
a two roll mill before the rubber is dissolved in blending. An exception to this is the traditional
the solvent. Such additions do, of course, use of zinc oxide in surgical plasters and tapes
stiffen the dried adhesive, and some softener and of whitings or clays where there is a need
may be required to balance this, though this for some gap-filling property. Solvent adhe-
could adversely affect adhesive performance. sives are not, in essence, good gap fillers, how-
Carbon black used to be added by means of ever.
whole tire reclaim but, as noted in the intro-
duction, the practice is declining. Formulations XVIII-XX illustrate the rela-
A different type of reinforcement is achieved tively high resin content required by perma-
by the use of polyfunctional isocyanates. As nently tacky, pressure-sensitive materials. In
180 HANDBOOK OF ADHESIVES

Fonnulation XX the high filler content option and one-half the rubber content in one solution
would tend to be used with a high resin con- and the accelerator and remaining rubber in the
tent, and certainly the very high loading of zinc other half.
oxide would now be regarded as extravagant An important consideration is that two solu-
for a commercial tape. tions of comparable kinematic viscosity .are
Fonnulations XXI-XXIII would at one time more easily mixed than two which differ mark-
have been used domestically in the do-it-your- edly. Comparable kinematic viscosities are
self market. Most adhesives now in this market most easily obtainable by arranging density and
are highly polar synthetic materials, which are viscosities to be equal. This is illustrated in
preferable for securing decorative laminates to Fonnulation XXIV. This compound is a self-
wooden and plaster substrates; but for many vulcanizing cement such as might be used for
purposes about the home such as securing pa- joining proofed fabrics. Fonnulation XXV
per, waterprooflabeling, or repairing leather or would serve the same purpose. 19 For joining
rubber articles, this series of adhesives could heavy duty proofed fabrics such as panels for
be used. hovercraft skirts and the like, a much more so-
The general-purpose black adhesive of For- phisticated compound would be used contain-
mulation XXII could be used for amateur re- ing tackifying resins, a substantial quantity of
pairs to car trim, securing car mats and carbon black, and polyisocyanate as well as
vibration damping which has become de- vulcanizing ingredients. However, because of
tached, although where appreciable engine the gelling reaction with rubber, the polyiso-
wannth is experienced Fonnulation XXIII cyanate would be added separately just before
would be preferable. The latter compound use so that, in effect, a three-part compound
could also be used in black leather footwear would be involved. The isocyanate might also
manufacture and in the assembling of rubber be mixed into a solution of chorinated rubber,
boots. Fonnulations XXII and XXIII both con- where it would have a reasonable pot life.
tain whole tire black reclaim, and for many Fonnulation XXVI is a two-part compound
purposes they could with economic advantage suggested as suitable for bonding vulcanized
be fonnulated with further reclaim replacing the rubber to vulcanized rubber.20 After curing for
new rubber. If this revised fonnulation is at- 7 days at room temperature the peel strength of
tempted, the coumarone resin could be usefully laminated NR strips was 1.8-2.8 N/mm de-
replaced with 50 parts of wood rosin or zinc pending on the nature of the rubber strips. De-
resinate to provide a higher acid number to as- tails of perfonnance under the other conditions
sist solution of the reclaim. are given in Ref. 20.
Such reclaimed rubber adhesives are suitable
for packaging, fitting padding in ammunition Mastics, Asphaltics, and Sealants
boxes, canvas-to-wood, and for making kraft
Mastics are sealing materials which adhere to
papers. They can also be used, if necessary,
the substrate and are used as fillers in metal or
with small additions of softeners, as gunnable
brickwork comers and angles. They are usually
adhesives, and on building sites for securing
of high viscosity and become effectively im-
wall panels.
mobile on loss of solvent or water, the shrink-
age occurring wholly from the free surface.
Vulcanizing Adhesives
Frequently such materials contain drying oils
Unlike vulcanizing latex adhesives, which have or bituminous components which harden with
a storage life measured in weeks, vulcanizing time and fonn a skin over the surface. Asphal-
solution adhesives have a limited pot life and tics are used in the preparation of waterproof
are stored as two-component mixtures. The two building and packaging papers in which coarse
parts are mixed immediately before use and the grade papers are bonded together by the im-
solution will then have a workable life of per- penneable asphaltic layer. They are also used
haps 2-4 hours before gelation occurs. It is extensively in roads and sidewalks (pave-
usual to fonnulate the two parts with the sulfur ments), and repairs to them are made with an
 NATURAL RUBBER ADHESIVES 181

asphaltic mass, the adhesive properties of ficient way of priming polar surfaces for the
which are greatly improved by the addition of reception of natural rubber adhesives is by use
small quantities of rubber. Natural rubber, usu- of Heaveaplus MG, the preparation of which
ally in the form of latex or a dispersion of re- has been outlined previously.
claimed rubber, is used as an additive to As a primer coat on polyvinyl chloride (PVC)
bitumen sealants used in the construction of backed adhesive tape, Formulation XXIX is
concrete roads. The rubber improves both prepared either directly by grafting in the sol-
adhesion to substrate and low temperature flex- vent, or by masticating solid graft polymer to
ibility. A typical general asphaltic-reclaim a suitable consistency, adding the filler on the
compound is given as Formulation XXVII. mill, and then steeping in solvent. The meth-
Palinchak and Yurgen 1 have given details of the acrylate graft proportion can be adjusted to the
preparation in which the compound is formu- desired figure by mixing two materials of higher
lated from dry components into which water is and lower methacrylate content. The titania is
mixed and alkali added to invert from a contin- optionally added as a marker to assist identifi-
uous rubber phase to a continuous water phase, cation. The solvent is conveniently made of
followed by additiion of the asphalt dispersion equal volumes of methyl ethyl ketone and tol-
and clay slurry. Formulation XXVII could form uene. As a priming solution for synthetic upper
the basis of a wide variety of adhesive com- materials when natural rubber soling is to be
pounds tailored to particular end uses. For the molded directly it is recommended that accel-
manufacture of draft-type papers a lower level erator be added to the adhesive solution; sulfur
of asphalt might be desirable, while for mastic- will migrate in adequate quantity to ensure vul-
like usage the level of clay could be consider- canization. The accelerator may be the same as
ably increased, with a reduction in the water that used in the soling, if this is known, oth-
content. erwise up to 3 pphr piperidinium pentamethy-
In any use the addition of 2.5 parts of casein lene dithiocarbamate may be used.
on 100 of reclaim would be expected to im- An MG latex has been suggested as an ad-
prove the compound. A road repair compound hesive for bonding a woven synthetic fabric
is illustrated in Formulation XXVIII. This rub- such as polyester to EPDM. 21 It was necessary
ber is conveniently added to the heated asphalt to clean the surface of the EPDM by solvent or
in the form of powdered rubber. Control of the scouring using wire wool and soap solution. A
heating process is very important, as overheat- wet bonding technique with MGlO latex gave
ing degrades the rubber. High molecular weight the best results with cohesive failure in the
is essential in the long-chain polymer compo- EPDM.
nent, and hence new natural rubber of good
quality rather than reclaimed rubber is desir-
able. ACKNOWLEDGMENT
The authors record their gratitude to the Board
GRAFTED COPOLYMER HEVEAPLUS of the Malaysian Rubber Producers' Research
MG Association for permission to quote extensively
The natural rubber adhesives, particularly when from their literature.
vulcanized, perform best with essentially non-
polar adherends or those where a strong me-
FORMULATIONS
chanical element is involved in the adhesion
mechanism. Adhesion to smooth polar surfaces These formulations are indicative of the gen-
suggests a polar adhesive, and when this re- eral principles and order of quantities and it
quirement conflicts with other requirements for should not be assumed that they can be made
which a nonpolar adhesive is preferable, it is without modification to suit the circumstances
common practice to prime coat the adherent and materials of manufacture of particular ap-
surface with a polar material which is also plications for which they are intended. All for-
compatible with the nonpolar adhesive. An ef- mulations are based on parts by weight.
182 HANDBOOK OF ADHESIVES

Adjustment should be made for concentrations VI. Tufted Carpet Anchor Coat Adhesive
or solids content differing from those stated. 60% NR latex, LA-SPP 167
25 % Surfactant solution 3
Tetrasodium pyrophosphate
I. Self-Adhesive Envelopes
Water (to 72-75% total solids content) as necessary
60% Natural latex 167 Filler, e.g., whiting 400
10% Potassium hydroxide solution 0.2 10% Thiourea solution 10
50% Aqueous dispersion of zinc 1.0 50 % Antioxidant dispersion 2
diethyldithiocarbamate
Antifoam agent as necessary
10% Thickener solution (polyacrylate) 4
II. Ceramic Tile Adhesive
Hydrocarbon resin (60% soln in 167 VII. Canvas Shoe Sole Adhesive
toluene) 60% NR latex (LA-TZ type) 167
Oleic acid 3 50% Titanium dioxide dispersion 10-20
5 % Potassium hydroxide 15
15% Casein 20 VIII. Leather Adhesive
65 % Clay slurry 232.5 60% Natural latex 167
60% NR latex 167 Sodium ethylenediaminetetraacetate,
Cellulose thickener 3-4 20% soln. 2.5
Water 10 Antioxidant, e.g., polymerized
50% ZDC 2 trimethyl hydroquinoline as 50%
10% Thiourea solution 10 dispersion

IX. Automobile Internal Trim

III. Ceramic Tile Adhesive
60% Natural latex 167
65 % Clay slurry 232.5
5% Methyl cellulose 40
Pale liquid Courmarone resin 100
50% Antioxidant (as 50% dispersion) 4
Polyethoxy sulphate stabilizer
15 50% Clay dispersion 100
(30% active)
60% NR latex 167
50% Coumarone-indene dispersion 20
Cellulose thickener 3-4 Coloring to give drab or neutral color
2 or as required.
50% ZDC
10% Thiourea solution 10
X. Can Sealant
NR latex, 60% rubber, HA type 167
IV. Adhesive for Bonding Vinyl Tiles to Concrete 10% Casein solution 10
Terpene-phenolic resina 100
50% Food-grade antioxidant dispersion 2
Pale liquid coumarone resin 50 66% Clay slurry 167
Process oil b 50 5 % Thickener solution 5
Oleic acid 22.5
SolventC 25 XI. Crown Cork Adhesive
10 % Potassium hydroxide solution 40 60% Natural latex 167
15 % casein solution 20 Fungicide 0.2
Water 75 Ammonium caseinate, 25% aq. sol. 11.2
50% Zinc diethyldithiocarbamate 4 Sodium hydroxide, 25 % sol. 0040
dispersion Formalin, 40% aq. sol. 5.10
60% NR latex, HA or LA-TZ type 167 Rosin ester, dispersion 10
Clay 100
Cellulose thickenefl as required XII. Washable Rug Anchor Backing formulation
60% NR latex, LA-TZ type 167
a. e.g., SP 560 (Schenectady). 25 % Surfactant solution 3
b. Aromatic oil, e.g., Dutrex 729 (Shell). Filler, e.g., whiting 50
c. White spirit or other suitable solvent. 50% Zinc oxide dispersion 6
d. High viscosity type, e.g., Celacol HPM 5000 (Brit- 50 % Sulfur dispersion 4
ish Celanese) or Methofas PM 4500 (ICI). 50% Zinc diethyldithiocarbamate
dispersion 2
V. Resealable Adhesive 50% Zinc 2-mercaptobenzothiazole
LA-TZ latex (60%) 111 dispersion 2
LR Revultex (60%) 56 50% Antioxidant dispersion (e.g., 2
10% Ammoniated casein 20 2246)
Dresinol902, 45% TSC (Hercules) 220 10% Thickener solution
10)
Devolite clay 40 or as required
 NATURAL RUBBER ADHESIVES 1B3

XIII. General-Purpose Adhesive Binder for Nonwoven XVIII. Surgical Tape Adhesive
Fabrics Natural rubber 100
60% Natural rubber latex 167 Colophony or ester Gum 100
20% Stabilizer solution 2 Lanolin 20
50% Sulfur dispersion 4 Zinc oxide 50
50% Zinc diethyldithiocarbamate
XIX. Industrial Pressure Sensitive Tape A
dispersion 3
Natural rubber (pale crepe) 100
50% Zinc 2-mercaptobenzothiazole
Poly(/3-pinene) resin, mp 70°C 75
dispersion 1. 5
Colorless petroleum oil 5
50% Antioxidant dispersion 2
Polymerized trimethy Idihydroquinoline 2
50% Zinc oxide dispersion 6
Soft or distilled water to adjust total XX. Industrial Pressure Sensitize Tape B
solids as required Natural rubber 100
Coumarone-indene resin (35°C) 30-150
Suggested cure 3-8 min at 120°C in hot air
Antioxidant 1.5
XIV and XV. Binders for Animal Hair and Coir Calcium carbonate or zinc oxide 30-150
Animal hair, Coir, XXI. General Purpose Transparent Adhesive
XIV XV Natural rubber 100
60% Natural rubber latex 167 167 Rosin, water white grade 10
25 % Stabilizer solution" 4 4 Antioxidant 1
20% Potassium hydroxide XXII. General Purpose Black Adhesive
solution 2 2 Natural rubber 100
50% Antioxidant dispersionb 3 3
Whole tire reclaim 100
50% Zinc Coumarone resin 50
diethyldithiocarbamate Whiting 50
dispersion 2 2 Antioxidant 1.5
50% Zinc 2-
mercaptobenzothiazole XXIII. General Purpose Black Adhesive with
dispersion 3 3 Better Heat Resistance
50% Sulfur dispersion 8 5 Natural rubber 100
50% Zinc oxide dispersion 10 10 Whole tire reclaim 100
Water (to 50-55% total solids Zinc resinate 50-80
content) as necessary Clay 50
Antioxidant 1.5
a. A sulfated alkyl phenol-ethylene
together with, in separate solution,
b. Polymerized 2,2,4-trimethyl-I,2-hydroquinoline,
Poly isocyanate 10
e.g., Flectol H (Monsanto).
XVI. Adhesive for Tennis Ball Covers XXIV. Vulcanizing Cement
60% Natural latex (LA-TZ) type) 167 Part A Part B
20% Nonionic stabilizer 3 Natural rubber 100 100
Dresinol 303 (Hercules) 66 Sulfur 2
50% Sulfur 4 Butyl Zimate 7
50% Zinc oxide 2 Zinc oxide 20
50% 2MBT 2.4 Antioxidant 5
50% Titanium dioxide 8
50% Antioxidant 2246 2 XXV. Fabric Combining for Double Texture
Thickener (poly acrylate) as required Waterproof
Part A Part B
XVII. Flock Adhesive Formulation
60% Natural rubber latex 167 Natural rubber 100 100
20 % Stabilizer solution 2.5 Zinc oxide 10
10% Potassium hydroxide solution 2 Sulfur 8
50% Sulfur dispersion 2 Zinc isopropyl xanthate 4
50% Zinc diethyldithiocarbamate 2
XXVI. Two-Part Adhesive for Vulcanized
dispersion
Rubber
50% Zinc oxide dispersion 2
Part 1 Part 2
50% Antioxidant dispersion 2
Antifoaming agent 0.1 Natural rubber (SMR 5) 100 100
10% Thickener solution 2 Zinc oxide 5 5
or as required Stearic acid 0.5 0.5
184 HANDBOOK OF ADHESIVES

Antioxidant" 5. Bristow, G. M., and Tomkinson, R. B., Viscosity of

Accelerator' 1.5 Solutions of SMR5L and SMR5CV, NR Technol.,
Accelerator" 0.5 6(part 2), 34-38 (1975).
Sulfur 4 6. Hales, W. F., and Conte, L. B., Adhesives Age, p. 29
(1971).
a. Phenol condensation product 7. Malaysian Rubber Producers' Research Assoc., Tech-
b. Zinc isopropyl xanthate nicalInf. Sheet Ll4 (1977).
c. Diethylammonium diethyldithiocarbamate 8. H. V. Hardman Co., Inc., 57 Courtland Street, Belle-
XXVII. Reclaimed Rubber Dispersion with Asphalt ville, NJ.
Whole tire reclaim 100 9. Chloride Lorival Ltd., Little Lever, Bolton, England.
Surfactant 2-5 10. Pautrat, R., and Marteau, J., US Patent No. 3,957,737
Caustic potash 1-2 (May 18, 1976), Anvar, Agence Nationale de Valor-
Ester gum 20-30 isation de la Recherche, Neuilly-sur-Seine, France.
Clay 30-40 II. Gazeley, K. F., and Mente, P. G., "Pressure-Sensi-
Asphalt emulsion 175-185 tive Adhesives from Modified Natural Rubber La-
Water 70-80 tex," Adhesive, Sealant and Encapsulants Conference,
Kensington, London, 5th November 1985.
XXVIII. Road Repair Compound 12. Kuraray Isoprene Chemical Co. Ltd., 8-2 Nihombashi
Natural rubber (powder) I 3-Chrome, Chuo-Ku, Tokyo, Japan.
Asphalt 60 13. Wake W. C., Elastomeric Adhesives, in "Treatise on
Fine aggregate consisting of broken 34 Adhesion and Adhesives," R. L. Patrick, ed., Vol.
stone of small size mixed with sharp II, Chap. 4, New York Marcel Dekker, 1969.
sand 14. Gazeley, K. F., "Natural Rubber Latex in Pressure-
XXIX. Heveaplus MG Primer for PVC Sensitive and Wet-Bonding Adhesives," Malaysian
Heveaplus MG Rubber Producers' Research Assoc., Symposium on
5
Titanium dioxide (optional) 0.1 Natural Rubber Latex, Wunburg, West Germany,
Solvent to 100 Oct. 1977.
IS. Gazeley, K. F., "The Use of Natural Rubber Latex
in Pressure-sensitive adhesives," Paper No. 28, In-
REFERENCES ternational Conference on Polymer Latex, Plastics and
Rubber Inst., London, 1978.
1. Palinchak, S., and Yurgen, W. J., in "Handbook of 16. Oldack, R. C., and Bloss, R. E., Compounding Nat-
Adhesives," I. Skeist, ed., pp. 209-220, New York, ural Latex in Water-based PSA's, Adhesives Age, pp.
Van Nostrand Reinhold, 1962. 38-44, April 1979.
2. "The International Standards of Quality and Packing 17. Malaysian Rubber Producers Research Assoc., Tech-
for Natural Rubber Grades," The Rubber Manufac- nical Inf. Sheet L31.
turers Assoc. of New York, 1969. 18. Gorton, A. D. T. G., "The effect of aqueous deter-
3. Bristow, G. M., and Rose, I. G., "Market Grades of gent solutions on dipped natural rubber latex vulcani-
Malaysian Natural Rubber," NR background series zates," NR Technol., 8,79 (1977).
No.4, Hertford, England, Malaysian Rubber Produc- 19. Borroff, E. M., and Wake, W. C., Trans. Inst. Rub-
ers' Research Assoc. ber Ind., 25 140 (1949).
4. "Revisions to Standard Malaysian Rubber Scheme 20. Malaysian Rubber Producers' Research Assoc., Tech-
1979," SMR Bulletin No.9, Kuala Lumpur, Rubber nicalInf. Sheet 049.
Research Inst. of Malaysia. 21. Rubber Developments, 37 (part 3), 68 (1984).
 10
Butyl Rubber and
Polyisobutylene
J. J. HIGGINS, F. C. JAGISCH, AND N. E. STUCKER
Florham Park, NJ; Baton Rouge, LA; Baytown, TX
Exxon Chemical Company, Polymers Group-Americas

INTRODUCTION
Butyl rubber and polyisobutylene are elasto-
meric polymers I used quite widely in adhesives
and sealants both as primary elastomeric bind-
ers and as tackifiers and modifiers. The prin- Isoprene Isobutylene
cipal difference between these polymers is that Unit Unit
butyl is a copolymer of isobutylene with a mi-
(n .. -SO)
nor amount of isoprene, which introduces un-
saturation, while polyisobutylene is a Fig. I. Butyl rubber molecule.
homopolymer.
Butyl rubber, as shown in Fig. 1, has a rel- are essentially free of double bonds in the poly-
atively long and straight carbon-hydrogen mer chain (they have only terminal unsatura-
backbone, containing between 47,000 and tion). Many of their characteristics are similar
60,000 units. This regular structure, with few to butyl, e.g., age and chemical resistance, very
double bonds or reactive sites, renders butyl low water absorptivity and low permeability.
very stable and quite inert to the effects of The polyisobutylenes are produced over a wider
weathering, age, and heat. It has good resis- molecular weight range than butyl. The low
tance to vegetable and animal oils and to attack molecular weight grades are soft, tacky, water-
by chemicals. Being an all-hydrocarbon mate- white semi-liquids, while the higher molecular
rial, the butyl polymer has a very low water weight grades are strong, tough, elastic rub-
absorption and is soluble in typical hydrocar- bers.
bon solvents. The many side groups attached Polymers ofthe isobutylene family (i.e., bu-
to the polymer chain produce a high degree of tyl and polyisobutylene) have very little tend-
damping. Since these side groups are not large ency to crystallize and depend upon molecular
in size and are regularly spaced, close, un- entanglement or crosslinking for their strength,
strained molecular packing results. This char- rather than upon crystallinity. The completely
acteristic leads to the unique low air, moisture, amorphous character of these polymers gives
and gas permeability of this polymer. an internal mobility which imparts flexibility,
The polyisobutylene polymers have a chem- permanent tack, and resistance to shock. Their
ical backbone similar to butyl rubber, but they low glass transition temperature, -60°C, in-

185
186 HANDBOOK OF ADHESIVES

dicates functional properties such as flexibility partially crosslinked forms. The grades of butyl
are maintained at temperatures considerably rubber and polyisobutylene available commer-
below ambient. Since these polymers are hy- cially from Exxon Chemical Company are
drocarbons with no or very little polarity, even listed in Table 1. In addition to those shown,
though their tack is high, their chemical attrac- various grades of butyl rubber and halogenated
tion to many surfaces is weak and therefore they butyl rubber are supplied by Polysar Limited,
are often mixed with resins and materials which and of polyisobutylene by BASP.
impart some polar character to the blend. Poly-
isobutylene polymers possess very good dielec- BASIC PROPERTIES
tric properties and electrical stability.
Butyl Rubber
The physical, chemical, and compounding
properties of the isobutylene family of poly- All grades of regular butyl rubber are tacky,
mers will vary with molecular weight, amount rubbery, light amber colored solids, manufac-
of unsaturation, the minor constituents in the tured by copolymerizing isobutylene with less
polymer and, in certain instances, chemical than 3% isoprene. Double bonds introduced
modification. With proper allowance for gross into the macromolecule by isoprene permit the
differences in molecular weights, butyl and polymer to be crosslinked or vulcanized.
polyisobutylene can often be used interchange- Though butyl rubber is "unsaturated" relative
ably in cement and adhesive compositions that to polyisobutylene, its 0.8-2.1 mole % unsat-
will not be cured. uration (number of isoprene units per hundred
Butyl rubbers are also available in halogen- monomer units in the polymer chain) is still far
ated form, as a low molecular weight semi-liq- less than the 100 % unsaturation of natural rub-
uid, as a latex, and in various modified and ber or the 60-80% unsaturation of SBR. This

Table 1. Commercial Grades of Butyl Rubber and Polyisobutylene Polymers.

Approx. Approx. Isoprene Units/
Viscosity Average 100 Monomer Units
Grade Molecular Weight (Mole % Unsaturation) Comments
Vistanex® LM-MS 44,000 0 Semi-liquid, tacky polymers used
LM-MH 53,000 0 mainly as tackifiers
LM-H 63,000 0
Exxon Butyl 065 350,000 0.8 Widely used in caulks and sealants
165 350,000 1.2 Specialty uses
268 450,000 1.6 Used for high cohesive strength
269 450,000 1.6 Highest viscosity/cohesive strength
grade
365 350,000 2.1 Used in curing applications
077 425,000 0.8 Special BHT stabilized FDA grade
Chlorobutyl 1065 350,000 1.9 Contain approximately 1.2 wt %
1066 400,000 1.9 chlorine
1068 450,000 1.9
Bromobutyl 2222 375,000 1.6 Contain approximately 2.0 wt %
2233 400,000 1.6 bromine
2244 450,000 1.6
2255 450,000 1.6
Vistanex MM L-80 900,000 0 Lowest viscosity of MM grades
MM L-l00 1,250,000 0 Widely used in PSA's
MM L-120 1,660,000 0 Widely used in PSA's
MM L-140 2,110,000 0 Highest viscosity of MM grades
Specific Gravity: 0.93 Bromobutyl; 0.92 all other grades.
All above grades manufactured by Exxon Chemical Company; butyl and halobutyl polymers are also available from Polysar Limited and
polyisobutylene polymers from BASF.
 BUTYL RUBBER AND POLYISOBUTYLENE 187

purposely limited functionality of butyl rubber The low molecular weight grades of polyiso-
accounts for its excellent resistance to environ- butylene, Vistanex® LM-MS, LM-MH and
mental attack. LM-H, are permanently tacky, clear white to
The various butyl grades differ in mole % un~ very light yellow semi-liquids, containing no
saturation, molecular weight, and nature of the stabilizer. They have broad acceptability in
stabilizer incorporated during manufacture to FDA regulated applications. These grades will
prevent degradation. A minor amount of me- show some degree of flow at elevated temper-
tallic stearate is also added to the rubber to pre- ature and can be pumped and handled as liquids
vent agglomeration of polymer particles during at temperatures of ISO-180°C. Primary uses
the manufacturing process. 2,3 are as permanent tackifiers in a variety of ce-
The stabilizer used in Exxon butyl rubber is ments, pressure sensitive adhesives, hot melt
the "nonstaining" zinc dibutyldithiocarba- adhesives, and sealants. These polymers pro-
mate. Stabilizer content is in the 0.05-0.20 wt vide tack, softness, and flexibility and can as-
% range. A BHT (butylated hydroxy toluene) sist in improving adhesion by "wetting out"
stabilized grade of butyl is also available for various hard-to-adhere substrates. They are
applications requiring broader FDA regulation. particularly useful for enhancing adhesion to
Nonstabilized butyl is produced for special ap- polyolefin plastic surfaces. They can also serve
plications. as primary binders in soft, tacky, 100% solids
In addition to the grades of Exxon butyl rub- sealant systems such as those used for insulated
ber described in the table, a series of butyl glass. 5
grades is marketed by Polysar Limited, desig- The high molecular weight polyisobutylene
nated Polysar Butyl 100, Polysar Butyl 301, grades, Vistanex MM L-80 through L-140, are
etc. white to light yellow, tough, rubberlike solids
Low molecular weight, semi-liquid analogs which contain less than 0.1 % BHT stabilizer.
of butyl rubber are also commercially avail- These grades have a fairly wide acceptance in
able. One such product series is Kalene, mar- FDA regulated applications. They are used to
keted by Hardman Inc. (Belleville, NJ).4 These impart strength and flow resistance to solvent
polymers are 100% solids (free of solvent or cements, pressure sensitive adhesive label
extenders) products with viscosity in the range stock, and some sealants. They are also used
of one million centipoises. They can be cured in certain hot melt coatings and adhesives,
through their un saturation at elevated or room where they provide improved flexibility and
temperatures to enhance cohesive strength. impact resistance, particularly at low tempera-
Low molecular weight butyl can be easily com- tures. 6
pounded into high solids sealants, mastics, and In addition to the Vistanex grades manufac-
coatings. Applications include specialty seal- tured by Exxon Chemical Company a series of
ants, electrical potting and encapsulation com- low and high molecular weight grades are
pounds, and as a curable tackifier/plasticizer in available from BASF under the trade name Op-
blends with higher molecular weight polymers. panol.

Polyisobutylene Halogenated Butyl Rubber

Polyisobutylenes (PIB) have the inertness of Chlorobutyl rubber7 is prepared by chlorinat-
paraffinic hydrocarbons and cannot be cured or ing the regular butyl polymer under controlled
vulcanized using standard rubber technology. conditions so that reaction is primarily by sub-
On a molecular weight basis they bracket the stitution and little of the unsaturation originally
butyl polymers, are compatible with them, and present in the macromolecule is lost. The chlo-
can function in a manner similar to butyl in ad- rine is believed to enter the molecule at the
hesive and sealant compositions that will not be highly reactive aUylic position, one carbon re-
cured. Contributions to finished composition moved from a double bond. Approximately 1.2
performance are strongly influenced by PIB wt % chlorine is present in the commercial
molecular weight. grades of Exxon chlorobutyl. The chlorine
188 HANDBOOK OF ADHESIVES

tends to enhance the reactivity of the double adhesives and specialty binders and coatings for
bonds as well as supply additional reactive sites both polyethylene and polypropylene. 9
for crosslinking. As a result, a wide variety of One supplier of butyl latex is Burke-Palma-
different cure systems can be used to vulcanize son Chemical Company (Pompano Beach,
this elastomer. Florida). This company also manufactures
Chlorobutyl can be readily blended and cured polyisobutylene emulsions. to
with other, more highly unsaturated elasto-
mers. In the adhesives and sealants area, it has Modified Butyls
been blended with both regular butyl and nat-
A number of partially crosslinked butyl rubbers
ural rubber and then preferentially cured
and other modified forms of butyl are commer-
through the chlorine to improve strength. The
cially available. Most of these are specifically
reactive chlorine will also tend to increase
produced for the adhesives and sealants mar-
adhesion to many polar substrates.
kets. II Partially crosslinked butyls include Poly-
A brominated butyl rubber can be prepared
sar's XL-20 and XL-50, 12 terpolymers in which
in a manner similar to the chlorinated version.
DVB (divinylbenzene) is added during poly-
Bromobutyl is structurally similar to chloro-
merization to impart a measure of cure. Hard-
butyl but contains approximately 2.0 wt % bro-
man Inc. produces Kalar, a series of pelletized,
mine (in the case of the Exxon product) and
partially crosslinked butyl products differing
provides an additional level of crosslinking ac-
primarily in degree of crosslinking.1 3 These
tivity.8
products have added toughness, strength and
In addition to the grades of halogenated butyl
flow resistance as a result of the crosslinks. The
rubber shown in the table, both brominated and
more tightly crosslinked grades are designed
chlorinated butyl polymers are produced by
primarily for 100% solids butyl sealing tape and
Polysar Limited, e.g., Polysar Chlorobutyl
can serve as a base for butyl mastics. The more
1240.
lightly crosslinked products are more appropri-
ate for low shear, low horsepower equipment
Butyl Rubber and Polyisobutylene Latices
and where hydrocarbon solvent solubility is
Butyl rubber can be emulsified using anionic necessary, such as in solvent release caulks,
emulsifiers. A butyl latex might typically have pressure sensitive adhesives, and protective
a solids content of approximately 60 wt %, a coatings.
pH of 5.5, a Brookfield viscosity of 2500 cps, Various depolymerized butyls, butyl rubber
and an average particle size of 0.3 /Lm. BHT solutions or cutbacks, butyl/plasticizer blends,
can be used as an antioxidant, with a small and highly plasticized/partially cured butyls are
amount of preservative sometimes added. also available. These products are used by
Butyl latex has excellent mechanical, chem- many adhesive companies where equipment
ical, and freeze-thaw stability which allows for limitations prohibit the use of the tougher, reg-
a wide latitude in compounding and blending ular bale forms of butyl rubber. Principal sup-
with other ingredients. Because of its stability, pliers of these type materials include Rubber
it cannot be coagulated in a controlled manner Research Elastomerics, Inc., Minneapolis,
using standard latex coagulants. When dried, it Minnesota; ADCO Products, Inc., Michigan
possesses the typical butyl characteristics of Center, Michigan; and A-Line Products, De-
good aging, flexibility, low permeability, tack, troit, Michigan.
etc.
Butyl latex can be used in packaging adhe- FORMULATING AND PROCESSING
sive applications and as a tackifying and flexi-
Choice of Polymer
bilizing additive in higher strength adhesives
based on more brittle polymers. It is noted for The family of isobutylene polymers is ex-
its compounded adhesion to polyolefin film and tremely broad. This wide selection of com-
fibers, and is used in laminating and seaming pletely compatible polymers permits the
 BUTYL RUBBER AND POLYISOBUTYLENE 189

knowledgeable compounder to achieve a wide Pigments and Fillers

range of properties. One example in adhesives
The same pigments and fillers commonly used
and sealants formulating is the desire to in-
with other rubbers can be compounded with
crease cohesive strength while maintaining
butyl rubber and polyisobutylene, and the gen-
other valuable characteristics such as tack.
eral principles of selection are the same. Very
There are a variety of ways in which cohesive
fine pigments increase cohesive strength and
strength can be modified by the proper polymer
stiffness, reduce cold flow, and also reduce
selection in polyisobutylene systems. The fol-
tack. Platy pigments such as mica, graphite,
lowing techniques are presently of commercial
and talc are preferred for acid and chemical re-
interest:
sistance and low gas permeability. Some of the
1. For strength, choose the highest molec- coarser pigments increase tack.
ular weight polyisobutylene (PIB) or bu- Zinc oxide increases tack and cohesive
tyl rubber grade consistent with strength in these polymers (and also plays an
application or processing requirements. important chemical role in the vulcanization of
2. Blend butyl rubber with polyisobutylene butyl). Aluminum hydrate, lithopone, whiting,
and cure the butyl portion. Since the PIB and the coarser carbon blacks such as thermal
does not cure, the extent of the cure in blacks also increase tack with moderate in-
the system and thus the cohesive strength crease in cohesivity. Clays, hydrated silicas,
is governed by the butyl content. calcium silicates, silico-aluminates, and the fine
3. Partially cure butyl rubber. This can best furnace and thermal blacks increase cohesive
be done by adding a carefully measured strength and stiffness. Stiffness can also be in-
amount of curative and fully curing to the creased by use of very fine silica pigment and
extent of the curative present, or by using magnesium oxide or carbonate.
one of the available precured grades. Special situations call for specific types of
4. Blend either PIB or butyl with halogen- pigments and fillers. Several examples illus-
ated butyl and cure only the halogenated trate this point:
butyl portion by utilizing the halogen
functionality. As an example, a curative 1. Where cost is a prime consideration the
that will react with chlorobutyl and not calcium carbonates often produce ade-
with butyl is zinc oxide. This technique quate physical characteristics and are a
is also of interest in blends of halogen- good choice.
ated butyl with either SBR or natural rub- 2. In the formulation of electrical tapes and
ber for pressure sensitive adhesives. mastics the fillers must be chosen for their
Another example of the compounding lati- electrical properties, both original and
tude afforded by polymer selection in the poly- after water immersion. Mistron Vapor
isobutylene family is tack. Tack is increased Talc and Satinton W /Whitetex clay are
with Vistanex LM low molecular weight PIB; good selections.
butyl rubber can be depolymerized to any de- 3. If a degree of flame resistance or self-ex-
sired tacky state, or a wide range of compatible tinguishing property is required, the fill-
tackifiers can be incorporated. ers must be chosen for this characteristic.
In terms of the butyl polymers the variable In butyl the combination of antimony ox-
of greatest interest to the adhesives compoun- ide and a halogenated flame retardant,
der is usually molecular weight. All grades of usually used at about the 10/30-15/45
butyl rubber are of such low un saturation that phr level, can impart substantial resis-
this characteristic does not affect most perfor- tance to flame.
mance properties in uncured or partially cured 4. In compositions such as tacky, flow re-
formulations. However, in applications not re- sistant sealing tapes (e.g., for automotive
quiring cure the lowest unsaturation grades are glazing), the filler must contribute to the
usually chosen for optimum aging. strength of the product. In this case a
190 HANDBOOK OF ADHESIVES

reinforcing black such as N330 (HAF) like A-I87. There is evidence that amino sil-
perfonns best. anes like A-l100 and methacryloxy silanes like
A-I74 may also be of value. In certain textile
Filler selection can be critical to the perfor-
applications isocyanate primers or adhesion
mance of the finished product and should be
promoters can be used with butyl cements.
given careful consideration.
Antioxidants are often used in butyl and PIB
adhesives and sealants to protect against severe
Tackifiers. Plasticizers. and Other
environmental aging conditions such as ultra-
Polymeric Additives
violet light or heat. Materials such as Ethanox
As has been pointed out previously a wide 702, Butyl Zimate, AgeRite White, Irganox
range of properties, particularly rheological 1010, BHT, and even sulfur have been used.
properties, can be obtained within the isobu-
tYlene family of polymers . .In addition, a broad
Curing Systems
range of tackifiers and plasticizers can be used
to extend the viscosity range and to control the There are four curing systems of general inter-
tack and cohesive strength level. A common est in cements, adhesives, caulks, sealants, and
plasticizer is polybutene. 14 This material is coatings based on butyl and halogenated bu-
available in a number of molecular weights so tyl.I6 These are (1) the quinoid cure, (2) cure
the viscosity and volatility can be selected for with sulfur or sulfur donor compounds, (3)
the application. Other liquid materials used as resin cure, and (4) for halogenated butyl only,
plasticizers include paraffinic oils, petrolatum, the zinc oxide cure. The introduction of cross-
and certain phthalates with long, aliphatic side linking increases cohesive strength and reduces
chains such as ditridecyl phthalate. cold flow as stated previously, but reduces tack
Resins are typically used in butyl and PIB- and solubility in hydrocarbon solvents. Thus,
based adhesives and sealants to develop the de- crosslinking systems must be carefully de-
sired level of tack. A wide range of resins can signed for the specific application; they are used
be used but the most common are probably the more in butyl based sealants than adhesives.
polyterpenes such as Piccolyte S115; the ter- The quinoid cure is perhaps the most com-
pene-phenolics such as Schenectady's SP-553; mon. It is an old, easily controlled system that
phenol-fonnaldehyde resins such as Schenec- typically is fonnulated as a split batch, two-
tady's SP-I068; the hydrocarbons like Es- part cement designed to cure at or even below
corez@ 1102, Escorez 1304, and Escorez 1315, ' room temperature. The resultant network is
and modified rosins and rosin esters like Stay- tightly cured, highly resistant to ozone, heat,
belite and Pentalyn. Usually these resins are chemicals, and other environmental attack, and
used with plasticizers to obtain the desired bal- provides good electrical properties. Dark color
ance of tack and cohesive strength. bodies are fonned during the reaction, so qui-
Many other polymeric additives are used in noid cures cannot be used to make white prod-
butyl and PIB adhesives and sealants. Most ucts, and even light colors require careful
worthy of mention are factice, which can lower compounding. Differences in butyl polymer
cost, improve processing, and reduce string- unsaturation have little effect on the speed of
ing; amorphous polypropylene, which can re- cure with quinoids.
duce cost and improve processing as well as Quinoid cures depend on crosslinking
impart thennoplastic character; various waxes, through the nitroso groups of aromatic nitroso
which function in much the same manner as compounds. A commonly used system em-
amorphous polypropylene; and asphalt, again ploys p-quinone dioxime (commercially known
for lower cost. 15 as QDO) or dibenzoyl p-quinone dioxime
Special materials used in butyl sealants or as (DBQDO), combined with an oxidizing agent
primers to obtain bonds of PIB-based products such as manganese dioxide, lead dioxide, red
to specific substrates such as glass are various lead oxide (Pb30 4), or benzothiazyl disulfide.
organic silanes. An example is an epoxy silane The DBQDO system is less active and thus is
 BUTYL RUBBER AND POLYISOBUTYLENE 191

easier to control at elevated temperatures. The tial cure. Alternatively, a portion of chlorobu-
actual crosslinking agent is believed to be the tyl or bromobutyl can be blended with a
oxidation product, p-dinitroso benzene; dini- polymer which does not cure via zinc oxide,
troso compounds introduced as such, for ex- for example butyl, an excess of zinc oxide can
ample p-dinitroso benzene on a clay base (Poly be added and the dispersed halogenated butyl
DNB), rather than formed by oxidation are also phase totally cured. The result of this "pref-
active crossiinking agents for butyl. An attrac- erential" cure technique is butyl with higher
tion of the quinoid cures to formulators is the cohesive strength for use as a sealant or adhe-
aforementioned split batch nature, one part sive base. 17 Similarly, halogenated butyl can be
containing the dioxime, the other the oxidizer blended with natural rubber and then the halo-
(usually either Mn02 or Pb0 2). The parts are genated butyl phase cured with zinc oxide. The
combined just before use. resultant material is a high cohesive strength
Sulfur curing systems for butyl include ele- base for pressure sensitive adhesives.
mental sulfur, thiuram or dithiocarbamate ac-
celerators and thiazole or thiazyldisulfide
Solvents and Solution Processing
activators. Zinc oxide or other metallic oxides
are necessary to attain satisfactory cure. The Butyl rubber and polyisobutylene polymers are
relatively minor differences in unsaturation be- soluble in hydrocarbon and chlorinated sol-
tween grades of butyl are significant with sulfur vents, but not in the common alcohols, esters,
cures, the rate of cure and number of attainable ketones, and other low molecular weight oxy-
crosslinks increasing with increasing polymer genated solvents. Volatile paraffinic solvents
unsaturation, while chemical and ozone resis- such as hexane, heptane, and naphtha are often
tance decrease. The need for elevated temper- used in cement and adhesive work. Cyclohex-
ature to attain crosslinking limits utility of ane and the chlorinated solvents like perchlo-
sulfur cures in adhesives and sealants applica- roethylene give solutions of much higher
tions. viscosity on an equal weight percentage basis
The resin cure of butyl normally uses one of than the common paraffinic and aromatic sol-
a series of active, brominated phenolic resins vents. A substantial part of this difference is
such as Schenectady's SP-10SS. The resin cure due to the much higher specific gravity of chlo-
of butyl can proceed at temperatures from am- rinated solvents. The low solubility in oxygen-
bient to very high depending on the specific ated solvents is often useful since butyl and PIB
resin chosen and on the concentration and type films can withstand immersion in these com-
of cure activator. Features of the resin cure are mon solvents.
high stability, heat resistance, and the capabil- An important consideration in solvent selec-
ity to be compounded into light colored and tion is air pollution requirements. For this rea-
white formulations. son solvents such as Laktane (quite fast),
The zinc oxide cure of chlorobutyl and bro- VM&P Naphtha (medium evaporation rate),
mobutyl is of interest in sealants and adhesives and mineral spirits (slow) are generally of in-
primarily because it allows these polymers to terest. The latter two can be purchased to com-
be cured in the presence of other elastomers ply with regulations such as Southern California
without affecting the other elastomers. The zinc Air Pollution Control District Rule 102 (for-
oxide cure is also of interest in certain FDA merly Rule 66).
sensitive applications where the elegant sim- The presence of minor amounts of stabilizer
plicity of a compound that contains only a poly- and metal stearate in butyl and PIB may cause
mer and zinc oxide has obvious appeal. pure gum cements to be slightly cloudy even
If it is desired to cure only a small fraction though the polymer is completely dissolved.
of the polymer base, this can be done in two Under certain circumstances, these materials
ways. A small and carefully measured amount will slowly settle out of low viscosity solutions
of curative can be used and reacted to the full of the polymers. The only deficiency is in ap-
extent of the curative present to produce a par- pearance, and the settling can be avoided or re-
192 HANDBOOK OF ADHESIVES

tarded by working with higher viscosity in solid, bale form. To facilitate solvation for
solutions. adhesives and mastics use, a common initial
The relationship between solids and viscosity step is to increase surface area greatly by phys-
for various butyl and PIB polymers is logarith- ical size reduction and thereby decrease solva-
mic as is shown in Figs. 2 and 3. 18 A small tion time. This can be accomplished using a (1)
change in solids can make a large difference in bale chopper or granulator, (2) sheet mill and
solution viscosity, especially at higher solids slab chopper, or (3) Banbury, sheet mill, and
levels. Viscosity is also strongly dependent on slab chopper. It is important that the shredded
polymer molecular weight and a small change polymer be stored for only a short time since it
in the molecular weight of the polymer can re- will reagglomerate.
sult in a relatively large change in the viscosity The output of the shredder is most efficiently
of polymer solutions. 19 utilized by directing it into the subsequent sol-
The optimum solids level of cements to be vation equipment. One clever and quite inex-
applied by various methods is, of course, sub- pensive unit uses a modified meat grinder
ject to broad variation depending on the solvent mounted on the solvation tank to feed polymer
selected (i.e., the viscosity which results), filler particles from the grinder directly into agitated
content, etc. In general, butyl rubber and poly- solvent.
isobutylene cements for application by spray- Butyl polymers do not require the work input
ing contain 5-10% solids, for dipping 10-30%, of a mill or Banbury to be solvated; simple
for spreading 25-55%, and for application by chopping is quite adequate. Mills and Banbu-
finger or spatula, 50-70%. rys, if available, can be used to incorporate
Due to the low permeability of butyl and PIB other materials such as fillers into the polymer
polymers, gum cements should be applied in before solvation.
thin coats to facilitate solvent release and avoid Low molecular weight polyisobutylene (e.g.,
porosity. Adequate drying time should be per- Vistanex LM) and low molecular weight butyl,
mitted between coats when multiple applica- with their semi-liquid forms, are much more
tions are needed to increase thickness. Cements rapidly solvated than the higher molecular
containing appreciable volumes of filler are less weight analogs. It is advantageous to permit
sensitive in this respect. these low molecular weight polymers to flow
The various butyl and high molecular weight gradually from their container directly into ag-
PIB grades (e.g., Vistanex MM) are marketed itated solvent. 20 Fillers and other compounding

100 1,000 10,000 100,000

100

50 50

~
::I:
<.!l (3)
W
?: 10 10
>-
aJ
If)
0 5
5 (]) VISTANEX LM-MS
:J
0 (2) EXXON BUTYL 165
If)
(3) CHLOROBUTYL 1066
(4) EXXON BUTYL 268
(5) VISTANEX MM L-80
(6)VISTANEX MM L-120

1 1
100 1,000 10,000 100,000
VISCOSITY, CENTIPOISES

Fig. 2. Solution viscosities of isobutylene elastomers in toluene.

 BUTYL RUBBER AND POLYISOBUTYLENE 193

100 1,000 10,000 100,000

100

50
50

..:
:::J:
~
ijj 10
~ 10
Eo
VI
Q (})VISTANEX LM-MS 5
5
:::i (6) (2) EXXON BUTYL 165
0
VI (3) CHLOROBUTYL 1066
(4) EXXON BUTYL 268
(5)VISTANEX MM L-80
(6) VISTANEX MM L-120
1
1 100 1,000 10,000 100,000

VISCOSITY, CENTIPOISES
Fig. 3. Solution viscosities of isobutylene elastomers in mineral spirits.

ingredients are then added to the solution. If cps), kneaders are most appropriate.
needed, the blend can then be processed Many kneaders have sufficient power to
through either a paint mill or ball mill to attain allow bales of rubber to be added directly
the desired degree of dispersion ("grind"). while others require either smaller pieces
The choice of equipment for the production or mill warmed and softened portions.
of solutions or mastics from butyl and PIB is
Once the rubber solutions are made, further
primarily based on the viscosity of the product.
compounding is carried on either in the same
Resins and other soluble or wettable ingredi-
equipment, as has been noted, or in another
ents are also often incorporated at this point.
unit. One example of two different pieces of
The following general guidelines may be use-
equipment being used is in the preparation of
ful:
butyl textile laminating adhesives. The butyl is
1. For very low viscosity cements (i.e., be- first pigmented and curative is added on either
low approximately 50,000 cps) the high a rubber mill or in a Banbury. The compounded
speed, high shear rotating saw blade type stock is then solvated in an adhesives chum
mixers can solvate a small amount of poly - where resins and other soluble ingredients can
mer into a relatively large volume of sol- also be added.
vent. Normally the polymer would be in- Butyl and polyisobutylene latices are very
troduced into the mixer in quite small low in viscosity and therefore are normally
particles. compounded with quite simple equipment, typ-
2. For low viscosity cements (i.e., probably ically a propeller mixer mounted on a closed
below 200,000 cps) high speed, high tank. When maximum filler dispersion is re-
shear, jacketed turbine mixers can be quired, ball mills or similar equipment may be
used. necessary for part of the mix.
3. For moderate viscosity cements and ad-
hesives that are probably the most com-
Mixing and Processing Techniques and
mon (i.e., viscosity about 200,000 to
Guidelines
about 1,000,000 cps), adhesives chums
or double arm planetary mixers are gen- Butyl and polyisobutylene polymers find use in
erally used. a variety of mastics, caulks and sealants where,
4. For high viscosity solutions (above 106 not infrequently, a high viscosity mixing phase
194 HANDBOOK OF ADHESIVES

is involved. By way of example the preparation The general outline of butyl caulk prepara-
of butyl caulks and mastics can follow several tion is shown in Fig. 4.
routes. The most common are as follows: The production of sealing tapes generally
follows similar procedures but solvents are not
1. A heavy duty kneader is used to make a used. One piece of equipment that should be
butyl rubber solution, normally in mineral spir- highlighted for tape production is the screw
its. The solution is made by charging the rub- discharge kneader. 21 This kneader type is par-
ber into the kneader and working the solvent ticularly efficient for tape production where it
slowly into the rubber. The solvent must be allows short total cycles. The tape compound
added particularly slowly at first, and each in- can be mixed and quickly extruded either in
crement of solvent must be incorporated into finished form or in slug preforms which are
the batch before more is added. If solvent is easy to use in subsequent extrusion operations.
added too rapidly, the polymer will be dis- Since a great deal of butyl and polyisobutyl-
persed in the form of small pellets and these ene is used to modify wax, and since the tech-
pellets can only be dissolved by extended sub- nique to make wax blends is quite sensitive, it
sequent mixing. Adding solvent too fast results deserves special mention. If PIB is used, it is
in either greatly increased batch cycle time to placed in a kneader and allowed to work until
obtain uniformity or in polymer particles in the it attains a maximum surface area. This is often
final solution. Normally the finished solution is termed ricing, since PIB at this stage looks like
transferred into another less expensive, lower cooked rice. The wax is slowly added to this
powered mixer for further compounding, e.g., riced rubber. It is especially important that the
the addition of the pigments, resins, plasticiz- quantitites of wax added, especially initially,
ers and other ingredients. be quite small and that the mix be allowed to
2. In a heavy duty kneader the butyl is mixed become homogeneous before more wax is
with all the nonvolatile ingredients and then added. Butyl rubber will tend to band rather
solvated. The same precautions apply to the than rice in a kneader, but the same slow initial
mixing and solvation steps as were outlined wax addition procedure must be followed.
above; that is, each increment must be well dis-
persed before subsequent additions are made.
APPLICATIONS AND FORMULATIONS
There are two different orders of addition used
in this technique: The inherent properties of polymers of the
polyisobutylene family, particularly the chem-
a. Normally the rubber is added first to the
ical inertness, age and heat resistance, long-
kneader and the dry ingredients are then
lasting tack, flexibility at low temperatures, and
slowly incorporated.
the favorable FDA position on selected grades,
b. Alternatively, the "upside down" tech-
make these products commercially attractive in
nique has been found to result in better
a variety of pressure-sensitive and other adhe-
dispersion in less time, especially in the
sives, in automotive and architectural sealants,
case of mastics based on partially cross-
and in coatings. An added dimension is
linked butyl. In this technique the fillers
achieved in the blendability of the polyisobu-
and a small amount of plasticizer are
tylene polymers with each other and with other
blended into a smooth, stiff paste in the
adhesive polymers such as natural rubber, sty-
kneader and the rubber is added last.
rene-butadiene rubber, EVA, low molecular
3. A masterbatch of polymer and filler can weight polyethylene, and amorphous polypro-
be prepared on a mill or in a Banbury and this pylene to achieve specific properties. They can,
masterbatch is then solvated in another mixer. for example, be blended with the highly unsat-
For very high viscosity mixtures (essentially urated elastomers to enhance age and chemical
like conventional rubber compounds), such as resistance. A description of polyisobutylene
blends of rubber with filler (and/or plasticiz- polymer family use in adhesive and sealant ap-
ers), mills and Banburys are the best choice. plications follows.
 BUTYL RUBBER AND POL YISOBUTYLENE 195

GUILLOTINE CUTTER

~
\
COVERED + JACKETED
DISPERSION OR
SIGMA BLADE
MIXER
HIGH POWER OR

FILLERS AND
OTHER
COMPOUNDING
INGREDIENTS

COVERED
SIGMA BLADE
MIXER
OR
MEDIUM POWER

FILLING MACHINE

L?~
Gal
YYYV
TUBES

Fig. 4. Typical flow plan for butyl caulk manufacture.

Adhesives and Mastics are well known and are used in a variety of ap-
plications where the properties of the butyl poly-
Miscellaneous Cements. Butyl and poly-
mer are desired. Two typical starting point for-
isobutylene are used in a range of cements.
mulations are shown in Table 3.
Several specific types shown in Table 2 illus-
trate their use. All concentrations in formula- Pressure Sensitive Adhesives. 22 Solution
tions in this chapter are expressed in parts by pressure sensitive adhesives (PSA's) for tapes
weight. and labels are primarily blends of rubber and
Two-part, self curing cements based on butyl tackifying materials such as resins. The low
196 HANDBOOK OF ADHESIVES

Table 2. Miscellaneous Cements. Table 3. Butyl Based Curing Cements.

a. Paper Cement a. Butyl Self Curing Cement
Vistanex MM L-l00 100 Part A Part B
Solvent 900
Exxon Butyl 268 SO SO
This cement is similar to that sold for hilme and office Zinc oxide 2.5 2.5
use. Stearic acid 1.5 1.5
N762 (SRF) carbon black 40
b. Laminating Cement For Polyethylene Film
Staybelite Ester 10 resin 20
Exxon Butyl 268 100 Sulfur 0.7 0.7
Terpene phenolic resina 5 QDO 2
Solvent to appropriate viscosity Lead dioxide 4
Solvent: heptane 400 400
This cement is solvent coated on one substrate and dried. 92% isopropanol 5 5
The second substrate is then laminated to the adhesive (wet)
with moderate roll pressure. In this way the natural tack The dry ingredients are milled into the rubber and the
of the formulation allows impervious material to be lami- resultant blend is dissolved as indicated. The two parts are
nated without solvent entrapment. mixed just before use.

c. Flocking Adhesive b. Chlorobutyl High Strength Cement

Vistanex MM L-l00 100 Chlorobutyll066 100

Terpene phenolic resina 20 Ditridecyl phthalate (DTDP) 5
Butyl Zimate 0.5 Diethyl thiourea (DETU) 5
Solvent to appropriate viscosity Toluene 360
'Schenectady SP-553 or similar resin.
Isopropyl alcohol 40

Procedure
molecular weight polyisobutylenes find use as 1. Preblend a paste of DETU in warm DTDP.
permanent tackifiers and modifiers. They en- 2. Banbury or mill mix the compound for 5 min at
hance tack and softness and can contribute to 240 to 280°F.
adhesion by improving wetting of the sub- 3. The temperature must be kept below 300°F.
4. Solvate the base stock.
strate. The higher molecular weight products
serve as the rubbery base materials. High shear mixing at moderate temperature will result
in the formation of a thiouronium salt which through
Two important parameters in the formulation
ionic bonding will increase the green strength of the
of pressure sensitive adhesives are tack and gum polymer while still maintaining full solubility.
hold, which is the ability to resist creep under This base is a good high strength cement in its own
deadload. As noted, butyl and polyisobutylene right. To obtain a room temperature curing cement,
are inherently tacky polymers. This tack can be add just before use:
enhanced with a wide variety of resins and other Zirex (Zinc resinate) 10
tackifiers. The hold or cohesive strength is low Toluene 10
compared to some other pressure sensitive ad-
hesive polymers, such as natural rubber, but
can be increased if required by (1) incorpora- permanency of tack, and this has led to their
tion of high molecular weight PIB or natural use where long service life or aged adhesive
rubber, (2) the choice of the other ingredients, integrity is required as, for example, in remov-
particularly resins and fillers, and (3) the partial able label pressure sensitive adhesives. A re-
or preferential curing techniques noted previ- movable label adhesive which ages poorly may
ously. The polyisobutylene polymers are pri- lose cohesive strength and consequently will
marily used in label pressure sensItIve not peel as cleanly as desired. The higher mo-
adhesives and in certain tapes where high co- lecular weight grades when used as the base
hesive strength is not necessary. polymer also die cut well, an important re-
The age resistance of polyisobutylene poly- quirement for use in labels. Butyl and polyiso-
mers manifests itself as a lack of hardening and butylene are thus preferred materials in
 BUTYL RUBBER AND POLYISOBUTYLENE 197

removable pressure sensitive label and protec- Table 4. Pressure Sensitive Adhesives.
tive tape adhesives. a. Simple PSA for Transparent Tape
The low temperature flexibility and tack of
these polymers results in a service temperature Exxon Butyl 268 or Vistanex 100
range extending below ambient. Vistanex LM MM L-IOO
Vistanex LM-MS 75
low molecular weight PIB is a particularly use- Solvent to coatable viscosity
ful low temperature tackifier. The polyisobu-
tylene polymers find application in solvent- b. Chlorobutyl Blend PSA for General Purpose Tape
borne, low temperature pressure sensitive ad-
hesives such as freezer label adhesives. Chlorobutyl 1066 50
SBR 1011 50
The low order of toxicity, favorable FDA Vistanex LM-MS 30
status, and light color result in a variety of Escorez® 2393 resin 30
medical pressure sensitive adhesive uses for se- Pentalyn H resin 30
lected polyisobutylene polymer grades. Appli- Antioxidant' 0.5
cations include surgical tape, oral bandages and Solvent to coatable viscosity
ostomy appliances.
c. Removable Label Stock PSA
Adhesives formulated with butyl and poly-
isobutylene are used for adhesion to a variety Vistanex MM L-IOO 100
of substrates including nonporous, hard-to-ad- Vistanex LM-MS 40
here-to materials such as polyethylene. Other Zinc oxide 20
Calcium carbonate 20
common substrates include paper, polyvinyl Escorez 5300 resin 30
chloride, and polyester film. Poly terpene resin (l15°C S.p.)b 30
Several typical or starting point solution Polybutene (avg. MW 1300)' 45
pressure sensitive adhesive formulations illus- Paraffinic process oil 15
trating some of the uses described above are Antioxidant 0.5
Solvent to coatable viscosity
given in Table 4. They are provided for general
guidance on materials selection and quantity but d. Vinyl Floor Tile PSA
likely require modification to suit specific in-
gredients, manufacturing, and finished prop- Exxon Butyl 268 100
erty requirements. Vistanex LM-MS 20
Terpene phenolic resind 70
Solvent to coatable viscosity
Hot Melt Adhesives. The isobutylene fam- e. Solvent Adhesive for Surgical Tape
ily of polymers can also be formulated in hot
melt compositions, both pressure sensitive and Vistanex MM L-iooe 100
non-pressure sensitive, and can impart many of Vistanex LM-MS 30
the same property benefits noted for solvent Zinc oxide 50
Hydrated alumina 50
based systems. These polymers improve flexi- USP white oil 40
bility, particularly at low temperatures, provide Phenol formaldehyde resin' 50
good aging and chemical resistance, and serve Solvent to coatable viscosity
to contribute toughness and strength in ther- 'e.g.,Irganox 1010 or Ethanox 702; these products can be used in
moplastic mixtures. Increases in hot tack, all recipes where antioxidant is indicated.
bpiccolyte SI15 or equivalent resin.
adhesion and overall seal strength have been 'e.g., Parapol® 1300.
widely documented. 23 - 27 Polyisobutylene grade dSchenectady SP-553 or similar resin.
'A minor percentage of the Vistanex MM L-IOO can be replaced
choice and concentration are important consid- by natural rubber if increased cohesive strength is desired. In this
erations, however, in that these elastomeric case, an antioxidant may be required for age stability.
'Schenectady SP-1068. Aliphatic hydrocarbon resins such as Es-
products become more difficult to melt mix, corez 1304 can also be used.
significantly increasing melt viscosity as PIB
molecular weight increases. High molecular For hot melt pressure sensitive adhesives 28
weight grades (e.g., Vistanex MM), in fact, are butyl rubber is usually blended with significant
limited in hot melt applications. amounts of melt materials, e.g., tackifying
198 HANDBOOK OF ADHESIVES

resin, petrolatum, and amorphous polypropyl- tion level, thus extending adhesive service tem-
ene, to reduce viscosity to desirable levels. Low perature range. Waxes and thermoplastics must
volatility hydrocarbon oils, polybutenes and be used in moderation, however, since they re-
paraffin, and microcrystalline waxes also de- duce the tack of the finished blend. Hydrocar-
press melt viscosity, but excessive wax can ad- bon oils and petrolatum plasticize and bring out
versely affect tack. Low molecular weight pm aggressive tack in low molecular weight pm,
is an effective butyl plasticizer and enhances resin mixtures.
tack. Applications for butyl hot melt pressure Blends containing low molecular weight PIB
sensitive adhesives often involve long service can be prepared with relative ease. Added in-
life, low temperature, and polyolefin plastic crementally, it dissolves quite effectively in the
film adhesion, capitalizing on the inherent fea- liquid and molten melt ingredients of an adhe-
tures of the polymer noted previously. An il- sive composition at 180°C with agitation.
lustrative starting point formulation for Several formulations illustrating low molec-
adhesive-backed carpet tiles is shown in Table ular weight PIB use in hot melt pressure sen-
5. sitive adhesives are provided in Table 6. 15 ,29
The low molecular weight PIB grades are This polymer functions as an age resistant tack-
perhaps the most functional polyisobutylene ifier, adhesion promoter and flexibilizer, and its
polymers for hot melt pressure sensitive adhe- favorable FDA regulatory position extends use
sives. They are easiest to melt mix and result to medical applications. Again, these formu-
in low viscosity blends due to their low molec- lations should be considered as starting points
ular weight. Brookfield viscosity at 177 °C only.
(spindle SC4-27) is typically 30,000-60,000 In non-pressure sensitive compositions all of
cps depending on grade, and melt viscosity can the above formulating approaches are applica-
readily be tailored to meet specific require- ble but now one need not be concerned with
ments by incorporation of thermoplastic ingre- room temperature tack, i.e., pressure sensitiv-
dients. 15 ity.
Petrolatum and waxes are most effective as Again low molecular weight pm is used as a
viscosity depressants. Resins, waxes, and ther- tackifier and adhesion promoter, 27 particularly
moplastics such as low density polyethylene in packaging applications where adhesion to
(LOPE), ethylene vinyl acetate, and crystalline polyethylene and other plastic film surfaces is
and amorphous polypropylene increase hard- desired. A general formulation illustrating use
ness and cohesive strength. LOPE and crystal- in packaging adhesives is shown in Table 7.
line polypropylene particularly raise blend Butyl rubber is used in preformed, hot melt
softening point, even at the 10 wt% concentra- adhesive rods which can be fed through various
types of automatic dispensing equipment. Bu-
tyl provides both strength and flexibility to the
Table 5. Butyl Rubber Hot Melt adhesive "rope" before application, flow con-
Pressure Sensitive Adhesive trol during application, and improves the prop-
Exxon Butyl 065 100 erties of the adhesive bond. 3D ,31 A formulation
Escorez 1304 resin 100 for a typical rope or coil form of hot melt ad-
Petrolatum (57°C M.P.) 50 hesive is shown in Table 8.
Amber microwax' 150
Antioxidant
Wax Blends. A related application for the
Brookfield viscosity at 121°C
Spindle SC4-29 (cps) 80,000 isobutylene polymers is as a specialty additive
Surface Tacky, firm in wax compositions. They serve to impart in-
Adhesionb creased viscosity, added toughness and
Vinyl foam to plywood Good-excellent strength, improved seal strength and adhesion,
Rubber foam to plywood Good-excellent
improved flexibility particularly at low temper-
'Be Square 175. atures, and also add a degree of aging and
bAdhesives coated on foam and subsequently manually pressed onto
plywood. chemical resistance. 32 In coatings low levels
 BUTYL RUBBER AND POL YISOBUTYLENE 199

Table 6. Low Molecular Weight Polyisobutylene Hot Melt

Pressure Sensitive Adhesives.
A. General Recipes

2 3

Vistanex LM-MS 25 35 45
Escorez 1310 resin 50 50 15
Petrolatum (57° C M.P.) 15 40
High MW LOPE" 10
Paraffinic process oil 15

Brookfield viscosity at 177 °C 1900 1200 850

spindle SC4-27 (cps)
Surface tacky, very very
firm tacky, tacky,
soft soft
Softening point, ring and ball (0C) 101 49 55

B. Low Temperature Label Pressure Sensitive Adhesive

Kraton 1107 b 50
Finaprene 1205 b 50
Vistanex LM-MS 90
Escorez 2393 resin 130
Naphthenic process oil 58
Antioxidant 2

Rolling ball tack (cm) 2.5

180° Peel (g/cm)
Stainless steel 880
Treated LOPE 570
180° Peel at O°F (g/cmt
Stainless steel 1250
Treated LOPE 90
Loop tack at O°F (g/cm)C
Stainless steel 950
Corrugated board 290
Waxed board 410

C. EVA Based Pressure Sensitive Adhesive

Elvax 40 100
Vistanex LM-MS 20
Escorez 2393 resin 80
Antioxidant
'A low MW LOPE grade such as Epolene C-1O would give lower viscosity and softening point.
bStyrene block copolymers.
'Adhesive and adherend conditioned at -ISoC before contact; adhesion detennined at -ISoC.

Table 7. Hot Melt Packaging Adhesive. (1-5 %) of butyl or high molecular weight PIB
Ethylene vinyl acetate copolymer 25 serve to promote holdout properties of many
Microcrystalline wax 30 formulated waxes by increasing viscosity. High
Escorez 2393 resin 35 molecular weight PIB is used as a component
Vistanex LM-MS 10 in coating for cheese wrap where it imparts
Antioxidant 0.5
flexibility and resistance to natural oils and fats.
200 HANDBOOK OF ADHESIVES

Table 8. Rope Form of Hot Melt manent bond). Additionally, PIB tapes, partic-
Adhesive. ularly those tackified with low molecular
Exxon Butyl 268 20 weight PIB, provide good adhesion to polyeth-
Beta-Pinene Resin (115°C S.P.) 20 ylene and thus are often the products of choice
Escorene® UL 7750 EVA polymer 20 for splicing crosslinked polyethylene insulated
Low MW polyethylene (12,000 MW) 20 cables. Splicing tapes are unsupported (as used
Low MW polyethylene (20,000 MW) 19
they do not have a fabric or film backing) and
Antioxidant
are typically available in roll form on a release
liner.
Pipe Wrap and Electrical Tapes. The There are numerous pressure sensitive tapes
polyisobutylene polymers have a history of ex- with various adhesive and backing combina-
cellent performance in pipe wrap tape and in a tions for specific electrical applications. The
variety of electrical tape areas. These applica- nonpolarity of the polyisobutylene polymers
tions exploit the age resistance, low water ab- makes them quite resistant to attack and swell-
sorptivity and permeability, inherent tack, and ing by the commonly used vinyl plasticizers.
electrical insulative properties of these poly- Thus, they are less susceptible to softening
mers. when used on vinyl film backings.
Pipe wrap tape is most commonly an adhe- Typical nonconductive splicing tape and
sive based on butyl rubber or possibly a blend pressure sensitive electrical tape formulations
of butyl and ethylene propylene rubbeil 3 on a are given in Table 10. The splicing tape mix is
polyethylene or polyvinyl chloride backing. A subjected to brief heat treatment in a Banbury
formula for the adhesive is shown in Table 9.
High molecular weight grade, Exxon Butyl Table 10. Electrical Tape Formulations.
268, is used for maximum cohesive strength at
a. Butyl Nonconductive Splicing Tape
high loading levels. Low unsaturation grade,
Exxon Butyl 065, can be used if maximum age Exxon Butyl 268 100
resistance is desired. Resins are chosen fortack Vistanex MM L-IOO 10
and cohesive strength balance, and high resin AgeRite Resin D 1
Zinc oxide 5
levels combined with polybutene provide a
Mistron Vapor Talc 60
tacky, pressure sensitive adhesive type pipe Satinton W/Whitetex clay 60
wrap tape. These adhesives are either calen- N990 (MT) carbon black 10
dered onto the backing, extruded, or solvated Low density polyethylene 5
and coated from solution. Escorez \315 resin 5
Alkyl-phenol resina 5
Electrical tapes based on butyl are actually
Poly DNB 0.5
bulk mastics compounded for good electrical, QDO 0.2
heat, aging, and ozone resistant characteris-
tics. 34 Tapes for splicing and terminating wires Tensile strength (psi) 650
and cables are self-fusing (i.e., when wrapped Ultimate elongation (%) 750
Dielectric strength (volts/mil) 745
upon itself the tape must fuse, forming a per-
Volume resistivity (ohm-cm x 10- 14 ) 140

Table 9. Butyl Mastic for Pipe Wrap This compound is prepared in a Banbury mixer and held
for about three minutes at 163°C to allow the promoters
Tape. (Poly DNB and QDO) to couple the polymer and fillers.
Exxon Butyl 065 100 All properties measured on 0.030 inch thick uncured pads.
N550 (FEF) carbon black 100
Mistron Vapor Talc 200 b. PSA for Plastic Film Backed Electrical Tape
Polybutene (avg. MW 950)" 100 Vistanex MM L-IOO 100
Escorez \304 resin 75 Escorez 2393 resin 35
Amorphous polypropyleneb 50 Hercolyn D resin 35
Paraffinic process oil 50 Polybutene (avg. MW 950)b 35
'e.g., Parapol 950 'e.g., Schenectady SP-I077.
b A-Fax 600 or similar product be.g., Parapol 950.
 BUTYL RUBBER AND POLYISOBUTYLENE 201

mixer to maximize cohesive strength and elec- ically designed to be applied at elevated tem-
trical properties. perature by pressurized hot melt applicators
directly to the substrates to be sealed.
Sealants
Butyl rubber and sometimes certain polyiso- Solvent Release Sealing Compounds. 37
butylene grades are used as the base or binder The low unsaturated butyl grades (e.g., Exxon
in a wide range of commercially available Butyl 065) are most commonly used in sealing
caulking and sealing compounds. The major compounds. The butyl polymer is usually pre-
advantages noted for butyl based sealants in pared or purchased as a high solids cutback in
field performance are their permanent flexibil- mineral spirits. The solvent serves to plasticize
ity, elongation, outstanding age and weather the tough rubber, and when the finished sealant
resistance, and resistance to hardening. 35 ,36 is put in place solvent evaporation causes the
Caulks and sealants made from the isobutyl- caulk to set and develop its properties. Other
ene polymer family are available in three forms. ingredients include a combination of extender
As bulk sealant materials, they are usually one- pigments such as talc, whiting, and titanium
part, plasticized systems, compounded with dioxide, tackifiers and plasticizers such as res-
suitable inert fillers and solvents and designed ins and polybutenes, and, many times, low mo-
for application with a standard caulking gun. lecular weight polyisobutylene (e.g., Vistanex
As preformed tapes or ribbon sealers, they are LM-MS) and other specialty additives. A typ-
100% solids, tacky materials, supplied in roll ical butyl caulk formulation is shown in Table
form on a release paper backing and designed 11.
for easy hand application in areas which usu- Butyl caulking compounds are used for gen-
ally require compressive confinement for an ef- eral purpose construction sealing, for the bed-
fective seal. Finally, in a newer format as 100% ding of glass, sealing various lap joints and
solids, hot melt compositions, they are specif- some butt joints, in channel glazing, for do-it-

Table 11. Butyl Rubber Based Caulking Compound.

Parts by
Formulation Weight Wt%
Exxon Butyl 065, 50% in mineral spirits 200 20.50
Vistanex LM-MS 20 2.05
Isostearic acid 5 0.51
Fibrous talc 300 30.75
Atomite whiting 200 20.50
Rutile titanium dioxide 25 2.56
Schenectady SP-553 resin 35 3.60
Parapol 1300 polybutene 100 10.25
Blown soya oil, Z3 15 1.54
Cobalt naphthenate drier, 6% 0.5 0.05
Cab-O-Sil M5 20 2.05
Mineral spirits 55 5.64
975.5 100.00

Solids, wt % 84
Density 1.37
Pounds per gallon 11.4

Mixing
This batch was mixed in the order listed above in a sigma bladed kneader. The hard
resin was predispersed in solvent for easier addition. Some slight formulation changes
may be required to accommodate individual needs and equipment. In particular. mix
times and shear rates can vary widely and slight variations in solvent contentlthixotrope
level may be needed to compensate for mixing differences.
202 HANDBOOK OF ADHESIVES

yourself home repair, and in various industrial, Table 12. Semi-

interior duct and panel sealing, and marine ap- resilient, Butyl Based
plications. The excellent aging and ability to Sealing Tape.
withstand some degree of movement are major Exxon Butyl 268 100
advantages for butyl sealants over the tradi- Silene 732D silica 50
tional oil-based caulking compounds. High Titanium dioxide 50
quality butyl caulking compounds will meet the Atomite whiting 300
Mistron Vapor Talc 150
requirements in Federal Specification TT-S-
Parapol 1300 polybutene 200
001657, "Sealing Compound-Single Compo- AgeRite White antioxidant 2
nent, Butyl Rubber Based, Solvent Release
Type." Canadian Government Specification
19-GP-14 also covers Butyl Caulking Com- silient sealing tape is shown in Table 12. Semi-
pounds. 38 resilient tapes are used in a number of appli-
A different type of butyl mastic with a much cations in curtain-wall and prefabricated con-
lower viscosity is used by the canning and clo- structions. They are often used as part of a
sure industry where highly automated applica- systems approach to glazing and sealing where
tion equipment applies a thin bead of sealant they are used in conjunction with other types
on metal can ends. Here the good FDA regu- of gunnable and/or chemically curing sealants.
latory status and chemical resistance of butyl The highly extensible, resilient tapes are
are valued. based on partially/preferentially cured butyl or
chlorobutyl rubber with pigments and plasticiz-
Sealing Tapes. 39 The 100% solids, pre- ers added to maintain a balance of properties.
formed tape sealants, because of their form and Once installed, these tapes exhibit excellent re-
ease of handling, provide economies in instal- covery from extension and compression so that
lation often unattainable with other sealants. an effective seal will be maintained despite
Tape rolls are available in a variety of widths wide latitudes of movement.
and thickness and many times contain an Resilient tapes are also used in the automo-
embedded string or cured rubber core to pre- tive area for the sealing of windshields and
vent stretching or drawdown in use. All tapes backlites. These tapes not only seal but also
have some degree of pressure sensitivity and serve as the primary adhesive to hold the win-
are sufficiently soft to allow for ease of dow glass in place. Although OEM use has de-
compression during installation. clined in recent years, tapes are still used
Tapes can be categorized as nonresilient, extensively in the aftermarket. Partially cured
semi-resilient, or resilient depending on their butyl is used exclusively in these tapes in order
elastic properties. The nonresilient tapes or rope to meet the requirements of high shear strength,
caulks are extremely soft materials which are absence of flow and sag, and the ability to
usually based on polybutenes. Small amounts withstand the varied exposure conditions and
of low molecular weight pm or butyl rubber vibrations encountered in a moving automo-
are often added to improve strength and flow bile.
resistance. They are used in noncritical sealing Two resilient tape formulations illustrating
and glazing applications where little movement the use of both commercially available pre-
is expected, e.g., in appliance sealing and in cured butyl and butyl cured during mixing are
sealing trailer bodies and mobile homes. shown in Table 13.
The semi-resilient tapes are more elastic in Fig. 5 illustrates two window seals made with
nature and are usually based on regular butyl butyl based sealing tapes. Fig. 5A shows tapes
rubber. Both reinforcing and extender pigments used to seal both the outside and inside of a
are used to maintain a balance between com- window. Having an initial thickness slightly
pressibility and elasticity. The higher molecu- greater than the width of the channel for the
lar weight polybutenes are used as plasticizers seal, the tape is compressed and held firmly
and tackifiers because of their better aging against the glass by the interior sash. Fig. 5B
properties. A typical formulation for semi-re- shows the tape being used to seal the outside of
 BUTYL RUBBER AND POL YISOBUTYLENE 203

Table 13. Resilient Sealing Tapes.

A. B.
Partially crosslinked butyl rubber 100 Exxon Butyl 065 60
Silene 732D silica 50 Chlorobutyl 1066 40
N326 (HAF-LS) carbon black 140 Coated calcium carbonate 50
Parapol 950 polybutene 140 N326 (HAF-LS) carbon black 100
Hercolyn resin 30 Parapol 950 poly butene liS
Zinc oxide 2
Magnesium oxide 0.4
Stearic acid 0.4

One step kneader mix Two stage mix:

• Banbury masterbatch: butyl, Chloro-
butyl, CaC0 3 , ZnO, MgO, stearic
acid; mix 5 min at 325°F
• Kneader mix: masterbatch plus other
ingredients.

a window while a gunnable caulk is employed Table 14. Insulated Glass

on the inside. Extruded Mastic.
Vistanex LM-MH 100
Insulated Window Sealants. 4o Sealants Mistron Vapor Talc 48
used in the construction of double pane, insu- N990 (MT) carbon black 2
lated window and door units must not only pos-
sess excellent weathering, aging, and durability
characteristics but must also have a low mois- which further enhances the moisture barrier
ture vapor transmission rate and be nonfog- properties of the system. Insulated glass seal-
ging. The butyl polymers fulfill all of these ants based on Vistanex LM are noteworthy for
requirements and have been successfully used their outstanding performance after more than
in insulated glass sealants for many years. 20 years of field service. 41
A typical construction involves a combina- Other insulated glass sealants are designed as
tion system employing a butyl mastic as the hot melt compounds with regular or partially
barrier sealant between the metal spacer and cured butyl as the base. These compounds are
glass and a back-up, chemically curing sealant either hot pumped into place or are applied in
serving as an adhesive to hold the unit together. a thermoplastic, preformed tape construction.
An insulated glass mastic formulation is shown
in Table 14. Vistanex LM low molecular Hot Melt Sealants. As mentioned above, a
weight PIB is combined with a platy talc filler newer approach to applying sealants involves

BUTYL
SEALING TAPE

BUTYL
SEALING --t-t,\\, SPACER SHIM
TAPE
SETTING INTERIOR RETAINING
BLOCK SASH OR CLIP
STOP OR
STOP

SPACER -+-......__r
SHIM
INSIDE -
SETTING
BLOCK
(A) (B)

Fig. 5. Typical architectural tape installations.

204 HANDBOOK OF ADHESIVES

the use of 100% solids, thennoplastic com- Oppanol BASF

pounds which are heated to lower their viscos- Pentalyn H Hercules Inc.
Parapolil Polybutenes Exxon Chemical Company
ity and then applied as hot melts. These Piccolyte S-115 Hercules Inc.
products are also known as hot flow sealants. Poly DNB Lord Corporation
Butyl rubber serves as the elastomeric binder Polysar Butyl Polysar Limited
with amorphous polypropylene and various QDO Lord Corporation
resins being used to impart thennoplastic prop- Satinton W IWhitetex Engelhard Corporation
Schenectady Resins Schenectady Chemicals Inc.
erties. 42 Blends of butyl and ethylene propyl-
Silanes Union Carbide Corporation
ene rubber and precured butyl can also be used, Silene 732D PPG Industries, Inc.
but in all cases fonnulations must be carefully Staybelite Ester 10 Hercules Inc.
tailored to avoid excessive melt viscosity. Vistanex@ pm Exxon Chemical Company
Polymers such as LDPE and EVA, fillers, and Zirex Reichhold Chemicals, Inc.
plasticizers like polybutene are used to modify
compound properties. 43 •44 These compounds
are applied by thennal pumping and dispensing REFERENCES
systems designed for bulk, hot melt materials 1. Buckley, D. 1., Elastomeric Properties of Butyl Rub-
or by a semi-portable, heated extruder gun. ber, Rubber Chern. Technol .• 32(5),1475 (Dec. 1959).
Applications involve mainly in-plant assembly 2. Fusco, 1. V., and Hous, P., Butyl and Halobutyl Rub-
line sealing of prefabricated buildings and win- bers in "Introduction to Rubber Technology," M.
dows, household appliances, and automotive Morton, ed., New York, Van Nostrand Reinhold,
1987.
adhesive/sealant end uses where the compound 3. Thomas, R. M., and Sparks, W. 1., Butyl Rubber, in
can flow into place and serve both to adhere the "Synthetic Rubber," G. S. Whitby, ed., Chapter 24,
substrates and to seal out the elements. New York, Iohn Wiley and Sons, 1963.
4. Hardman Inc., "Kalene," Technical Data Sheets
32983ms and 4483ms, Belleville, 1983.
SUPPLIERS OF TRADE NAMED
5. Exxon Chemical Co., "An Introduction to Vistanex@
FORMULATING INGREDIENTS LM Low Molecular Weight Polyisobutylene," Bro-
A-Fax 600 Hercules Inc. chure 204-0188-01A, Houston, 1988.
AgeRite Resin D R. T. Vanderbilt Company 6. Exxon Chemical Co., "Vistanex Polyisobutylene,
AgeRite White R. T. Vanderbilt Company Properties and Applications," Brochure SYN 82-1434,
Atomite ECC America Inc. Houston, 1982.
Be Square 175 Petrolite Specialty Polymers 7. Exxon Chemical Co., "Chlorobutyl Rubber, Com-
Grp. pounding and Applications," Brochure SYN 76-1290,
Bromobutyl Exxon Chemical Company; Houston, 1976.
Polysar Limited 8. Exxon Chemical Co., "Bromobutyl Rubber, Com-
Butyl Zimate R. T. Vanderbilt Company pounding and Applications, " Brochure SYN 86-1801,
Cab-O-Sil M5 Cabot Corporation Houston, 1986.
Chlorobutyl Exxon Chemical Company; 9. Gunner, L. P., Butyl Latex Adhesives for Polyolefins,
Polysar Limited J. Adhesive and Sealant Council. 1(1), 23 (1972).
DBQDO Lord Corporation 10. Burke-Palmason Chemical Co., "Butyl Latex BL-
Elvax 40 E. 1. DuPont, Inc. 100," Brochure, Pompano Beach, 1984.
Epolene C-I0 Eastman Chemical Products 11. Berejka, A. 1., and Lagani, A., Ir., U.S. Patent
Inc. 3,597,377, to Esso Research and Engineering Co.
Escorene@ EVA Exxon Chemical Company (Aug. 3, 1971).
Exxon Butyl Exxon Chemical Company 12. Paterson, D. A., XL Butyl Rubber Improves Pre-
Escorezil Resins Exxon Chemical Company formed Sealant Tapes, Adhesives Age, 12(8),25 (Aug.
Ethanox 702 Ethyl Corporation 1969).
Finaprene 1205 Fina Oil & Chemical Com- 13. Hardman Inc., "Kalar," Technical Data Sheet
pany 12382ms, Belleville, 1982.
Hercolyn D Hercules Inc. 14. Amoco Chemicals Corp., "Amoco Polybutenes,"
Irganox 1010 Ciba-Geigy Corporation Bulletin 12-1, pp. 22-25, Chicago, 1981.
Kalar Hardman Inc. 15. Jagisch, F. C., "Performance of Vistanex LM Poly-
Kalene Hardman Inc. isobutylene in Blends with Thermoplastic Hydrocar-
Kraton 1107 Shell Chemical Company bon Materials," Exxon Chemical Technical Report
Laktane Exxon Corporation TB-AP-35, Baton Rouge, 1979.
Mistron Vapor Talc Cyprus Industrial Minerals 16. Smith, W. C., The Vulcanization of Butyl, Chloro-
 BUTYL RUBBER AND POL YISOBUTYLENE 205

butyl and Bromobutyl Rubber, in "Vulcanization of 30. Morris, T. C., and Johnson, E. C., U.S. Patent
Elastomers," G. Alliger and I. J. Sjothun, eds., p. 2,894,925, to B. B. Chemical Co. (July 14, 1959).
230, New York, Van Nostrand Reinhold, 1964. 31. Battersby, W. R., Karl, C. 0., and Kelley, J. S., U.S.
17. Eby, L. T., and Thomas, R. T., U.S. Patent Patent 3,318,977, to United Shoe Mach. Co. (May 9,
2,948,700, to Esso Research and Engineering Co. 1967).
(Aug. 9, 1960). 32. Brillinger, J. H., and Stucker, N. E., Elastomers in
18. Exxon Chemical Co., "Viscosities of Solutions of Hot-Melt Formulations, TAPPI, 52(9) (Sept. 1969).
Exxon Elastomers," Bulletin SC 75-108, Houston, 33. Harris, G. M., "Plastic Tapes-Twenty Years of Un-
1975. derground Corrosion Control," Paper at 26th NACE
19. Stucker, N. E., and Higgins, J. J., Determining Poly- Conference, March 2-6, 1970.
mer Solution Viscosities with Brookfield and Burrell- 34. Federal Spec. HH-I-553, "Insulation Tape, Electri-
Severs Viscometers, Adhesives Age, 11(5), 25 (May cal," Grade A-Ozone Resistant.
1968). 35. Panek, J., and Cook, J. P., "Construction Sealants
20. Exxon Chemical Co., "Vistanex LM Poly isobutyl- and Adhesives," Second Edition, New York, John
ene, Handling Suggestions," Bulletin SC 83-130A, Wiley and Sons, Inc., 1986.
Houston, 1983. 36. Jagisch, F. C., Polyisobutylene Polymers in Sealants,
21. Trelf, A., Labor Savings Pay for Kneader-Extruder, Adhesives Age, 21(11), 47 (November 1978).
Adhesives Age, 12(8),20 (Aug. 1969). 37. Higgins, J. J., Butyl and Related Solvent Release
22. Higgins, J. J., Jagisch, F. C., and Stucker, N. E., Sealants, in "Sealants," A. Damusis, ed., Chap. 13,
Butyl Rubber and Polyisobutylene, in "Handbook of New York, Van Nostrand Reinhold, 1967.
Pressure-Sensitive Adhesive Technology," Second 38. Dalton, R. H., McGinley, C., and Paterson, D. A.,
Edition, D. Satas, ed., p. 374, New York, Van Nos- Developing a Quality Standard for Butyl-Polyisobu-
trand Reinhold, 1989. tylene Solvent Release Sealants, Adhesives Age, 16(11)
23. Tyran, L. W., U.S. Patent 3,321,427, toE. I. Dupont (Nov. 1973).
(May 23, 1967). 39. Berejka, A. J., Sealing Tapes, in "Sealants," A. Da-
24. Moyer, H. C., Karr, T. J., and Guttman, A. L., U.S. musis, ed., Chap. 14, New York, Van Nostrand Rein-
Patent 3,338,905 to Sinclair Research Inc. (August 29, hold, 1967.
1967). 40. Mazzoni, R. J., and King, L. K., Performance of
25. Cox, E. R., U.S. Patent 3,396,134, to Continental Oil Double Glazed Units in Accelerated and Service Tests,
Co. (Aug. 6, 1968). Mater. Res. STD, 517 (Oct. 1965).
26. Kremer, C. J., and Apikos, D., U.S. Patent 41. Kunkle, G. E., U.S. Patent 2,551,952, to PPG Co.
3,629,171, to Atlantic Richfield Co. (Dec. 21,1971). (Sept. 9, 1948).
27. Hammer, I. P., U.S. Patent 3,322,709, to Mobil Oil 42. Jagisch, F. C., "Vistanex Polyisobutylene and Es-
Corp. (May 30, 1967). corez Resins in Hot Flow Sealants, " Exxon Chemical
28. Trotter, J. R., and Petke, F. D., U.S. Patent Technical Report TB-AP-IO, Baton Rouge, 1977.
4,022,728, to Eastman Kodak Co. (May 10, 1977). 43. Berejka, A. J., and Higgins, J. J., Broadened Hori-
29. Exxon Chemical Co., "Escorez® Resins and Vistanex zons for Butyl Sealants, Adhesives Age, 16(12) (Dec.
LM Polyisobutylene in Low Temperature Pressure 1973).
Sensitive Adhesives," Bulletin R 79-54, Houston, 44. Callan, J. E., Cross-linked Butyl Hot-Melt Sealants,
1979. J. Adhesive and Sealant Council, 3(1) (1974).
 11
Nitrile Rubber Adhesives
DONALD E. MACKEY AND CHARLES E. WElL
THE B. F. GOODRICH COMPANY
ELASTOMERS AND LATEX DIVISION
AVON LAKE, OHIO

INTRODUCTION easily adapted by proper formulation to many

applications. Nitrile rubbers have been used to
Nitrile rubbers are broadly defined as copoly-
bond cured and uncured nitrile rubbers to them-
mers of a diene and a vinyl unsaturated nitrile.
selves, to vinyls, to polychloroprene, and to
This chapter will focus primarily on emulsion-
other elastomers. They have been used for
polymerized copolymers of 1,3-butadiene and
coating fabrics to provide oil resistance and
acrylonitrile, which represent the bulk of the
wear resistance and to adhere vinyls and elas-
commercially available nitrile elastomers.
tomers to fabrics. Blended with phenolic res-
Commercial nitrile rubbers contain between 15
ins, they have been used for many applications.
and 50% acrylonitrile, and have the following
Nitrile rubbers have excellent compatibility as
general structure:
adhesives with polar adherends such as protein
fibers, textiles, paper, and wood.

PREPARATION OF NITRILE RUBBER

Emulsion Technology
Several excellent review articles describe ni-
trile rubber in great detail. \-6 This chapter will Commercial nitrile rubber is produced using an
also briefly discuss the solution-polymerized emulsion polymerization process. Emulsion
functionally terminated telechelic liquid copol- polymerization systems are commercially at-
ymers of butadiene and acrylonitrile. The latter tractive in that they allow the production of high
materials, though much smaller in commercial molecular weight polymer at high polymeriza-
volume, are achieving increased importance in tion rates. There are five major nitrile rubber
high performance adhesive systems. producers that supply the U.S. market, includ-
Nitrile rubbers are compatible with phenol- ing BFGoodrich, Uniroyal Chemical (recently
formaldehyde resins, resorcinol-formaldehyde sold to Avery International), Polysar, Good-
resins, vinyl chloride resins, alkyd resins, cou- year, and Copolymer. Some of these suppliers
marone-indene resins, chlorinated rubber, hy- have a very limited product line since they use
drogenated rosins, coal-tar resins, epoxies, and a continuous manufacturing process. Other
other resins, forming compositions which can suppliers use a batch manufacturing process and
be cured and which can provide excellent ad- offer a large number of products, e.g., the
hesives of high strength, high oil resistance, BFGoodrich product line contains approxi-
and good resilience. Nitrile rubber cements are mately 70 different nitrile rubber products. A

206
 NITRILE RUBBER ADHESIVES 207

list of all commercial nitrile rubbers would be many nitrile elastomers of < 35 % acrylonitrile
quite lengthy. Table 1 lists the commercial content are not homogeneous compositionally,
"hot" nitrile rubbers since the hot rubbers are but instead exist as mixtures of copolymers with
generally preferred in adhesive applications. variable acrylonitrile contents. This has been
In an emulsion polymerization process, there shown to produce incompatible polymer mix-
are numerous variables that may be changed. tures that exhibit two glass transition tempera-
Blackley'S recent book? discusses emulsion tures. 9- 11
rubber production and provides an outline of Through the years other monomers have been
the mechanism of emulsion polymerization. investigated. The diene commonly employed is
Some of the major polymerization variables 1,3-butadiene, although isoprene, 2-ethyl bu-
will be discussed here, as they affect the ad- tadiene, 2,3-dimethyl butadiene, piperylene,
hesive properties of the resulting polymers. and other substituted dienes have been inves-
tigated. The nitrile commonly employed is
Monomer Type/Level. Typically, nitrile acrylonitrile. It has been reported that when part
rubbers of greater than 25 % acrylonitrile con- of the acrylonitrile is replaced by methacrylo-
tent are employed in cement/adhesive applica- nitrile or ethacrylonitrile, the cement-making
tions. 8 As the acrylonitrile level of nitrile rubber properties of the rubber are improved. 6 Small
is increased from 15 to 50 %, the polar nature proportions of a third monomer may also be
ofthe polymer increases. This is reflected by a used in conjunction with the two principal
change in the solubility parameter (Fig. 1). components. Hycar 1072, which employs
The second major effect of increasing the methacrylic acid as the third monomer, is oc-
acrylonitrile content of nitrile rubber is an in- casionally used in adhesive applications. Other
crease in the glass transition temperature. Glass monomers including ethyl acrylate, methyl
transition temperatures for nitrile rubbers of methacrylate, styrene, vinylidene chloride,
homogeneous compositions may vary from ap- acrylic acid, N-vinyl-2-pyrrolidone, and vinyl
proximately -60 to -lOoe as the acrylonitrile acetate have been employed in varying amounts
content is increased from 15 to 50%, respec- to adjust the adhesive and elastomeric proper-
tively. However, it is also well known that ties.

Table 1. Hot Nitrile Rubbers.

Nominal
Supplier Trade Name % Acrylonitrile Mooney Viscosity Remarks
HycaJ'll' lOOOX88 43 80
Hycar lOOICG 41 87 cement grade
Hycar 1002 33 85
Hycar 1022 33 48 directly soluble
BFGoodrich
Hycar 1014 21 80
Hycar 1312LV 26 10,000 cpa liquid
Hycar 1422X5 33 48 ground form of
1022

Paracril ® CJ 38.5 47
Paracril C 35 75
Uniroyal Chemical Paracril CV 35 65
crumb form
(Avery International) Paracril B 29.5 80
Paracril AJ 23.5 50
Paracril 1880 22 75

Chemigum® N3 39 84
Chemigum N5 39 87
Goodyear
Chemigum N6B 33 54
Chemigum N7 33 86
'Brookfield viscosity.
208 HANDBOOK OF ADHESIVES

s
o 11.------------------------------------------------.
L
U
B
I
L
101--------------
I
T
Y
* *
P
A 9 I---------~'---*----*------------
R
A ~
M
E
T
E
8L----L----L---~----~--~-- __ J __ _~~_ __ L_ _ _ _L __ _~

R o 5 10 15 20 25 30 35 40 45 50
PERCENT ACRYLONITRILE IN POLYMER
Fig. 1. Solubility parameter vs. percentage acrylonitrile nitrile rubbers.

Polymerization Temperature-Hot vs. Emulsifier Type/Level. Nitrile rubbers are

Cold. Most commercial nitrile rubber pro- polymerized with anionic emulsifiers. 4 A large
duction today is conducted at a polymerization number of anionics can be used as primary
temperature of 5°C (41 OF) and is referred to as emulsifier including: the sodium, potassium, or
cold rubber. Cold rubber, with its improved ammonium salts of fatty acids, rosin acids, al-
processing properties, is generally preferred for kyl sulfates, and alkyl aryl sulfonates. Since
applications where mixing, calendering, or ex- emulsifier residues remain in the nitrile rubber
truding are encountered. s However, in adhe- after the latex is coagulated and dried, it has
sive applications, hot nitrile rubbers are been found that the type and level of emulsifier
generally preferred (although not exclusively). used can affect the adhesive properties.
Hot polymerizations are conducted at temper-
atures of 2S-S0°C. Hot polymers tend to ex-
Molecular Weight Modifier. In order to
hibit higher levels of branching and a slightly
control the molecular weight of the polymer,
higher cis-l ,4 microstructure for the butadiene
various molecular weight modifiers or chain
segments. Infrared spectroscopy has been uti-
transfer agents are used. These modifiers are
lized to analyze nitrile elastomers for their mi-
frequently aliphatic mercaptans and, occasion-
crostructural architecture,12 since it is well
ally, diisopropyl xanthogen disulfide. Without
known that three different structures can exist
a modifier, a very high molecular weight pol-
for the butadiene segments:
ymer would result with undesirable branching
CH2 - and, as a result, extremely poor processing
/
/CH=CH -CH2 -CH- characteristics. It has been reported that the use
-CH 2 I of dimethyl xanthogen disulfide produces an
CH
II
emulsion nitrile rubber with superior adhesive
CH 2 properties compared to a nitrile rubber pre-
trans-1,4 cis-l,4 1,2 or vinyl pared with a n-dodecyl mercaptan.13 For ad-
 NITRILE RUBBER ADHESIVES 209

hesive and sealant applications where a very polymer compositions constant. As a result,
low molecular weight nitrile rubber is desired, batch and continuous production methods can
high levels of molecular weight modifier are produce nitrile rubbers with different sequence
used to produce a viscous, liquid polymer. Liq- distributions (arrangement of the monomer
uid nitrile rubbers, e.g. Hycar 1312, are useful units) which affect their properties in adhesive
as tackifier agents. applications.

Conversion of Monomer to Polymer. Coagulation and Drying. Since residual

Commercial nitrile rubber polymerizations are nonpolymer components (emulsifier, coagu-
typically run to final conversions (of monomer lant, antioxidant, electrolyte, etc.) can affect
to polymer) between 7S and 90%. As conver- the adhesive properties of a nitrile rubber, the
sion increases, the resulting polymer is more method of coagulation, washing, and drying of
highly branched and crosslinking or gel for- the latex is important. Common coagulants in-
mation is increased. If a gel-free or clear ce- clude aluminum sulfate and calcium chloride,
ment is desired, lower conversions need to be although other materials are also used. The
employed, since the solubility of the nitrile co- conditions employed to wash the coagulated
polymer is dependent on the ultimate conver- crumb rubber and any mechanical squeezing of
sion and molecular weight. the wet rubber crumb will also affect the resid-
ual level of emulsifier and coagulant.
Batch vs. Continuous. Some nitrile rubber
producers use a batch process. The batch pro- Grinding. As a final production step, some
cess has the advantage of making small nitrile rubbers are ground to a particulate form.
amounts of many different products, thus ena- The larger surface area of these products makes
bling the producer to tailor-make polymers for them more readily soluble and, as such, often
relatively low-volume specialty applications. desirable in cement applications. To prevent
Obviously, however, the disadvantage is the reagglomeration of these products an anti-cake
relatively high changeover costs. On the other or dust must be added. Soapstone, talc, resins,
hand, some nitrile rubber producers use a con- powdered polymers, or other materials are used
tinuous process. This process is relatively low for this purpose and may ultimately affect the
cost but limits the number of products that can performance of the adhesive.
be economically produced since minimum run
quantities are relatively large.
Functionally Terminated Telechelic Liquid
The copolymerization kinetics are such that
Polymers
nitrile rubbers produced at a polymerization
temperature of SoC have an azeotropic com- As mentioned in the introduction, there is a new
position of 42.S % acrylonitrile. 5 In other class of butadiene acrylonitrile copolymers that
words, the composition of the monomer feed has found increasing utility in various adhesive
and the copolymer produced will be equal and systems. These polymers are terminally func-
constant as the polymerization conversion in- tional (telechelic) liquids. The preparation of
creases. On the other hand, hot polymerization these materials varies significantly from the
conditions (SO°C) have an azeotropic compo- normal emulsion polymers. These materials are
sition of 37.S % acrylonitrile. In either case, if solution polymerized with a suitable initiator/
a batch polymerization is conducted at a com- chain transfer agent that results in a nearly di-
position which differs from the azeotropic mix- functional molecule. These polymers have
ture, the composition of the nitrile rubber number average molecular weights in the range
formed will vary as a function of conversion. of 3,SOO. Polymers with acrylonitrile contents
This effect is especially pronounced for low from 10 to 27 % are commercially available. If
acrylonitrile levels, which are relatively far increased functionality is required, pendent
from the azeotropic composition. Continuous groups can be introduced into the backbone by
production methods meter in the faster reacting copolymerization with small amounts of a car-
monomer in order to keep the monomer and boxyl-containing monomer. The terminal func-
 210 HANDBOOK OF ADHESIVES

Table 2. Hycar Reactive Liquid Polymers.

/3oox8 /3OOX9 /3OOX/3 /3ooX2J /3ooXJ6 /3OOX22 /3OOX23 /3ooXJ7
CTBN CTBNX CTBN ATBN ATBN vrBN vrBNX vrBNX
Acrylonitrile content, % 18 18 26 10 16 16 16 16
Functionality carboxyl carboxyl carboxyl 2° amine 2° amine acrylated acrylated I ° hydroxyl
Brookfield viscosity, 135,000 160,000 570,000 180,000 200,000 225,000 250,000 140,000
centipoise @ 27°C
Specific gravity 0.948 0.955 0.960 0.938 0.956 0.984 0.985 0.960
Equivalent weight 1,920 1,490 1,750 1,200 900 1,400 1',100 1,880

tionality can be manipulated to give carboxyl • High Mooney viscosities are preferred. A
groups, secondary amine groups, primary hy- good indication of the potential bond
droxyl groups or acrylate groups, Table 2 lists strengths obtainable from nitrile rubbers is
the major commercially available materials, 14 given by the Mooney viscosity of the raw
These reactive liquid polymers differ signif- polymer. In general, the higher the Moo-
icantly from the older high molecular weight ney viscosity, the higher the strength of
analogs in several important aspects. First, the cement adhesive.
since they are nearly difunctional, they can eas- • Hot-polymerized nitrile rubbers are often
ily be reacted with other polymers or prepoly- preferred. However, this is not always the
mers to give high molecular weight materials case; e.g., cold-polymerized Hycar
containing short nitrile rubber blocks in the VT455 and Hycar VT480 are finding sig-
backbone. The variety of functional groups en- nificant application in the adhesive area.
ables these materials to react with many other
materials including epoxy, polyester, and po- Depending upon the particular nitrile rubber
lyurethanes. Secondly, these materials are vis- that is selected, it mayor may not require mill-
cous liquids at room temperature and can be ing prior to cement preparation. Details con-
mixed with other liquid materials such as epox- cerning the milling and processing of nitrile
ies to yield a 100% active liquid system. This rubbers are available in suppliers' bulletins8 ,15
allows the formulator or end user to avoid the and literature reviews. 5 ,6 Milling on tight, cold
use of volatile solvents and the associated en- mill rolls is probably the most efficient method
vironmental emission problems. Thirdly, since of breaking down nitrile rubbers and rendering
these materials are solution-polymerized, the them soluble. Nitrile rubbers and their com-
end product can be easily produced virtually pounded stocks, prepared for cement use by
free of inorganic salt contamination. This is milling, should be put into solution as soon as
particularly important in areas such as printed possible after milling since solubility is pro-
circuit boards where very small amounts of gressively lost with time. Even though some
mobile ions can destroy the electrical charac- nitrile rubbers are directly soluble, milling can
teristics of the adhesive or encapsulant. be employed to reduce the cement viscosity.
The effect of milling on the viscosity and shelf
stability of nitrile rubber cements is shown in
COMPOUNDING NITRILE RUBBER
Table 3. 8
CEMENTS
Sarbach and Garvey l6,17 studied the solubil-
Polymer Selection and Solubilization ity of nitrile rubber in eighty typical solvents.
They concluded that such rubbers are soluble
There are numerous nitrile rubbers used in ce-
in aromatic hydrocarbons, chlorinated hydro-
ment and adhesive applications, although some
carbons, ketones, esters, and nitroparaffin
general trends may be noted:
compounds, and are insoluble in aliphatic hy-
• High acrylonitrile levels are frequently drocarbons, hydroxyl compounds, and acids.
used. Superior bonding and film proper- Among the solvents commonly employed with
ties are obtained from high acrylonitrile nitrile rubbers, where rapid evaporation is de-
containing nitrile rubbers. sired, are acetone, methyl ethyl ketone, chlo-
 NITRILE RUBBER ADHESIVES 211

Table 3. Effect of Milling on Viscosity and Shelf Stability of Cements.

Recipe No.: 1 2 3 4
Hycar 1041 20.0 20.0
Hycar 1042 20.0 20.0
Methyl ethyl ketone 80.0 80.0 80.0 80.0
Totals 100.0 100.0 100.0 100.0
Treatment Milled Unmilled Milled Unmilled
LVF Brookfield Viscosity, cps
(#4 spindle, 30 rpm)
Initial 1,200 Gel 940 2,380
24 hr 1,200 940 2,380
48 hr 1,200 1,080 2,800
72 hr 1,200 1,080 2,940
144 hr 1,200 1,080 3,300

roform, ethylene dichloride, ethyl acetate, and ment, the poorer its stability). It has been re-
trichloroethylene. Slower evaporating solvents ported that l-chloro-l-nitropropane 19 is effec-
include nitromethane, nitroethan~, the nitro- tive in stabilizing nitrile rubber solutions.
propanes, dichloropentenes, chlorobenzene, Final selection of a solvent for a nitrile rub-
chlorotoluene, methyl isobutyl ketone, butyl ber cement will be determined, in addition to
acetate, and methyl chloroform. effective solvent action, by such factors as
Cements of 20-35 % total solids are easily availability, cost, toxicity, odor, flammability,
obtainable in methyl ethyl ketone and chlori- and rate of evaporation. Some solvent mixtures
nated solvents. Nitroparaffins may be used as which have been recommended for use with ni-
solvents when highly concentrated cements (up trile rubbers to achieve a desired balance of
to 50% total solids) are desired. 18 (In general, cost, evaporation rate, and good solvent action
the more concentrated the nitrile rubber ce- are given in Table 4. Since many of these sol-

Table 4. Solvent Mixtures for Hycar Rubber (percentages by volume).

Two-Component Mixtures Three-Component Mixtures
I. Nitroethane or nitromethane 10-30% I. Chlorotoluene 10-20%
Benzene, toluene, or xylene 90-70% Nitroethane 10-20%
Benzene 80-60%
2. Ethylene dichloride 10-30% 2. Ethylene dichloride 10-20%
Benzene, toluene, or xylene 90-70% Chi oro benzene 10-20%
Methyl ethyl ke- 80-60%
tone
3. Chlorotoluene or chlorobenzene 10-30% 3. Butyl acetate 33~%
Benzene, toluene, or xylene 90-70% Chi oro benzene 33~%
Acetone 33~%

4. Chlorobenzene 10-30% 4. Ethy lene dichloride 10%

Methyl ethyl ketone 90-70% Toluene 10%
Benzene 80%
5. Nitroethane 10-30% 5. 1-Nitropropane 25%
Methyl ethyl ketone 90-70% Acetone 50%
Benzene 25%
6. Chlorotoluene 10-30%
Diisopropy I ketone 90-70%
212 HANDBOOK OF ADHESIVES

vents are toxic, cements and adhesives contain- alkyd resins, coumarone-indene resins, liquid
ing them should always be prepared and used nitrile rubbers, coal-tar resins, etc.
in well ventilated and preferably hooded areas.
Curatives. Curing agents are used with ni-
Types of Compounding Ingredients trile rubbers when high strength and especially
strength at elevated temperatures is a requisite
Nitrile rubbers may be compounded for many
of the adhesive. The usual cure packages (cu-
cement applications. Normal rubber com-
ratives, accelerators, activators, etc.) em-
pounding techniques should be employed, in-
ployed in dry nitrile rubber compounding are
cluding the types of compounding ingredients
applicable for curing nitrile rubber cements.
described below.
Sulfur/benzothiazyl disulfidelzinc oxide (2/1.51
5) is a common system. When low temperature
Pigments. Pigments are added to nitrile rub-
curing cements are desired, ultra accelerators
ber cements for a variety of purposes. A major
such as the zinc salts of the thiuram disulfides
reason to add pigments is for their reinforcing
or accelerators activated by aldehyde-amine
qualities; other reasons include promotion of
complexes may be used. Preferably, these are
tack, extension of storage life, improvement of
incorporated just before use of the cement.
heat resistance, and reduction of cost. Carbon
blacks enhance the strength of cured nitrile rub-
ber films. The best properties are obtained with Tackifying Agents/Resins. High strength,
channel black, usually added in amounts of 40- oil resistant, resilient adhesives are prepared
60 parts (based on 100 parts nitrile rubber). with nitrile rubbers by modification with resins
Softer furnace blacks give lower tensile prop- and other rubbers. The phenolic resins are ex-
erties with a slight loss in adhesion, but provide tensively employed for this purpose. Resorci-
longer shelf life and somewhat lower costs. nol-formaldehyde resins, polyvinyl chloride
Among the nonblack pigments, iron oxide, zinc resins, and alkyd resins have also been em-
oxide, hydrated silica, titanium dioxide, and ployed. "Vinsol" resin, hydrogenated rosin
clays are the most commonly employed. Iron and its derivatives, coal-tar resins, coumarone-
oxide is commonly used at levels of 75-100 indene resins, and liquid nitrile rubber (e.g.,
parts per hundred rubber (phr). It yields smooth Hycar 1312) are useful tackifying agents.
cements of relatively high tensile strength, im- Chlorinated rubber has been used to improve
proved tack and storage life, but lacking good tack, stability, and adhesion to a variety of ma-
abrasion resistance. Zinc oxide (25-50 phr) terials, including metals. Tack and adhesive
improves tack but not film strength. Hydrated properties of nitrile rubbers have been im-
silica (20-100 phr) is used to improve tensile proved for some applications by the inclusion
strength where blacks are objectionable and is of chlorinated alkyl carbonates such as chlori-
especially useful in fabric adhesions, although nated dibutyl carbonate. 20 •21
excessive loadings tend to reduce adhesion. Ti-
tanium dioxide (5-25 phr) is used to impart Antioxidants. All nitrile rubber producers
whiteness, promote tack, and extend storage add an antioxidant to their raw nitrile rubbers.
life. Clays are employed to reduce cement costs However, where heat resistance and the maxi-
at the expense of tensile strength and adhesion. mum in durability and service is demanded, ad-
ditional antioxidant may be added to the
Plasticizers. Softeners are sometimes em- cement. Antioxidants commonly used in nitrile
ployed with nitrile rubbers to improve tack and rubbers (e.g., amine antioxidants) may be used
adhesive properties. They are added to high ni- if staining is not a factor. Antioxidants may also
trile content rubbers to aid processability. contribute stability and tack.
Commonly employed in cement applications
are esters (e.g., dibutyl phthalate, dioctyl Thickening Agents. Thickening agents are
phthalate, tricresyl phosphate, tributoxy ethyl sometimes added to nitrile rubber cements to
phosphate, dibenzyl sebacate), ester gums, give them desired pseudoplasticity wherein ap-
 NITRILE RUBBER ADHESIVES 213

parent viscosity decreases rapidly with increase Table 5. Applications for Laminating
in rate of shear. This property, together with a Adhesives of Nitrile Rubber.
high yield value, is very desirable for cements Unvulcanized nitrile to: Leather to:
to be employed in spreadcoating operations. Unvulcanized nitrile Leather
Such properties also tend to prevent excessive Rayon Vinyl
strike-through during spread coating. Low total Cotton Composition sole
Nitrile to: Synthetic rubber sole
solids, low viscosity solvent cements can be Cotton
SBR
thickened to usable viscosities. Such thicken- Neoprene Vinyl film to:
ing agents are also employed to improve the Leather Vinyl film
properties of spray~type cements, especially Nylon Cotton
where thick coatings are desired. A carboxylic Teflon Vinyl
Steel Vinyl to vinyl foam
vinyl polymer, Carbopol® 934, has been very Cork to cork
Brass, tin plate
effective for thickening nitrile rubber cements Aluminum Glass to glass
based on methyl ethyl ketone. 8 •22 Nylon to nylon Wood to wood
Orlon to Orion Grit to polyurethane foam
Cotton to cotton Copper to:
APPLICATIONS Phenolic board
Epoxy board
Nitrile polymers have found a varied number Asphalt board to mohair
of applications in the adhesive area. These ap- fabric
plications are based on the excellent elasto-
meric properties of the polymer coupled with
its polarity which gives the material good sol- The polymeric film and the metal are coated
vent resistance and compatibility with other po- with an adhesive shown in Table 6. The re-
lar materials. The various commercially sulting laminates are pressed together under 200
available physical forms of nitrile polymers psi pressure at 300°F for 15 minutes. 23
(slab rubber, crumb rubber, liquid rubber and Cellulose acetate flock has been adhered to
latex) have also increased the ease of process- textile materials to make a pile surface using
ing of the material and broadened the applica- the cement composition shown in Table 7. 24
tion base. In an attempt to review this broad Cements of nitrile rubber and Vinsol ester
area, the applications have been subdivided into gum25 in ethylene dichloride or a similar sol-
three parts. In the first section applications in- vent have been recommended as adhesives and
volving solely nitrile rubber as the base poly- surface coatings. An adhesive for leather and
mer as well as miscellaneous nitrile rubber shoe fabrication has been formulated from
blends are reviewed. Due to the large number blends of nitrile rubber, pyroxylin,26,27 and
of applications involved, nitrile rubber/pheno- other ingredients such as sulfur, zinc oxide, and
lic blends have been separated into the second calcium silicate. A room temperature adhesive
section. For the same reason, nitrile rubber/ for vulcanized rubber to rubber having excel-
epoxy blends are covered separately in the third lent initial adhesive strength and oil resistance
section. was prepared from a high acrylonitrile hot po-
lymerized nitrile rubber (e.g., Hycar IOOICG),
Nitrile Rubber Systems
Table 6. Laminating Adhesive for
Laminating Adhesives. Nitrile rubbers
Polymeric Films to Metals.
have found a large number of applications in
the area of laminating adhesives. Table 5 lists Hycar 1002 150
Vinyl chloride-vinylidene chloride co- 50
the varied applications for these adhesive sys-
polymer
tems. Several ofthese specific application areas Diocty I phthalate 20
will then be covered in more detail. Polyvinyl Paraplex G-30 10
chloride, polyvinyl acetate, and other poly- Barium Stabilizer (e.g., Staflex QXMA) 6
meric films have been laminated to a wide va- Sulfur
riety of metals including aluminum and brass. _B_en_z_o_th_ia_z_ol_y_1d_i_su_lfi_d_e_ _ _ _ _ _ _ _ _ __
214 HANDBOOK OF ADHESIVES

Table 7. Adhesive for Cellulose Medium high acrylonitrile latices like Hycar
Acetate Flock. 1552 or carboxylated acrylonitrile butadiene
Hycar 1002 100 latices like Hycar 1572 have been found to give
Sulfur 3 good bond strength to fabric-vinyl foam lami-
Mercaptobenzothiazole 2.4 nates without altering the desirable character-
Phenyl guanidine 0.6 istics of the fabric. Normally the latex is first
Zinc oxide 7.5
Coumarone resin 37.5
thickened with a sodium polyacrylate before
Dimethyl phthalate 300 use. The nitrile latex gives a laminate which is
Bis-(2-ethy Ihexy I)phthalate 45 softer and more flexible than the corresponding
Methyl ethyl ketone 378 laminate made with the carboxylated poly-
Methyl isobutyl ketone 256 mer.35
A medium high acrylonitrile latex in combi-
nation with an emulsion of a liquid nitrile rub-
carbon black and a large amount of zinc dithio- ber has been found to be an excellent adhesive
carbamate. 28 for sculptured styrene foam sections. Such an
A blend of Hycar 1432 and chlorinated adhesive provides excellent "wet grab" and
poly(4-methyl-1-pentene) in a ratio of 3 to 1 thus need not be entirely dried to realize opti-
was found to give excellent adhesive properties mum adhesive properties. A stable emulsion of
for bonding a plasticized PVC sheet to steel. 29 the liquid nitrile is made by first adding a po-
A PVC impregnated conveyor belt carcass was lyacrylate thickening agent to water. Normally
bonded to a layer of unvulcanized neoprene a high shear mixer like an Eppenbach is em-
rubber. 30
ployed to insure good dispersion. The poly-
Nitrile rubber adhesives have been used to acrylate is then neutralized with ammonium
bond medium-to-high polarity rubbers with po- hydroxide and finally the liquid nitrile is added
lyamide substrates. In an early work, nitrile to this solution. A typical composition for the
rubber in solvent was treated with 10-20 parts liquid nitrile emulsion is given in Table 8. The
of phosphoric acid at 50-100°C and subse- final adhesive would contain one part of nitrile
quently neutralized. 31 In more recent work, latex and six or more parts of liquid nitrile
acrylic acid, methacrylic acid, dicumyl perox- emulsion.
ide and phenol ether were added to a mixture A medium high acrylonitrile latex can be
of nitrile and formaldehyde-phenol oligomer to compounded with a resorcinol-formaldehyde
give a rubber-to-poIyamI'de adh' eSIve. 32 solution to give a good adhesive to bond nitrile
The adhesive properties of nitrile rubber can rubber stocks to cotton or rayon fabric. This
be further improved by chemical modification. treatment results in adhesion as good or better
Nitrile rubber treated with isocyanate was than that obtained by saturation of the fabric
mixed with a polyisocyanate33 and found to be with solvent cement. A typical recipe is shown
an excellent adhesive for rubber to sailcoth in Table 9. 35 This adhesive would be cured for
laminates. In other work, methyl methacrylate 1-5 minutes at 160°C.
was grafted onto nitrile rubbe~ to give a ma- Nitrile latices have also found applications in
terial with good adhesive strength. adhering fabric backed vinyl wall covering to
Nitrile rubber which is commercially avail- SBR foam. Nitrile latices can be used to give
able as a latex has also found widespread use effective adhesion of Saran film to food pack-
in adhesive applications. The distinct advan-
tage to the latex form is that the material can
be spread on the substrate directly without first Table 8. Recipe for Stable Liquid Nitrile
dissolving the polymer with solvent. This is Emulsion.
very advantageous to formulators that can not Hycar 1312 99.25
handle the environmental aspects of later re- Polyacrylate resin (e.g., Carbopol934) 0.60
moving the large amounts of hydrocarbon di- Ammonium hydroxide (20%) 0.14
Water 100.00
luent.
 NITRILE RUBBER ADHESIVES 215

Table 9. Adhesive for Nitrile Rubber to Cotton or Rayon.

Dry Wt. Wet Wt.
Nitrile latex (e.g., Hycar 1562XI02) 85 212
6.5% Resorcinol formaldehyde solution 15 231
Water for dilution 57

aging paper. Such an adhesive maintains integ- Cements of High Tack. Cements of high
rity under heating, immersion, and vacuum. 35 tack can be produced by formulating the ma-
A very versatile adhesive for manufacture of terial to include tackifying and plasticizing
a wide variety of laminates can be made by agents combined with large amounts of zinc
mixing a nitrile latex with Vinsol, a high melt- oxide. Table 11 contains an illustrative exam-
ing thermoplastic resin from Hercules Inc. The ple of such a formulation. A liquid nitrile such
Vinsol resin, which is compatible with most ni- as Hycar 1312 may also be used to enhance
trile latices, provides the following advantages: tack.
1. Improved surface wetting and penetra- The high-tack cement in Table 11 would be
tion. prepared by dissolving 1,400 grams of formu-
2. Improved specific adhesion to metal sur- lation A in ! gallon of chlorotoluene and then
faces. diluting this mixture to one gallon with chlo-
3. Reduced moisture vapor transmission of robenzene. Likewise 1,400 grams of formula-
the adhesive film. tion B would be dissolved in ! gallon of
4. Improved water resistance with no loss in chlorotoluene and then diluted to one gallon
resistance to liquid hydrocarbons. with chlorobenzene. Just before using equal
5. Reduced cost. volumes of the two solutions would be mixed. 8

Nitrile latex can be mixed with PVC latex to Spreading Compounds. Spreading com-
give excellent adhesion of polypropylene car- pounds are recommended for maximum resis-
pet and plywood backings. The formulation tance to gasoline and oil combined with good
shown in Table 10 was found to give good low temperature flexibility (Table 12).8
adhesion even after seven days immersion in
water. 35 White Cement Formulation. In some cases
Combinations of nitrile latices and styrene- it may be desirable to formulate a cement with
butadiene latices give good laminating bonds white pigmentation. This can be done with ti-
for saturated paper and woven fabrics. A po- tanium dioxide, silica or similar materials (Ta-
tential application is soft-shell luggage with ble 13). Just before use add four parts of Butyl
multiply construction. Finally, nitrile latex in
combination with various other polymers has
been shown to be a good adhesive for bonding Table 11. High-Tack Cement.
polyurethane foam to concrete. 36 Part Part
A B
Table 10. Adhesive to Laminate Hycar 1001 CO 100.0 100.0
Polypropylene Carpet to Plywood. EPC black 10.0 10.0
Zinc oxide 150.0 150.0
Total Solids Dry Parts
AgeRite Resin D 5.0 5.0
Hycar 1562XI03 41.0 1250 Refined coal tar 35.0 35.0
Oeon 450X20 55.0 500 (BRT-7)
Picconol A600E 55.0 750 Benzyl alcohol 18.0 18.0
AcrysolOS 5.0 25 Dibutyl metacresol 35.0 35.0
Toluene 100.0 125 Sulfur 5.0
Dixie clay disper- 65.0 750 Butyraldehyde-aniline 8.0
sion (Accelerator 808)
216 HANDBOOK OF ADHESIVES

Table 12. Spreading Compounds Using Nitrile Rubber.

l' 2b J< 4'
Hycar l00ICG 100.0 100.0
Hycar 1042 100.0 100.0
Zinc oxide 5.0 5.0 5.0 5.0
Spider sulfur 2.0 2.0 1.5 1.5
N770, SRF-HM black (Sterling S) 75.0 60.0 75.0 75.0
Triacetin 35.0
Litharge 10.0
AgeRite Resin D 2.0
Dioctyl phthalate 25.0
Flexricin P-4 Baker Castor Oil 10.0 10.0
Synthetic resin extender (Turpol 20.0
1093)
Benzothiazyl disulfide (Altax) 1.5 1.5 1.5
Stearic Acid 1.0 1.0
Total 218.5 204.0 194.0 214.0
• Dissolve 675 grams in one quart of nitromethane and make up to one gallon with Solvesso No. I.
b Make up as a 45% total solids solution in ethylene dichloride and then dilute to a 25% total solids solution by adding methyl ethyl
ketone.
, The spreading compound (see A and B below) is made from blends of the two compounds by weighing small pieces into quart cans
adding methyl ethyl ketone and rolling for 24 hours.
A B
Compound No.3 194.0
Compound No.4 214.0
Methyl ethyl ketone 776.0 642.0
Total 970.0 856.0

Eight (activated dithiocarbamate, R. T. Van- volve blends with either phenolic or epoxy
derbilt Co.) as a 5-10% solution in MEK.8 resins. These will be covered in detail in the
Similar nonblack cements have been next two sections.
suggested37 for the adhesion of cotton, wood, Besides phenolic and epoxy blends, there are
paper, compositions, leather, and nuclear shoe other structural applications of nitrile rubber
soling. Leather adhesives 38 .39 have been for- noted in the literature. A two-component ad-
mulated from nitrile rubbers using the compo- hesive for zinc-plated substrates has been
sition shown in Table 14. described40 with a significant amount of nitrile
rubber in both parts.
Another example of a structural adhesive is
Structural. Many of the applications of ni-
a two-part solventless liquid system. One part
trile rubber in the structural adhesive area in-
contains carboxylated nitrile rubber, methyl
methacrylate, and cobalt naphthenate. The sec-
Table 13. Typical White Cement ond part is composed of carboxylated nitrile
Formulation. rubber, methyl methacrylate, and cumene hy-
Hycar 1022 polymer 100.0
droperoxide. In this example the carboxylated
Zinc oxide 5.0 nitrile rubber used was Hycar 1072. 41
Sulfur 1.5
Titanium dioxide (Titanox) 15.0 Table 14. Nitrile Leather Adhesive.
Hydrated silica (HiSil) 25.0
Chlorinated paraffin wax (Chlorowax 40) 10.0 Nitrile rubber 100.0
Tetramethylthiuriam monosulfide 0.4 Vinyl chloride-vinyl acetate polymer 100.0
(Unads) Zinc oxide 5.0
Stearic acid 1.0 Stearic acid 1.5
Total 157.9 Calcium silicate 2.0
Solvent 600-800
Mix to 15% total solids in MEK.
 NITRILE RUBBER ADHESIVES 217

Hot Melt Adhesives. Nitrile rubbers can be trile rubber/phenolic adhesives in the manufac-
used in combination with thennoplastic poly- ture of printed circuit boards. Much of this
mers to give a hot melt adhesive. Liquid nitrile work is being done in Japan; two of the more
rubber (Hycar 1312) was added to an acrylic active participants are Hitachi Chemical
acid-ethylene copolymer. The resulting hot CO. 44 - 52 and Toshiba Corp. 53-59
melt adhesive gave a bond strength between These patents discuss various adhesive for-
aluminum plates of 11. 9 lb / in. vs. 5.1 lb / in. mulations and techniques which may be em-
for the same thennoplastic adhesive without the ployed to prepare printed circuit boards.
liquid nitrile rubber. 42 Laminates are electrolessly plated with copper
to produce these heat resistant boards. As an
Nitrile Rubber/Phenolic Adhesives example, a Toshiba patent53 describes hot
pressing prepregs with films coated with ad-
Nitrile rubber and a phenolic resin have been
hesives to make such laminates (Table 18).
used together in many adhesive applications.
Equal parts by weight of a nitrile rubber and a Bonding Metal to Various Rubbers, Abra-
phenolic resin (e.g., Durez 12687) in a suitable sives, Polyamide, and to Other Metals.
solvent (e.g., methyl ethyl ketone) at a total Various literature references discuss the use of
solids level of 20-30% is suitable for many ad- nitrile rubber/phenolic adhesives for the bond-
hesive purposes. Commonly, 30-100 phr of ing ofmetals. 60- 65 ,15 Tanaka63 discussed a two
phenolic resin is employed. Some indication of part liquid adhesive system based on solutions
the bond strength developed by such adhesives of nitrile rubber dissolved in methyl methac-
is shown in Table 15. 8 rylate. Aluminum plates were bonded together
The more phenolic resin employed, the with the resulting adhesive. Kub0 65 reported
greater the bond strength and the more brittle that the adhesive composition of Table 19 was
the adhesive. The increase of bond strength good for bonding steel plates.
with resin content for nitrile rubber/phenolic Nitrile rubber/phenolic adhesives are also
resin cements is illustrated by the data in Table quite useful in adhering rubber to various met-
16. 43 The rubber and resin were dissolved sep- als,66-69 e.g., in the manufacture of rubber cov-
arately in methyl isobutyl ketone as 20% total ered metal rollers. Hube~8 reported that a
solids solutions and then blended. The adhe- nitrile/phenolic adhesive composition provided
sive was coated on steel and the cloth was excellent bonding of rubber to a magnesium roll
bonded after tack developed. (Table 20). Other metal bonding applications
When preparing nitrile rubber/phenolic ad- with nitrile rubber/phenolic adhesives include
hesives, the higher the nitrile content of the laminating aluminum foil to paper and then to
rubber, the greater its compatibility with phe- wood,7o bonding abrasives to metal,71 and
nolic resins. High acrylonitrile content rubbers bonding polyamide to metal. 72
thus produce adhesives with superior bonding
and film properties, although lower acryloni- Structural Adhesives. Films of nitrile rub-
trile content rubbers will produce adhesives ber/phenolic resins (i.e. tapes) have been em-
with better low temperature properties. Table ployed in the aircraft industry for bonding metal
17 illustrates the effect of acrylonitrile content to metal surfaces in both plain and honeycomb
on the tensile properties of nitrile rubber/phe- sandwich constructions. Several Wright Air
nolic resin blends. 15 Development Center reports73-77 describe in
Some of the more important applications for detail the preparation of a nitrile rubber/phe-
nitrile rubber/phenolic adhesives are described nolic resin tape, the metal surface preparation
below. methods, and the methods of evaluating struc-
tural adhesives of this type. A fonnulation for
Printed Circuit Board Manufacturing. In a high-temperature liquid phenolic resin adhe-
the last ten years there has been an increasing sive suitable for structural fabrication is given
number of literature references to the use of ni- in Table 21. 73
218 HANDBOOK OF ADHESIVES

Table 15. Hycar/Phenolic Cement-Adhesion Tests.

123
Hycar l00ICG 100 100
Durez 12687 50 100 100
Hycar 1022 100

Totals 150 200 200

Adhesion.
Pounds per Inch
Cotton duck to cotton duck (#633) 20 5 5
Cotton duck to cotton duck (#674) 5 5 4
Nylon to nylon (#936) 5 2 2
Nylon to nylon (#937) 6 6 5
Cotton duck #633 to wood 20 18 15
Cotton duck #674 to wood 18 15 25
Nylon #936 to wood 9 7 9
Nylon #937 to wood 7 10 10
Wood to wood (yellow pine) 387 619 641
Wood to cured Hycar 1022 35 12 23
Wood to cured acrylic rubber 25 12 10
Wood to cured natural rubber 15 25 20
Wood to cured SBR 10 5 6
Wood to steel 1400 1245 1360
Wood to brass 1000 930 1230
Wood to aluminum 860 758 883
Hycar to Hycar 1022 (cured) 33 28 30
SBR to SBR (cured) 6 18 25
Uncured Hycar 1022 compound to:
Aluminum 5 4 3
Brass 28 23 18
Steel 5 5 3
Uncured acrylic rubber compound to:
Aluminum 8 10 4
Brass 23 20 21
Steel 17 18 20
Uncured natural rubber compound to:
Aluminum 9 7 6
Brass 21 25 18
Steel 12 20 20
Uncured SBR compound to:
Aluminum 0 0
Brass 0 0
Steel 0

In addition to aircraft applications, adhesives Bonding PVC to Steel, Aluminum Foil,

of this type are employed in the bonding of Copper, and Polyurethane. Nitrile rubber/
friction materials (e.g. grinding wheels), brake phenolic adhesives have been utilized to bond
lining to brake shoes, clutch facings, etc. The PVC to a variety of substrates, including
cement shown in Table 22 is suitable for such steel,78-81 aluminum foil,82 and copper.83 Con-
diverse jobs as metal-to-metal bonding or brake tact adhesives have been reported for plasti-
lining bonding. cized PVC. 84- 86 A heat-resistant adhesive has
 NITRILE RUBBER ADHESIVES 219

Table 16. Influence of Resin Content on Table 20. Adhesive Composition for
Adhesion to Steel. Bonding Rubber to Magnesium.
Rubber-to- ResinA, Resin B, Hycar lOOICG
Resin Ratio lb/in. lb/in. Sulfur
Tin oxide
10: 1 8.3 8.1
N-phenyl-beta-naphthylamine
4: 1 15.6 14.1
Black pigment
1: 1 18.3 15.8
2-mercaptobenzothiazole
Resin A-Monsanto Resin 378 (conditioned 16 hr at 12ZOF). Ourez 12687
Resin B-Durez Resin 11078 (conditioned 2 hr at 121°F).
Ourez 7031A
Hexamethy lenetetramine
Chlorobenzene

Table 17. Physical Properties of Nitrile

Rubber and Phenolic Resin Blendsa •
Polymer
Type % Acrylonitrile Tensile at Break (psi)b
Paracril CV 35 2650
Table 21. Nitrile Rubberl
Paracril C 35 2650 Phenolic Resin Tape
Paracril B 29.5 1850 Formulations.
Paracril BJ 29.5 1600
Nitrile rubber 100
Paracril AJ 23.5 1400
Phenolic resin 75:-200
'100 parts rubber, 60 parts Durez 12687, 500 parts MEK. Zinc oxide 5
bfilms cast on glass, cured 2 hr at 212°F.
Sulfur 1 to 3
Accelerator 0.5 to 1
Antioxidant o to 5
Stearic acid o to 1
Carbon black o to 20
Table 18. Adhesive Composition for Filler o to 100
Printed Circuit Boards. Plasticizer o to 10
Hycar 1072 50 Bonding metals to themselves requires heat
(20-120 min at 300-400°F) and pressure (50-
Nicamol PR-I440 30 150 psi).
(Xylene modified phenolic resin)
Epikote-152 20
Oicyandiamide 0.6
Curazol 2E4MZ 0.2
Aerosil-2oo 10
in MEK and BuOCH 2 CH20H
Table 22. Structural Adhesive.
Parts
Part A
Table 19. Adhesive Composition for Phenolic resin (SP-8855) 45.0
MEK/m-chlorobenzene 90.0
Bonding Steel Plates. (70/30 by vol.)
Nitrile rubber (40% VCN) 100
Stearic acid Part B
Zinc oxide 5 Hycar loolCG polymer 100.0
Accelerator OM 1 Carbon black 50.0
Antioxidant 2 Zinc oxide 5.0
Talc 46 Stearic acid 0.5
Resol-type phenolic resin 100 Sulfur 3.0
Novolak-type phenolic resin 100 Benzothiazyl disulfide (Altax) 1.5
Hycar 1312 10 MEK/m-chlorobenzene
Sulfur 2 (70130 by voL)
220 HANDBOOK OF ADHESIVES

Table 23. Adhesives for Leather-to-Leather or Leather-to-Composition Soling.

&~~ 1 2 3 4
Hycar 1432 20.0 10.0 20.0 10.0
UCARVYHH 10.0 5.0
Phenolic resin 10.0 5.0 10.0 5.0
Triphenyl phosphate 2.0
~onochlorobenzene 90.0 40.0
~ethyl ethyl ketone 100.0 75.0 30.0 40.0
Totals 130.0 100.0 150.0 102.0

been used to bond a polyurethane foam to a Automotive trim94 ,15 and clips95 have been
plasticized PVC sheet. 87 The bonding of PVC, bonded with nitrile rubber/phenolic adhesives
leather substitutes, and shoes has also been re- and polyamide has been bonded to rubbef6 and
ported with nitrile rubber/phenolic adhesives. 88 to pavement97 in a road marking application.
Plastic/paper laminates98 for printing blankets
Bonding Leather to Leather, Composition have been prepared. Finally, grit tiles have
Soling, and PVC. In the shoe industry, ni- been bonded to paperboard and other
trile rubber/phenolic adhesives have been used substrates99 to produce prefabricated tile struc-
to bond leather to leather, rubber, and vinyl. A tures which are stable on application to build-
medium high nitrile content rubber (33 % VCN) ings.
with half as much by weight of a phenolic resin,
or this same rubber with half as much or an Sealant Applications. The repair of engine
equal weight of a PVC resin is an effective ad- bodies has been reported using a nitrile rubber/
hesive for heat activation in the temperature phenolic composition as a sealant. 100 The wing
range of 120-130°F. For a higher temperature fuel tanks of C130 aircraft have also used ni-
range adhesive, the use of twice as much of a trile rubber/phenolic materials to seal the
PVC resin as nitrile rubber is effective. Some tanks. 101 Finally, electrolyte leakage in a sheet
suggested combinations8 which yielded adhe- battery has been prevented using nitrile rubber/
sive bonds of 25-40 lb lin. for leather-to- phenolic adhesives. 102
leather, composition soling, or vinyl, are given
in Table 23. Nitrile Rubber/Epoxy Adhesives
Nitrile rubber and epoxy resins have been
Rubber-to-Rubber Bonding. Adhesives for
blended together for use in many adhesive ap-
rubber-to-rubber bonding have been designed
plications. The combination of flexibility and
using nitrile rubber/phenolic compositions.
good low temperature properties of nitrile rub-
Bonding to polar rubbers 89 is especially im-
ber, along with the excellent strength of the
proved with this type of adhesive. The adhe-
sive composition in Table 24 was designed for
splicing cured or uncured nitrile rubber com- Table 24. Splice Adhesive.
pounds to themselves with heat and slight pres-
Paracril Bl 100
sure. 15 Zinc oxide 15
Aminox 2
Miscellaneous Bonding Applications. EPC carbon black 50
Applications have been reported for the use of Coumarone indene resin (~.P. 25°C) 25
nitrile rubber/phenolic adhesives in the bond- Durez 12687 (phenolic resin) 20
~-B-T 2
ing of wood90•91 and polyurethane foam92 to Sulfur 2
various substrates. Mitsubishi Electric Corp. 93 216
patented a two-part adhesive composition for Solvent: methyl ethyl ketone.
Nomex paper (Table 25). Solids content: 20% by weight.
 NITRILE RUBBER ADHESIVES 221

Table 25. Adhesive Composition for Nomex Paper.

Part A Part B
Hycar l00ICG 100 DEN 438 100
Durez 12687 50 2-methyl-4-ethylimidazole 10
MEK 150 MEK 100

epoxy matrix, has led to adhesives with supe- Table 26. Low Temperature
rior properties in both the laminating and struc- Curing Nitrile Epoxy Adhesive.
tural area. Hycar 1042 10-50 parts
Epon 820 90-50
Laminating. Nitrile rubbers blended with Methyl ethyl ketone 80
various epoxy resins and activated by suitable Trimethy lenetetramine 2-20
amines and/or acidic agents have been em-
ployed to bond elastomers, plastics, fabrics,
wood, and metals to themselves and each other. Foamable adhesive sheets have been pro-
Normally good bond strength can be developed duced by blending carboxylated nitrile rubber
at or near room temperature. Any information and epoxy resins, and then adding blowing
must be adapted to the substrate being bonded agents. 108 An epoxy resin containing nitrile
but Table 26 gives a starting formulation. The rubber has been described to yield increased
triethylenetetramine is added as a 50% solution adhesion of metallic coatings to printing
plates. 109
in methyl ethyl ketone just prior to use. Such a
cement will cure in 4-24 hours at room tem- One of the largest areas of use of nitrile rub-
perature and less than 30 minutes at 150°F. ber modified epoxy systems is in the printed
An adhesive consisting of an epoxy resin, a circuit board area. A number of systems have
medium high acrylonitrile rubber, and Pb, Cu, been described that are composed of carboxyl-
Ni, Pd or Co compound fillers was used to bond containing nitrile rubber such as Hycar 1072
EPDM vu1canizates. 103 Peel strengths of 22.5 mixed with epoxy resin. I 10-117 The low molec-
kg/20 mm after a 1 hour at 100°C cure were ular weight functionally terminated nitrile rub-
obtained. Another adhesive composition in- bers have also found significant application in
· area. 118 Other workers have found useful a
thIS
volving a blend of carboxylated nitrile rubber,
epoxy resin and a reactive metal filler has been system that combines a high molecular weight
described for bonding EPDM vu1canizates or nitrile rubber with the liquid functionally ter-
EPDM rubber-nitrile or butyl rubber blends. 104 minated materials. 119 ,120 Finally, other refer-
Other nitrile rubber epoxy adhesives have ences describe the use of non carboxylated
been described for rubber to rubber and rubber nitrile rubbers in circuit board applica-
tions. 121 ,122
to metal bonds. Liquid carboxylated nitrile ma-
terials have been found useful in a number of
· t'Ions. 105 An adheSlVe
app1lca . compnsed. of car- Structural. Flexibilized epoxy resins are
boxylated nitrile rubber, epoxy resins, imida- important commercial structural adhesives.
zole, or tertiary amine and an organic peroxide
has been described lO6 for bonding metals, pa- Table 27. An Adhesive for Bonding
per, plastics, and inorganic materials. Nylon Fabric.
Combinations of carboxyl-, vinyl-, and 100.0
Epikote 815
amine-terminated liquid nitrile materials in Bisphenol A 24.0
conjunction with an epoxy resin have been de- Hycar 1300XI5 223.0
scribed as an excellent adhesive for bonding (carboxyl-terminated nitrile)
.
vanous f ab'
ncs. 107 A clormulatlOn
' .
for bondmg Hycar 1300XI6 25.0
(amine-terminated nitrile)
nylon fabric is shown in Table 27.
222 HANDBOOK OF ADHESIVES

Without the addition of a ftexibilizing agent, of maleic anhydride and butadiene, fumaric
epoxy resin adhesives have relatively poor acid, thioamide, and cumene hydroperoxide.
characteristics due to the brittle nature of the This adhesive was a two part system with the
epoxy matrix. 123 Liquid functionally termi- hydroperoxide in one part and the thioamide in
nated nitrile rubbers have proved to be an ex- the other part. 129
cellent ftexibilizing agent for the epoxy resins.
It has been theorized that toughening of the
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 NITRILE RUBBER ADHESIVES 225

111. Japanese Patent JP 84/81370, to Matsushita Electric Japanese Patent JP 851226582, to Hitachi Chemical
Works, Ltd., May 11, 1984; CAI0l(l8): 153150c. Company, Ltd., November 11, 1985; CAI04(24):
112. Japanese Patent JP 84/81369, to Matsushita Electric 208694c.
Works, May 11, 1984; CA101(l8): 153149j. 122. Kato, S., and Fujii, T., Japanese Patent JP 80/42839,
113. Japanese Patent JP 83/58265, to Toshiba Corpora- to Toshiba Chemical K. K., March 26, 1980;
tion, April 6, 1983; CA99(l8): 141256u. CA93(8): 87100z.
114. Japanese Patent IP 83/10877, to Hitachi Chemical 123. Pocius, A. V., "Elastomer Modification of Struc-
Company and Bostik Japan Ltd, February 28, 1983; tural Adhesives," Rubber Chern. Technol., 58(3),
CA99(16): 123915d. 622, 1985; CA103(24): 197149c.
115. Japanese Patent JP 811135579, to Nitto Electric In- 124. Eby, L. T., and Brown, H. P, "Treatise on Adhe-
dustrial Company, October 23, 1981; CA96(8): sion and Adhesives, Volume 2," R. L. Patuck, ed.,
53429k. New York, Marcel Dekker, 1969.
116. Dokoshi, N., and Nishidono, c., Japanese Patent JP 125. Drake, R. S. and Siebert, A. R., "Adhesive Chem-
75/14736, to Toray Industries, Inc., February 17, istry," L. H. Lee, ed., pp. 643-656, New York,
1975; CA83(6): 44390v. Plenum Publishing Corp., 1984.
117. Japanese Patent JP 85179079, to Mitsui Petrochem- 126. Hyca!'!' Reactive Liquid Polymers Preliminary Data
ical Industries, Ltd., May 4, 1985; CA103(20): Sheet AB-16, "Hyca!'!' Reactive Liquid Polymer
161489b. Modified Epoxy Adhesives Poly ether Diamine Har-
118. Furihata, T., European Patent EP 87311, to Mitsui deners," BFGoodrich, August 1983.
Petrochemical Ind. Ltd, August 31, 1983; CA99(22): 127. Hycar® Reactive Liquid Polymers Preliminary Data
17722lt. Sheet AB-8, "Hyca!'!' CTBN-Modified Epoxy Ad-
119. Japanese Patent JP 84/89380, to Mitsui Petrochem- hesives," BFGoodrich, May 1983.
ical Industries Ltd., May 23, 1984; CA101(24): 128. Hycar® Reactive Liquid Polymers Preliminary Data
212314j. Sheet AB-9 "Hycar® ATBN Modified Epoxy Adhe-
120. Cifkova, Z., et ai., Czech Patent 204545, October sives," BFGoodrich, May 1983.
29,1982; CA99(24): 196331v. 129. Japanese Patent JP 81114572, to Sekisui Chemical
121. Tokahashi, H., Morozumi, N., and Takanezawa, S., Company, Ltd., February 12? 1981; CA95(2): 8483s.

Materials Composition and Source.

Accelerator 808 Butyraldehyde-aniline accelerator; Elastochem Inc.
Accelerator DM Accelerator; Naftone, Inc.
Acrysol GS Sodium polyacrylate; Rohm and Haas
Aerosil 200 Colloidal silicas; Degussa Inc.
AgeRite Resin D Polymerized 1,2-dihydro-2,2,4-trimethylquinoline; R. T. Vanderbilt
Altax Benzothiazyl disulfide; R. T. Vanderbilt
Aminox Diphenylamine acetone reaction product, Uniroyal Chemical
Butyl Eight Activated dithiocarbamate; R. T. Vanderbilt
BRT-7 Refined coal tar; Allied Chemicals Corporation
Carbopol 934 Poly(acrylic acid); BFGoodrich, Speciality Polymers and Chemicals Divi-
sion
Chemigum Nitrile rubbers; Goodyear Tire and Rubber Co.
Chlorowax 40 Chlorinated paraffin; Diamond Shamrock
Dixie Clay Hydrate aluminum silicate; R. T. Vanderbilt
Durez Phenolic resins; Occidental Chemical
EPC Carbon black; J. M. Huber Corp
Epikote 152 Epoxy resin; Shell Chemical Co.
Epikote 815 Epoxy resin; Shell Chemical Co.
Epon 820 Epoxy resin; Shell Chemical Co.
Flexricin P-4 Plasticizer; Baker Castor Oil Co.
Geon 450x20 PVC latex; BFGoodrich, Elastomers and Latex Division
HiSil Precipitated hydrated amorphous silica; PPG Industries Inc.
Hycar Nitrile rubbers; BFGoodrich, Elastomers and Latex Division
Litharge Lead oxide; Eagle Pitcher Industries, Chemical Division
MBT 2-Mercaptobenzothiazole; Uniroyal Chemical Co.
Monsanto Resin 378 Phenolic resin; Monsanto Chemical Co.
Nicamol PR-I440 Xylene modified phenolic resin; Mitsubishi Gas Kagu KK
Paracril Nitrile rubbers; Uniroyal Chemical (Avery International)
Paraplex G-30 Polymeric plasticizer; C. P. Hall
Picconol A600E Aromatic resin emulsion; Hercules Inc.
226 HANDBOOK OF ADHESIVES

Materials Composition and Source (Continued)

SP-8855 Phenolic resin; Schenectady Chemicals
Staftex QXMA Barium stabilizer; Reichold Chemical
Sterling S Carbon black
Titanox Titanium dioxide; Titanium Pigment Corp.
Turpol 1093 Polymeric plasticizer; Irvington Chemical Division of 3M
UcarVYHH Vinyl chloride-vinyl acetate copolymer; Union Carbide Corporation
Unads Tetramethylthiuram monosulfide; R. T. Vanderbilt Co.
Vinsol Thermoplastic Resin; Hercules Inc.
 12
Styrene-Butadiene Rubber Adhesives
C.A. MIDGLEY*
BASF Corporation
Chattanooga, Tennessee
AND
J.B. REA
Polysar Limited, Sarnia, Ontario
Canada N7T 7VI

INTRODUCTION tured in North America was produced in sev-

eral plants under government programs and was
Perspective
known as GR-S (government rubber-styrene).
Adhesives have long represented a market, al- After the war the production facilities were sold
beit relatively small, for styrene-butadiene rub- to private enterprise and the product became
bers. The original commercial SBR was used known as SBR.
successfully in this application and today all of The wartime SBR was essentially a single
the SBRs, solution types as well as hot and cold grade multi-purpose rubber. Relative to natural
emulsion types, are used in a variety of adhe- rubber it was deficient in tensile strength, elon-
sive compositions. They are used by adhesive gation, resilience, hot tear, and hysteresis. On
formulators as latexes or as solid rubbers. the other hand it represented an advance over
In 1985 the consumption of SBR in the natural rubber in such key characteristics as
United States was about 1.8 billion pounds. Of abrasion resistance, aging and product uni-
this, about 64 % was used in the manufacture formity.
of tires and related products. Although SBR is Following World War II the focus on SBR
significant among the polymers used in adhe- turned to development of specific products
sives, less than 1% of the total SBR consump- demonstrating improvement in selected prop-
tion was accounted for by this end use. erties over natural rubber as well as the original
SBR. The first such development was the emul-
History of SBR sion polymerization of styrene and butadiene at
low temperature in the presence of a redox cat-
Styrene-butadiene rubber first established its alyst system. The product from this type of
industrial importance during World War II, process represented a marked improvement
when it played a key role as a substitute for over natural rubber in tread stocks for passen-
natural rubber which was in short supply. The ger car tires. Subsequently, application of or-
original styrene-butadiene rubber manufac- ganolithium catalysis permitted development of
solution-polymerized SBRs that offered im-
*Fonnerly with Polysar provements over emulsion SBR in curing rate

227
228 HANDBOOK OF ADHESIVES

and abrasion resistance, although the short sty- vent system of an appropriate polarity or by
rene blocks characteristic of these polymers ad- complexing the catalyst with ether.
versely affected resilience in tire applications. A random solution SBR will have almost
equal amounts of cis and trans configuration,
Manufacture of SBR but this can be varied. For example, a change
in catalyst composition can increase the trans
The process of manufacturing styrene-buta-
content to 70 %.
diene rubber consists of three distinct steps:
The double bond in butadiene-derived mac-
polymerization, monomer recovery, and
romolecules can be subject to attack by the free
finishing. The basic characteristics of the poly-
radicals in the emulsion polymerization reac-
mer, which are outlined below, are determined
tion. Growing chain radicals can propagate
in the polymerization step, and the product
through the double bond of an already formed
form, whether latex or dry rubber, oil extended
chain so that two chains become joined or
or not, is a function of the finishing process.
crosslinked. If this process is allowed to con-
tinue, more and more chains become linked to-
Basic Chemistry of SBR
gether until all molecules become linked to all
SBRs are produced by addition copolymeriza- other molecules and the molecular weight ap-
tion of styrene and butadiene monomers in proaches infinity. Such structures are called
either an emulsion or a solution polymerization gels. The amount of crosslinking and the gel
process. The ratio of styrene to butadiene con- content of the polymer can be controlled in
trols the glass transition temperature (Tg) of the emulsion polymers by the polymerization tem-
copolymer and thus the stiffness of the elasto- perature, the extent of conversion of monomer
mer. The higher the styrene content, the higher to polymer, and the use of chain transfer agents
the Tg and stiffness. Polymers can be made over (so-called modifiers). High reaction tempera-
the whole range of Tg from about -80°C for tures enhance the crosslinking reaction.
polybutadiene to about + lOO°C for polysty- Initiation of the solution SBR reaction is very
rene. rapid in comparison with chain propagation,
Because butadiene has two double bonds, two and because there is little termination or chain
modes of addition can take place: 1,2 and 1,4. transfer, a very narrow molecular weight dis-
The 1,2 addition yields a pendent vinyl group tribution may be produced. Broadening can be
on the growing chain, which increases Tg • The achieved by use of polar additives and contin-
1,4 addition can occur with the polymer chains uous rather than batch polymerization pro-
cis or trans to the residual in-chain double cesses. The molecular weight can be influenced
bond. The more regular trans configuration by the monomer-to-catalyst ratio. Branching
leads to better cured tensile properties. and crosslinking can be encouraged by the ad-
The microstructure of the elastomers can be dition of a third monomer or branching agent,
controlled by the manufacturing process. In such as divinyl benzene or tin tetrachloride.
emulsion polymerization, which is a free radi-
cal process, the proportion of cis and trans SBR LATEXES IN ADHESIVES
structures can be varied by changing the tem-
General
perature of polymerization. High trans (about
70% of polybutadiene) results at low tempera- An important feature of latexes is that they are
tures (about -lO°C) and higher cis at high sold and used as such. This means that in most
temperatures, where the trans content can drop applications the consumer does not normally
to about 50% (at about lOO°C). The pendent have the opportunity to modify latex properties
vinyl content remains fairly constant at about before use. In dry rubber systems the molecular
20%. The presence of styrene in the system has weight of the polymer is modified by the con-
little effect on the relative proportions of the sumer to his specific needs by milling, masti-
different butadiene structures in the polymer. cation, etc. Hence a few grades cover a
In solution SBR the pendent vinyl content can multitude of applications. This flexibility gen-
be varied from 10 to 90% by choosing a sol- erally is not possible with latex. The desired
 STYRENE-BUTADIENE RUBBER ADHESIVES 229

properties in the final end use must be built in agglomeration process to increase the particle
by the latex manufacturer during polymeriza- size and broaden the particle size distribution
tion. Much proliferation of latex grades has re- so that they can be concentrated to the usual
sulted compared with dry rubber grades and a commercial level of about 60-70% solids. Ag-
low level of standardization prevails among glomeration can be achieved by controlled
manufacturers, particularly in functional sty- freezing, high shear, or use of chemical addi-
rene-butadiene grades. tives.
Because a natural soap type of surfactant is
Classification used in the polymerization these latexes are
only stable at pH above 8.5-9.0 and are sold
Three broad classes of SBR latex are available
in the pH range 10-11 to ensure stability. In
in the market place.
general they are not very stable to added mul-
1. Cold-polymerized, high-solids latex, tivalent metal salts, although more so than nat-
often called high solids or cold latex. ural rubber latexes, and care must be exercised
2. Hot-polymerized, medium-solids latex, in compounding.
often called medium solids or hot latex. Films made from these latexes show high ex-
3. Hot-polymerized, medium solids latex tensibility and low modulus. The best physical
produced in the presence of small properties are only realized when a cure system
amounts of an unsaturated carboxylic acid such as a conventional sulfur/accelerator com-
termonomer, and hence usually referred bination is used.
to as carboxylated latex.
The characteristics of the three classes are dis- Medium-Solids Hot Latexes. These la-
cussed below. texes are manufactured by emulsion polymeri-
zation at temperatures above 30°C. The styrene
Cold Latexes. These latexes are normally content of the polymer is normally about 45 %
produced by emulsion polymerization at tem- and the remainder is butadiene, although sty-
peratures below 15°C, although higher rene content can be anywhere in the 0-100%
temperatures can sometimes be used. Polymer- range. These products are the direct descen-
ization at subzero temperatures is feasible as dants of the original GR-S polymers.
well in the presence of a suitable freezing point Because of the relatively high polymerization
depressant. temperature the polymer molecules are much
These latexes usually contain polymers with less linear than cold polymers and they have a
styrene content in the range 20-35 %, the re- lower primary molecular weight because mod-
mainder of the polymer being made up of the ifiers are used to attempt to control gel content.
butadiene component. They are usually poly- The gel content is potentially higher in grades
merized with a redox initiator system (on a which are not short-stopped at relatively low
batch or continuous basis), and because of the conversion. Typical Mooney viscosities lie in
low polymerization temperature are character- the range 45-80 (ML I + 4' @ 100°C) but
ized by fairly linear, high-molecular-weight products with much higher values are avail-
polymer content. The gel content is controlled able. Films from this type of polymer tend to
by short-stopping the reaction at a relatively have lower elongation and higher modulus than
low (50-75 %) conversion level. A typical their cold counterparts. Again, for the best
Mooney viscosity of the rubber component of properties a cure system may be necessary.
such a latex would be about 120 (ML 1 + 4' Aside from a lower solids content of 40-
@ 100°C). 50 %, medium-solids latexes are similar to cold
The surfactant system is usually of the nat- latexes in most other respects. The surfactant
ural soap type, i.e., either rosin or more often systems are either fatty or rosin acids, with the
fatty acid. The latexes, at this stage, are of latter probably more common in this instance.
small particle size (less than 1000 A) and of The latexes are generally of somewhat larger
low to medium solids content. Some latexes are particle size than unagglomerated cold latexes
sold in this state, but most are put through an and the stability of the two classes is similar.
230 HANDBOOK OF ADHESIVES

A special subclass of this type of latex is the dispersions of rubber particles in water, the vis-
vinyl pyridine (VP) group. Members of this cosity and rheology of which are in general in-
group contain up to 30% vinyl pyridine as ter- dependent of the polymer properties, unlike
monomer and 15-25% styrene. Cold polymer- solutions. The vehicle (water) is nontoxic, non-
ized analogs are also available. flammable, and inexpensive. They offer a wide
range of molecular weight and glass transition
Carboxylated Latexes. Carboxylated la- temperatures. Particularly with the lower sty-
texes are produced over a wide range of styrene rene (lower Tg) polymers one has the advan-
contents and incorporate at least one type of tage of a very rubbery elastomer with low
unsaturated carboxylic acid in quantities up to thermoplasticity when compared to most other
about 10% by weight of total monomers. Other polymers available in emulsion form. The gel
functional monomers can also be used either portion of the polymers represents internal
instead of or in conjunction with acidic mono- crosslinks which are often sufficient to give
mers in order to modify such properties as sta- good strength and creep resistance properties
bility and crosslinkability. Such modified without recourse to further curing.
products generally are classed as carboxylated
latexes though they will sometimes be termed Compounding Ingredients
self-crosslinking or heat-reactive, as well.
The major ingredients for rubber based adhe-
Carboxylated latexes usually are made by hot
sives in addition to the elastomer are given be-
polymerization processes characterized by high
low:
conversion. They tend to have high gel content
and very high Mooney viscosities. As a con- 1. Tackifiers.
sequence the Mooney test is not often used to 2. Plasticizers/oils
characterize them. 3. Solvents.
Because these materials are polymerized at 4. Fillers.
acid pH to ensure incorporation of the acidic 5. Curing agents (not required in all in-
monomer, synthetic surfactants such as dode- stances).
cylbenzene sulfonic acid are used. Normally the 6. Stabilizers:
pH of the system is raised with alkali at the end light, oxidation.
of reaction and the product is sold in the range colloidal.
of p H 6-10 depending on manufacturing pro- 7. Thickeners.
cess and grade. 8. Miscellaneous.
The chemical and mechanical stability of this
For latex systems, all these materials must be
class of latex usually is much greater than that
water dispersed, water dispersable, or water
of the other two classes.
soluble.
Films of carboxylated latexes vary consid- .
erably in properties but generally are of lower
Tackifiers. Although SBRs can be produced
elongation and higher modulus than their non-
with tack, the physical properties of such poly-
carboxylated counterparts. Cure systems are not
mers usually do not fully satisfy the application
normally necessary but may be used in some
requirements. For this reason tackifying resins
special applications for the development of
are normally incorporated into adhesives based
specific properties. Conventional sulfur vul-
on SBRs. These resins improve the kinetics of
canization can be used in some cases (lower
wetting and increase the overall Tg of the ad-
styrene, lower gel) but more often materials that
hesive composition. Typical tackifiers for SBR
react with the functional groups are used (e.g.,
are rosin-based materials, aromatic-containing
zinc oxide or melamine formaldehyde resins).
petroleum hydrocarbon resins, alpha-pinene,
coumarone-indene, and some phenolic resins.
Benefits of SBR Latexes
Latexes offer several advantages over other Plasticizers/Oils. Oils and plasticizers are
elastomer systems. They respresent high-solids added to adhesive compositions for a number
 STYRENE-BUTADIENE RUBBER ADHESIVES 231

of reasons. They can be used to soften the elas- compatible surfactant and/or wetting agent to
tomer, improve the compatibility between the satisfy the total surface area needs of the sys-
polymer and other additives, act as a vehicle tem, particularly if the fillers are of small par-
for introducing other additives, or act solely as ticle size.
an extender to reduce cost. They also change
the wetting characteristics of the elastomer and Curing Agents. Although SBR latexes often
its film-forming ability. Typical examples are do not require use of curing agents in the nor-
organic phosphates, phthalate esters, and aro- . mal sense, a number of cure systems are avail-
matic hydrocarbon oils. able. For noncarboxylated latex compositions,
conventional sulfur systems may be used where
Solvents. Solvents are added for much the external heat can be applied. Otherwise phe-
same reasons as oils and plasticizers. Addition- nolic cures may be used or self crosslinking
ally they may interact with the substrate, e.g., resins may be blended into the formulation.
by partially dissolving it. Because they can be While carboxylated latexes are widely ac-
volatile they may also be used as fugitive plas- cepted as not needing a cure system, those de-
ticizers to modify the drying and coalescence scribed above for SBRs are applicable, as are
behavior of the adhesive. melamine formaldehyde or other formaldehyde
Water soluble solvents such as alcohols can condensates. Multivalent metal compounds
easily destabilize the latex and care must be ex- may also be used with carboxylated systems;
ercised in their use.· As aliphatic hydrocarbon the most common of these is zinc oxide, but
solvents tend not to be compatible with SBR other materials such as zirconium ammonium
polymers, aromatic or polar solvents are pre- carbonate may also be used. Some of these
ferred. types of materials have the advantage that they
In view of the current trend to replacement are effective at room temperature. Some func-
of solvent-based systems by latexes in many tional SBR latexes have their own cure system
adhesives it is desirable to limit the use of sol- built into the polymer and are often referred to
vents so that the advantages of water-based as self-crosslinking, or as heat-reactive in in-
systems can be fully exploited. stances where heat is involved in the curing
process.
Fillers. Fillers are added to latexes to reduce
materials cost, increase volume or weight, and/ Stabilizers. With polymers, the term stabi-
or modify properties. The major modifications lizers normally refers to materials which pro-
which can be achieved with filler are changes vide UV light and thermal oxidative protection.
of color or opacity, changes of density, in- However, with latex, two other needs arise-
crease of solids content, change of rheology, resistance to bacterial attack, and colloidal sta-
and increase in stiffness or modulus of the ad- bility. The latter will be dealt with in more de-
hesive. tail in the following section.
Often fillers are added to latexes as separate Latexes, as sold, will normally contain a
slurries, particularly in the case of noncarbox- bactericide. However when compounds are
ylated latexes, though preaddition of wetting or produced from these latexes the bactericide is
dispersing agents and surfactants can promote diluted and other potentially biodegradable ma-
distribution of a dry filler. Carboxylated latexes terials are included. Hence it is prudent to add
have the advantage of being tolerant of dry filler bactericidal agents to water based adhesive
additions. compounds.
Typical fillers in latex systems are calcium Most commercial latexes contain an antiox-
carbonate in a variety of forms, clays and sili- idant, although some, such as the cold, high-
cas. Materials such as barytes are employed to solids types, usually do not. A check with the
increase density; titanium dioxide, carbon latex manufacturer is advisable to establish
black, or iron oxides are used to change color. whether his product contains sufficient antiox-
The main guideline in compounding fillers idant to provide adequate protection against
into latex systems is to be sure to add sufficient thermal oxidative degradation for the final ad-
232 HANDBOOK OF ADHESIVES

hesive compound. Hindered phenols are the which is often necessary is an antifoam. The
most commonly used nonstaining antioxidants. latter is usually of one of three basic types: sil-
Under some end-use conditions, where an icone, mineral oil, or surfactant. The latter two
adhesive may be exposed to UV light, addition are preferred for temporary or short-term ef-
of suitable UV absorbers and stabilizers might fects; silicones are preferred for more perma-
be considered. nent action but with the danger of defects in the
films such as fish-eyes.
Colloid Stabilizers. In many water-based
systems it is necessary to add colloid stabilizers Major Applications
for specific purposes. One can distinguish three
General. SBR latex adhesives are normally
classes:
used in applications where there will be rela-
1. SurJactants. Common surface active tively low stress but where durability, flexibil-
agents may be added to enhance the col- ity, and a measure of shock resistance are
loid stability against mechanical and required. They have relatively low surface free
chemical stress, to help to disperse other energy and are therefore useful in general pur-
particulate materials (e.g., fillers or cur- pose adhesives which have to bond to a variety
ing agents), to aid in wetting substrates, of substrates. When properly compounded they
or to enhance foaming. Dodecylbenzene have good resistance to environmental deteri-
sulfonates and potassium oleate are typi- oration, though they will not retain good color
cal of this class. when exposed to ultraviolet light.
2. Wetting Agents. These materials are used
primarily to wet particulate materials and Tufted Carpet Backing. The major appli-
to aid colloidal stability without foaming. cation of SBR latex is as an adhesive in the
The naphthalene sulfonate/formaldehyde tufted carpet industry. Carboxylated SBR latex
condensates are examples of this class. compounded with calcium carbonate filler is
3. Sequestrants. These materials are added used as the adhesive to secure the tufts in the
to protect the latex from soluble multi- backing and as an adhesive for so-called sec-
valent ions through complex formation. ondary backings.
A common agent is ethylenediamine- For anchoring tufts alone, either as a unitary
tetraacetic acid (EDT A). Some materials backing or more commonly as a so-called tie
can also assist in dispersion of inorganic coat prior to foam backing, the latex is com-
materials in latex as well as act as se- pounded with up to 500 phr filler (typically
questrants. Typical of this class is tetra- ground limestone) and applied to the raw tufted
sodium pyrophosphate (TSPP). carpet by means of lick roll and doctor blade.
The adhesive is dried by infrared heaters or by
Thickeners. Because the rheology of the la- passage through a hot-air circulating oven. For
tex aqueous phase is largely independent of the secondary backing a layer of cloth is wet-lam-
nature of the dispersed phase, semi-indepen- inated to the back of the carpet before drying.
dent control of rheology is feasible. Hence vis- Traditionally the cloth was woven jute (burlap)
cosity modifiers or thickeners become but is now more commonly woven or non-
important compounding ingredients. Examples woven polypropylene or polyester. A typical
of such materials include natural products such adhesive compound is described in Table 1.
as gums, starch, proteins, and alginates; syn-
thetic materials such as polyacrylates; and Paper Coatings. Carboxylated SBR latexes
modified natural materials such as carboxy- are also important either alone or in combina-
methyl cellulose. Thickeners can also act to tion with other material such as starch or casein
control water loss both to substrates and during as an adhesive or binder for clay coatings for
drying. printing papers.

Miscellaneous. A number of other mate- Nonwovens. Carboxylated SBR is the pri-

rials may be added for special purposes. One mary adhesive or binder in a number of non-
 STYRENE-BUTADIENE RUBBER ADHESIVES 233

Table 1. Carpet Secondary Backing Table 2. Adhesive for Lamination of

Adhesive. Aluminum Foil to Kraft Paper.
phr Carboxy lated SBR latex (42 % styrene) 100 phr (dry)
(dry) Sodium poly acrylate thickener to 2,000-3,000 mPa· s
Water to a total solids content of 50 %
Carboxylated SBR latex (55% styrene) 100
Sequestrant (e.g., tetrasodium pyrophosphate) 0.3
Ground limestone 350 industry and its suppliers, and the shoe indus-
Water to 78 % total solids content (TSC)
Poly acrylate thickener to 15,000 mPa· s
try. A typical fonnulation is shown in Table 2.

Construction Adhesives. Much SBR latex

woven cloths, principally those used for wipes, is used in adhesives directed to the construction
diaper cover stocks, and gannent interlinings. industry. Wall tile and vinyl floor tile adhesives
Typically the latex is self-curing or com- are typical examples (see Table 3 for fonnula-
pounded with a curing agent (e.g., melamine- tion). SBR latexes, both carboxylated and non-
fonnaldehyde resin) and applied by spraying, carboxylated types, are often added to cement
by saturation on a foulard, or by print bonding. mixtures to improve adhesion in repair work.
High-styrene latexes are used in the shoe in- Sealants and caulks can be based on SBR.
dustry as saturants for woven or nonwoven
shoe-stiffening fabrics. The dried, saturated Tire Cord Dip. Tire cord adhesives is an-
sheet material is molded and laminated to other other important outlet for latexes. A basic for-
materials in one operation. Sometimes an ex- mulation is given in Table 4. The latex is
ternal adhesive is used, but the dried latex can mainly a vinyl pyridine (VP) type. Depending
itself act as the adhesive either by activation on the fiber to be bonded, the VP latex can be
with a solvent such as toluene or by heating. diluted with hot SBR or nonagglomerated cold
SBR latex. The dilution depends on the diffi-
Doubling Adhesives. SBR latexes are used culty of bonding the different fibers. Rayon was
for a variety of laminating or doubling opera- easy to bond to the carcass and did not require
tions. There are two basic processes, one where VP latex. Substitution of rayon by nylon and
the two materials are combined with the adhe- polyester tire cords necessitated the develop-
sive in the wet state and the other where the ment and use of VP latex.
adhesive is dried before the materials are
brought together. In the latter case both mate-
Table 3. Typical Vinyl Flooring
rials to be laminated are nonnally coated
Adhesive.
whereas in the fonner case only one substrate
may be coated. phr (dry)
For the wet process, latex is used alone or Part A:
with filler and thickened to a viscosity appro- 25 0 S.P. hydrocarbon resin 212.5
Mineral spirits 37.5
priate to the process. Traditionally many of
Dioctyl phthalate 12.5
these operations were carried out using hot Methanol 12.5
noncarboxylated types with or without sulfur Nonionic surfactant 7.5
vulcanization, but carboxylated latexes are in- Clay 50.0
creasing in importance.
Part B:
In the dry process, latex is nonnally com-
High-solids SBR latex 100
pounded with tackifying resins to create suffi- Phosphate stabilizer 0.5
cient tack for the dry combining operation. Potassium hydroxide 0.25
Typical materials which can be combined are Defoamer 0.10
woven textiles, paper, paper to metal foil, plas-
Water to 60 % total solids content
tic films, plastic film to paper, leather, and
leather to cloth. This type of process is com- A and B are mixed under good agitation. Sodium poly-
mon in the textile industry, the paper convert- acrylate is used to adjust viscosity to 50,000-60,000
mPa·s.
ing and packaging industry, the automotive
234 HANDBOOK OF ADHESIVES

Table 4. Typical Tire Cord Dip. SBR (SOLID) IN ADHESIVES

pans by weight General
dry wet
Solid SBRs offer unique value to the market-
Water 25.8 place in spite of being thought of, originally,
Resorcinol 9.4 9.4
Fonnaldehyde
as a mediocre substitute for natural rubber.
5.1 13.8
Caustic soda 0.7 7.0 They are often preferred to natural rubber be-
Latex 84.8 212.0 cause of performance advantages in areas such
100.0 500.0 as thermal oxidative stability, abrasion resis-
tance and processability, that have resulted
from extensive development activity. In addi-
Pressure-Sensitive Adhesives. A rela- tion they usually have a manufacturing cost ad-
tively new application area for SBR latexes is vantage over natural rubber.
that of the pressure sensitive adhesives. Tradi- Emulsion SBRs have been standardized to a
tional solvent-based adhesives are being re- large degree among manufacturers, with the
placed by hot melt and water-based systems. IISRP* offering a standard numbering scheme
SBR latex is being used increasingly in a num- to identify the different manufacturers' grades
ber of specific areas. Typical formulations are (see Table 8). Solution SBRs, however, have
shown in Tables 5-7. only recently begun to proliferate and manu-
facturers' product lines cannot be compared
readily.
Table 5. Pressure-Sensitive Adhesive
for Paper Labels.
Classification
phr (dry)
Solid SBRs are usually grouped in four major
Carboxylated SBR latex (25% styrene) 100
85 0 S.P. rosin ester resin 75 families by method of production, which de-
Sodium polyacrylate thickener to 700-800 mPa· s. termines some broad differences in properties.
Total solids content 50 %
Emulsion SBR. Two of the four families,
cold and hot emulsion rubbers, are made by the
Table 6. Pressure-Sensitive Adhesive polymerization processes described earlier for
for Masking Tape.
phr (dry) *Intemational Institute of Synthetic Rubber Producers.
Information presented in this review article is given in good
Carboxylated SBR latex (25% styrene) 50 faith, without warranty, representation, inducement or a
Low-ammonia natural latex 50 license of any kind. Polysar Limited does not assume any
85 0 S. P. rosin ester resin 20 legal responsibility for use or reliance upon this informa-
85 0 S.P. hydrocarbon resin 60 tion.
Antioxidant 2.0
Titanium dioxide 1.0
Sodium polyacrylate thickener to 600-800 mPa· s
Table 8. IISRP Numbering System.
Total solids content 50% Series SBR
1000 Hot-emulsion polymers
1100 Hot-emulsion black masterbatch with 14 or
Table 7. Pressure-Sensitive Adhesive less parts per hundred SBR
for Biaxilly Oriented Polypropylene Tape. 1200 Solution SBR
1500 Cold-emulsion polymers
phr (dry)
1600 Cold-emulsion black masterbatch with 14 or
Carboxylated SBR latex (25% styrene) 100 less parts of oil per hundred SBR
85 0 S. P. rosin ester resin 40 1700 Cold-emulsion oil rnasterbatch
Hexamethoxymethyl melamine 3 1800 Cold oil black masterbatch with more than 14
Sodium poly acrylate thickener to 400-600 rnPa· s parts of oil per hundred SBR
Total solids content 50% 1900 Miscellaneous dry polymer masterbatches
 STYRENE-BUTADIENE RUBBER ADHESIVES 235

latex products. The solid rubber is isolated from do not dissolve in low-boiling aliphatic hydro-
the latex by a coagulation process. Hot SBRs carbons (pentane, hexane).
are used more frequently than cold SBRs in ad- SBR adhesives provide good flexibility and
hesive formulations. water resistance and offer better aging charac-
teristics than natural rubber or natural rubber
Solution SBR. The manufacturing process reclaim. They are not generally used for high
for solution SBR generates a product essen- sustained load or where aging characteristics
tially free of such nonrubber polymer ingredi- are critical.
ents as the surfactants required in the emulsion
process. These rubbers are gel-free and have a
narrower molecular weight distribution than Pressure-Sensitive Adhesives. SBR is
their emulsion-polymerized counterparts. This widely used in pressure-sensitive adhesives for
narrow distribution makes it more difficult to such applications as labels, surgical tape,
modify the polymer viscosity by milling. masking, protective wrapping, and splicing. A
formulation for a pressure-sensitive adhesive
Oil and Carbon Black Masterbatches. with stable medium viscosity and good peel
These grades, geared to the tire and retread in- strength is shown in Table 9.
dustries, are high molecular weight, high vis- Compositions of this type are usually coated
cosity, raw polymers, plasticized for easy to tape-backings (paper, plastic, cellophane,
processing with extender oils (15-65 phr) and/ cloth). The coated substrate should adhere te-
or mixed with carbon black (40-100 phr) in the naciously on application of light pressure, yet
SBR production process. Better dispersions allow a clean release.
than those obtained by conventional mixing are
generated in this manner. Sprayable Adhesives. Sprayable adhesives
are widely used in tire building and retreading,
Compounding Ingredients and for application to other substrates such as
paper, wood, plastic, and cloth. The use of
Compounding ingredients for dry rubber are crosslinked hot SBR helps produce discrete
similar to those used with latex except that they particles when the adhesive is sprayed, and
reflect the absence of the aqueous phase. Thus controls webbing of the adhesive on applica-
latex water-phase-type ingredients such as tion. When crosslinked grades are used for this
thickeners are not needed but the ingredients purpose in conjunction with regular SBR, the
that are used must be soluble or dispersible in polymers should be milled separately and then
the solvents used to dissolve the rubber. dissolved together to create a solvent blend.
This procedure will make the most of the cross-
Major Applications linked grade's contribution to the blend's rheo-
logical properties.
General. Solid SBRs play an important role
in the adhesives industry. They are used in
many general purpose and specialty applica- Table 9. Pressure-Sensitive Adhesive.
tions, including general purpose construction Compound phr
adhesives, tape adhesives, and pressure-sensi-
SBR 1570 50
tive adhesives. SBR 1509 50
Solid SBRs find their major adhesive role in Antioxidant 1. 9
solvent-based adhesives, with small amounts Glycerol Ester of Hydrogenated Rosin 131
also used in mastics and hot melts. Most SBRs Petroleum Hydrocarbon (b.p. 67-87°C) 525
Total 757.9
are easily dissolved in aliphatic, aromatic, and
chlorinated hydrocarbons. Highly crosslinked Viscosity (mPa' s) Brookfield LTV. Sp. #3, 12 rpm
grades, however, may swell or form a gel-like after 48 hours 1600
after one month 1580
solution, and high bound-styrene copolymers
236 HANDBOOK OF ADHESIVES

Table 10. Spray Grade Cement. wet binding is feasible if at least one of the sur-
Compound phr faces is porous. Otherwise, both surfaces are
coated and bonding pressure is applied after the
SBR 1006 50
SBR 1009 50
solvent has evaporated. The cement can be
Natural rosin 70 sprayed on or applied by knife or roller. A typ-
Dimerized rosin 30 icallow-temperature-curing adhesive is shown
Antioxidant 2 in Table 11. The catalyst is added just prior to
Petroleum hydrocarbon (b.p. 67-87°C) 800 application and the mixture cures within one
Total 1002
week.
Viscosity (mPa' s) Brookfield LVT, Sp. #2, 12 rpm
after 48 hours 450
after one month 400 Fabric-to-Metal Adhesive. The formula-
tion in Table 12 is designed for good heat re-
sistance which is often required in automotive
The formulation in Table 10 shows consid-
applications. One-way wet binding is feasible
erable improvement in spraying properties
if the fabric is permeable.
compared to compounds based on regular SBR.

Laminating Adhesive. Laminating adhe- Expanded Polystyrene Cement. In the

sives are used to combine two or more plies of case of adhesives for bonding to expanded poly-
materials to form a new composite. One-way styrene, the choice of solvents is critical. Ex-
panded polystyrene cells will collapse when at-
Table 11. Low-Temperature-Curing tacked by aromatic hydrocarbons, ketones or
Laminating Adhesive. esters. Even the low aromatic concentrations
Mill Compound phr found in textile spirits, for example, will cause
cell collapse as the material ages. The chosen
SBR 1570 50
SBR 1516 50
solvent must be free of harmful contaminants,
Hard Clay 50 and used with a polymer which will form a sta-
Titanium dioxide 10 ble solution of acceptable viscosity. The for-
Sulfur 3 mulation in Table 13 produces good adhesion
Zinc oxide 5
to metal, wood, and concrete. It is applied to
Stearic acid
Diethylene glycol both surfaces and dried before bonding under
Total 170 hand pressure.

Adhesive Compound parts by weight Ceramic Tile Cement. Organic adhesives

Mill compound 25.0 are popular for bonding ceramic tile to plaster,
Pentaerythritol ester of dimerized rosin 7.0 concrete and plywood in interior installations.
Antioxidant 0.2
Petroleum hydrocarbon (b.p. 67-87°C) 68.0
Table 12. Fabric-to-Metal Adhesives.
Total 100.2
Compound phr
Viscosity (mPa's) Brookfield LVT, Sp. #3, 12 rpm
after 48 hours 2100 SBR 1006 100
after one month 2400 Natural rosin 33
Polymerized rosin 85
Catalyst parts by weight
Pentaerythritol ester of dimerized rosin 33
Activated dithiocarbamate 10 Zinc oxide 10
1,1, I-Trichloroethane (inhibited) 90 Antioxidant 2
Total 100 Petroleum hydrocarbon (b.p. 67-87°C) 414
Total 677
[T -Peel strength for 100 pts adhesive, 10 pts catalyst, Viscosity (mPa' s) Brookfield L VT, Sp.
Cotton Duck No.8. #3,12 rpm
after 1 week 14 Ib/in. (2.5 kg/cm) after 48 hours 2750
after 1 month 19 lb/in. (3.4 kg/cm)] after one month 3000
 STYRENE-BUTADIENE RUBBER ADHESIVES 237

Table 13. Expanded Table 14. Ceramic Tile Cement.

Polystryene Cement. Compound phr
Compound phr SBR 1018 18.6
SBR 1570 100 SBR 1009 81.4
Dimerized rosin 106 Petroleum hydrocarbon (b.p. 116-136°C) 407
Hydrogenated rosin 45 Calcium carbonate 151
Antioxidant 2.7 Hard clay 232
Hexane 654 Antioxidant 2.3
Total 907.7 Polymerized rosin 244
Total 1136.3
Viscosity (mPa· s) Brookfield LVT, Sp.
#3,12 rpm
after 48 hours 1575 gradually as the solvent dissipates from the glue
after one month 1500
line. The open time can be altered by using
lower- or higher-boiling fractions of petroleum
These adhesives are masticlike solvent com- hydrocarbons. A typical formulation is given in
positions which develop final bond strength Table 14.

Suppliers of Styrene-Butadiene Rubbers.

Supplier SBR Type Trademark
American Synthetic Rubber Corporation Series 1000, 1500, Amsyn
P.O. Box 32960 1700, 1900 and ASRC
Louisville, KY 40232 latexes Flosbrene
Flostex
Copolymer Rubber and Chemical Corporation Series 1500, 1600, Copo
P.O. Box 2591 1700 and 1800 Carbomix
Baton Rouge, LA 70821
DiversiTech General Series 1500, 1600, Gentro
Chemical/Plastics Division 1700, 1800 and Gentro-Jet
P.O. Box 951 latexes Gen-Tac
Akron, OH 44329 Gen-Flo
Dow Chemical USA Latexes Dow
Coatings and Resins Department
Midland, MI 48674
Firestone Synthetic Rubber Company Series 1200 Duradene
381 W. Wilbeth Road Steron
Akron, OH 44301
BF Goodrich Ameripol Tire Division Series 1000, 1500, Ameripol
500 S. Main St. 1600, 1700, 1800, Good-Rite
Akron, OH 44318 1900 and latexes
Goodyear Tire and Rubber Company Series 1000, 1200, Pliolite
Akron, OH 44316 1600, 1700, 1800, Plioflex
1900 and latexes
W.R. Grace and Company Latexes Darex
Organic Chemicals Division
55 Hayden Ave.
Lexington, MA 02173
BASF Corporation Latexes Butofan
Fibres Division Butonal
3805 Amnicola Highway Styrofan
Chattanooga, TN 37046 Sty ronal
238 HAND800K OF ADHESIVES

Suppliers of Styrene-Butadiene Rubbers (Continued)

Supplier SBR Type Trademark

Polysar Limited Series 1000 Polysar SlO18

1265 Vidal Street S.
Samia, Ontario
N7T 7M2
Reichhold Chemicals Incorporated Series 1000 and Tylac
P.O. Box Drawer K latexes
Dover, DE 19901
Shell Chemical Company Latexes Kraton
One Shell Plaza
P.O. Box 2463
Houston, TX 77001
SYNPOL (Inc.) Series 1000, 1500, SYNPOL
P.O. Box 667 1600, 1700, 1800
Port Neches, TX 77651 and 1900
Uniroyal Inc. Series 1900
Chemical Group
Middlebury, CT 06749
Unocal Corporation Latexes
Chemicals Division
1900 East Golf Road
Schaumburg, IL 60195
 13
Thermoplastic Rubber (A-B-A Block
Copolymers) in Adhesives
J. T. HARLAN* and L .. A. PETERS HAGEN
Shell Chemical Company
Houston, IX

Revised By:

E. E. EWINS, JR. and G. A. DAVIES

Shell Chemical Company
Houston, IX

WHAT IS THERMOPLASTIC RUBBER?

Thermoplastic rubber is truly a useful and ver-
satile class of polymer. It has the solubility and
thermoplasticity of polystyrene, while at am-
bient temperatures it has the toughness and re- Fig. 1. Simplified representation of a thennoplastic rub-
silience of vulcanized natural rubber or ber molecule.
polybutadiene. This characteristic results from
its unique molecular structure. Visualize the (A-B-A-B-A), and so forth.a The key require-
simplest thermoplastic rubber molecule: a rub- ment is that the thermoplastic rubber molecules
bery midblock with two plastic endblocks. This
terminate with hard, glasslike endblocks which
situation is pictured schematically in Fig. 1 are incompatible with the rubbery midblocks.
where the diamonds represent monomer units All such polymers consequently consist of two
in the plastic endblocks and the circles repre- phases in the solid state-a continuous rubber
sent monomer units in the rubbery midblock. phase and a basically discontinuous plastic
Such a molecule is called a block copolymer. phase which "locks" the rubber molecules in
Patent and scientific literature l -4 describes
place.
numerous molecular variations: the structure The principles which apply to the simplest
pictured in Fig. 1 (A-B-A), more than two version shown in Fig. 1 also apply generally to
monomers (A-B-C), branched or radial config- other configurations. For simplicity, discus-
A sions in this chapter will be focused on the sim-
I
urations (A - B - A), repeating segments
'Segmental polyurethanes are not included in this discus-
sion. Their properties and behavior have been discussed
*deceased elsewhere. 5

239
240 HANDBOOK OF ADHESIVES

plest version, yet will apply broadly to other Table 1. Typical Physical Properties of
structures as well. Discussion will also be fo- S-8-S and S-I-S Thermoplastic Rubber
cused on two basic classes of thermoplastic at 23°C.
rubber. One class consists of block polymers in Tensile strength at break (TB), psi 3000-5000
which the rubbery midblocks of the molecule 300% Modulus (M300)' psi 100-400
is an unsaturated rubber. The two types of poly- Elongation at break (EB), % 800-1300
mers in this class are the polystyrene-poly- Hardness, Shore A: 30-80
butadiene-polystyrene (S-B-S) polymers
and the polystyrene-polyisoprene-polystyrene
(S-I-S) polymers. The second class of ther- The same range of properties may also be ob-
moplastic rubber consists of block polymers in tained on casting these polymers from a melt.
which the elastomeric mid block is a saturated In neither case is chemical vulcanization re-
olefin rubber. The polymers in this class are quired. That thermoplastic rubber really is a
the polystyrene-poly(ethylene/butylene)-poly- new class of polymer is depicted in Fig. 3.
styrene (S-EB-S) polymers and the poly sty- Thermoplastic rubber as defined above was
rene-poly(ethylene/propylene) (S-EP) poly- first marketed commercially in 1965 by Shell
mers. Chemical Company. A list of the trade names,
When many A-B-A molecules are combined manufacturers, and types of thermoplastic
in the solid phase, a two-phase structure is polymers produced is presented in Table 2.
formed by the clustering of endblocks. An Thermoplastic rubber polymers act as high
idealized and simplified representation of this strength film-formers when used alone or act to
is shown in Fig. 2. increase the cohesive strength or viscosity of
The plastic endblocks phase regions, called systems to which they are added. They dissolve
"domains", are shown in sphere-like form. rapidly, without premastication, in a range of
Other forms are discussed later. These domains low-cost solvents to give useful high solids, low
act as crosslinks between the ends of the rubber viscosity solutions. They can be mixed readily
chains, serving to lock the rubber chains and with many compounding ingredients, and the
their inherent entanglements in place. The sys- resulting formulations may be applied to sub-
tem acts like a conventionally vulcanized rub- strates either by solution or by hot-melt tech-
ber that contains dispersed reactive filler niques. High-tack pressure-sensitive adhesives
particles. or nonblocking assembly adhesives may be for-
This physically crosslinked matrix exhibits mulated by varying the types of resins and plas-
typical physical properties shown in Table 1. ticizers used.
The data represent various neat S-B-S and Thermoplastic rubber polymers are resistant
S-I-S thermoplastic rubber samples cast from to attack by most aqueous reagents, normally
toluene solutions . have good electrical insulating properties, and

.....----\U8.ER MIO'LOCKS FORMING RU,,'R .~ THERMOSEnlNG THERMOPLASTIC

tr~~l
epoxy POLYSTYRENE
PHENOL-FORMALDEHyDE POLYVINYL CHLORIDE:

~'~)!I\
RIGID
UREA- FORMALDEHYDE POLYPROPYLENE
HARD RUBBER

POL.YETHYLENE
HIGHLY LOADED AND/OR ETHYLENE-VINYL
HEXl8LE HIGHl. Y VULCANIZED ACETATE COPOLYMER
RUBBERS PLASTICIZED PVC

~P'OlYSTYRENE
"-
\ £ND8LOCI($
VULCANIZED
~ FORMING DOMAINS
RUB8IERS
RUBBERY

,/'
tNFI.SBR.IA. ETC .'

THERMOP"A.STIC RUBBER
Fig. 2. Idealized two-phase network of thennoplastic
rubber molecules. Fig. 3. Polymer classification.
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOlYMERSI IN ADHESIVES 241

Table 2. Trade Names of Thermoplastic Rubber.

Trade Name Manufacture Polymer Types
Kraton® D Shell S-B-S, S-I-S, (S-B)., (S-I).
Cariflex® TRa Shell S-B-S, S-I-S
Kraton G Shell S-EB-S, S-EP (Diblock)
Europrene® SOL Ta Enichem S-B-S, S-I-S
Stereon® Firestone S-B-S
Tufprene® & Asaprene* Asahi S-B-S
Finaprene* Fina (S-I).
Solprene* Phillips (S-B).
'Not manufactured in U.S.A.

have excellent low temperature properties. two homopolymers. Only one phase is present
They are soluble in many hydrocarbon solvents in SBR.
and are thermoplastic at elevated temperatures. In commercial thermoplastic rubbers, the
A measure of solvent resistance and high tem- endblock phase is present in the smaller pro-
perature strength can be imparted by mechani- portion (see Table 2) and is dispersed in a con-
cally mixing them with insoluble polymers such tinuous rubber matrix as suggested by Fig. 2.
as polypropylene or by crosslinking. The uniform dispersion of spherical endblock
The behavior of thermoplastic rubber in ad- domains shown in this figure, however, is ap-
hesives is dependent on (1) the morphology or proached only in carefully prepared laboratory
geometry of the submicroscopic endblock phase samples with low endblock phase concentra-
as it is dispersed in the rubber matrix, and (2) tion. Depending on the endblock phase concen-
the compatibility of added ingredients with the tration and on actual processing conditions used
two phases present. These topics are discussed to prepare a given sample, the geometry or
in subsequent sections. morphology of the dispersed phase may be
sphere-like, rod-like, or plate-like as depicted
BASIC CONCEPTS - MORPHOLOGY in Fig. 5.
AND COMPATIBILITY In the latter two cases, the endlock phase may
extend as a continuous plastic network
The structure of thermoplastic rubber is
throughout the rubber matrix. This tends to be
unique. It does not behave like conventional
the case when the endblock phase concentra-
elastomers such as natural rubber or styrene-
tion is above about 20%w. In this situation, as
butadiene rubber (SBR) in a number of impor-
the sample is stretched, the initial stress is borne
tant respects. The next several sections explain
by the plastic network, and the stress-strain
the fundamental principles of its behavior.
properties are greatly affected as discussed be-
Thermoplastic Rubber Is A Two-Phase low. The existence of these different morphol-
System
Much work has been published on the physical

J\,
,-
SBR
structure of thermoplastic rubber.6-16 Two glass PSD

transition temperature (Tg) peaks are found in PS

dynamic mechanical tests with an S-B-S block

copolymer. 1 In contrast, only one peak is found
in a random SBR copolymer with the same sty-
rene/butadiene ratio. This difference is shown
in Fig. 4.
................
The two peaks in S-B-S polymers indicate ~oo 100
TEMPERATURE. OF
that separate polystyrene and polybutadiene Fig. 4. Glass transition temperatures (Tg) in S-B-S and
phases are present in these block copolymers SBR. PBD = Polybutadiene; PS = Polystyrene; SBR =
just as they would be in a physical blend of the Styrene-butadiene rubber.
242 HANDBOOK OF ADHESIVES

(discussed more fully in the appendix at the end

of this chapter) is a basic property characteris-
tic of every solid or liquid including polymers,
resins, plasticizers, solvents, stabilizers, and
fillers. Expressed in units of (cal/cm3) 1/2 called
"hildebrands," the solubility parameters of in-
terest in this chapter fall generally in the range
Fig. 5. Polystyrene domain configurations or morpholo-
6 to 12 hildebrands. If two substances have sol-
gies. ubility parameters close enough together, they
will tend to be mutually soluble. The higher the
molecular weight of the two materials, the
ogies has been confinned by electron
smaller the difference between their solubility
micrographs. \3
parameters must be for mutual solubility to oc-
Under all conditions the dimensions of the
cur. For example, isooctane (0 = 6.85) and tol-
dispersed phase are restricted. Since the junc-
uene (0 = 8.9), both low molecular weight
tures between the endblocks and midblocks are
solvents, are mutually soluble. On the other
located at the phase boundary, the domain
hand, the high molecular weight polymers,
thickness is limited to the distance which can
poly isoprene (0 = 8.1) and polybutadiene (0 =
be reached by the endblock segments extending
8.4), will not mix on a molecular scale. Simi-
into the domains from opposite sides. For com-
larly, the polystyrene endblock phase (0 = 9.1)
mercial polymers, domain thicknesses have
and the rubber matrix (0 = 8.1 or 8.4) in com-
been both calculated and measured to be a few
mercial thennoplastic rubbers do not mix and
hundred Angstrom units or only a small frac-
therefore fonn the two-phase systems shown in
tion of the wavelength of visible light. If the
Figs. 2 and 5.
domains are spheroidal, they do not scatter
Solubility parameter and molecular weight
light. Thus, pure thennoplastic rubber is gen-
data are not readily available for many adhe-
erally transparent, in spite of the large differ-
sive components. However, compatibility data
ences in refractive index between the two
are available for a number of resins, plasticiz-
phases. With rod-like or plate-like morpholo-
ers, and solvents. Some of them are listed in
gies some light scattering and turbidity may ex-
later sections or in the literature. 19 ,22-27 In any
ist.
particular case, infonnation on specific com-
ponents can be obtained by simple tests. For
Additives Are Compatible With One
example, the solubility range of a given for-
Phase, Both Phases, or Neither Phase
mulation can be detennined by attempting to
Infonnation on how additives, such as resins, dissolve the components in a series of solvents
plasticizers, and other polymers, distribute be- of interest. One can also detennine qualita-
tween the two phases in thennoplastic rubbers tively with which phase of a thennoplastic rub-
is important in interpreting the behavior of ad- ber a given resin is compatible as follows: Cast
hesive fonnulations. For example, adding a a thin film from a toluene solution of (1) a 1 to
resin which dissolves solely in the plastic end- 1 mixture of the resin and crystal grade poly-
block phase may produce a hard, nontacky ma- styrene and (2) a 1 to 1 mixture of the resin and
terial, while adding a resin which dissolves only natural rubber or polyisoprene for S-I-S poly-
in the rubber phase may result in an extremely mers or the resin and polybutadiene for S-B-S
sticky, soft, flexible composition. Yet both polymers. Clarity of the dried film indicates
mixtures may have high cohesive strength as mutual solubility; tubidity indicates phase sep-
long as the endblock domains fonn properly. aration. Qualitative interpretation of experi-
The solubility parameter (0) and molecular mental observations on a new system in tenns
weight of an additive detennine how it will dis- of the above compatability concepts can often
tribute between the two phases present in ther- suggest means of changing the system to im-
moplastic rubber. Solubility parameter prove its perfonnance in the desired direction.
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN ADHESIVES 243

PHYSICAL PROPERTIES OF THERMO- ber. At concentrations above about 33%w, the

PLASTIC RUBBER-ALONE AND IN phenomenon of "drawing" commonly exhib-
SIMPLE MIXTURES ited by thennoplastics appears. This occurs
when a continuous rod-like or plate-like end-
This section discusses specific examples of the
block network exists as suggested in Fig. 5.
concepts introduced in the previous section.
When such a sample is stretched, an initial yield
The general principles illustrated here are im-
stress is observed. Then, as the relatively weak
portant to the effective use and modification of
plastic structure is disrupted by further elon-
the starting fonnulations presented later.
gation, drawing occurs. When the stress is re-
leased, the plastic network will gradually
Stress-Strain Properties
refonn. Higher temperatures will speed re-
The cohesive strength of an adhesive film is fonning of the plastic network. At high end-
closely related to its stress-strain behavior. The block concentrations, the plastic phase is
stress-strain properties of thennoplastic rubber continuous and the midblock phase dispersed
fonnulations are in tum closely related to the to give a system resembling high impact poly-
volume ratio of endblock phase to midblock styrene.
phase and to the morphology of these two
phases. Effects of Additives. The ratio of endblock
phase to midblock phase can be varied by add-
Effect of Phase Ratio. As the endblock ing materials which associate preferentially
concentration in an unfilled thennoplastic rub- with one phase or the other. Coumarone-indene
ber increases, the shape of the stress-strain resins, for example, associate with the end-
curves change as shown in Fig. 6. These par- block phase in S-B-S and S-J-S polymers.
ticular curves apply to solution-cast films pre- Figure 7 shows how the initial portion of the
pared from a series of experimental S-B-S stress-strain curve of the neat polymer, Curve
polymers. The total molecular weight for each B, is shifted upward to Curve A when the end-
polymer was held constant; only the styrene block phase concentration is increased by add-
content was varied. ing a resin of that type. Curve C shows how
At concentrations of 20-30%w, the stress- the reverse occurs when, for example, a tacki-
strain curve resembles that of a vulcanized rub- fying resin or a plasticizing oil which associ-
ates with the rubber phase is present instead.

4ooo~----------------------------~ Effect of Previous Processing. By proper

selection of processing conditions, both draw-
_8O%WSTYRENE
ing and nondrawing samples can be prepared
3000 from the same thennoplastic rubber fonnula-

i! 1.000

i~~
~ BOO

ORA¥:
~600
~
:: 400
A

_._.-.-.-.-.-.-.~. -' ....

DRAW ~ 0 :..... '--:--'£)

r""oo_ _
1000 o 100 200 300 400 500
ELONGATION. "

DRAW
...........- .. 13%W
Fig. 7. Effect of endblock and midblock resins or pref-
I erential solvents on endblock morphology and tensile prop-
erties.
o 100 200 300 400 500 600 700 800 900 1000
Curve Resin Type Casting Solvellt
ELDNGATlDN. "
A Endblock Methyl ethyl ketone (MEK)
Fig. 6. Effect of endblock concentration on S-B-S tensile B None Toluene
properties. C Midblock C6-C 7 Paraffin hydrocarbons
244 HANDBOOK OF ADHESIVES

tion when the endblock concentration is above

about 20%w. Thus, endblock morphology can
be modified in a third way. If a film is cast from
a solvent which is, or which becomes during
"z
evaporation, good for the endblock phase and
poor for the rubber phase, the formation of a I
continuous endblock phase is favored. Draw- ~
:;
ing may then occur as indicated by Curve A of
Fig. 7 discussed in the previous paragraph.
When the opposite type of solvent is used, the
drawing is inhibited and a rubbery film is pro- -100 o 100 200

duced with characteristics of Curve C in Fig. TEMPERATURE, OF

7. Fig. 8. Effect of endblock resins on endblock glass tran-

Similar effects can be obtained with hot-melt sition temperature (Tg ).
formulations. Subjecting such a mixture to high Tg = 210°F: No resin.
shear and quickly quenching it to room tem- Tg = 240°F: 75 phr LX-685, 180 (softening point
perature, produces behavior indicated by Curve 150°C).
A in Fig. 7. Alternatively, using no shear and Tg = 95°F: 75 phr Piccovar AP-25 (softening point
slowly cooling to room temperature produces 25°C).
behavior indicated by Curve C in Fig. 7.
These effects of solvent and thermal-shear given stress may be shifted upward by adding
history are not equilibrium states. Annealing an endblock compatible resin with a high soft-
samples of this sort at 140°F, for example, will ening point. Conversely, a similar low soften-
tend to bring the curves in Fig. 7 closer to ing point resin can lower the temperature at
Curve B. Nevertheless, such techniques ap- which a mixture softens and becomes heat
plied alone or in conjunction with others may bondable. The addition of resins and plasticiz-
be very useful in tailoring a product to a spe- ers which are soluble in the midblock phase
cific application. similarly change the low temperature Tg of the
rubber phase.
Glass Transition Temperatures and
Service Temperature Range Solubility and Solution Viscosity
The temperature range over which thermoplas- The behavior of thermoplastic rubber toward
tic rubber compositions can be used as elasto- solvents is unique because of the two segments
meric solids depends on the glass transition present in each molecule. Each segment retains
temperatures (Tg ) for the two polymer phases. its own solubility properties.
As illustrated in Fig. 4, this useful range lies
between the Tg of the rubber phase and the Tg Solvent Selection. As mentioned above, a
of the endblock phase. Below the Tg of the rub- given polymer will dissolve only in solvents
ber phase, the midblocks become hard and brit- whose solubility parameters are close to that of
tle. Above the Tg of the plastic phase, the the polymer. In thermoplastic rubber, two sol-
domains soften and cease to crosslink the rub- Ubility parameters are involved, one for the
ber midblocks. endblock and one for the midblock. A "good"
Each Tg depends on the nature of that poly- solvent for a thermoplastic rubber must there-
mer segment itself and also on the nature of any fore be one which dissolves both endblocks and
materials dissolved in it. Figure 8 illustrates midblocks.
how the normal Tg of about 210°F for the end- To illustrate, Fig. 9-A indicates the approx-
block phase in an S-B-S polymer can be shifted imate range of solvents for polydiene mid-
by adding endblock compatible resins of differ- blocks. The boundaries are not sharp near the
ing softening points. extremes because the polymer molecules tend
The limit of upper service temperature at a to collapse while still solvated. The location of
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN ADHESIVES 245

I :·::::::····· '.::::: .. ,}: :.>..

I :.
I"
I,
I ··
I
I
I
I
I I
1 I I .11 I I
7.0 7.5 8.0 8.5 9.0 9.5 10.0
Solubility parameter

(a) Solubility parameter range of solvents useful for rubber phase.

/ Poly"y,,",

I I I I I ! ! I I I I • ! I
7.0 7.5 8.0 8.5 9.0 9.5 10.0
Solubil ity parameter

(b) Solubility parameter range of solvents useful for polystyrene phase.

I" .I
. I
.:... :'. I
:.: ... 1
I·I .... ;,' I
I
I I
I
II I
I
7.0 7.5 8.0 8.5 9.0 9.5 10.0
SOLUSI LlTY PARAMETER

Ie) Solubility parameter range of solvents useful for KRATON rubber.

Fig. 9. Solvents for thennoplastic rubber.

the boundaries and several solvents are shown endblocks tend to remain associated and form
for illustrative purposes . what might be termed solvated endblock do-
Figure 9-B indicates in a similar way, the mains. In this region, solution viscosity in-
range of solvents for polystyrene endblocks. creases rapidly with decreasing solubility
Figure 9C shows what happens when both parameter until rigid crosslinked gels are
types of polymer are combined in a single block formed. With solvents at the high solubility pa-
copolymer molecule. A central range of sol- rameter end, the situation is somewhat differ-
vents readily dissolves both blocks and gives ent. First, the midblocks become less and less
low viscosity solutions. With solvents at the soluble and tend to associate together while the
lower solubility parameter end, the polystyrene endblocks are highly solvated. Opalescent so-
246 HANDBOOK OF ADHESIVES

lutions with time-dependent viscosities are nents present in the thermoplastic rubber
formed. Thermoplastic rubber crumb can be formulation. Resins and plasticizers are usually
dispersed in this sort of borderline solvent (for the most important components in this respect.
example, methyl ethyl ketone). As an example, the effect of adding 100 phr of
A practical application of these principles is a tackifying resin (Foral 85) to a 15 %w solu-
shown in Fig. 10. The curves represent the vis- tion of an S-B-S polymer is shown in Fig. 11.
cosities of 15 %w solutions of an S-B-S ther- The presence of the resin has made the toluene/
moplastic rubber in a series of n-hexane/toluene n-hexane blends better endblock solvents, so
blends. As the toluene concentration is re- that less toluene percentage is required to ob-
duced, the viscosity increases rapidly due to tain minimum viscosity even at the higher total
endblock association as the endblock domains solids concentration.
tend to precipitate from solution. About 20%w
toluene must be present in the mixed solvent if Viscosity and Polymer Concentration.
low viscosities are to be achieved in this situ- Thermoplastic rubbers without premastication
ation. The solvent mixtures can also be char- have lower solution viscosities than do conven-
acterized by solubility parameter and Kauri tional elastomers such as SBR, natural rubber,
Butanol Value as shown on the abscissa. A sol- and neoprene after milling. This is because
ubility parameter of 7.6 or above and a Kauri thermoplastic rubbers have low, precisely-con-
Butanol Value of 37 or higher are required for trolled molecular weights. Figure 12 compares
low solution viscosity in this case. the viscosities of a typical S-B-S polymer with
In the selection of a solvent, one should con- two conventional elastomers in toluene solu-
sider all soluble low molecular weight compo- tion.

Melt Viscosity
The viscosities of thermoplastic rubber melts
are strongly non-Newtonian, decreasing as

'04

'O~ ____ ~ ____ ~ ____- L____ ~ ____ ~

20 40 60 BO '00
SOL VENT BLEND, %W TOLUENF.
I I II
32 42
KAURI-BUTANOL VALUE
'0 ~ ____ ~ ____ ~ ____ ~ ____ ~ ____ ~

20 40 60 BO '00
7.4 7.6 7.8 B.O 8.2 B.' B.B
SOLUBILITY PARAMETER (hi HILDEBRANDS SOL VENT BLEND. '%oW TOLUENE

Fig. 10. Viscosity of S-B-S thennoplastic rubber in poor Fig. 11. Effect of a resin on the viscosity of S-B-S ther-
endblock solvents. moplastic rubber in poor endblock solvents.
 THERMOPLASTIC RUBBER IA-B-A BLOCK CO POLYMERSI IN ADHESIVES 247

,,
\
1~r---~-----r--r-~----T-----r---~

/ -- r~~:~FP£
/ ' SBR ·1011IMl· &&)

/ 109 ,,
/
/
/
108
, \

..
\
\
\
.
~
>-
10 7 \
\ ,,
1~0----~--~1~0----~15~--~20----~2~5--~
30 § ,
SOLIOS CONTENT. %W POLYMER

Fig. 12. Solution viscosity of polymers in toluene.

.....
!!
> 108
'"
I ' .... O.2SEC'1
.........
105 ..........
~
102SEC.l ....................
shear rate increases. Figure 13 shows the melt
..........
viscosity of an S-B-S thennoplastic rubber at
......................................
1~ 103 SEC· 1 .....
350°F. Also shown is the plasticizing effect of
100 phr of a tackifying resin. Through selec-
1~~__~~__~____~____~____~__~
tion of appropriate types and amounts of resins 150 200 250 300 350 400 450
and plasticizers, the melt viscosity of a given TEMPERATURE. OF

hot-melt adhesive can be controlled over a wide Fig. 14. Effect of temperature on S-B-S melt viscosity.
range.
The effect of temperature on melt viscosity is
sired and in product assembly applications
illustrated in Fig. 14. Here the viscosity of a
where long open time is desired.
typical S-B-S polymer is shown at three shear
rates. It is important to note the long plateau
Permeability to Nitrogen and Water
followed by a rapid increase in viscosity on
Vapor
cooling. Through control of application tem-
perature, either long or short open times fol- The vapor penneability of thennoplastic rub-
lowed by rapid setup can be achieved. These bers with polydiene midblocks is similar to that
characteristics are advantageous in high speed of the rubber which fonns the midblock. How-
packaging where rapid hot tack buildup is de- ever, as the fraction of endblock is increased,
as for example by adding endblock compatible
resins, the penneability is somewhat reduced.
Conversely, as the rubber phase fraction is in-
creased, for example by adding a midblock
compatible oil, the nitrogen penneability in-
KRATON 1102
creases. While the penneability of thennoplas-
tic rubbers is about the same as SBR, natural
rubber, and polybutadiene, it is much higher
111 MIX. than polyolefins and other materials used in
KRATON 110V
FORAl'5
packaging. This can be an advantage where
high air or moisture vapor transmission is de-
sired.

FORMULATING INGREDIENTS
In this section, major types of fonnulating in-
10 gredients and their roles in the design of ad-
SHEAR RATE. SEC· 1 hesives are discussed. This generalized
Fig. 13. Melt viscosities of S-B-S and S-B-S/resin infonnation is focused in the section on the for-
blends. mulation of specific adhesives. The fonnulator
248 HANDBOOK OF ADHESIVES

will find a recent tabulation of adhesive raw phase increases and its morphology becomes
materials and suppliers useful in selecting spe- more rod-like or plate-like.
cific components. 17 High softening point resins in this category
may also tend to increase the glass transition
Which Resins? temperatures (Tg) of the endblock phase (Fig.
8). This results in the formulation retaining its
Resins for use with thermoplastic rubbers are
cohesive strength at higher temperatures. Res-
selected to perform one or more functions. To
ins effective in this direction are indicated in
aid in the selection process, resins can be
Table 3 by their effect on the Shear Adhesion
grouped first according to their tendency to as-
Failure Temperaturea of an adhesive formula-
sociate with one phase or the other in thermo-
tion.
plastic rubber. Within these groups, other
Low softening point resins have the reverse
subdivisions can be made depending on the ef-
effect, namely to lower the tensile strength at
fect on adhesive properties.
elevated temperatures, to cause the tack in heat
activated adhesives to develop at lower tem-
Predominantly Endblock Compatible Res-
peratures, and to reduce the temperature at
ins. Polyaromatics, cumarone-indene resins,
which the formulation can be handled as a hot-
and other high solubility parameter resins de-
melt.
rived from coal tar or petroleum and having
softening points above about 85°C tend to as-
Predominantly Midblock Compatible Res-
sociate with the polystyrene endblocks and not
ins. Aliphatic olefin derived resins, rosin es-
with the polydiene midblocks. As the molecu-
ters, polyterpenes, and terpene phenolic resins
lar weights or softening points of these resins
derived from petroleum or terpentine sources
are lowered, their solubility in the midblocks
and having relatively low solubility parameters
increases. A list of typical commercial resins
tend to associate with the polydiene midblocks
in this category is presented in Table 3.
and not with the polystyrene endblocks. As the
Resins in this category are used to improve
molecular weights or softening points of these
the specific adhesion of the endblock phase, to
resins are lowered, their solubility in the end-
adjust melt viscosity, and to control the mod-
ulus of the resulting adhesive formulation. Ad-
dition of predominantly endblock associating 'Shear Adhesion Failure Temperature (SAFT): Tempera-
resins tends to stiffen the formulation and in- ture at which complete failure of a I in. x I in. shear
adhesion sample (polyester to polyester) occurs under a load
crease the tendency to draw as discussed pre- of I kg in a circulating air chamber whose temperature is
viously. This occurs as the fraction of endblock raised 40°F per hour starting at 100°F.

Table 3. Endblock-Phase-Associating Resins for Thermoplastic Rubbers.

Softening
Trade Name Point, °C Chemical Type Supplier
Amoco@ 18 Series 100, liS, 145 Alphamethyl styrene Amoco
Kristalex@ Series 85-140 Alphamethyl styrene Hercules
Piccotex@ Series 75-120 Alphamethyl styrene/vinyl toluene Hercules
Nevchem@ Series 100-140 Aromatic hydrocarbons Neville
Picco 6000 Series 70-140 Aromatic hydrocarbons Hercules
Nevindene@ LX Series 100-150 Heat reactive hydrocarbon Neville
Cuma~ Series 10-130 Coumarone-indene Neville
Cumar LX-509 ISS Coumarone-indene Neville
Piccova~ AP Series Liquid' Alkylaryl resin Hercules
Piccovar 130 130 Alkyl aromatic polyindene Hercules
'Because of the low molecular weight, these resins are soluble in both endblock and midblock phases of thennoplastic rubbers.
 THERMOPLASTIC RUBBER (A-B-A BLOCK COPOLYMERS) IN ADHESIVES 249

blocks increase. A partial list of commercial block phase. This can result in reduction of low
resins in this category is presented in Table 4. temperature flexibility. Partial compensation
Resins in this category are used to impart for this reduction can be obtained through the
pressure-sensitive tack, to improve the specific use of midblock plasticizers. There may also be
adhesion of the midblock phase toward polar some effect on the upper service temperature as
substrates, as processing aids for the midblock the result of some unavoidable plasticizing of
phase, and to control the modulus of the re- the endblocks.
sulting adhesive formulations. Addition of pre-
dominantly midblock associating resins tends
Why Plasticizers?
to soften the formulation and reduce the tend-
ency to draw as discussed earlier. These latter Plasticizers may perform the following useful
effects occur as the addition of midblock resin functions in adhesives based on thermoplastic
increases the fraction of midblock phase in the rubbers: decrease hardness and modulus, elim-
system and causes the morphology of the dis- inate drawing, enhance pressure-sensitive tack,
persed endblock phase to become more sphere- improve low temperature flexibility, reduce
like (less continuous). melt and solution viscosity, decrease cohesive
Resins in this category may also increase the strength or increase plasticity if desired, and
glass transition temperature (Tg) of the mid- substantially lower raw material costs. The

Table 4. Rubber-Phase-Associating Resins for Thermoplastic Rubbers.

Trade Name Softening Point, °C Chemical Type Supplier
Adtac® B Series 10,25 Synthetic C s Hercules
Betaprene® BC 100, 115 Synthetic Cs Reichhold
Eastman® Resin 100, 115, 130 Synthetic C s Eastman
Escorez® 1300 Series 80, 100, 120 Synthetic C s Exxon
Hercotac® 95 100 Synthetic Cs Hercules
Nevtac® Series 80, 100, 115, 130 Synthetic C s Neville
Piccopale® HM-200 100 Synthetic C s Hercules
Piccotac® 93, 100 Synthetic Cs Hercules
Quinton® Series 85, 100 Synthetic C s Nippon
Zeon
Sta-Tac® R 100 Synthetic Cs Reichhold
Super Nevtac® 99 99 Synthetic Cs Neville
Super Sta-Tac 80, 100 Synthetic C s Reichhold
Wingtack® Series 10, 75, 85,95, 115 Synthetic Cs Goodyear
Arkon® P Series 70, 85, 115, 125 Hydrogenated Hydrocarbon Arakawa
Escorez 5000 Series 85, 105, 125 Hydrogenated Hydrocarbon Exxon
Regalrez® Series 18, 76, 94, 126 Hydrogenated Hydrocarbon Hercules
Super Nirez® Series 100, 120 Hydrogenated Hydrocarbon Reichhold
Nirez® Series Poly terpene Reichhold
Piccofyn® Al00 100 Terpene phenolic Hercules
Piccolyte® A 85,115,135 Poly terpene Hercules
Piccolyte SIO 10 Poly terpene Hercules
Zonarez® 7000 Series 85, 100, 115, 125 Poly terpene Arizona
Zonarez B Series 10, 100, 125 Poly terpene Arizona
Zonatac® Series 85, 100, 115 Poly terpene Arizona
Foral® Series 82, 104 Rosin Ester Hercules
Hercolyn® D Liquid Rosin Ester Hercules
Pentalyn® H 104 Rosin Ester Hercules
Staybelite Ester 10 Liquid Rosin Ester Hercules
Sylvatac® Series 70-110 Rosin Ester Sylvachem
Zonester® Series 83,95 Rosin Ester Arizona
Piccovar® AP Series Liquid' Alkylaryl Hercules
'Because of the low molecular weight, these resins are soluble in both endblock and midblock phases of thermoplastic rubbers.
250 HANDBOOK OF ADHESIVES

properties of a plasticized formulation are typically results from using oils containing as
highly dependent upon the plasticizer compo- little as 2-3 % aromatics.
sition, its solubility parameter, and its molec- Typical hydrocarbon plasticizing oils and 01-
ular weight. igomers are listed in Table 5. They are ar-
ranged in order of increasing solubility
parameter. Oils with the lowest solubility pa-
Selecting a Plasticizer for High Perfor- rameter and highest molecular weight are the
mance Adhesives. The ideal plasticizer for least soluble in the endblock phase and will
use with thermoplastic rubbers in high perfor- have least effect on high temperature strength
mance adhesives is one which is completely in- of thermoplastic rubber formulations. These
soluble in the endblock phase, completely same oils will also have the lowest solubility in
miscible with the midblock phase, and low in the rubber phase and thus the most tendency to
cost. Low volatility, low viscosity, low den- bleed-out at high concentrations.
sity, and resistance to degradation are also de- Swelling data for S-B-S in each oil are also
sirable characteristics. Various hydrocarbon listed in Table 5. Although actual bleed-out
oils whose average solubility parameters are tests are required to establish acceptable oil
below those of the midblocks, but not too far levels for each application, there is usually no
below, satisfy these requirements reasonably tendency for oil to bleed out of compositions
well. containing less than half the amount absorbed
Process oils are usually mixtures of molecu- during the swelling test. The presence of rub-
lar species which can be classed as aromatic, ber-compatible resins reduces the tendency fur-
naphthenic, and paraffinic. When these oils are ther. Selection of a plasticizer involves
added to thermoplastic rubber, fractionation balancing the various plasticizer characteristics
may occur with the aromatics concentrating in to best fit any specific application.
the endblock domains. Reduced cohesive The effect of oil type on the tensile properties
strength at ambient and elevated temperatures of a compression molded S-I-S polymer is

Table 5. Properties of Plasticizing Oils.

Solubility Volatility
Parameter Average Specific Loss,' Oil
li," Mole Gravity Weight Absorbed,d
Trade Name Supplier Hildebrands Weight b (15. 6°C) % phr
Polypropene D-6O Amoeo 6.55 800 0.86 0.1 25
Poly butene-I 8 Chevron 6.95 600 0.88 0.1 39
Tufflo 6206 Areo 7.06 660 0.88 0.05 31
Polybutene-12 Chevron (7.04) 530 0.88 (53)
Tufflo 6056 Areo 7.18 550 0.87 0.3 56
Polybutene-8 Chevron (7.18) 440 0.86 (75)
Kaydol Witeo 7.34 480 0.89 82
Tufflo 6026 Areo 7.29 410 0.86 1.0 76
Polybutene-6 Chevron 7.34 315 0.84 10.0 103
Tufflo 6016 Areo 7.51 390 0.85 2.0 106
Tufflo 6204 Area 7.60 440 0.92 0.5 96
Shellflex® 371 Shell 7.60 410 0.90 0.9 112
Tufflo 6094 Areo 7.60 410 0.92 0.8 95
Tufflo 6054 Area (7.66) 380 0.92 1.3 (127)
Tufflo 6014 Areo 7.73 320 0.89 12.0 214
'Calculated from experimentally determined surface tension, average mole weight, and specific gravity. Values in parentheses were
interpolated.
"By ebullioscopic methods of Mechrolah osmometer.
'22 hours and 107°C.
dGrams of oil absorbed by 500-1000 micron films of Kraton"' DIIOI Rubber at room temperature per 100 grams original weight after
soaking 100 hr. Films were prepared by casting from toluene solution on mercury and drying very slowly. Values in parentheses were
interpolated or extrapolated from related data.
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN ADHESIVES 251

~~----~------.-------r------,
hesive strength in a situation of this type is to
replace the DOP with a nonmigrating plasti-
cizer. a Another way is to use a primer or barrier
~----- ~
coating which restricts the tendency for plasti-
cizer migration.

Other High Polymers

Elastomers. Low levels of thermoplastic

rubber added to adhesives based on conven-
10 15 20
tional unvulcanized rubber like natural rubber,
Oil CONTENT. PHR poly isoprene , and SBR, upgrade cohesive
Fig. IS. Effect of oil type (see Table S) on the tensile strength, lower solution viscosity, and may im-
strength of an S-I-S thermoplastic rubber. prove adhesive strength. At the other end of the
1. Decrease due to dilution alone (calculated). scale, use of a limited amount of a conven-
2. Tuffio 6206 oil (observed). tional rubber in a thermoplastic rubber formu-
3. Tuffio 6204 oil (observed). lation may increase solution or melt viscosity
4. Shellftex@ 371 (observed). and lower costs with limited loss in cohesive
S. Shellftex 314 (observed).
strength or other properties.
The degree of compatibility between high
shown in Fig. 15. These curves lie in the order polymers must be considered in formulating
of increasing solubility parameter and aromatic adhesives. S-I-S polymers are essentially mis-
content shown in Table 5.
cible with polyisoprene and natural rubber.
S-B-S polymers mix well with SBR and poly-
Plasticizers Which Reduce Cohesive
butadiene. In other combinations, however,
Strength. Plasticizers which are readily
turbidity of cast films, slow phase separation in
compatible with the polystyrene endblocks pre-
solution, and other evidence of molecular in-
vent the formation of strong crosslinks between
compatibility may appear. Nevertheless, rub-
the rubber molecules. Endblock domains will
bers of the incompatible type, including
form as a separate phase, but instead of being neoprene and nitrile rubbers, may form com-
hard and rigid at room temperature, they will
mercially useful mixtures if mixing problems,
be soft and fluid. Stress applied to the network tendency to phase separate, and turbidity, etc.
will cause irreversible flow. are appropriately handled. Methods of offset-
An example of a plasticizer which destroys ting incompatibility include use of high shear
cohesive strength is dioctylphthalate (DOP) , mixing, formulating for high solution viscosi-
commonly used in plasticized polyvinyl chlo- ties, mixing immediately before use, and inclu-
ride (PVC) compositions. A relatively small sion of compatibilizing resins in the
amount of DOP added to an S-B-S thermo-
formulation.
plastic rubber reduces the ultimate tensile Blending thermoplastic rubber into ethyl-
strength from above 4000 psi to zero. Low mo- enevinyl acetate (EVA) polymers with low to
lecular weight liquid tackifying resins are also
medium vinyl acetate content is roughly equiv-
often soluble in both phases and tend to reduce alent to increasing the vinyl acetate content.
cohesive strength. However, they may still be The mixtures become softer and exhibit better
useful in some adhesive applications.
flexibility at ambient and low temperatures.
Adhesives based on a thermoplastic rubber
with polystyrene endblocks should be carefully
Thermoplastics. Specific desirable charac-
tested when intended for direct contact with
teristics may be obtained by blending a wide
PVC highly plasticized with DOP. The latter
can diffuse into the rubber phase and destroy
"For example, Paraplex O-SO or 0-54, intermediate and
the cohesive strength as discussed above. The medium high molecular weight polyesters (Rohm and Haas
most effective way to prevent the loss of co- Company).
252 HANDBOOK OF ADHESIVES

range of plastic materials into thennoplastic bers represent potentially useful flexibilizers
rubber. A third phase is fonned by three ma- and tougheners for wax. However, when ther-
terials. They can be made into continuous net- moplastic rubber and wax are mixed in solution
works by mechanical mixing and applying or at elevated temperature, they tend to sepa-
under high shear conditions. Polystyrene (crys- rate on cooling as the wax crystallizes. Low
tal grade homopolymer), for example, can be levels of wax can therefore function as anti-
blended in solution or melt mixed to increase blocking agents. Physically stable three-com-
hardness and modify other physical properties. ponent mixtures which include an appropriate
Crystalline polyethylene and crystalline poly- resin (e.g., a polyterpene) can be prepared. Mi-
propylene can also be blended in a high shear crocrystalline waxes tend to fonn more physi-
mixer to raise service temperature limits or to cally stable mixtures than do paraffinic types,
increase solvent resistance. Polar polymers may but are less chemically stable at mixing and ap-
increase adhesion to metal and polar surfaces. plication temperatures.

What About Fillers?

MIXING AND APPLICATION
Nonreinforcing fillers-clay, tales, whitings,
etc.-may be used to increase hardness, mod- Adhesive fonnulations are most frequently pre-
ulus, abrasion resistance, density, and to lower pared from thennoplastic rubber by solution or
raw material costs. Carbon black, which can be hot-melt techniques because commercial ther-
used as a pigment and screening ultraviolet sta- moplastic rubber is available in dry fonn only,
bilizer, fonns pennanent gel structures with the usually as crumb or pellets. However, fonnu-
unsaturated midblocks. This reduces solubility lations can be prepared as emulsions or as pow-
and thennoplasticity. Thennoplastic rubbers ders if desired.
generally will tolerate high filler levels while
retaining satisfactory cohesive strength. Solution Compounding and Application

Blends with Asphalt Solvating the plastic endblock domains serves

to "unlock" the physically crosslinked rubber
Asphalt is a low cost thennoplastic material network. Consequently, solution blending of
which is highly temperature dependent. The thennoplastic rubber with resins, plasticizers,
addition of a thennoplastic rubber at 1-5-w in fillers, etc., requires a solvent which will dis-
an appropriately selected asphalt greatly re- solve the endblocks as well as the rubber mid-
duces the dependence of viscosity on temper- blocks. The selection of solvents was discussed
ature. Useful operating temperature ranges can previously.
often be doubled in this manner.
The addition of a thennoplastic rubber at 10-
Dissolving Thermoplastic Rubber Crumb.
30%w produces a truly thennoplastic product
The dissolving process may be carried out in
with elasticity, resilience, and high adhesive
various types of equipment which provide ad-
strength. Such mixtures can fonn the basis for
equate shearing action to the solvent/crumb
a variety of sealants as discussed in the section
mixture. Suitable equipment includes: chums
on pennanent crosslinking. Although the selec-
or stirred vessels, planetary (Hobart-type) mix-
tion of the asphalt and its modifications with
ers, and internal (Sigma blade type) mixers.
aromatic or paraffinic oils is not simple, a bal-
Enough shear must be used to prevent agglom-
ance between resistance to phase separation at
eration of the swollen crumb into large lumps.
300 0 P and the fonnation of a coherent network
Short dissolving times are assisted by use of
at ambient temperatures can be obtained by
high shear, small rubber particle size, and high
empirical tests.
temperatures. The use of solvents which are
poor for either the rubber phase or endblock
Blends With Paraffin Waxes
phase will increase the dissolving time. Low
Paraffin waxes represent potentially useful low molecular weight and small particle size gen-
cost diluents or, conversely, thennoplastic rub- erally make dissolving times for thennoplastic
 THERMOPLASTIC RUBBER (A-B-A BLOCK COPOLYMERS) IN ADHESIVES 253

rubber much shorter than those for masticated about 210°F for polystyrene, "unlocks" the
natural rubber or SBR in good solvent systems. physically crosslinked rubber network. Appli-
cation of shear stress then makes possible mix-
Static Electricity Safety Precautions. ing with other materials and application of the
Because of the small particle size and insulat- melt to substrates. As discussed earlier, the
ing nature of thermoplastic rubber, pouring melt viscosity decreases as the shear stress or
rubber crumb from shipping containers directly shear rate increases. Mixing efficiency is then
into a processing vessel can generate sufficient improved.
static electric charge to produce sparks capable With commercial S-B-S and S-I-S thermo-
of igniting combustible vapor mixtures. The plastic rubbers, 250 to 400°F is the normal
chance for ignition must be guarded against range for mixing and application. Tempera-
through such measures as proper polymer han- tures above 350°F may lead to excessive oxi-
dling methods, equipment design, bleeding off dative degradation of the rubber network and
the charge, or blanketing with inert gas. Ag- above 425 OF to thermal degradation. At tem-
glomerated crumb should not be separated in peratures below 250°F, the viscosity becomes
an explosive atmosphere. Conveyor systems so high that mechanical breakdown of the rub-
should minimize abrading, scuffing, or rubbing ber may occur. Since oxidative degradation is
of the crumb. Equipment should be properly reduced by lowering temperature, the preferred
grounded. Surface conductivity of the crumb mixing method is in high shear equipment at
may be improved to favor dissipation of sur- 275-325 OF.
face charge by passing the crumb through hu-
mid air, dusting it with antistatic agents, or Batch Mixing Equipment. Melt mixing can
dusting it with conductive inorganic fillers. Ra- be carried out in a variety of heated mixing
dioactive static electricity discharge devices equipment. In order of increasing effective-
may also be used. ness, these include: vessels stirred with pro-
pellers, vessels with high shear (Cowles-type)
Application of Solutions to Substrates. dispersers, planetary mixers (Hobart-type), in-
Formulated thermoplastic rubber solutions can ternal mixers (Sigma-blade or Banbury type),
be applied to various substrates with conven- and modifications of these.
tional equipment such as doctor blades, roll In low shear mixers, resins, plasticizers, and
coaters, etc. Solution viscosity can be adjusted stabilizers should be melted first and thermo-
both through solids concentration and solvent plastic rubber crumb added incremently. Fill-
composition as discussed earlier. ers should be added last. In high shear devices,
A significant advantage of thermoplastic rub- the order of time of adding the various com-
ber solutions is their faster drying rate in film ponents is also important to minimize mixing
form compared to solutions of conventional cycle time. Rubber crumb should be added first
elastomers. When 1 mil films (dry basis) were with resins, plasticizers and fillers added in in-
cast from lO%w toluene solutions, a ~pical crements which do not disrupt the mixer ac-
S-I-S polymer reached a given level of resid- tion. Stabilizers should be introduced before the
ual solvent in 90% of the time required for nat- crumb receives appreciable shearing action in
ural rubber. The films were dried in an 86 %F any case. Presoaking plasticizers into the. ther-
recirculating air oven. If the comparisons were moplastic crumb will speed mixing.
made between solutions of the same solution
viscosity (a more practical case), the drying
times for the thermoplastic rubbers would be Continuous Mixing Equipment. Where
roughly half those for SBR or natural rubber. production rates are high enough, continuous
mixers are desirable since they reduce degra-
dation of the rubbery midblock by excluding
Melt Mixing and Processing
air and shorten residence time. Single-screw
Heating the endblock domains above the glass extruders often do not give adequate mixing.
transition temperature (Tg) of the endblocks, Twin-screw mixing extruders are much more
254 HANDBOOK OF ADHESIVES

effective. Some of the newer continuous mixer air, may degrade. Cooling in thin cross sec-
designs are also very effective. a tions is thus desirable. Because of the low heat
conductivity and high viscosity at zero shear
High Shear Melt Mixing Precautions. conditions, remelting should involve oil heat-
Thermoplastic rubbers, particularly those with ers to prevent surface overheating and a source
the highest melt viscosities, may build up ex- of pressure to cause the adhesive to flow past
cessive temperatures in high shear internal the heating surface as melting occurs. Grid
mixers (e.g., Banbury mixersb) if exposed to melters or "melt-on-demand" equipment are
the high shear conditions in the absence of useful in this respect.
plasticizers and stabilizers. Certain precautions
should be noted. While mass temperatures up Emulsions
to 400°F (425°F maximum) are normal in the
mixing of thermoplastic rubber formulations, Formulations based on thermoplastic rubbers
higher temperatures indicate too high a melt can be made into emulsions by dispersing so-
viscosity or too vigorous a mixing action. If the lutions or melts into water containing appro-
temperature were allowed to rise uncontrolled priate surface active agents. Normally, any
in such a situation (to 500°F and above), va- organic solvent present would be stripped from
porization of plasticizer light ends and polymer the emulsion. High shear devices, such as col-
decomposition could occur creating a potential loid mills or centrifugal pumps, have been suc-
fire hazard. Excessive temperatures can be cessfully used for the emulsifying step.
avoided during the mixing operation by adding Compounding prior to emulsification enables
a resin or plasticizer or by reducing mixer resin and plasticizers to be distributed in an
speed. It is often desirable to investigate the equilibrium manner between the thermoplastic
mixing characteristics of a new composition on rubber phases as in the adhesives discussed ear-
a small scale before undertaking large scale lier. If the neat or plasticized thermoplastic
runs. rubber is emulsified alone and then mixed with
a resin emulsion, the thermoplastic rubber will
Application Equipment. Depending on act only as a binder for the resin in the finished
melt viscosity and on the nature of the adhesive product.
applications, various types of equipment are Dried films are not likely to be continuous in
available. These include: pressure nozzle, print either case. Dried films do not tend to coalesce
wheel, doctor blade, calender, die-coater, unless heated above the Tg of the endblock do-
fountain coater, and extrusion coater. Where mains. Heating causes the endblock domains to
high strength, high viscosity products are in- soften which allows the individual particles de-
volved, equipment is now available with closed posited from the emulsion to coalesce. Contin-
or pressurized melting zones plus screw feed to uous films are not always necessary for
the point of application. Applicators using adequate performance, and endblock coales-
strands of adhesive fed to a melt zone just be- cence is not needed in these cases.
fore application are also suitable.
Powders
Cooling and Remelting of Formulated Ad-
hesives. Provision is often made for cool- Mechanical size reduction of the thermoplastic
ing, storage, and remelting of adhesives rubber crumb can be accomplished using com-
between mixing and use. Since thermal con- mercial rotating blade plastic granulators. Par-
ductivity of thermoplastic rubber is lower than ticle sizes down to at least 40-mesh can be
that of EVA and polyolefins, thick layers of produced without loss in tensile properties.
melted adhesive cool slowly, and if exposed to However, as adjustments are made to produce
progressively smaller particle sizes, throughput
drops rapidly and cooling may be needed to
aFor example, Multipurpose Continuous Mixers, Baker
Perkins Inc. prevent agglomeration of the small particles.
bFarrel Co., Div. ofUSM Corp. Reagglomeration of the small particles may oc-
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOL YMERSI IN ADHESIVES 255

cur on long-time storage unless inorganic fillers ygen attack on neat thermoplastic films, as
or antiblocking agents are added to the powder. measured by decrease in tensile strength and by
Nonblocking powdered thermoplastic rubber degree of scission or crosslinking upon heating
can be made through the use of a special sol- in air at 158°F, is greatly reduced by a number
vent system. In this method, rubber crumb is of commercial rubber stabilizers. The list in
dispersed in a high solubility parameter solvent Table 6 is roughly in order of decreasing effec-
which will barely dissolve the endblock do- tiveness with S-B-S or S-I-S thermoplastic
mains and which will not dissolve the rubber rubber.
phase at all. One such single solvent is acetone. The addition of tackifying and other resins,
Particle size of the crumb is controlled by the even those which have been hydrogenated or
amount of shear used in dispersion. Addition otherwise stabilized, greatly increasing the rate
of water totally precipitates the small particles. of oxygen attack on thermoplastic rubbers. a The
This powder may then be separated from the first four stabilizers listed in Table 6 alone or
liquid and dried. The particles do not tend to blended with others on the list, have been found
agglomerate because the hard endblock phase to be effective for resin-containing formula-
preferentially coats the outside of each particle. tions.
Accelerated aging tests in which pressure-
PROTECTION AGAINST DEGRADATION sensitive adhesives are directly exposed to cir-
culating air show much greater effects on the
Thermoplastic rubber with polydiene rubber
surface than in the film as a whole. Tests in
midblocks is subject to chemical attack at the
which the surface is covered by a release paper
carbon-carbon double bonds (as are NR and
show less oxidation and are more representa-
SBR) and requires protection appropriate to the
tive of conditions in rolled tapes or label stock.
environment. Chain scission and crosslinking Oxygen bomb testing (exposure to pure ox-
proceed simultaneously. In S-I-S polymers, ygen at 300 psig and 158°F) is often used in
scission predominates, and aging usually tends the evaluation of construction and other types
toward softening, stickiness, decrease in co- of adhesives required to perform for periods of
hesive strength, and decrease in melt viscosity. many years. Formulated S-B-S thermoplastic
In S-B-S polymers, on the other hand, cross- rubber films stabilized with 2 to 5 phr of an-
linking predominates and aging usually tends tioxidants selected from Table 6 have retained
toward hardening, lower cohesive strength, in- flexibility for more than 1,000 hr in the oxygen
creasing viscosity, and gel formation. In for-
bomb.
mulated products, both S-I-S and S-B-S
polymers may tend to harden. In solutions, both Protection Against Ozone Attack. Ther-
may show viscosity decreases during aging. moplastic rubber with diene rubber midblocks
is subject to attack by ozone when stressed.
Protection During Use Antiozonants found to be useful include NBC,b
In formulated adhesives the resins, plasticizers, Pennzone B, C and Ozone Protector 80. d
other polymers, etc., present must be protected
Protection During Exposure to Ultraviolet
as well as the thermoplastic rubber. Even hy-
Radiation. Commercially available ultravi-
drogenated rosin esters, polyterpenes, and ole-
finic hydrocarbon resins are reactive and must
"Tack loss occurring during aging of pressure-sensitive ad-
be protected. hesives has been traced in some cases to the hydration of
The most appropriate stabilizer combination ester-type resins in the formulation. Therefore, in case of
will depend on the selection of other formula- a tack loss problem, it should be determined whether the
loss is oxidative or due to moisture pickUp. Where hydra-
tion ingredients, as well as on the accelerated tion occurs, control of water pickUp during manufacture or
aging test conditions, and on the properties se- storage, change in resin type, or the removal of the mois-
lected as indexes of product stability. ture in a vacuum oven are possible solutions.
bNickel dibutyldithiocarbamate (E. I. duPont deNemours
& Co.).
Protection Against Oxygen Attack at CDibuty!thiourea (Pennwa!t Corp.).
Moderate Temperatures. The rate of ox- dReichhold Chemicals, Inc.
256 HANDBOOK OF ADHESIVES

Table 6. Antioxidants for Thermoplastic Rubbers.

Starting
Trade Name Chemical Type Supplier Level, phr
Irglmox® 1010 Tetra-bis-methylene-3-(3,5-di-tert- Ciba-Geigy 0.3-2
butyl-4-hydroxyphenyl)
propionate methane
Antioxidant 330® 1,3 ,5-trimethyl-2 A,6-tris(3 ,5-di- Ethyl Corp. 0.3-2
Irganox 1330 tert-butyl-4-hydoxybenzl) Ciba-Geigy
benzene
Cyanox® 2246a 2,2-methylene-bis(4-methyl-6-tert- American Cyanamid 0.5-2
Vanox® 2246a butyl phenol) R. T. Vanderbilt
Cyanox 425" 2,2-methlyene-bis(4-ethyl-6-tert- American Cyanamid 0.5-2
butyl phenol)
Santowhite® Crystals 4,4-thio-bis-(6-tert-butyl-m-cresol) Monsanto Co. 1-2
Irganox 565 2(4-hydroxy-3 ,5-tert-buty lanilino)- Ciba-Geigy 0.5-2
4,6-bis( n-ocxtylthio)-I,3,5-
triazine
Polygard®b Tri(nonylated phenyl) phosphite Uniroyal Chern. 0.3-5
Butyl Zimate® Zinc dibutyl dithiocarbamate R. T. Vanderbilt 1-4
Butazate® Uniroyal Chern. Co.
Butasan® Monsanto Co.
Butyl Ziram® Pennwalt Co.
aMay produce colored fonnulations.
bPolygard may be useful at high temperatures (l50-200'C).

olet stabilizers are effective in thennoplastic fonnulations will improve ultraviolet resistance
rubber fonnulations. Table 7 is a list of such markedly.
with the more effective at the beginning.
In opaque products, the addition of a reflec- Protection During Processing
tive filler such as zinc oxide or titanium diox-
idea or a light absorber such as carbon blackb Protection During Hot-Melt Mixing. Ex-
may provide satisfactory protection. clusion of oxygen during high shear mixing at
Oils containing small amounts of aromatic 250-400°F has been found to be an effective
compounds are particularly unstable with re- means to prevent polymer degradation. Figure
gard to ultraviolet radiation. The use of aro- 16 shows that no change in melt viscosity oc-
matic free' 'white oils" in thennoplastic rubber curs during high shear mixing when the mixer
is nitrogen blanketed. With oxygen present and
apor example: Titanox RA-50 (Titanium Pigment Corp.). distributed throughout the mixture significant
bPor example: Past extrusion fumance (PEP) blacks. viscosity changes result at increasing rotor

Table 7. UV Inhibitors for Thermoplastic Rubbers.

Trade Name Chemical Type Supplier
Eastman OPS Octylphenyl salicylate Eastman
Eastman RMB Resorcinol monobenzoate Eastman
Permasord MA 2-hydroxy-4-(2-hydroxy-3-methacrylyloxy) National Starch
propiobenzo-phenone
Tinuvin P Substituted benzotriazole Ciba-Geigy
Tinuvin 326 Substituted hydroxypheny I benzotriazole Ciba-Geigy
Tinuvin 770 Hindered amine Ciba-Geigy
Antioxidant 330 1,3 ,5-trimethyl-2 ,4,6-tris(3 ,5-di-tert-butyl-4- Ethyl Corp.
hydroxybenzyl) benzene
Irganox 1076 Octadecyl-3-(3,5-di-tert-butyl-4-hydroxy- Ciba-Geigy
phenyl) propionate
Irganox 10 10 Tetra-bis-methylene-3-(3,5-di-tert-butyl-4 Ciba-Geigy
hydroxyphenyl)propionate methane
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN AOHESIVES 257

20.000 ,------,.-----r----r----, 2. Select a starting formulation in the same

50 RPMlNITROGEN/295'"f
way.
i
215 RPMINITROGEN/320 c F

;::
3. Prepare a series of formulations based on
Z
~ 15,000 50 RPM/AIR/295'F
related resins, plasticizers, fillers, etc.,
using simplified solution casting meth-
~..
.
~
ods, and measure the important proper-
ties of the product.
~ 10,000
;; 4. Using these results and the principles il-
~ 275 RPM/AIR/320~F
lustrated below, optimize the balance be-
lE
tween the various properties including
5.000 L..-_ _--'-_ _ _....I-_ _ _L--_ _-...J
raw material cost.
15 30 45 60
MIXING TIME. MINUTES
5. Prepare samples by the actual manufac-
turing process to confirm the results of the
Fig. 16. Effect on melt viscosity of oxygen contact dur-
ing high shear mixing of a pressure sensitive adhesive based
screening program.
on an S-I-S thermoplastic rubber.
Some Formulating Principles
speeds. Degradation can also be reduced by the The characteristics of formulations based on
use of certain stabilizers (e.g., zinc dibutyldi- thermoplastic rubber depend, as already dis-
thiocarbamate at levels of 1-5 phr). cussed, on how the various compounding in-
Contact with air is greatest in open stirred gredients interact with the two phases present.
vessels and least in closed sigma-blade mixers. The following generalizations, although they
The data in Fig. 16 show that, in the absence may not be valid for all compositions, provide
of oxygen, moderate temperatures and me- useful clues which can guide formulation de-
chanical shear are not major causes of degra- velopment studies.
dation.
1. Endblock resins may either raise or lower
Protection During Solution Processing. the upper service temperature limit. Mid-
Adequate protection during solution mixing, block resins will raise and midblock plas-
application to the substrate, solvent evapora- ticizers may decrease the lower
tion, and storage of thermoplastic rubber for- temperature limit.
mulations can be provided by a combination of 2. Midblock resins and plasticizers tend to
the chemical stabilizers listed in Table 6. A lower the modulus and soften formula-
high temperature drying step for solvent evap- tions by decreasing the concentration of
oration may require special consideration, but hard endblock phase; endblock resins
degradation is not usually a problem in such a tend to raise the modulus for the reverse
case due to the short exposure times involved. reason.
3. Pressure-sensitive tack tends to be fa-
vored by polyisoprene midblocks over
FORMULATING FOR SPECIFIC polybutadiene midblocks; such tack is
APPLICATIONS produced by some midblock resins and
not by others; all solid endblock resins
In general, each new adhesive product must
tend to lower pressure-sensitive tack by
meet a definite set of performance specifica-
increasing modulus; rubber phase plasti-
tions and must fall within certain manufactur-
cizers tend to increase aggressive tack by
ing cost limitations. How is a thermoplastic
lowering modulus.
rubber formulation developed to match such re-
4. Peel strengths tend to increase with in-
quirements? One effective approach is outlined
creasing formulation modulus; specific
below:
adhesion to polar or metal substrates tends
1. Select one or two thermoplastic rubbers to be increased by polar, unsaturated, or
based on manufacturer's suggestions or aromatic resins and to' be decreased by
on previous experience. hydrocarbon plasticizers.
 258 HANDBOOK OF ADHESIVES

5. Melt and solution viscosities tend to be A Condensed Case Study - Formulating a

markedly decreased by both resins and Hot-Melt Pressure-Sensitive Adhesive
plasticizers; inorganic fillers will tend to
Binary mixtures of an S-I-S polymer (KRA-
increase viscosity.
TON 1107) and a number of midblock resins
Other guiding principles can be established were examined first. Solutions in a good sol-
by experience and by considering a given ap- vent were cast to form 1 mil fUms on a 1 mil
plication in the light of background information polyester film. After thorough drying, the film
already presented in this chapter. was tested for several properties. Figure 17

2500r-------r------,------~------,

2000
en
w

....•..
l:
! 4
~
:i
...~
c(
a:
~1500
,r
3
:.: /
/
..J
~
..J
c( ...
CD
CI
w
CD
, /F
z
:::i 2
o
g: 1000 )/
..J
oa:

500
oL-______ ~ _____...I_ _ _ _ _ _ ~ ______ ~ 100
o 50 100 150 200 °0~------~5~0------~10~O----~1~50~----~200
RESIN LEVEL, PHR RESIN LEVEL, PHR

10 220
I&.
o
9 ~. 210
...:5
:::)
....
.
8
a:
200
, '. ., ....
-- .,.......
:::i
... 7 !iw 190
...
~f
iii
w
l:
6 ~ 180
:::)
""",...".,......
"F ,.:. .
..J
~ 5 <i 170 ....
I&.
..J

" ' ....

W Z
~ 4 2en 160
w
l:
" ':·•••.c
3 o 150
c(

"'"'"-
a: "' S..... .
2 c( 140
w
l:
en
130

120~-----..J------~------~------~
50 100 150 200 o 50 100 150 200
RESIN LEVEL, PHR RESIN LEVEL, PHR
'BRITTLE PEEL AT 200PHR FOR C;AT 150 AND 200PHR FOR W

Fig. 17. Effect of midblock resins (Table 4) on adhesive properties of two-component pressure sensitive adhesives (see
Table 8).
 THERMOPLASTIC RUBBER (A-B-A BLOCK COPOLYMERS) IN ADHESIVES 259

shows how four properties varied with the level Shear Adhesion Failure Temperature, peel
of five dissimilar resins. Because of its high adhesion, and holding power. To restore these
shear adhesion failure temperaturea and accept- properties, high softening point endblock res-
able peel adhesionb and probe tack,C 100 phr ins were added. Figure 18 summarizes the ef-
WingTack 95 was selected for further work. fects of four such resins in the formulation
(See first column, Table 8.) containing 25 parts of oil (Table 9). Cumar LX-
More aggressive tack was desired, so a plas- 509 resin was selected for use in a final for-
ticizer was added. Shellflex 371 oil was se- mulation because it had the greatest beneficial
lected from Table 5 because of its good effect on shear adhesion failure temperature and
compatibility with the midblock phase (i.e., showed only moderate loss in rolling ball tack.
low bleedout tendency) and low cost. The data The final four component composition is
in Table 9 show the effect of adding increasing compared in Table 8 with the intermediate two
amounts of oil. and three component formulations. The final
Addition of the plasticizer caused a loss in composition combines the same Shear Adhe-
sion Failure Temperature as the first with much
aTest method described previously. more aggressive tack, a much lower melt vis-
bpressure-Sensitive Tape Council (PSTC) Test Methods, cosity (for low-cost application), and lower raw
Ref. 28. materials cost. This set of properties or any
<Probe Tack: Determined by a Polyken Probe Tack Tester
(Testing Machines, Inc.) Conditions: 1 cm/sec Speed, I other set of properties can be obtained in more
sec dwell, 100 gm/cm2 pressure. than one way. Given a growing background of

Table 8. Hot-Melt Pressure-Sensitive Adhesive Based on 5-1-5.

Two Three Four

Components, Components, Components,
(parts) (parts) (parts)

S-I-S (Kraton 1107 Rubber): 100 100 100

Midblock resin (Wingtack 95): 100 100 100
Plasticizing oil (Sheuflex 371): 40 40
Endblock resin (Cumar LX-509): 60
Stabilizer (zinc dibutyldithio-carbamate): 5 5 5
TOTAL 205 245 305

Shear adhesion failure temp., OF 210 188 220

Rolling ball tack (PSTC-6), cm 5.9 0.6 1.8
Probe tack, gm 1300 700 1100
1800 peel adhesion (PSTC-l), pli 5.3 2.5 3.7
Melt viscosity at 3500 F, cp 200,000 30,000 40,000
Holding Power to Kraft paper, min. >2800 5 150
Thermoplastic rubber content, %w 49 38 33

Table 9. Effect of Plasticizing Oil on Adhesive Properties.

Oil Level, phr: 0 25 40 60

Shear adhesion failure temperature, °F 218 192 188 177

Rolling ball tack (PSTC-6), cm. 5.6 0.9 0.6 0.7
Probe tack, gm 1600 1000 700 600
Peel Adhesion (PSTC-1), pli 5.5 3.6 2.5 1.8
Melt Viscosity (350 0 F), cp 200,000 100,000 30,000 20,000
Holding Power to Kraft paper >2800 100 5 <1
(PSTC-7), minutes
260 HANDBOOK OF ADHESIVES

6 2500r---------r----------r--------~--~

I
5

i/
!/
1/
2000
I
II .
,.
N
4
~I .. J..
Ia:
;'"

../ c.....
I •• - .
I .,,'" c

,
;' • .,,'p

#' .····i
CJ 1500
"
3 +' /
/ ~~/. ",.'" .'.....'
'" .,"
...'fI••••••
_.{J..
. ,
."
",
..c,O ••• / ~
c," ,,'
-61'
......
2
~-..
to"..··
/ c, •
/. '..-.'" 0'\~.,.'\ ......
filii" ~ ............

..-..' ".,..
•• /
•• "." ~\~
"CP
~.

500

oL---------~------~--------~~
10 20 30 10 20 30
RESIN LEVEL, PHR RESIN LEVEL, PHR

11r---------~------_,--------_r_, 230

10 220
.,. C
."
....

.
IL
0

w' ."
9 a: 210

8
:J
l-
C
a:
w 200 ........
...... ....................
~
•
." A

....... """..
""","
a.

----------
:2 P
N w

--- -"
7 I- 190

6
." " w
a:
:J 180
N

....I
;'" <
IL

.-.-.-._.-c
5
Z
170
/ " 0
4 _.i " __ ..
,.--;........
. " .•••••••••
- ..r:•• ·········AP iii
w 160
::&:
Q
C
3 a: 150
w
w
::&:
2 Ul 140

130

120
o~-------L------~--------~
10 20 30 0 10 20 30
RESIN LEVEL, PHR RESIN LEVEL, PHR

Fig. 18. Effect of endblock resins (Table 3) on adhesive properties of Kraton 1107 (100 parts), Wingtack 95 (100 parts),
and oil (25 parts) (see Table 9).
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN ADHESIVES 261

property data and an understanding of the ver- with SBR. However, S-B-S/natural rubber and
satility of thermoplastic rubber, the formulator S-I-S/SBR blends may also be useful if some
has a broad range of tailored products at hand. turbidity can be tolerated.

Starting Formulations Hot Melt Applied Assembly Adhesive.

Table 12 describes an assembly adhesive based
Pressure Sensitive Adhesive Based on
on an S-B-S polymer. A different combination
S-B-S. The formulation shown in Table 10
of properties can be obtained by using an
has high holding power, but little aggressive
S-I-S base polymer. Several useful features
tack. However, as in the case study above, all
may result from the use of S-I-S: (a) generally
properties including Rolling Ball Tack can be
better clarity, (b) lower melt viscosities, and
adjusted by adding plasticizing oil (e.g., TufHo
(c) freedom from gel formation which can oc-
6054) or by varying type and amounts of res-
cur when S-B-S formulations are exposed to
ins.
oxygen at high mixing and application temper-
atures.
Improving the Strength of General Pur-
pose Rubber Formulations. The Shear Heat-Activated Assembly Adhesive. Ta-
Adhesion of natural rubber or SBR masscoats ble 13 describes a solution adhesive which can
can be improved by the addition of thermo- be coated on two substrates, dried, activated by
plastic rubber as shown in Table 11. S-I-S heating both surfaces to 165°F, and bonded by
polymers are most compatible with natural rub- pressing the substrates together. The adhesive
ber, and S-B-S polymers are most compatible is nonblocking at room temperature.
Table 10. Pressure-Sensitive Adhesive
Contact Type Assembly Adhesive. Mod-
Based on S-B-S.
ifying the above formulation to include equal
Composition (wt. parts) parts of midblock and endblock resins with high
softening points gives the contact adhesive
S-8-S (Kraton 1101 Rubber) 100 shown in Table 14. Essentially nontacky to
Midblock resin (Super Sta-Tac 80) 200
Stabilizer 1
most surfaces, this type of adhesive bonds
strongly to itself after open times of several
Properties minutes to a few hours when cast from a hex-
Rolling ball tack (PSTC-6), in. 10 ane/toluene/acetone solvent system in the ratio
Probe tack, gm 1700 60/20/20.
180· Peel Adhesion, (pSTC-I), pli 7.6
Shear adhesion failure temperature, • F 180
The development of film-to-film adhesion
(canvas/canvas peel strength, ASTM-D-1876)
Thermoplastic rubber content, %w 33
with bonding after 30 min open time is shown
Endblock/Midblock Ratio 10/90 in Fig. 19 for the two formulations given in
Table 15.

Table 11. Pressure-Sensitive Adhesive - Effect of S-B-S on Shear Strength.

Composition (wt. parts)

SBR (S-1006, ML-50) 100.0 75.0

S-8-S (KRATON 1101 Rubber) 25.0
Midblock Resin (Foral 85) 100.0 100.0
Stabilizer (Irganox 101O/DLTDP = 1/1) 0.6 0.6

Properties
Shear adhesion to glass (PSTC-7), hr 0.1 1.0
180· peel adhesion (PSTC-l), pli 1.1 0.9
Rolling ball tack, (PSTC-6), in. 4 4
262 HANDBOOK OF ADHESIVES

Table 12. Hot-Melt Applied Assembly Table 14. Contact Type Assembly
Adhesive. Adhesive.
Composition (wt. parts) Composition (parts by wt.)

S-B-S (Kraton 1102 Rubber) 100 S-B-S (KRATON 1101 Rubber) 100
Endblock resin (Piccotex 120) 150 Endblock resin (PICCO N-I00) 37.5
Midblock resin (Wingtack 115) 50 Midblock resin (Pentalyn H) 37.5
Plasticizing oil (SHELLFLEX 371) 50 Stabilizer (Antioxidant 330) 0.6
Stabilizer 2-5
Properties: (30 min. open time, no heat or solvent
Properties activation) 180° Peel Strength (PSTC-l), pH
Melt viscosity at 350° F 16,000 cp
Tensile strength, TB 600 psi (draws) Canvas/fir plywood 14
Elongation, EB 700% Canvas/stainless steel 14
Shore A Hardness 90 Canvas/vinyl asbestos floor tile 9
Lap Shear (Plywood/plywood) 214 psi Lap shear strength (0.5 in./min. Instron
Flexibility at 0° F . Good crosshead speed) 137
Shear adhesion failure Endblock/Midblock ratio 39/61
Temperature
Endb1ock/midblock ratio
~~----------------------------~

Table 13. Heat Activated Adhesive.

/"'/.--.
. ,/
50

Composition (wt. parts)

J
40
./ .' COMMERCIAL
S-B-S (Kraton 1101 Rubber) 100 , NEOPRENE

Endblock resin (Cumar R·16) 75 30 ADHESIVE

Low molecular weight Endblock resin

(Piccovar AP·25) 25 / ;
Stabilizer (Antioxidant
20
.......... ,,/
330/DLTDP = 1/l) 0.6 ...••• ,;.",
Solvents
Toluene 120
10
.....
o' .,'

Cyclohexane 120
Methyl ethyl ketone 60 24 72 168 400
BONDING TIME. HRS.
Properties
Peel adhesion (PSTC-l), pli 50 Fig. 19. Development of contact adhesive bond strength.
Creep (180° Peel at 140°F, 3 pli load),
in/l0 min. 0.2 Table 15. Contact Adhesives.
Endblock/Midblock ratio 65/35
Composition (wt. parts) 2

Reactive Contact Adhesives. The heat re- S-B-S (Solprene 406 Rubber) 100
sistance of contact adhesives can be increased S-B-S (Solprene 411 Rubber) 100
by using curing phenolic resin systems. Table Endblock resin (pICCO 6115) 40 40
16 compares two fonnulations, one with and Midblock resin (pentaiyn H) 10 10
one without a reactive resin system. Solvents
Hexane 150 150
Building Construction Adhesive. The Acetone 150 150
starting composition of Table 17, suitably for- Toluene 150 150
mulated with solvents, is a high strength ad-
hesive which can be used for factory or field
assembly of housing components. With stabi- Wax-Containing Hot-Melt Assembly Ad-
lizer systems similar to that shown, oxygen hesive. Blends of paraffin wax, S-B-S, and
bomb aging exceeds current building require- a compatibilizing resin may be used for bond-
ments. ing paper, textiles, etc as shown in Table 18.
 THERMOPLASTIC RUBBER (A-B-A BLOCK COPOlYMERSI IN ADHESIVES 263

Table 16. Contact Adhesive - Effect of Heat Reactive

Resin.
Nonreactive Reactive
Composition (wt. parts) Resin Resin

S-B-S (Solprene 411 Rubber) 100 100

Reactive resin (Schenectady SP-154) 45
Endblock resin (pICCO 6115) 40
Midblock resin (pentalyn H) 10
Magnesium oxide 8.6
linc oxide 5.0
Stabilizer 1
Solvents
Hexane 150 127
Acetone 150 127
Toluene 150 127
Properties
Peel strength (canvas/canvas), pH 48 25
Peel adhesion failure temperature
(canvas/canvas, 0.22 pH; 40°F/hr), of 176 230

Table 17. High Viscosity Construction Table 19. Sealant for Concrete Joints.
Mastic.
Composition (wt. parts)
Composition (wt. parts)
S-B-S (Kraton 1101) 100 S-B-S (Kraton 1101 Rubber) 100.0
Endblock resin (PICCO N-100) 75 Asphalt 250 dmm pen, 233 poise @ 140°F) 180.0
Soft clay 200 Plasticizing oil (Shellflex 881) 60.0
Stabilizers Midblock resin (picco LTP-I00) 60.0
linc dibutyldithiocarbamate 2 Stabilizers 1.0
Plastanox 2246 1
Properties
Properties Penetration at 77°F, dmm 86
Lap shear strength Resilience at 77°F, % 83
(Wood/wood, 0.5 in./min crosshead Flow at 140°F, in. o
speed), psi 590 Viscosity at 400°F, cps 2060
Softening point R&B, ° F 218
Table 18. Hot-Melt Assembly
Adhesive.
expand and contract without losing adhesion.
Composition (wt. parts) In some applications, however, stress is carried
by the sealant such that the material is effec-
S-B-S (Kraton 1102 Rubber) 100 tively an adhesive-sealant. Thermoplastic rub-
Midblock resin (Super Sta-Tac 100) 100
Paraffin wax (Shell wax 300) 85
ber polymers can be formulated to meet the
Stabilizer 1 requirements of either kind of sealant. A con-
crete/concrete sealant is shown in Table 19.
Properties
Peel strength (canvas/ canvas), pli 45
Binders. Binders should be elastic while still
maintaining strong adhesion to the substance
In this case, the wax functions in the same way being bound. The resulting product can be soft
as the plasticizing oils discussed above. and flexible as in a carpet backing or stiff and
hard as in an abrasive. Thermoplastic rubber
Sealants. Sealants often require only gap- has the capacity for great extension, particu-
filling characteristics. Such products are gen- larly with inert fillers. An example of a flexible
erally low modulus compounds which readily carpet backing is shown in Table 20.
264 HANDBOOK OF ADHESIVES

Table 20. Binder for Carpet Backing. linking system could contain 1-4 phr of per-
oxide (e.g., DI CUP, dicumyl peroxide,
Composition (wt. parts) Hercules), and could be used in combination
with 5.25 phr of a reactive acrylic monomer
S-B-S (Kraton 11 01 Rubber) 100
Plasticizing oil (Shellflex 371) 150 (e.g., Sartomer SR 351, an acrylic monomer,
Whiting 700 Sartomer Corp.). Either the sulfur or the per-
Stabilizer 1 oxide crosslinking package can. be mixed di-
Properties rectly into the adhesive solution, and
Hardness, Shore A 55 crosslinking occurs thermally as the adhesive
Specific gravity 1.8 tape passes through the solvent evaporation
ovens.
Another approach to improve the high tem-
PERMANENT CROSSLIN KING perature cohesive strength of adhesives based
on thermoplastic rubber is by establishment of
Pressure sensitive adhesives based on thermo-
a thermoset network extending throughout the
plastic rubbers perform well over the tempera-
rubber phase. This can be accomplished by the
ture range required in the majority of pressure
use of reactive phenolic resins in combination
sensitive product applications. However, as the
with a metal catalyst. An example of a formu-
temperature at which the product will be used
lation which is claimed to be effective is given
approaches the glass transition temperature of
in Table 21. This type of crosslinking system
the endblock phase of the rubber (usually about
can be mixed directly into the adhesive solution
92°C), the polystyrene endblock domains be- and crosslinking is initiated thermally in the
gin to soften and unlock the physical cross-
solvent evaporation ovens.
links. When this occurs, the rubber midblocks
A thermally initiated crosslinking reaction
are no longer crosslinked and the adhesive would almost always be used to crosslink an
shows a drastic reduction in cohesive strength. adhesive applied from solvent because cross-
Therefore adhesives based on thermoplastic
linking can be conveniently initiated in the sol-
rubber cannot be used, for example, on high
vent evaporation ovens. However, thermally
temperature masking tapes, which must have
initiated crosslinking systems present consid-
some solvent resistance and withstand a signif-
erable handling problems for hot melt adhe-
icant load at temperatures in paint baking ovens
sives in that they may crosslink the adhesive in
of up to 170°C. This limitation can be over-
the hot melt processing equipment.
come by crosslinking the rubber in the adhesive
A crosslinking system which can be initiated
so that it will no longer be thermoplastic.
by exposure to radiation is a more practical
The double bonds in the midblocks of the un-
route to crosslink a hot melt adhesive. The for-
saturated S-B-S and S-J-S polymers provide
the sites for crosslinks. These unsaturated ther-
moplastic rubbers can be crosslinked with the Table 21. Pressure Sensitive Adhesive
usual sulfur, sulfur donor, or peroxide curing Crosslinked with Phenolic Resin.
systems traditionally used for crosslinking un- Parts by Weight
saturated rubbers. There are many combina- S-I-S Polymer" 100
tions of ingredients which could be used in a Cs resin b 50
sulfur based crosslinking package. For exam- Phenol-formaldehyde resinc 20
ple, the crosslinking package could contain Zinc resinated 10
0.3-1.5 phr of elemental sulfur or a sulfur do- Zinc dibuty ldithiocarbamate e 2
2,5-di-tert-amylhydroquinone
nor (e.g., Sulfads, dipentamethylene thiuran
hexasulfide, Vanderbilt), 0.3-1 phr of an ac- %w solids in toluene 50
celerator (e.g., Altax, benzothiazyl disulfide, 'Kraton® D 1107 Rubber; Shell.
Vanderbilt or Methyl Zymate, zinc dimethyl- "Wingtack® 95; Goodyear.
'Amberol ST-137; Rohm and Haas.
dithiocarbamate, Vanderbilt), and 0.3-1 phr of dReichhold.
zinc oxide and stearic acid. A peroxide cross- 'Santovar® A; Monsanto.
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN ADHESIVES 265

mulations shown in Table 22 can be cross- in Table 22 is based on a conventional S-I-S

linked by exposure to ultraviolet (UV) polymer and requires a belt speed of 3.0 m / min
radiation. The reactive monomer, SR-351 (tri- to obtain sufficient crosslinking. Formulation
methylolpropane triacrylate), is used in the for- B, on the other hand, is based on a new (S-I)n
mulation to reduce the radiation dose required radial block polymer, Kraton® D1320X Rub-
to achieve crosslinking of the adhesive. In ad- ber, designed for crosslinked adhesives and ob-
dition, a photoinitiator, Irgacure® 651, is tains sufficient crosslinking at a belt speed of
needed to generate free radicals by dissociating 12.0 m/min.
rapidly under UV exposure, which initiate the Adhesives can also be crosslinked by expo-
crosslinking reaction. Both adhesive formula- sure, under a nitrogen blanket, to electron beam
tions in Table 22 tend to crosslink when held (EB) radiation at a dose of 1 to 10 megarads.
at hot melt processing temperatures. However, Table 23 demonstrates the effectiveness of Kra-
both adhesives crosslink slowly enough that ton® D1320X Rubber, Formulation B, in ob-
they can be extrusion coated onto the tape sub- taining a crosslink network at 5 megarads
strate before significant crosslinking has oc- without the use of a reactive monomer. For-
curred. The formulations can be crosslinked by mulation A is based on a typical S-I-S polymer
exposure, under a nitrogen blanket, to ultravi- and shows a lack of crosslinking at the 5
olet light by passing the adhesive under a high megarad dose. Electron beam crosslinking of
pressure mercury lamp. However, it is required typical S-I-S polymers require the addition of
that the light be filtered to remove the portion reactive monomers and usually higher EB
of the spectrum whose wavelength is less than doses.
310 nanometers in order to prevent degradation Because their midblock is saturated, the
of the surface of the adhesive. Formulation A, S-EB-S and S-EP-S polymers are much more

Table 22. Pressure Sensitive Adhesive Formulations Crosslinked by Exposure to UV

Radiation.
Formulation
A B
S-I-S polymer' 100
KratonQl D1320X rubber' 100
WingtackQl 95' 80 80
TMPTAd 7.5 7.5
IrgacureQl 651 e 1.0 1.0
Adhesive Propenies
A B
Before After UV Before After UV
UVCure Cure UVCure Cure
Belt speed, m/min 3.0 12.0
Gelcontent, %1 o 92 0 89
Rolling ball tack, cm 1.4 14.3 2.8 4.1
PolykenQl probe tack, kg 0.9 0.8 1.0 0.9
180° peel,N/m 720 530 630 540
Holding power to steel, hrll >70 >44 >88 >88
Holding power to kraft, hrll >70 0.3 >88 >88
70°C holding power to kraft, hr' 1.5 0.5 5 27
'KRATON'" DII07 Rubber; Shell Chemical.
bShell Chemical.
'Goodyear.
dTrimethylolpropane triacrylate, SR-35 I ; Sartomer.
'Ciba-Geigy.
fpercent polymer fraction not soluble in toluene.
812.7 x 12.7 cm with 2 kg load.
h25.4 x 25.4 cm with I kg load.
266 HANDBOOK OF ADHESIVES

Table 23. Pressure Sensitive Adhesive Formulations Crosslinked with Electron

Beam Radiation.
Formulation
A B
S-I-S polymer" 100.0
Kraton~ D1320X rubber" 100.0
Wingtac~ 95' 88.9 88.9
Adtac~ B 10<1 ILl ILl
Antioxidant 33()fIC 0.4 0.4
BHT 0.3 0.3
Adhesive Properties
A B
E.B. Dose, Mrad 0 5 0 5
Gel content, %f 0 0 0 90
Rolling ball tack, cm 1.4 3.4 1.2 1.8
Polyken~ probe tack, kg 1.3 1.4 1.2 1.4
180· peel, N/m 1050 930 875 980
Holding power to steel, h~ >67 >67 >67 60
Holding power to kraft, ~ 63 >67 60 >67
95·C holding power to Mylar, hr" 2.0 2.1 1.9 >17
'Kraton~ D 11 07 Rubber; Shell Chemical.
'Shell Chemical.
'Goodyear.
"Hercules.
'Ethyl Corp.
'Percent polymer fraction not soluble in toluene.
"12.7 x 12.7 cm with 2 kg load.
"25.4 x 25.4 cm with 1 kg load.

difficult to crosslink. A fonnulation similar to electron beam doses to obtain a high gel con-
the fonnulations in Table 22, with a reactive tent and an improvement in SAFT or 95°C
monomer, containing an S-EB-S polymer holding power.
rather than an S-I-S polymer cannot be cross- It must be noted that while crosslinking an
linked at commercially acceptable rates by ex- adhesive based on a thennoplastic rubber brings
posure to ultraviolet light. It can be crosslinked about the desired improvement in high temper-
by exposure to electron beam radiation, but ature cohesive strength and solvent resistance,
doses of at least 6 megarads are required. it can also cause a reduction in aggressive tack
Resins can also affect the rate of crosslinking of the adhesive. Unless the rubber has been de-
on exposure to radiation. Table 24 demon- signed specifically for use in crosslinked ad-
strates the effectiveness of hydrogenated res- hesives, chemical crosslinking of a thenno-
ins, Sample No.1, in obtaining a crosslink plastic rubber corresponds roughly to overcur-
network in a fonnulation based on the (S-I)n ing a conventional rubber vulcanizate.
polymer, Kraton@Dl320X Rubber. At an elec-
tron beam dose of 1 megarad, Sample No.1
APPENDIX
has a gel content (that portion of the polymer
SOLUBILITY PARAMETER UU-A
that is not soluble in toluene) of 45 % and an
POWERFUL TOOL
increase in high temperature perfonnance
(shear adhesion failure temperature, SAFT) of Hildebrand's solubility parameter (0) has been
30°C. At 3 megarads the gel content has in- used in the text to correlate the solubility be-
creased to 90% and the holding power at 95°C havior of thennoplastic rubber (e.g., Figs.
(i.e., above the Tg of the endblock) has in- 9-11). This parameter is potentially an ex-
creased to 11 hours. The unsaturated resins, tremely powerful tool for studying fonnula-
Samples No.2, 3 and 4, required much higher tions based on two-phase thennoplastic rubber.
 THERMOPLASTIC RUBBER (A-B-A BLOCK COPOLYMERS) IN ADHESIVES 267

Table 24. Effect of Resins on Electron Beam Crosslin king of (S-I)n Thermoplastic
Rubber Pressure Sensitive Adhesives.
Rolling Ball Saft Mylar, C °C 95°C Holing
ID No." EB Dose, Mrad Gel Content,b % Tack, cm Power,d min 180 0 Peel, Nlm

Escore~ 5380lRegalrez® 1018

1 0 0 1.7 74 6 540
1 45 1.4 104 50 470
3 90 1.6 112 670 470
5 93 3.2 113 800 420
7 95 4.0 114 1000+ 390

Wingtack® 95lAdtac® B10

2 0 0 2.5 92 23 840
1 4 2.5 97 50 720
3 69 1.9 115 165 720
5 89 4.3 122 290 680
7 95 4.3 114 500 700

Wingtack 951Wingtack 10
3 0 0 1.5 88 11 630
o 1.3 93 26 610
3 62 1.3 100 125 530
5 77 3.0 116 130 600
7 90 1.8 114 140 560

. Escorez 1310IAdtac BlO

4 0 0 2.9 91 12 770
1 3 1.8 96 33 770
3 74 1.7 110 180 630
5 75 3.1 III 190 650
7 82 4.6 115 650 670
aFonnulations: 2 3 4
Kraton® D 1320X Rubber; 100.0 100.0 100.0 100.0
Shell
Escorez 5380; Exxon 60.8
Regalrez 1018; Hercules 61.4
Wingtack 95; Goodyear 69.4 50.1
Escorez 1310; Exxon 74.2
Adtac B 10; Hercules 52.8 48.0
Wingtack 10; Goodyear 72.1
Antioxidant 33041 ; Ethyl Corp. 0.4 0.4 0.4 0.4
BHT 0.3 0.3 0.3 0.3
bpercent polymer fraction not soluble in toluene.
'25.4 x 25.4 cm with I kg load, temperature at failure of adhesive bond.
d25.4 X 25.4 cm with I kg load.

It has an exact value for each compounding in- terials and better methods will be developed for
gredient: solvent, polymer, resin, plasticizer, applying it. This appendix is intended to clarify
stabilizer, etc. The distribution of any ingre- the significance of 0 and to point out its rela-
dient between the two polymer phases and its tionship to thermoplastic rubber compounding.
consequent effects on formulation behavior is
usually a function of the values of 0 for the var- Significance of o. For two materials to be
ious components. Unfortunately, at present, mutually soluble, the free energy of mixing
values of 0 are readily available only for sol- must be negative. This situation is usually fa-
vents, oils, and certain polymers. However, vored if the values of 0 for the two materials
due to its usefulness, it is probable that in the are close. In general, the higher the molecular
near future 0 will be determined for more ma- weight of one or both materials is, the closer
26B HANDBOOK OF ADHESIVES

must be the values of 0 for miscibility to occur. components and must be represented as fol-
Thus, for example, if one knew the values of 0 lows:
and molecular weight for a series of resins, one
might be able to select or design a resin which
would optimize a certain property.
Definition of 0-Hildebrand 1s proposed the where
name "solubility parameter" for the following
quantity:
Od = bond energy due to van der Waal's
forces,
o = (cohesive energy density, CED) 112 op = bond energy due to all polar interac-
tions, and
in (call cm3 )112 Oh = bond energy due to all hydrogen bond-
ing interactions.
Thus, 0 is actually a three-dimensional quantity
which could be represented as a point in three-
where dimensional space. 19-21 Furthermore, it is now
not enough that 01 and 02 be close together for
E. = isothermal energy of vaporiza- miscibility to occur. Each of the components
tion into a vacuum, cal I mole of 01 must be similar to the corresponding com-
and Vm = molar volume, cm3 /mole. ponents of 01 must be similar to the correspond-
The units, (cal/cm 3 )1I2, have been desig- ing components of ~, that is (Od)1 = (Odh.
nated as "hildebrands" in honor of the origi- (Op)1 = (oph. and (Oh)l) = (Oh)2, for misci-
nator of the term solubility parameter. 19 As bility to occur. Table 25 lists solubility param-
defined, 0 is a measure of the total intermolec- eters for some solvents. In addition to the three
ular bond energy holding the molecules of a dimensional character of 0, temperature, com-
substance together. If the bonds holding the ponent molecular weight, and molecular weight
molecules of substance (1) together are much distribution affect the outcome of a specific
stronger than those holding substance (2) to- blending situation.
gether (Le., 01 > 02), each species of mole- The complexities of such a system appear
cule will prefer its like neighbors and will overwhelming and might cause one to lose in-
refuse to mix with molecules of the other sub- terest in the solubility parameter approach. This
stance. Conversely, if 01 = 02, the molecules reaction is not entirely justified as discussed in
of (1) will tolerate the proximity of the mole- the next paragraph. However, as a result of this
cules of (2), and vice versa. Many discussions
and tabulations of solubility parameter have ap- Table 25. Three Dimensional Solubility
peared in the literature; several of the more Parameters.
useful are included as references. 1S-27
Solubility Parameter
Molar (hildebrands)
Simple Cases. Nonpolar hydrocarbon sol-
Volume
vents like cyclohexane and nonpolar polymers Solvent (cm 3/mole) 68 Sd 6p 6h
like polyisoprene follow the above rules, and
correlations like that presented in Fig. 10 are n-Hexane 131.6 7.3 7.3 0 0
quite precise. Here the intermolecular bonds are n-Octane 163.5 7.6 7.6 0 0
Cyclohexane 108.7 8.2 8.2 0 0.1
almost solely due to van der Waal's forces.
Toluene 106.8 8.9 8.8 0.7 1.0
l,l,l-Trichloro-
Complex Cases. Where molecules are ap- ethane 100.4 8.6 8.3 2.1 1.0
preciably polar in nature and where intermolec- Methyl ethyl
ular hydrogen bonding is possible, 0 is no ketone 90.1 9.3 7.8 4.4 2.5
longer a simple number. In such a case, 0 is Acetone 74.0 9.8 7.6 5.1 3.4
actually the sum of three different bond energy 86 =(6d 2 + 6 p 2 + 6h2)1/2
 THERMOPLASTIC RUBBER IA-B-A BLOCK COPOLYMERS) IN ADHESIVES 269

discussion, one will realize that representing the 6. Meier, D. J., J. Poly Sci., Pan C, 26, 81-98 (1969).
solubility of thermoplastic rubber in solvents as 7. Morton, M., et aI., ibid, p. 99-115.
8. Beecher, J. F. et aI., ibid, p. 117-134.
a one-dimensional function of 0 is incorrect and
9. Bradford, E. B., and Vanzo, E., J. Poly Sci., Pan A-
somewhat misleading for solvents above ap- i, 6, 1661-1670 (1968).
proximately 9 hildebrands. 10. LeGrand, D. G., Polymer Letters, 8,195-198 (1970).
II. Folkes, M. J., and Keller, A., Polymer, 12,222-236
How to Handle Complex Cases. There is (1971).
12. Kaelble, D. H., Trans Soc. Rheology, 15, 235-258
currently no convenient way to handle accu-
(1971).
rately cases involving polar or hydrogen-bond- 13. Inoue, T., et aI., Macromolecules, 4, 500-507 (1971).
ing components. One-dimensional correlations 14. Lewis, P. R., and Price, C., Polymer, 13, 20-26
with 0 are largely misleading. Two-dimen- (1972).
sional correlations involving 0 and dipole mo- 15. Uchida, T., et aI., J. Poly Sci., Part A-i, 10, 101-
121 (1972).
ments or 0 and hydrogen bonding indexes have
16. Kampf, G., et aI., J. Macromol Sci-Phys., B6, 167-
been developed24- 26 and may be useful in lim- 190 (1972).
ited applications. Three-dimensional systems 17. "Raw Materials for Hot Melts," CA Report No. 55,
involving computer matching have been devel- Technical Assn. of the Pulp and Paper Industry, 1
oped,20 but data for real cases are meager. Dunwoody Park, Atlanta, Ga. 30341.
18. Hildebrand, J. H., "The Solubility of Nonelectro-
There is considerable interest, especially from
lytes, " New York, Van Nostrand Reinhold, 129, 424-
the paint industry in developing useful methods 439 (1950).
for handling solubility parameter, and it is pos- 19. Hansen, C. M., and Beerbower, A., in "Kirk-Othmer
sible that progress in the future may benefit the Encyclopedia of Chemical Technology," Supplemen-
thermoplastic rubber formulating field. tary Vol., 2nd Ed., Interscience Division of John
Wiley & Sons, 889-910, 1971 (includes tabulation).
Meanwhile, it is important that the formula-
20. Nelson, R. C., et aI., J. Paint Technology, 42, 636-
tor working with thermoplastic rubber be aware 652 (1970).
of compatibility concepts as he is preparing and 21. Burrell, H., Paper 44, ACS Div. of Org. Coat. and
testing formulations. It may be possible to use Plast. Chern., Washington D.C., Preprints, 367-375,
one, two, or three-dimensional correlations (Sept. 1971).
22. Gardon, J. L., "Encyclopedia of Polymer Science and
over limited regions, for example, when com-
Technology," Vol. 3, New York, Interscience Divi-
paring the relative performance of members of sion of John Wiley & Sons, 833-862, 1965 (includes
a homologous series in one type of thermoplas- tabulation) .
tic rubber. At the least, solubility parameter 23. "Shell Chart of Solvent Properties," Bulletin IC:71-
may serve as a semi-quantitative basis for plan- 18R, Shell Chemical Company, Houston, Texas
77001.
ning experiments and for interpreting results.
24. "Solubility Parameters-Synthetic Resins, Related
Materials, Solvents," Hercules Inc., Wilmington, Del.
REFERENCES 19899.
25. "Solubility Contours for Hydrocarbon Resins,"
I. Ceresa, R. J. (ed.), "Block and Graft Copolymeriza- Pennsylvania Industrial Chemical Corp., 120 State St.,
tion," Vol. 1, New York, John Wiley & Sons, 1973. Clairton, Pa. 15025.
2. U.S. Patent 3,239,478 (1966). 26. Hagman, J. F., "Solvent Systems for Neoprene-Pre-
3. Zelinski, R., and Childers, C. W., Rubber Chem. and dicting Solvent Strength," E. I. duPont deNemours
Tech., 41, 161 (1968). and Co., Wilmington, Del.
4. Marrs, O. L., and Edmonds, L. 0., Adhesives Age, 27. Hoy, K. L., J. Paint Technology, 42, 76-118 (1970)
15-20 (Dec. 1971). (includes tabulation).
5. Saunders, J. H., and Frisch, K. C., "Polyurethanes, 28. "Test Methods for Pressure Sensitive Tapes," 6th
Chemistry and Technology," New York, Interscience Ed., Pressure Sensitive Tape Council, 1201 Wauke-
Division of John Wiley & Sons, 1962. gan Rd., Glenview, Ill. 60025.
 14
Carboxylic Polymers in Adhesives
C. D. WEBER, L. A. Fox AND M. E. GROSS*
The B. F. Goodrich Adhesives Systems Division
Akron, Ohio

This chapter is based on the chapters which ap- and other hydrolyzing agents into carboxylic
peared in the two previous editions of this elastomers and were first described by Bacon
Handbook. I ,2 As stated in the second edition, and Farmer4 ,5.6 in 1938 and later by Compag-
it is our intent to cover the broad topic of car- non, Le Bras, and coworkers7 ,8,9 in 1941. An
boxylic copolymers as employed in, or useful anhydride rubber prepared from natural rubber
for adhesive applications. was used as an adhesive agent lO for bonding
Many theories have been proposed in an at- rubber to artificial silk in 1944.
tempt to explain how carboxylic functional A patent II issued in 1952 described the use
groups improve the adhesion of polymers to of copolymers of higher acrylate or methacry-
various substrates. These groups may act as late esters with acrylic acid or methacrylic acid
centers for chemical reactions to effect inter- in the preparation of improved pressure sensi-
and intrachain crosslinkages of the polymers as tive tapes and liners for adherent rubber sur-
well as linkage to the adherends. It seems prob- faces. The carboxyl content of these
able that acids or other electron accepting copolymers was so high that they could be con-
groups which enhance adhesion are involved in sidered to be plasticized polyacrylic acids rather
the transfer of electrons across the interface be- than carboxylic elastomers.
tween the polymer and the adherend. A recent The preparation of copolymers of butadiene
paper on the peel behavior of carboxylated pol- and of isoprene with methacrylic acid and with
ymers attributes the improved adhesion of a acrylic acid, described by Frank, Kraus, and
carboxylated polybutyl acrylate copolymer to Haefner l2 ,13 in 1952, for use in rubber to metal
glass to be caused by two effects: (1) an in- bonding, was probably the first preparation of
crease in the thermodynamic work of adhesion carboxylic elastomers made specifically for use
and (2) a change in the viscoelastic state of the as adhesives. They indicated that their consid-
adhesive material. 31 eration of carboxyl groups as a means for en-
hancing adhesion was stimulated by the
observations of Doolittle and PoweU I4 in 1944.
HISTORY
They found that low proportions of maleic an-
The first carboxylic elastomers were derived by hydride (0. 1-1 %) when copolymerized in co-
treating rubber and other unsaturated elasto- polymers of vinyl chloride with vinyl acetate,
mers with maleic anhydride. These anhydride improved the adhesion of such films to metal
rubbers were then easily converted by moisture surfaces. McLaren has described an increase in
adhesion with increasing carboxyl content of
*Retired vinylite copolymers to unmodified cellulose. 15

270
 CARBOXYLIC POLYMERS IN ADHESIVES 271

In 1966, a patent 16 was granted to Seibert (B. hydride in an extruder plasticator 19 has been
F. Goodrich) which covered the preparation of described. Elastomeric carboxylic groups have
carboxyl terminated liquid polymers. These been used20 ,21 to prepare carboxylic elasto-
polymers have been used in adhesives and mers. Adducts of fumaric and itaconic esters22
composites as toughening agents, mainly with to unsaturated polymers such as liquid poly-
epoxy resin based systems. butadiene and copolymers of butadiene subse-
quently hydrolyzed to carboxylic elastomers
have also been described as adhesives.
PREPARATION OF CARBOXYL Smarook and Bonott023 described the param-
FUNCTIONAL POLYMERS eters of carboxylic polyolefins made from eth-
ylene and acrylic acid by copolymerization.
Carboxylic polymers have been prepared prin- The ability to vary the carboxyl content on the
cipally by the copolymerization of olefins and polyethylene backbone provides resins which
diolefins with acrylic acid type monomers. have a wide spectrum of physical properties that
References and details concerning such prepa- have exceptional adhesion to various sub-
rations are available in the literature and have strates, both polar and nonpolar. The highly
been summarized in a review article by polar carboxyl groups in the polymer chain
Brown. 17 In the preparation of carboxylic elas- readily enter into covalent, ionic, and hydrogen
tomers, the types used in adhesives usually bonding which can impart various degrees of
contain between 0.1 and 25 % of the carboxylic adhesion and crosslinking with cellulosics,
comonomers. Factors influencing the adhesive metals, rubbers, and plastics. These polymers
properties of the carboxylic elastomers are are produced by the copolymerization of ethy-
method of polymerization, molecular weight, lenically unsaturated carboxylic acids with ole-
molecular weight distribution, distribution of fins.
the carboxyl groups in the polymer backbone,
carboxyl content, the degree of neutralization
or sequestering of the carboxyl groups, and the
nature of the elastomer backbone. 17 -CH2-CR-CH2-CH2-CH2-CR-CH2-
The adhesive characteristics of an elastomer I I
are recognizably altered by the inclusion of as O=C-OH HO-C=O
little as 0.01 equivalent of carboxyl per hundred
grams of rubber (ephr) although larger Examination of Table indicates that an in-
amounts, even in excess of 0.1 ephr, are often crease in the acrylic acid content reduces soft-
preferable. The optimum carboxyl content, ening point and modulus, which are normally
molecular weight, and the particular elasto- correlated with crystallinity. In addition, ten-
meric polymer selected for use as an adhesive sile strength and adhesion to metallic substrates
depend on the nature of the surfaces to be ad- are increased. Cernia24 reported similar data on
hered and the requirements of the adhesive the bulk polymerization of ethylene and acrylic
bond. acid which was accomplished at a temperature
Carboxylic elastomers have also been of -200°C and a pressure of 171.6 MPa. The
prepared 17 by the addition of a carboxyl~bear­ acrylic acid content of the copolymers ranged
ing molecule such as thioglycollic acid, maleic from 2. 1-16 %. When used as adhesives for
anhydride, or acrylic acid to rubber in solvent, bonding aluminum, the strength of straight pol-
on the mill, or in latex. The preparation of a yethylene was 0.003 N / cm as compared to
carboxylic polymer from a butadiene-acrylo- > 0.59 N / cm for l6% acrylic acid copolymer.
nitrile copolymer in an internal or Banbury Rieke and coauthors 25 describe in a series of
mixer has been mentioned in the adhesives papers the formulation and properties of grafted
patent 18 literature. The carboxylation of vul- polyethylene formed by means of irradiating
canized natural rubber and of butadiene-styrene polyethylene with a Van de Graaff accelerator
copolymers, including reclaimed stocks of and then treating the irradiated polyethylene
the~e elastomers, by treatment with maleic an- with acrylic acid in a solvent medium. The ad-
 272 HANDBOOK OF ADHESIVES

Table 1. Ethylene Acrylic Acid Copolymers. 23

Low
Density
PE Increasing AA Content
Acrylic acid, % wt 11 14 19
% moles 4.6 6 8.2
Melt index ASTM-DI238-52T,
Dg. Min-I 1.5 83 58 52
Secant modulus ASTM-D638-
58T, MPa 159 74 60 42
Tensile strength (Instron): MPa 10.3 15.5 19 29
Vicat softening ASTM-DI525-
58T,oC 90 71 63 54
DT A melting point, °C 107 99 98 95
Peel strength to aluminum,
N/cm width at cross-head rate
of 0.85 mmls < 1.75 98 142 175
'Rate, 0.S5 mm/s. 50S !Lm thick specimen.

hesivity to metals was reported to be markedly USE OF CARBOXYLIC ELASTOMERS

improved. In a patent Marans26 also claims a IN ADHESIVES
method of bonding wherein acrylic acid mon-
omer was applied to layers of polyethylene, The carboxylic elastomers may be employed as
polypropylene, polyesters, polyviny1chloride, adhesives in solution of suitable solvents, as la-
nylon, polymethylmethacrylate, or poly- texes, as aqueous solutions or dispersions in al-
(tetrafluoroethylene) and subsequently irradi- kaline or ammoniacal media when the carboxyl
ated. A review article by Ogata27 covers the in- content and molecular weight are suitably se-
crease in adhesive properties of polyethylene or lected. Powders and film products may also be
polypropylene by graft copolymerization of prepared using carboxylic elastomers.
acrylic acid to the polymer in the presence of For the preparation of adhesive cements the
electron beam radiation. solubility criteria for the carboxylic elastomers
Carboxyl-terminated liquid polymers (CTLP) can be predicted from those of analogous non-
can be prepared by using bis-cyanoacid initia- carboxylic elastomers. Literature36 . 37 on the
tors and solvents which have low chain transfer solubility and ease of solution of raw polar
to the monomers being polymerized. 16 The in- elastomers in various solvents, allowing for the
itiator starts the polymerization and in the ab- influence of the carboxyl level, suggests the
sence of transfer to solvent, terminates the solvents most suitable for given carboxylic
growing chain and yields a carboxyl terminated elastomers. As the carboxyl content increases
polymer. Carboxyl groups can also be placed in a given elastomer type, solubility in hydro-
along the chain by using unsaturated acids. carbon solvents decreases, and solubility in po-
Several other patents2S - 32 have been issued lar solvents increases. Milling procedures are
covering methods of manufacturing carboxy similar to those for analogous noncarboxylic
functional elastomers. elastomers, except that carboxyl groups tend to
Carboxylic functional polyols can be pre- make the milling somewhat more difficult.
pared by reacting hydroxyl terminated polyeth- When solid carboxylic elastomers are to be dis-
ers with unsaturated acids and a free radical persed in solvents, it is best to use methyl ethyl
initiator. 34 Also carboxylic groups can be added ketone, nitroparaffins, and chlorinated hydro-
to poly(ester/ethers) or other hydroxy termi- carbons for the nitrile types. For the carboxylic
nated polymers by reacting with dianhy- polyacrylates, acetone, methyl ethyl ketone,
drides. 35 methyl isobutyl ketone, and toluene are pre-
 CARBOXYLIC POLYMERS IN ADHESIVES 273

ferred. For carboxylic polybutadiene, or co- polymer cement applied to grit-blasted steel in-
polymers of butadiene, toluene, or methyl ethyl serts and vulcanized 30 min at 150 °C against
ketone are usually employed. the rubber stock, following ASTM D429-39
For some adhesive applications it is advan- procedures. Copolymers of acrylic acid and bu-
tageous to polymerize the carboxylic copoly- tadiene or isoprene were less effective as ad-
mers in a solvent medium. Such a procedure hesives. Methacrylic acid-isoprene copolymers
avoids emulsifiers and certain other additives were less effective than the analogous buta-
of emulsifier polymerization, as well as the ne- diene copolymers. A butadiene-methacrylic
cessity of milling. However, it has the disad- acid copolymer of 70 % conversion containing
vantage of yielding lower molecular weight 22-24% methacrylic acid, when used with cu-
copolymers. While a given carboxylic elasto- mene hydroperoxide accelerators, was reported
mer may approximate the requirements of many to give adhesion of rubber to steel having shear
applications and permit a rather wide variety of strengths of approximately 7.68 MPa.
uses, the maximum performance for a given In the bonding of rubber to metal with un-
pair of surfaces to be adhered is best achieved saturated carboxylic elastomers in the presence
by tailor making the polymer for the selected of vulcanizing or other agents not reactive with
application. Some degree of adaptation can be carboxyl groups, the bond to rubber is accom-
achieved by the incorporation of foreign poly- plished by crosslinkages dependent on the un-
mers and reagents such as resins, pigments, saturation, while the bond to the metal arises
elastomers, thickening agents, crosslinking from interaction of polar groups with the metal.
agents, and the like. This requires fairly simultaneous cures of the
Powder adhesives can be prepared by react- cement, the rubber stock and the metal-to-ce-
ing carboxylic elastomers with epoxy resins to ment interface. When curing agents for the car-
convert the system into a RT solid which can boxyl groups are also present, the several
be ground into a powder. Powders can be elec- vulcanizing mechanisms undoubtedly proceed
trostatically applied or coated using a fluidized simultaneously and are competitive.
bed. Films are prepared by solvent coating or Cements prepared from carboxylic buta-
by melt coating the carboxyl containing elas- diene-acrylonitrile copolymers blended with
tomer or compound onto a suitable carrier. phenolic resins,38 like the analogous cements
prepared with noncarboxylic butadiene-acryl-
onitrile copolymers, are adhesive agents for
CARBOXYLIC ELASTOMERS AS
steel to rubber. Employed without curative
METAL-TO-RUBBER ADHESIVES
agents, the carboxylic copolymers give better
From studies of copolymers of butadiene with steel-to-rubber adhesion than the analogous
methacrylic acid, Frank and coworkers 12,13 noncarboxylic copolymers. Confirmation of
concluded that, in order to achieve maximum this is cited in the patent literature. 39-41
adhesion of rubber to steel, the copolymer Jaeger and Korb41 described the use of added
should be of as high a molecular weight as pos- carboxyl nitrile rubber to modify a standard
sible and still remain soluble in the solvents of rubber-to-metal adhesive containing chlori-
application. It should also possess sufficient nated rubber and phenolic resin and thereby en-
diene groups for vulcanization to rubber, and a hance the rubber-to-metal bonding capability.
sufficient number of carboxyl groups to secure Cylinders of natural rubber were bonded by
high adhesion to steel. They concluded that the vulcanization for 25 min at 145°C and 70
optimum level of methacrylic acid was 15- kg / cm 2. The bond strength for the control ad-
24 %. Their data were based on the adhesion to hesive was 59 kg as compared to 74 kg for the
steel of a diphenyl guanidine accelerated natu- modified adhesive. This adhesive was also used
ral rubber compound containing 38 % zinc ox- successfully for bonding cis-polybutadiene
ide and having a 52 Shore A hardness. Fortheir rubber and nitrile rubbers to steel, aluminum,
tests, they used a single coat of unmodified, and brass adherends. The Dunlop Rubber
unformulated butadiene-methacrylic acid co- Company patene9 claims the use of a butadiene
274 HANDBOOK OF ADHESIVES

(37), styrene (36), acrylic acid (18), and meth- binder compounds during the spinning opera-
acrylic acid (9) copolymer as a metal primer for tion. SKD-5 (19: 1 butadiene-methacrylic acid)
rubber-to-metal bonding. copolymer was combined with FR-12 (resor-
A compounded SBR rubber sheet was sur- cinol-formaldehyde resin) to form the binder
face coated with a copolymer cement derived coatings. In related work on tire carcass cord
from butadiene (70), styrene (15), and cin- bonding, Dostyan and coauthors46 showed a
namic acid (15). The assembly was cured and computer assisted statistical analysis of the op-
tested to show peel strength of 210-263 N / cm timum amounts of modifier RU-l, methacrylic
at a 90° angle. Natural rubber was bonded to acid, and FR-12 (resorcinol-formaldehyde
aluminum and brass in a similar manner. The resin) in carboxylic latex SKD-l and latex
carboxylic copolymer cements generally show DSVP-15 containing vinyl pyridine functional
greater bond strength as well as a desired co- groups.
hesive failure within the rubber, whereas the The bonding of fibers of paper, fabric or sim-
analogous noncarboxylic copolymers show ilar materials by rubber latexes or cement may
failure at the steel surface. Thus carboxyl be enhanced by the inclusion of carboxyl
groups enhance the adhesion of the rubber to groups47 in the adhesive or binder copolymer
the metal surface and improve the cohesive molecules. For example, in the bonding of
strength of the bonding agent. Inclusion of car- semi-bleached kraft crepe paper with polyethyl
boxyl groups in the butadiene-acrylonitrile co- acrylate latex, the inclusion of 0.045 ephr of
polymers widens their range of compatibility carboxyl gave approximately a 50% further im-
with phenolic resins and increases the strength provement in internal bond strength. Similarly,
and hardness of the resultant adhesive. while a butadiene-acrylonitrile copolymer im-
proved the internal bond strength of semi-
CARBOXYLIC ELASTOMERS IN bleached kraft crepe paper, a latex of a co-
ADHESIVES FOR NONMETALLIC polymer having the same butadiene content but
ADHERENDS including 0.09 ephr of carboxyl, showed a 15 %
Dispersions of copolymers of butadiene with or more additional improvement in the internal
acrylic acid or methacrylic acid in aqueous po- bond strength. The beneficial action of the car-
tassium hydroxide have been mentioned in the boxyl group is probably due to improvement in
patent literature42 as a dip for adhering rayon copolymer adhesive penetration and subse-
tire cord to rubber. The effect is most evident quently greater hydrogen bonding with the pa-
when carboxyl groups are present in the adhe- per cellulose.
sive, the tie cement, and the cover stocks. The In cotton-cotton lamination, the use of car-
adhesive may be applied as latex, aqueous dis- boxylic elastomer latexes is reported48 to dou-
persion, or cement. A patent issued to the Dun- ble the bond strength and improve the solvent
lop Company Ltd. 43 describes the use of a resistance over that normally found with con-
styrene-butadiene-itaconic acid copolymer with ventional noncarboxyl latexes. A typical co-
Gen-Tac Latex (GenCorp) in formulating an polymer latex was based on isoprene (54-64),
RFL (resorcinol formaldehyde latex) type ad- acrylonitrile (35-45), and methacrylic acid (1-
hesive for bonding a natural rubber compound 3). A Dow Chemical Company patent49 claims
to Nylon 66 and rayon tire cords. Brodnyan44 the use of a film-forming carboxylic copolymer
also claims carboxylic adhesives for rayon, ny- latex, an epichlorohydrin-polyamide adduct,
lon, and Dacron cords. In this case, the tire with a calcium carbonate filler as an improved
cords were treated with a mixed polymer latex adhesive for bonding scrim to the back of tufted
containing resorcinol-formaldehyde conden- carpeting.
sate, a butadiene-vinyl pyridine copolymer, an
CARBOXYLIC ELASTOMERS AS
SBR copolymer, and a multifunctional copol-
METAL-TO-METAL ADHESIVES
ymer from methyl acrylate, 2-hydroxypropyl
methacrylate, and acrylic acid. A different ap- Carboxylic butadiene-acrylonitrile copolymers
proach was reported by Badenkov45 whereby have been employed in blends with selected
rayon or nylon tire cords were coated with phenolic resins as metal-to-metal adhesives. 50
 CARBOXYLIC POLYMERS IN ADHESIVES 275

Hycar 1072 CG rubber gives bonds similar to CARBOXYL REACTIVE LIQUID

the noncarboxylic polymers in both curing and ELASTOMERS IN STRUCTURAL
noncuring systems. In combination with epoxy ADHESIVES AND COMPOSITES
resins, Hycar 1072 imparts elongation, elastic-
During the past several years there has been ex-
ity, and resilience and has been used exten-
tensive use of carboxyl functional liquid nitrile
sively in bonding rigid adherends including
copolymers for toughening structural plastics,
~etals. Clougherty51 claims thermally stable,
adhesives, and composites such as those made
hIgh strength adhesives for bonding rigid brake
from crosslinked epoxy resins. The term tough-
linings to metal shoes by modifying a thermo-
ening is used to denote a marked increase in
setting phenolic resin with Hycar 1571 latex, a
impact resistance and an ability to absorb en-
carboxy I-containing butadiene-acrylonitrile
ergy without catastrophic fracture. This phe-
polymer. The use of maleic anhydride elasto-
nomenon of toughening occurs without
mer adducts in adhesives for metals has been
appreciable loss of mechanical properties such
mentioned 19 ,52 in the literature.
as is normally seen with flexibilized cross-
The inclusion of carboxyl groups in poly-
linked resins. As applied to structural adhe-
ethyl acrylate improves the adhesion to steel. 53
sives, it is observed that the area under the
This is shown graphically in Fig. 1, where in-
stress-strain curve is tremendously increased
creasing the carboxyl content from zero to
without significant loss of tensile strength or
about 0.2 ephr provides a corresponding in-
heat resistance. This feature has made this
crease in steel-steel lap shear strength from 0,69
technology of great interest to the adhesives in-
to 6.9 MPa. These values were obtained with
dustry.
uncompounded copolymers. Larger amounts of
Carboxyl reactive liquid polymers (CRLP)55
carboxyl and reinforcing resins can be used to
are chemically reactive with epoxy resins and
achieve even higher bond strengths.
capable of chain extension and crosslinking
Terpolymers of ethyl acrylate, acrylonitrile,
through the carboxyl groups. The reactions
and acrylic acid have been cited as thermoset-
most important in adhesive applications are
ting adhesives for aluminum. 54
those with epoxide groups and with aliphatic
A poly(ester/ether) blocked copolyme~5 was
hydroxyl groups. A list of several commer-
reacted with a dianhydride to yield a carbox-
cially available CRLP products is shown in Ta-
ylated thermoplastic having very high peel and
ble 2.
tensile strength when bonding to metal sub-
A weak amine catalyst will cause reaction (1)
strates. Furthermore these carboxylated ther-
to be predominant. 56 If a strong acid, i.e.,
moplastics were crosslinked with a diepoxide
p-toluenesulfonic acid, is used, reaction (2) will
to yield an adhesive for metal which had higher
be predominant. Therefore CRLP with termi-
temperature creep resistance.

o 0
;f STEEL to STEEL II / \ <a'
~ - -CRLP-C-OH + CH 2 -CH-R--
~
E
E
C\J

8 - -CRLP-C-O-CH,-CHOH-R- - (I)
>-
....a:::::E II -
.... o
....
~
1::.
z
o o
....u; II <a'
SI
<I: - -CRLP-C-OH + HOR' --->

- -CRLP-C-OR' + HP (2)
Fig. 1. Adhesion as a function of carboxyl content in car- II
boxylic polyethyl acrylates. o
276 HANDBOOK OF ADHESIVES

Table 2. Properties of Carboxyl Reactive Polymers. 55

Hycar Hycar Hycar Hycar Hycar
CTB (2()()() x CTBN CTBN CTBN CTBNX
162) (1300 x 15) (1300 x 8) (1300 x 13) (130 x 9)

Brookfield viscosity at
27°C, MPa's 35,000 50,000 125,000 625,000 135,000
Percent acrylonitrile 10 18 28 18
Color light amber amber amber amber
Molecular weight, Mn 4,000 3,600 3,400 3,400 3,400
Carboxyl functionality 2.01 1.90 1.85 1.80 2.4
EPHR carboxyl 0.045 0.051 0.055 0.055 0.077
Specific gravity at 251
25°C 0.097 0.948 0.955
Heat loss, 2 hr at
130°C, % 0.5 1.0 1.0 1.0 1.0
Tg (by DTA), °C -80 -59 -54

nal reactivity, when added to a difunctional with small rubber particles embedded in the
epoxy resin and a weak selective56 ,57 catalyst, glassy epoxy matrix. These types of materials
results in chain extension through epoxy car- appear to be toughened only at temperatures
boxylic reactions. It is necessary to carefully near 25°C. In adhesive applications and espe-
control this reaction to yield a prereact that is cially structural adhesives any improvement in
reproducible and suitable for a particular ad- toughness must be effective over the entire
hesive fonnulation. If reaction conditions are range of temperatures encountered in service.
not controlled, side reactions can result in Proprietary work by adhesive manufacturers
higher epoxide equivalent weights and partial has been concerned with toughening epoxy res-
crosslinking. This of course can yield different ins for use in structural adhesives. 6I ,62,63 Sev-
properties in the final adhesive. It is important eral products have been toughened with Hycar
that a particular system be studied to detennine 1300 x 8, 1300 x 9, 1300 x 13 and 2000 x
the correct CRLP and suitable reaction condi- 162. Several products also utilize a high mo-
tions. lecular weight carboxylated acrylonitrile-buta-
Crosslinking can then be accomplished by diene copolymer, i.e., Hycar 1072. 61 This
using a poly functional acid or epoxy resin or combination of high molecular weight and low
through the use of curatives such as aromatic molecular weight carboxyl functional polymers
and aliphatic amines, dicyandiamide, or Lewis yields a bimodal distribution of rubbery parti-
acids. Curing can take place at ambient tem- cles which appears to be necessary for devel-
perature to 177°C but the most highly tough- oping good properties across a broad
ened adhesives are generally cured at 120°C. temperature range.
There are now commercially available pre- Several sources have shown that toughness
reactions of CRLP and liquid epoxy resins 58 ,59 can be improved if a dihydric phenolic, i.e.,
which can be used to toughen adhesives. bisphenol A, is added to the epoxy resin and
The early work of McGarry and coworkers60 CRLP. 64 It is reported that this fonnulation
revealed that brittle epoxy resins could be yields a bimodal distribution of particles when
toughened by incorporating small amounts of cured with piperidine and utilizing 5 ~hr of Hy-
CRLP. The most effective polymers are copol- car CTBN (1300 x 8). This bimodal distribu-
ymers of acrylonitrile and butadiene (Hycar tion of rubber particles gives adhesives with
CTBN). The level of acrylonitrile can be varied higher fracture toughness and good peel prop-
from 0 to 28 %. Also additional acid groups can erties over a broad range of temperatures. Two
be inserted into the polymer chain. Analysis of patents65 have been issued covering work using
fractured surfaces reveal a two-phase system 1,5-naphthalenediol, bisphenol A, resorcinol
 CARBOXYLIC POLYMERS IN ADHESIVES 271

Table 3. Formulation and Properties of Structural Adhesive

Films Using Dihydric Phenolics.
A B C
Epoxy resin (i.e., Epon 828) 98 48 103.5
1,5-Naphthalenediol 12.4
Bisphenol A 18
2,2-bis(4-hydroxyphenyl)sulfone 18
HycarCTBNX 15 15 15
A-C reacted 1 hr at 130-160 °C,
then add dicyandiamide 8 8 8
2-ethyl-4-methylimidazole
121°C lap shear (MPa) 22.4 10 22.1
T-Peel at 25°C (N/cm) 42 44
Cured 1 hr at 121°C.

and 2,2-his(4-hydroxyphenyl)sulfone along PARTICULATE STRUCTURAL

with Hycar 1300 X 9 to produce tough epoxy ADHESIVES USING CARBOXYLATED
resin based structural adhesive films (Table 3). RUBBERS
Although most of the development work in
toughening of epoxy resins has made use of Reaction products of solid epoxy resins, e.g.,
some type of prereaction with carboxylic nitrile DER 664 (Dow), and Hycar carboxyl reactive
copolymer in the presence of a suitable cata- liquid polymers can be used to toughen solid
lyst, various techniques have been used to ac- epoxy resins for use in powder adhesives or
complish this. Generally the epoxy resin and coatings69 (see Table 4).
the CRLP are reacted with heat and agitation Particulate structural adhesives have also
to give whatever combination of reaction prod- been prepared by the combination of epoxy res-
ucts that are desired. This depends upon the ins and elastomeric carboxylated rubber, Hycar
type of epoxy resin, the type of CRLP, the cat- 1072. The epoxy resins are milled into the rub-
alysts and the reaction conditions. ber and then the curatives are added. The stock
Clark66 introduced a copolymer into epoxy is sheeted from the mill and ground into a pow-
resin in the form of a latex which was vacuum der. The adhesives can be applied by electro-
stripped and reacted. However, the surfactants static spraying, fluidized bed, or powder
are not easily removed and can cause the re- bed. 66 ,70
sultant product to be moisture sensitive.
The variation of the ratio of epoxy resin to
CRLP can give cured systems resembling either Table 4. Typical Formulation for
rubber toughened plastics or epoxy reinforced Particulate Structural Adhesive. 68
rubbers. By varying the epoxy resin to CRLP
Parts
ratio and by varying the type of qRLP and
epoxy resin one can prepare compositions Epoxy Resins
Epon 1002 (Shell) 89
which could bond a variety of substrates pro-
ECN 1280 (Ciba) (epoxidized cresol novo-
viding the proper curing agents and curing con- lac resin) 11
ditions are used. Hycar 1300 x 8 36
CRLP's have also been used to toughen Dicyandiamide 3.5
epoxy resins used in composite applications. Monuron (DuPont (3-p-chlorophenyl-l, I-di-
methyl urea) 2.25
This has not been as fruitful an area as tough-
ening of adhesives for a variety of reasons too T-Peel at 24°C, N/cm 42
complex to be discussed here. However, ex- 82°C lap shear, MPa 14.7
cellent publications covering composites and 121°C lap shear, MPa 5.2
composite properties are available. 67,68 Cured 1 hr at 120°C.
278 HANDBOOK OF ADHESIVES

CARBOXYLIC ELASTOMERS AS 25 r

PRESSURE-SENSITIVE ADHESIVES ~
~
The carboxylic polyacrylates are effective as 2Of-
~ ~ ~ V
V
laminating adhesives52 for both flexible and ~ ~ V
rigid surfaces. The particular carboxylic acry- 5f-
V ~ ~
late used for a given laminating application is ~ /
/ ~ /
detennined by the characteristics of the sur-
~
V ;:;
faces to be adhered, whether adhesive or co- r- ~
/ ~ ~ ~ V
/
hesive bond failure is desired, the bond strength ~ ~ /
~ V
required of the adhesive, and many other fac- 1/ ~ ~ 1/
5f-
V V
~ '/ '/
tors. These may include stiffness, friability, ex-
tensibility, clarity, cold flow, moisture
resistance, solvent or chemical resistance, heat
o r
COOH .ph, 0.11
~ r 1/
007 0.14
1/
,..V
0.14
~
0.21
~
0.11
~
0.14
r-
0.11
ALKYL CARBON I 2 4 6 8 8 10 13
and light insensitivity, radiation resistance, CONFIGURATION .. 2Bg~L .. 2H~mL ..
compatibility with resins and other polymeric
Fig. 2. Influence of carboxyl content on Mylar-to-alu-
materials or pigments, and vulcanizability. The minum bond strength of polyacrylate adhesives.
carboxylic polyacrylates may be varied to meet
the adhesive requirements of a specific appli-
strength enhancement using the corresponding
cation by:
carboxyl acrylates is most striking. The car-
1. Carboxylic content, boxyl contents of the copolymers are expressed
2. The acrylate or acrylates constituting the as equivalents per 100 grams of rubber (ephr).
polymer chain, The patent literature on carboxylic polyacry-
3. Molecular weight, late pressure-sensitive adhesives is extensive.
4. Molecular weight distribution, KOlpman71 describes the use of carboxylic bu-
5. State of crosslinkage, tadiene-acrylonitrile copolymer (Hycar 1072)
6. Degree of inter- and intrachain reactivity in conjunction with tackifying resins and a bu-
induced by the inclusion of other func- tylated melamine-fonnaldehyde curing resin as
tional groups in addition to carboxyl, a pressure-sensitive adhesive on a polyester film
7. Degree of solubility or dispersibility in backing. The composite sheet was useful as a
solvents of application, and pressure-sensitive adhesive after air drying and
8. Copolymerization or superimposed poly- curing for 1 min at 120°C, whereas, noncar-
merization. boxylic elastomers remained uncured after 1 hr
The influence of carboxylic groups on the at 120°C. A copolymer of 2-ethylhexyl acry-
laminating power of pennanently tacky adhe- late, methyl acrylate, glycidyl methacrylate,
sive copolymers used in non-load-bearing ap- and acrylic acid was reported by Knapp72 to be
plications is well illustrated by the perfonnance so pressure-sensitive that it would bond poly-
of polyacrylates53 in the lamination of Mylar ester film to a steel sheet and resist a shear
(duPont polyester) films to aluminum foils, loading of 1.8 N / cm2 at 60°C without creep-
each 1 mil thick. Noncarboxylic polyacrylate ing. One of the useful attributes of pressure-
polymers are weak laminating adhesives for sensitive adhesive tapes made with carboxylic
Mylar to aluminum bonding. The adhesion var- polyacrylates is that essentially no compound-
ies with the polyacrylate used. In a series of ing is required provided that proper balance of
comparable poly-n-alkyl acrylates, ranging creep, peel, shear, and tack properties are built
from polymethyl through polytridecyl acrylate, into the elastomer during its preparation. 53,73
applied from methyl ethyl ketone cements, the Another interesting way of altering the tack,
strongest bond (180° peel strength) between peel strength, and creep resistance of carboxyl
Mylar and aluminum was obtained with poly- functional pressure-sensitive adhesives is
ethyl acrylate. A value of 8.8 N / cm for a sep- through partial ionic bonding of carboxyl
aration rate of 5.1 mm / s was typical for non- groups with metal ions. 74 In general, modulus
carboxylic polyethyl acrylate (Fig. 2). The peel increases, tack and peel strength decrease, but
 CARBOXYLIC POLYMERS IN ADHESIVES 279

resistance to creep increases in relation to the by grafting small amounts of maleic anhydride
degree of ionic bonding. Such modified poly- on polyolefins. Incorporation of the polar mon-
mers exhibit some characteristics typical of omer improved adhesion to polar textiles, met-
crosslinking. A significant difference is that als, and plastic films. Thermal grafting of
ionic bonding, while effective at room temper- maleic anhydride or maleic acid to polypropyl-
ature, is greatly weakened at elevated temper- ene gives waxy adhesives useful for aluminum-
atures. This property permits easy processing paper laminates. 63 Although itaconic acid is
by the simple expedient of raising the operating considerably more expensive than the other
temperature. major carboxylic monomers, it has gained ac-
Some pressure-sensitive tapes including sur- ceptance as a comonomer in specialty applica-
gical tapes have been reported to contain car- tions. It is a more active monomer than maleic
boxylic acrylate copolymers. 75,76,77 A pressure or fumaric acids and can therefore be incorpo-
sensitive tape consisting of foil, polyester, rated into copolymers more readily. Copoly-
polyolefin, or acrylic adhesive layer and a car- mers of vinylidene chloride, acrylic
boxylated polymer-aminofunctional silane comonomers, and itaconic acid have consider-
primer layer has been patented. 78 The silane able commercial utility in packaging. The in-
alone is reported to interfere with adhesion of corporation of the acid provides strongly
the tape to the substrate; but excellent adhesion bonded heat seals that are resistant to boiling
is obtained if a carboxylated EVA copolymer water. When a 95: 5: 2 latex copolymer of vi-
is added to the primer. nylidene chloride, methyl acrylate, and ita-
conic acid was applied to cellophane film the
heat seal strength was 2.36 MPa as compared
ADHESION WITH NONELASTOMERIC,
to 0.91 MPa for a copolymer lacking the acid. 84
CARBOXYL FUNCTIONAL, OLEFIN
COPOLYMERS
CARBOXYLIC POLYMERS IN HOT-
It was reported by Doolittle and Powell 14 as
MELT ADHESIVES
long ago as 1944 that the adhesive qualities of
vinyl polymers were enhanced through the ad- Several publications have described the basic
dition of maleic anhydride. Since then much properties of carboxylic polyethylene copoly-
information has appeared on the adhesive na- mers including their adhesive characteris-
ture of carboxylated olefin copolymers. tics. 85 ,86,87 In general, increasing acrylic acid
Guthrie79 was issued a patent in 1971 which content results in increasing both tensile
claims that polar copolymers of olefins contain- strength and flexibility which are important
ing pendant carboxylic acid groups may be both for adhesion and bond retention under ag-
bonded to wood, metals, and other substrates. gressive environmental attack. 23 In flexible hot-
Sato and coauthors 8o found enhanced adhesive melt packaging applications, the use of ethyl-
qualities by using a grafted copolymer product ene-acrylic acid (EAA) copolymers provides
obtained by reacting an ethylene-vinyl acetate improved hot tack and reduced heat seal tem-
copolymer with a carboxylic acid, and in 1973, peratures. EAA copolymers achieve the con-
Steinkamp and coauthors 81 reported that mod- tact angle characteristics of hot melts and also
ified polyolefins with < 5 % acid functionality exhibit superior cohesive strength. Increasing
showed improved bonding to reinforcing inor- the carboxyl content does have some effect
ganic fibers such as asbestos, glass, and alu- upon water sensitivity. However, water ab-
minum. They also described a series of acidic sorption is relatively low even at a 20 % AA
olefin copolymers which bond tenaciously to content (0.08% wt increase after one week at
unprimed metals such as copper, lead, steel, RT).23 Tensile strength and elongation are not
and aluminum as well as glass and some ther- significantly changed. It has been observed that
moplastics. Their physical, chemical, and ad- the bond strength shows a greater decrease after
hesive properties suggest use in wire and cable moisture exposure when bonding to metal ad-
coverings. herends rather than to nonpolar types such as
Waxy adhesive products have been prepared low density polyethylene. In general, the best
280 HANDBOOK OF ADHESIVES

polymer for adhesion of composite structures nyl chloride and vinyl acetate substantially im-
may be obtained by balancing polymer perfor- proves their adhesion. The typical range of
mance in relation to water sensitivity and the compositions of commercial products, such as
substrate to be used. Metal substrates are best Vinylite VMCH is 85-88 : 11: 1-3 vinyl chlo-
bonded with the medium range (15% AA) car- ride-vinyl acetate-maleic anhydride. Applica-
boxyl polymers while nonpolar materials tions for these terpolymers include heat sealing
should be bonded with low AA (3 %) polymers. of packaging films and vinyl plastisols with im-
Hot-melt adhesives for packaging applica- proved adhesion to substrates. \01-103
tions have been formulated using carboxyl pol- Vinyl dispersion resins have typically con-
ymers in combination with many other sisted of inert homopolymer or copolymers of
materials. A discussion of the properties of eth- vinyl chloride and vinyl acetate, and although
ylene-ethyl acrylate (EEA) copolymers as raw the inertness has been of importance for a mul-
materials for heat sealing and thermoplastic ad- titude of applications, there are occasions when
hesives was presented by Kirckner in 1969. 88 reactive functionality is an aid. An example of
The patent literature is replete with claims con- such a reactive vinyl resin is Geon 137, a car-
cerning the formulation, use, and properties of boxyl modified dispersion resin with a carboxyl
hot-melt adhesives containing a variety of car- content equivalent to 1.79% on a resin weight
boxyl copolymers. 89- 92 Guiman93 reported that basis or an acid equivalent weight of about
thermoadhesive films have been made by the 2500. 104 One adhesive application of consid-
radiochemical grafting of high density polyeth- erable interest is in the production of flocked
ylene with acrylic acid. Two additional product, notably wall and floor coverings. A
patents94 ,95 described the coextrusion of nylon, 50% replacement of standard copolymer dis-
carboxyl olefin, and polyethylene to produce a persion resin with carboxyl functional resin
self-supporting multilayer film having a nomi- doubles the force required to pluck fibers loose.
nal thickness of only 1 mil. These laminates Test results of laminating carboxylic vinyl
which are useful in packaging, have high plastisol with nylon fabric have shown a three-
strength, toughness, and clarity, excellent seal- fold increase in adhesion. I04 Such plastisols
ability, and firm bonding between the layers. also show improved adhesion to glass and
The development of high strength thermo- polyester fabrics. \05
plastic adhesive copolymers of the EAA type Strong durable bonds can be formed between
containing reactive carboxyl groups has made metals and vinyl chloride polymers by using a
it practical to bond insulation such as polyeth- polymeric adhesive which contains carboxyl
ylene to metal conductors to provide adequate groups and a phenol formaldehyde resin.l06
bonding and long term environmental resis- Plasticized PVC and vinyl chloride-vinyl
tance. Frequently, the EAA copolymer is ex- acetate copolymers can be wiped with solutions
truded around the cable. Peacock90 reports that of adipic, maleic, citric, and other acids, giv-
when a layer of acrylic acid-ethylene copoly- ing improved adhesion when bonding with hot-
mer (7 :43) was extruded at 140°C over a flex- melt polyester adhesives. 28
ible aluminum conductor followed by a layer
of polyethylene insulation, the bond strength CARBOXYLIC FUNCTIONAL
between the insulation and the conductor was NEOPRENES AS CONTACT
72 N/cm compared with 1.4 N/cm for a control ADHESIVES
assembly without the copolymer adhesive.
There are numerous similar patent claims for Smith77 has described in detail the practical ad-
insulated conductor cable. 97 ,loo vantages of carboxyl functional Neoprenes AF
and AJ for making improved contact adhe-
sives. The early room temperature bond
CARBOXYL FUNCTIONAL VINYL
strength of conventional neoprene contact ad-
COPOLYMER RESINS IN ADHESIVE
hesive is dependent on the crystallization rate
APPLICATIONS
of the polymer. Single component adhesive
The incorporation of small amounts of maleic systems based on carboxyl functionality
anhydride or maleic acid into copolymers of vi- undergo crosslinking reactions with divalent
 CARBOXYLIC POLYMERS IN ADHESIVES 281

metal oxides such as magnesium oxide. The 8. Compagnon, P., and Delalonde, A., Rev. Gen.
crosslinks fonned in this manner have the re- Caoutchouc, 20, 133-5 (1943).
9. Compagnon, P., and LeBras, 1. N. L., U.S. Patent
versible character typical of ionic bonds, and
2,388,905 (to Alien Property Custodian) (1945).
the reversibility is used to inhibit gelation in 10. Kambara, S., Mizushima, H., and Saito, K. 1., Soc.
solution. The early hot bond strength of a Neo- Chern. Ind. Japan 45, 141-3 (1944); CA., 43, 1595
preneAF based adhesive is considerably higher (1949).
than that of an adhesive based on the noncar- 11. Hendricks, 1. 0., U.S. Patent 2,607,711 (to Min-
nesota Mining and Manufacturing Company) (1952).
boxylic Neoprene AC when rubbers have a
12. Frank, C. E., Kraus, G., and Haefner, A. 1., Ind.
comparable Mooney viscosity. 77 The effect of Eng. Chern., 44,1600-1603 (1952);J. Polymer Sci.,
the carboxyl groups in Neoprene AF is also 10,441 (1953).
quite pronounced at room temperature. Bond 13. Frank, C. E., and Kraus, G., U.S. Patent 2,692,841
strength development is rapid in an AF adhe- (to General Motors Corp.) (1954).
14. Doolittle, A. K., and Powell, G. M., Paint, Oi/,
sive as compared to an AC adhesive even when
Chern. Rev., 107(7),9-11,40-2 (1944).
the bond is assembled wet. 15. McLaren, A. D., "Adhesion and Adhesion," pp.
Carboxylated Neoprene latices 107 have been 57-9, New York, lohn Wiley and Sons, 1954.
reported to have good contact adhesive prop- 16. Seibert, A. R., U.S. Patent 3,285,949 (to The
erties without the problem generally related to BFGoodrich Company) (1966).
17. Brown, H. P., Rubber Chern. Technol., 30, 1347-
the use of solvents.
1399 (1957).
18. Fischer, W. K., U.S. Patent 2,710,821 (to United
MISCELLANEOUS USES OF States Rubber Company) (1955).
CARBOXYLATED ELASTOMERS 19. Green, 1. and Sverdrup, E. F., Ind. Eng. Chern., 48,
2138, (1956).
Several patents lOS- 1I2 have been issued cover- 20. Brown, H. P., and Gibbs, C. F., Ind. Eng. Chern.,
ing various uses of carboxylic functional elas- 47, 1006-1012 (1955).
tomers and the resultant improvement in 21. Brown, H. P., U.S. Patent 2,671,074 (to The
BFGoodrich Company) (1954); U.S. Patent
adhesion of a variety of substrates when car-
2,710,292 (to The BFGoodrich Company) (1955).
boxyl groups are added to the polymer chain. 22. Dazzi, 1., U.S. Patents 2,782,228 and 2,782,229 (to
A patent issued in 1976 113 also shows that Monsanto Chemical Company) (1957).
polyfunctional carboxylic aziridinylester can be 23. Smarook, W. H., and Bonotto, S., Polyrn. Eng. Sci.,
incorporated into vinyl resins to give improved 8(1),41-9 (1968).
24. Cemia, E., Nuova Chirn., 48(4), 31-6 (1972).
adhesion to metals and glass without using
25. Rieke, 1. K. (Dow Chemical Company), U.S. Atomic
primers and other adhesion promoters. Energy Commission, TID-7643, 398-413 (1962);
Rieke, 1. K., and Hart, G. M., J. Polyrn. Sci.,
REFERENCES Pt.C.,(1), 117-33 (1963); Rieke, 1. K., Hart, G. M.,
and Saunders, F. L., J. Polyrner Sci., Pt.C.,(4), 589-
1. Brown, H. P., and Anderson, 1. F., "Carboxylic 604 (1964).
Elastomers as Adhesives," in "Handbook of Adhe- 26. Marans, Nelson S., U.S. Patent 3,424,638 (to W. R.
sives", 1st Ed., I. Skeist (ed.), Chapter 19, New Grace and Company) (1969).
York, Van Nostrand Reinhold Co., 1962. 27. Ogato, Y., Secchaka, 11(3), 177-81 (1967).
2. Gross, M. E., and Weber, C. D., "Carboxylic Pol- 28. Ackerman, 1. I., U.S. Patent 3,532,533 (to USM
ymers in Adhesives," in "Handbook of Adhe- Corporation) (1970).
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Behavior of Carboxylic Elastomers," Journal of Aline, 1. A., U.S. Patent 3,976,723 (to Rohm and
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4. Bacon, R. G. R., and Farmer, E. H., Rubber Chern. 31. Ohtsuki, A., et aI., U.S. Patent 4,358,493 (to Toyo
Technol., 12, 200-209 (1939). Ink Manufacturing Company Ltd.) (1982).
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C. R., and Errington, K. D., Rubber Technol. Conf., Wyandotte Corporation) (1984).
London Reprint No. 56, May, 1938; CA. 32, 8201 33. Fitko, C. W., U.S. Patent 4,478,667 (to the Conti-
(1938). nental Group, Inc.) (1984).
6. Farmer, E. H., Rubber Chern. Techno!., 15, 765 34. Frentzel, R. L., U.S. Patent 4,521,615 (to Olin Cor-
(1942). poration) (1985).
7. Compagnon, P., and LeBras, 1., Cornpt. Rend., 212, 35. Schure, R. M., et aI., U.S. Patent 4,093,675 (to Un-
616 (1941); Rev. Gen. Caoutchouc, 18, 89 (1941). itech Chemical Inc.) (1978).
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36. Sarbach, D. V., and Garvey, B. S., India Rubber Kucherenko Central Scientific Institute of Building
World, 115, 798-801 (1947); Rubber Chern. Tech- Structures) (1966).
nol., 20, 990-7 (1947). 64. Riew, C. K., Rowe, E. H., and Siebert, A. R., pre-
37. Marsden, C., "Solvents and Allied Substances Man- sented at American Chemical Society meeting, At-
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38. BFGoodrich bulletins. 65. Klapprott, D. K., and Paradis, D., U.S. Patents
39. Brit. Patent 1,055,928 (to Dunlop Rubber Company 3,678,130 and 3,678,131 (to The Dexter Corpora-
Ltd.) (1967). tion) (1972).
40. Bums, E. A., Lubowitz, H. R., and Dubrow, B., 66. Clarke, J. A., South African Patent 67 00,722 and
French Patent 1,534,452 (to TRW Inc.) (1968). British Patent 1,103,676 (to Dow Chemical Com-
41. Jaeger, F., and Korb, A., French Patent 1,511,882 pany) (1968).
(to Metallgesellschaft A.G.) (1968). 69. McKown, A. G., U.S. Patent 3,655,818 (to Min-
42. Reynolds, W. B., U.S. Patent 2,774,703 (to Phillips nesota Mining and Manufacturing Company) (1972).
Petroleum Company) (1956). 70. Taylor, C. G., German Patent 2,253,153 (to Dow
43. Osborne, A. P., German Patent 1,920,917 (to Dun- Chemical Company) (1973).
lop Company, Ltd.) (1969). 71. Korpman, R., U.S. Patent 3,345,206 (to Johnson and
44. Brodnyan, J. G., U.S. Patent 3,516,897 (to Rohm Johnson) (1967).
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45. Badenkov, P. F., Safonova, M. M., and Uzina, R. Chemical Company), 1966.
V., Kauch. Rezina, 27(1), 18-70 (1968). 73. Ulrich, E. W., U.S. Patent 2,884,126 (to Minnesota
46. Dostyan, M. S., Uzina, R. V., Shvarts, A. G., Tu- Mining and Manufacturing Company) (April 28,
manova, A. I., Frolikova, V. G., and Esaulova, A. 1959).
V., Kauch. Rezina, 29(2), 29-31 (1970). 74. Satas, D., and Mihalik, R., J.A.P.S., 12(10),2371-
47. BFGoodrich Chemical Company data. 9 (1966).
48. Mason, C. P., Canadian Patent 791,792 (to Polymer 75. Doehnert, D. E., German Patent 1,961,615 (to John-
Corp. Ltd.) (1968). son and Johnson) (1970).
49. Strasser, J. P., and Dunn, E. R., U.S. Patent 76. Netherlands Application 6,408,888 (to Johnson and
3,338,858 (to Dow Chemical Company) (1967). Johnson) (1965).
50. "Hycar Nitrile Rubber in Adhesives," Manual HM- 77. Smith, J. F., Adhesives Age, 21-4 (Dec. 1970).
12, BFGoodrich Chemical Company. 78. Puskadi, F., U.S. Patent 4,196,254 (to Johnson and
51. Clougherty, L. B., Kerarnedjian, J., and Nickrand, Johnson) (1980).
J., U.S. Patent 3,326,825 (to Chrysler Corporation) 79. Guthrie, J. L., U.S. Patent 3,620,878 (to W. R.
(1967). Grace and Company) (1971).
52. Jarrijon, A., and Louia, P., Rev. Gen. Caoutchouc, 80. Sato, K., Niki, A., and Kitamura, H., U.S. Patent
22, 3 (1945). 3,760,031 (to Asahi Kasei Kogyo KK) (1973).
53. Brown, H. P., and Anderson, J. F., "Adhesive 81. Steinkamp, R. A., Bartz, K. W., Christiansen, A.
Properties of Carboxylic Rubbers," unpublished pa- W., and VanBrederode, R. A., U.S. Dept. of the
per presented at Gordon Research Conference on Ad- Army, Army Electronic Comm. 22nd Wire and Ca-
hesives, Aug. 1958. ble Symposium (1973); Steinkamp, R. A., Bartz, K.
54. Milne, J. N., and Crick, R. G. D., U.S. Patent W., and VanBrederode, R. A., SPE Journal, 29(6),
2,759,910 (to The Distillers Company, Ltd., Edin- 34-7 (1973); SPE Technical Papers, 19, 110-14
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55. Technical Literature on Hycar Carboxyl Reactive 82. Luskin, L. S., "Acidic Monomers," in "Functional
Liquid Polymers, The BFGoodrich Chemical Co. Monomers," R. H. Yocum and E. B. Nyquist (eds.),
56. Shecter, L., and Wynstra, J., Ind. Eng. Chern., 48, New York, Marcel Dekker, 1973. .
86-93 (1956). 83. Brunson, M. D., U.S. Patent 2,570,478 (to Du-
57. Son, P. N., and Weber, C. D., J.A.P.S., 17,2415- Pont); 3,481,910 (to Eastman Kodak) (1969).
26 (1973).
84. Pitzl, G., U.S. Patent 2,570,478 (to DuPont) (1951).
58. Product Literature, Spencer Kellogg.
85. Clock, G. E., Klumb, G. A., and Mildner, R. C.,
59. Product Literature, Wilmington Chemical.
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63. Frieden, A. S., et aI., U.S.S.R. 183,311 (to V. A. Corporation) (1973).
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91. Kehe, A. W., U.S. Patent 3,485,783 (to Continental 102. Belgian Patent 640,999 (to Solvay and Cie) (1964).
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92. Hoh, G. L. K., British Patent 1,199,696 (to DuPont) 104. Ward, D. W., SPE Journal, 28, 44-50 (1972).
(1970). 105. Russell, J. R., and Ward, D. W., Coated Fabrics
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 15
Neoprene (Polychloroprene)-Based
Solvent and Latex Adhesives
SANDRA K. GUGGENBERGER
E. l. du Pont de Nemours & Co., Inc.
Polymer Products Department
Wilmington, Delaware

Neoprene, or polychloroprene, was the first tions, monovinylacetylene could be readily

synthetic elastomer used by the adhesives in- prepared, with divinylacetylene present only as
dustry, and is one of the most versatile mate- an impurity. They also discovered that mon-
rials ever developed as a backbone for ovinylacetylene could be reacted with hydro-
elastomeric adhesives. Neoprene combines chloric acid to form chloroprene, 2-chloro-l ,3-
rapid bond strength development with good butadiene, which formed a rubberlike polymer
tack or auto-adhesion, and resistance to deg- upon polymerization.
radation by oils, chemicals, water, heat, sun- The first public announcement of this poly-
light, and ozone. It is popular in numerous mer was made in 1931; commercialization be-
areas such as shoe sole attachment, furniture gan in April 1932. At first known as
construction, automobile assembly, and a va- "DuPrene, " the polymer was designated
riety of construction applications. "Neoprene" by DuPont in 1936.
The domestic consumption of Neoprene in Prior to the second World War, natural rub-
adhesive applications will be approximately 30 ber was the only elastomer widely used in ad-
million dry pounds in 1990. From one-quarter hesives. It was used for such applications as
to one-third of this amount will be in latex tire building, adhering of sponge weatherstrips
form. to automobile doors, and the temporary attach-
ment of shoe soles. However, rubber cements
were limited by their low cohesive strength and
HISTORY poor aging of the uncured film.
Neoprene was the first synthetic elastomer de- Following its development in 1931, DuPont
veloped which had many of the properties of Neoprene was slow in displacing natural rubber
natural rubber. Its development began when Dr. in the adhesive industry for the following rea-
Nieuwland of Notre Dame synthesized divinyl sons:
acetylene from acetylene using CuCI as a cat- 1. It was high in price, selling for two or
alyst. DuPont scientists, learning of his re- three times the price of natural rubber.
search, joined Dr. Nieuwland in pursuing the 2. It had to be dissolved in aromatic sol-
possibility of producing a synthetic elastomer vents, which were several times as costly
from acetylene chemistry. In the late 1920s, as the petroleum naphtha used to dissolve
they found that by varying the reaction condi- natural rubber.

284
 NEOPRENE IPOLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 285

3. It was necessary to use about five times G types, but cures considerably more slowly at
as much Neoprene as natural rubber to room temperature.
obtain equivalent viscosities. Neoprene type AD, developed in 1958, is
considerably more stable than AC. It does not
The situation did not change until 1942, soon change color appreciably when in contact with
after the start of World War II. At that time, a iron, and solutions maintain stable viscosities
critical shortage of natural rubber developed over longer time periods. Neoprene AC and AD
because it was allocated chiefly for the war ef- are now considered the general purpose types
fort. Neoprene was chosen as a replacement for for solvent-based adhesives. They will be dis-
natural rubber in adhesives because it was the cussed in more detail, along with other Neo-
only other synthetic rubber available. Animal prene solvent types and latexes commonly used
glue and other water-soluble materials avail- in adhesives, in the following sections.
able at the time were unsatisfactory because of Neoprene was manufactured via the acety-
their slow drying rates, poor adhesion to many lene route for many years. However, the tech-
surfaces, inflexible films, and rusting of met- nology is difficult and the starting material,
als. The two Neoprene polymers available at acetylene, gradually increased in price over the
the time were Neoprene GN, a general purpose years. By 1960 a second, less expensive method
type, and Neoprene CG, a fast-crystallizing
of chloroprene production had been developed
type. Both are copolymers of chloroprene and and commercialized. The second, preferred
sulfur which contain a thiuram disulfide modi- method involves the production of chloroprene
fier. from butadiene via a chlorination step.
One of the first applications in which Neo-
prene proved satisfactory was in the shoe in-
THE EFFECT OF POLYMER
dustry, for both temporary and permanent sole
STRUCTURE
attachment. However, early Neoprene cements
were plagued by two problems: a decrease in Neoprene is produced from the chloroprene
viscosity on aging and a black discoloration monomer, 2-chloro-l ,3-butadiene, in an emul-
during storage in steel drums. sion process. During polymerization, the mon-
The discoloration was found to be caused by omer can add in a number of ways as shown in
trace amounts of hydrochloric acid which form Table 1. The proportion of each configuration
when Neoprene oxidizes on aging. This acid determines the amount of crystallinity in the
reacts with iron to form ferric chloride, which polymer and its reactivity.
in tum reacts with the thiuram disulfide modi- The trans-l,4 addition is the most common.
fier to form a black iron sulfide compound. Very high percentages of this structure give
Acid acceptors such as magnesia and zinc ox- high crystallinity and rapid bond strength de-
ide were found to be effective in preventing this velopment in contact adhesives. Neoprene AC
discoloration. However, their addition tended and AD, both fast crystallizing grades, contain
to decrease the viscosity stability of adhesive about 90% trans-l,4 structures; whereas Neo-
cements even further. prene W, a slow-crystallizing type, contains
The stability of Neoprene cements contain- only 85 % trans-l,4. The other three types of
ing metal oxides could be increased with about monomer addition shown decrease bond
10 parts of hydrated calcium silicate, (e.g., Sil- strength development and lengthen open time
ene EF, PPG Industries) or terpene phenolic by disrupting polymer crystallinity. In addi-
resin (e.g., Durez 12603, Occidental Chemical tion, the 1,2 structure provides active sites for
Co.). The presence of the former increased the polymer vulcanization.
cohesive strength of Neoprene about threefold, The ability of Neoprene adhesives to crystal-
while the latter lowered its cohesive strength at lize sets them apart from other elastomeric
elevated temperatures. binders. As a result of crystallization, their co-
Neoprene type AC, developed in 1947, has hesive film strength is much greater than that
somewhat better viscosity stability and resis- of amorphous polymers. Crystallization is a re-
tance to discoloration than the sulfur-modified versible phenomenon, and at temperatures over
286 HANDBOOK OF ADHESIVES

Table 1. Molecular Structure of ~r-----------------------------,

NeopreneAF

Neoprene.
50
Chloroprene Monomer
Cl
I
CH 2 C - CH = CH 2

Type of Addition Formula

Nitrile

trans-l,4 -CH H
2 ..... C = C"
Cl" ..... C H - Natural Rubber
2
- - : - - - - - : - - - - - : - - - - - : - - SBR

cis-l,4 -CH CH-

2 .... C C" 2 Bond Age, Days

Cl" -- H Fig. 1. Canvas/canvas bond strength development: neo-

prene vs. other elastomers.
1,2 Cl
I
-CH2 - C- ferred to as sol polymers, while those with con-
I siderable branching are referred to as gel
CH
II polymers. All of the solvent grade polymers,
CH 2 with the exception of Neoprene AG, are sol
polymers. They are highly linear and soluble in
3,4 -CH - CH2' aromatic solvents. The Neoprene latexes, on
I the other hand, vary widely in the percentage
C - Cl
1/
of polymer gel. As shown in Fig. 3, properties
CH 2 which are affected by the amount of gel in the
polymer include cohesive strength, resilience,
resistance to permanent set, elongation, open
tack time and oil swell. Thus, particularly in
52°C (126°F) uncured adhesives lose their high latex systems, varying the gel content of the
cohesive strength. Upon cooling, the film re- system through polymer choice offers another
crystallizes and cohesive strength is regained. means of adjusting adhesive properties.
A comparison of Neoprene AD, a fast-crystal-
lizing type, and Neoprene AF, a reactive poly-
mer, with several other elastomers is shown in
Fig. 1. In addition to high film strength, crys-
tallization is responsible for the quick grab for
which Neoprene adhesives are noted. This rapid
bond strength development allows the forma-
tion of immediate dry bonds without the need
for further clamping, pressing, or airing. Since
Neoprene polymers are produced which crys-
tallize at various rates, the adhesive compoun-
der can use polymer blends to get the balance
of properties he requires. The effect of crystal- Elongation
linity on polymer properties is summarized in Hardness OilSweJl
Extensibility
Fig. 2. Resistance to Permanent
Set
The Neoprene polymers also vary in the
amount of branching present in the polymer. Crystallinity - - - - -

Those which have little or no branching are re- Fig. 2. Effect of crystallinity on polymer properties.
 NEOPRENE (POLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 287

pounding ingredients, particularly resins, are

used to achieve good specific adhesion to many
porous and nonporous substrates. The com-
pounding versatility associated with Neoprene
adhesives allows the formulation of one-part
contact cements, two-part curable adhesives,
pressure-sensitive adhesives, and mastics and
caulks.

Types of Neoprene
Resilience
Resistance to Permanent Set
The principal types of Neoprene used in sol-
vent adhesives are summarized in Table 3,
along with their physical properties. Neoprene
Sol Increasing Gel Content - - - - - _ Cured AC and AD are considered the general purpose
Crosslink Density - - - -_ _
adhesive types. Because they crystallize rap-
Fig. 3. Effect of sol, gel, and curing on polymer prop- idly, both give quick grab and high uncured
erties. strength. When properly formulated, they also
give good application properties and resistance
to heat and phasing. Most adhesive manufac-
NEOPRENE SOLVENT-BASED turers prefer Neoprene AD over Neoprene AC
ADHESIVE CEMENTS because it offers superior viscosity stability in
both raw polymer and adhesive form.
Neoprene provides a versatile elastomeric base The fast crystallizing types are widely used
in the fomlUlation of solvent based adhesives. in shoe sole attachment, adhering decorative
Properly compounded adhesives are resistant to high pressure laminates and automotive trim
degradation from exposure to heat, sunlight, and in many other industrial applications. A
ozone, water, oils, and chemicals. Neoprene general purpose adhesive formulation is pre-
can be dissolved in many solvent blends to give sented in Table 2.
adhesive solutions which are stable for ex- Neoprene AD-G is a Neoprene AD variant
tended periods of time. Solvent selection, designed especially for use in grafting appli-
therefore, allows a great deal of variation in ad- cations, although it is suitable for use in stan-
hesive viscosity and drying rate. Other com- dard contact bond formulations as well. In the

Table 2. Neoprene Contact Bond Adhesive.

General Formulation Parts Typical Formulation Parts
Neoprene 100 Mill Mix
Magnesium oxide 4-8 Neoprene AD 100
Zinc oxide 5 Magnesium oxide 8
Antioxidant 2 Zinc oxide 5
Resins as required Antioxidant 2
Solvents as required

Chum Mix
Milled stock 115
t-Butyl phenolic resin 45
Water 1
ToluenelHexanel Acetone 640
(2/4/4 by volume)
 288 HANDBOOK OF ADHESIVES

Table 3. Properties of DuPont Neoprene Types Used in Solvent Adhesives.

MLI + 4 5% Solids
Type of Specific Rilte of at l()()OC in toluene.
Neoprene Characteristics Gravity Crystallization Grade (212°F) cps
AC General purpose elastomer with fast bond 1.23 Very fast Soft * 31-45
strength development, good stability and co- Medium * 46-63
hesive strength. Hard * 64-100
AD General purpose elastomer with fast bond 1.23 Very fast AD 10 * 25-34
strength development and good cohesive AD20 * 35-53
strength. Provides better viscosity stability AD30 * 54-75
than Neoprene AC. AD40 * 76-115
AD-G Similar to Neoprene AD but gives smoother, 1.23 Very fast * 28-46
less stringy solutions and longer pot-life in
isocyanate cured systems.
AF Very slow-crystallizing, room-temperature- 1.23 Very slow * 145-275"
curing elastomer. Bond strength develop-
ment and hot strength are superior to Neo-
prel!e AC and AD.
AG High gel elastomer which gives thixotropic so- 1.23 Does not >80 *
lutions with good application properties crystallize
even at high solids content.
AU Acrylic copolymer of chloroprene which forms 1.23 Does not * < 175b
colloidal dispersions in hydrocarbon sol- crystallize
vents. Good application properties at high
solids.
FB High viscosity, fluid elastomer. 1.23 Slow * 500,000-
1,300,000"
GN Sulfur-modified elastomer with low cohesive 1.23 Slow 44-65 *
strength and fast cure rate at room tempera-
ture.
GNA Similar to Neoprene GN but contains a stain- 1.23 Slow 41-61 *
ing antioxidant.
GRT Similar to Neoprene GN but with a very slow 1.23 Very slow 36-55 *
crystallization rate.
W General purpose elastomer with good tack. 1.23 Slow 42-51 *
Lower cohesive strength than Neoprene AC
orAD.
WHV Similar to Neoprene W. 1.23 Slow WHV-
90-105
100
106-125 *
WHY *
WHV-A Similar to Neoprene WHY but designed specif- 1.23 Slow * 52-85
ically for adhesives. Gives better resistance
to phasing and more reproducible solution
viscosity.

WRT Similar to Neoprene W but with very slow rate 1.25 Very slow 41-51 *
of crystallization.
·Not sold to this specification.
'Viscosity at 20% solids in a milled adhesive formulation.
"Viscosity at 40% solids in a dispersion.
'Viscosity of ftuid polymer at 50°C (122 OF).
 NEOPRENE (POLYCHLOROPRENEI-BASED SOLVENT AND LATEX ADHESIVES 2B9

shoe industry, Neoprene AD-G is generally rate is very slow and plays no significant role
grafted with methyl methacrylate using a com- in cohesive strength development.
pound and procedure similar to that shown in In compounding Neoprene AF adhesives the
Table 4. The resulting graft polymer has very polymer interaction with metal oxides must be
good adhesion to plasticized PVC, EVA considered. Variables which are important in-
sponge, thermoplastic rubber, and other diffi- clude resin type, solvent system, water con-
cult-to-bond substrates. Further information on tent, polymer heat history and the order of
the graft procedure can be found in Ref. 2. The addition of compounding ingredients. A typical
principal use of graft adhesives is in isocyan- Neoprene AF formulation is shown in Table 5.
ate-crosslinked cements for shoe sole attach- A comparison of the bond properties of Neo-
ment. Neoprene AD-G differs from standard prene AF and Neoprene AD is shown in Table
Neoprene AD in that it provides better brush- 6.
ability at equal viscosity and solids content and Brief milling of Neoprene AF, on a cool mill,
a longer pot life in two-part systems. is suggested to break down a light, gel-like as-
Adhesives based on Neoprene AF, a reactive sociation which builds up as the polymer ages
copolymer of chloroprene and methacrylic acid, and prevents preparation of a smooth solution
are characterized by faster bond strength de- under low shear conditions. Overmilling (past
velopment (Fig. 1), increased heat resistance, five minutes) will lead to increased solution
and better resistance to phasing than the fast- viscosity and poor solution stability.
crystallizing types. However, because of its Neoprene AG is a gel polymer which ex-
reactivity, the use of Neoprene AF requires hibits a high degree of thixotropy and provides
special attention to processing, compounding, improved application properties in both low
and raw polymer inventory control. If it is sub- viscosity sprayable adhesives and in high sol-
stituted directly into a formulation based on ids, high viscosity mastics. Mastics based on
Neoprene AC or AD, the results may be dis- Neoprene AG have a nonstringy, buttery con-
appointing. sistency and can be easily applied by troweling
The improved bond strength development or extruding. Because they are highly thixo-
and hot strength of Neoprene AF results from tropic, they resist slump after application.
the interaction of its polymer carboxyl func- Neoprene AG is often blended with Neo-
tionality with metal oxides. Its crystallization prene WHV -A or Neoprene AC or AD to ad-
just mastic properties. Blends with Neoprene
Table 4. Adhesives Based on Graft AC or AD give increased shear strength but ex-
Polymers of Neoprene and Methyl trude less easily and provide less slump resis-
Methacrylate. tance. Blends with Neoprene WHV-A decrease
Formulation PaNs
Table 5. Neoprene AF Formulation
Neoprene AD-G 100
Methyl methacrylate" 100 Formulation PaNS
Benzoyl peroxide (50% dispersion)b 1
Mill Mix
AntioxidantC 2
Neoprene AF (5 min break down) 100
Toluene 472
Antioxidant 2
Methyl ethyl ketone 118
Magnesium oxide 8
Procedure: Zinc oxide 5
I. Slowly heat solution of Neoprene AD-G, methyl
Chum Mix"
methacrylate, toluene, and MEK in a closed reactor
Milled stock 115
vessel to 60°C (l40°F).
t-Butyl phenolic resin 40
2. Add benzoyl peroxide to initiate polymerization.
Water 1
3. Continue heating to 80°C (l76°F). React at 80°C
Solvent 610b
(l76°F) for 2-8 hours.
4. Add antioxidant to terminate the polymerization. 'Gelation can be minimized if the milled stock is added to a pre-
dissolved resin and solvent solution.
'Grade H-112 from DuPont. bA blend of aromatic/aliphatic/oxygenated solvents is used. Ap-
bCadox BFF-50 from Noury Chemical. proximately 20% of an oxygenated solvent is required for good
'Wingstay L from Goodyear. solution stabiliry.
 290 HANDBOOK OF ADHESIVES

Table 6. Adhesive Properties: Neoprene AF vs. Neoprene AD.B

NeopreneAF Neoprene AD
NeopreneAF Neoprene AD Pulled at Pulled at
Adhesive Propenies Pulled at R. T. Pulled at R. T. ]()()OC (212°F) ]()()OC (212 OF)

Bond Strength Development,

Canvas/canvas peel, pli
After 1 hr at R.T. 16 1
After 2 hr at R.T. 20 2
After 4 hr at R.T. 24 4
After 6 hr at R.T. 26 8
After 1 day at R.T. 32 32
After 7 days at R. T. 13 3

Adhesion to Various Substrates

After 14 days at R.T., pli
Canvas 39 38 18 1
Aluminum 30 26 16 0.5
Maple 30 21 15 0.5
Decorative laminate 38 37 13 1
Composition soling 40 37 7 0.5
Stainless steel 28 25 15
'Using formulation shown in Table 5.

cost and increase tack at the expense of both prene AC or AD to lengthen tack time and to
application properties and shear strength. A obtain better substrate wetting and subse-
comparison of Neoprene AG and AC in a mas- quently higher peel strength.
tic fonnulation is presented in Table 7. Neoprene AH is an acrylic copolymer of
Mastics based on Neoprene AG can be pre- chloroprene which fonns a colloidal dispersion
pared in a sigma blade mixer from polymer when peptized in aliphatic solvents. The use of
which has first been preswollen in solvent. aliphatic solvents alone, without toluene or ke-
Milling is not required to produce smooth, non- tones, offers the advantages of low cost, ac-
stringy products. ceptability under Rule 66, and the capability to
In low solids fonnulations, the gel structure bond substrates such as polystyrene which are
of Neoprene AG provides improved spray per- sensitive to aromatic or ketone solvents.
fonnance compared to products based on other The stability of the dispersion is due to sterlc
Neoprene types. Properly fonnulated compo- stabilization of the acrylic portion of the poly-
sitions can be sprayed in unifonn patterns with mer in the solvent. The dispersion nature of
no cobwebbing at low atomization pressures Neoprene AH systems allows the fonnulation
( < 70 psi). Preferred solvent systems for of high solids, low viscosity adhesives with ex-
sprayable compositions fall in the range of 3.5- cellent application properties. The sprayability
5.5 hydrogen bonding index and 7.5-9.8 sol- of fonnulations with solids contents as high as
Ubility parameter. A low atomization pressure, 50% (2500 cps) is good, exhibiting none of the
sprayable adhesive fonnulation is presented in cobwebbing nonnally seen in Neoprene sys-
Table 8. To obtain the best application prop- tems. The open tack time of Neoprene AH is
erties, either milling or high shear processing shorter than that of the other types, generally
is required to break up loose gel agglomerates around fifteen minutes.
in the polymer. The preparation of a stable dispersion is the
Neoprene AG is compounded like Neoprene key requirement to obtaining a stable adhesive
AC and AD. However, fonnulations based on system. Neoprene AH should be peptized in a
Neoprene AG give lower ultimate cohesive low-napthenic, aliphatic hydrocarbon solvent.
strength, specific adhesion, and open tack time The suggested peptization system consists of
than the fast crystallizing types. For this rea- the peptizing agent tetraethylthiuram disulfide
son, Neoprene AG is often blended with Neo- activated by Vanax 552 (R. T. Vanderbilt), as
 NEOPRENE (POLYCHLOROPRENEI-BASED SOLVENT AND LATEX ADHESIVES 291

Table 7. Neoprene Mastic Compound. a

Formulation Pans
Neoprene 100
Antioxidant 2
Magnesium oxide 4
Zinc oxide 5
Treated calcium carbonateb 100
Ethylene glycol 2
t-Butyl phenolic resin 20
Terpene phenolic resin 15
Hexane/MEK/Toluene to 65 % sol-
ids (5/3/2 by weight)
Polymer Type NeopreneAG NeopreneAC
SlumpC after 20 min, inches 0.0 2.9
Extrusion Rate,d g/5 sec
AtR.T. 70 19
Shear strength· at R.T.,
Plywood/plywood, psi
After 3 days at R.T. 150* 140
After 7 days at R. T. 240* 250*
After 14 days at R.T. 240* ~20*

Shear strength· at R. T.,

Maple/maple, psi
After 3 days at R.T. 40 38
After 7 days at R. T. 140 156
After 14 days at R.T. 160 250
·Indicates wood failure. All other failures were adhesive.
"Ref. 7
"Omya BLH, OMYA, Inc.
'Flow measured on 1.5 in. drain; 'Is-in.-thick adhesive sample on a vertical surface.
"Extruded at 50 psi, lAo-in. orifice
'I/Io-in. glueline tested at III in.lmin.

is shown in the adhesive formulation presented Mixer to a few hours in a Struthers-Wells

in Table 9. The dispersion should be prepared chum.
under shear, the degree of which affects the Other Neoprene polymers which find use in
time to disperse and the final viscosity. The solvent adhesives are Neoprene WHY -A, Neo-
time to make a 40 % dispersion varies from
about 30 minutes in a high-shear Silverson
Table 9. Neoprene AH Formulation.
Table 8. Sprayable Formulation Based Formulation Pans
on Neoprene AG. Disperse by churn mixing:
Formulation Pans Neoprene AH 100
Heptane 150
Mill Mix Tetraethylthiuram disulfide 0.5
Neoprene AG 100 Vanax 552" 0.5
Antioxidant 2
Magnesium oxide 8 Add the following to the above dispersion:
Zinc oxide 5 t-Butyl phenolic resin 20-40
Tackifier 0-20
Churn Mix Magnesium oxide 2
Milled stock 1I5 Zinc oxide 4
t-Butyl phenolic resin 40 Antioxidant 2
Water 1 Water 1
MEK/Cyclohexane (4/1 by volume) 620
"Piperidinium pentamethylene dithiocarbamate, R. T. Vanderbilt
292 HANDBOOK OF ADHESIVES

prene GN and Neoprene FB. Both Neoprene Metal Oxides

FB and Neoprene GN are sulfur-modified types
which can be mechanically or chemically pep- Metal oxides serve several functions in Neo-
tized to reduce molecular weight if desired. prene adhesives as shown below:
Both exhibit a faster cure rate than the fast crys- Role of Metal Oxides
tallizing types and can be used in formulations
which are intended as either two-part adhesives Acid acceptor ZnO, MgO
or curable compositions. Neoprene FB differs Scorch retarder MgO
from the other solvent types in that it is a vis- Curing agent ZnO, MgO
cous, pourable fluid at 500C (122°F) which t-Butyl phenolic resin reactant MgO
can be used in the formulation of 100% solids
The prime function is that of an acid acceptor.
caulks and sealants. Neoprene WHV-A, a
Small amounts of HCI are released as Neo-
member of the W-family of polymers, is a
prene films age. The HCl must be absorbed by
slow-crystallizing, high molecular weight poly-
the adhesive to prevent substrate degradation.
mer which is generally used in blends with
This is particularly important when the adhe-
lower molecular weight crystallizing types to
sive is applied to acid-sensitive materials such
increase solution viscosity. As a minor com-
as rayon or cotton. Both magnesium oxide and
ponent in such blends, it will not have too ad-
zinc oxide function as acid acceptors. A com-
verse an effect on bond strength development.
bination of the two is more effective than either
alone.
Antioxidants
Magnesium oxide serves a second function
The presence of a good antioxidant is essential as a processing stabilizer. It is mill mixed with
in all adhesive formulations for adequate pro- Neoprene before adding zinc oxide to retard
tection against oxidative breakdown and acid scorch during processing.
tendering of substrates. Octylated diphenyl- Metal oxides also act as curing agents in ad-
amine antioxidants, such as Agerite Stalite S hesive films. Zinc oxide is the most effective,
(R. T. Vanderbilt), afford the best protection leading to increased strength as the bond line
but can be used only in applications where ages. At higher levels (20-40 phr) magnesium
staining is of no concern. If discoloration can- oxide also is effective, particularly if the bond
not be tolerated, a nonstaining hindered bis- is briefly exposed to elevated temperatures.
phenol such as Wing stay L (Goodyear) or As will be discussed in the section on resins,
Antioxidant 2246 (American Cyanamid) should metal oxides also react in solution with t-butyl
be used. Two parts of an antioxidant is gener- phenolic resins. The reaction product, an in-
ally sufficient. For very demanding applica- fusible metal resinate, increases the heat resis-
tions higher amounts may be advisable. aance of adhesive films. Although oxides of
The hindered bisphenol antioxidants, while calcium, lead, and lithium also exhibit reactiv-
useful for minimizing staining, can present ity, magnesium oxide is the most useful and
problems in some formulations. For example, widely used reactant.
milled stocks containing some hindered bis- Generally about five parts of zinc oxide and
phenols such as Santowhite Crystals (Mon- four to eight parts of magnesium oxide are used
santo) have relatively short bin stability. On in adhesives with 40 phr resin. Four parts of
aging, for as little as one week at 38°C the magnesium oxide are included to act as an
(100°F), the stock may not make a smooth so- acid acceptor and to retard scorch. An addi-
lution. If the stocks are dissolved within two or tional four parts are included as a resin reactant
three days of milling, no problems are nor- if the adhesive system contains a t-butyl phe-
mally encountered. Antioxidant 2246 (Ameri- nolic resin.
can Cyanamid) has been known to create color There has been some interest in reducing or
problems: a pink discoloration in latexes, a eliminating metal oxides in adhesive films in
bluish or blue-green discoloration in some sol- order to produce clear adhesives. The amount
vent systems, particularly those based on chlo- of magnesium oxide should not be reduced be-
rinated solvents. low that required to react fully with the t-butyl
 NEOPRENE (POLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 293

phenolic resin. Epoxy resins and zinc resinate salt is infusible. It has no melting point, and
have been used in place of zinc oxide as acid decomposes above 200°C (392°P). It there-
acceptors, but are not as efficient. Some sacri- fore reduces the thermoplasticity of the system,
fice in tendering resistance must be acceptable, providing good bond strength up to 80 °C
therefore, if a clear adhesive is desired. At least (l76°P) or higher in properly formulated ad-
2 phr of an antioxidant is essential to obtain the hesives. The resinate also increases adhesive
best possible tendering resistance. bond strength development by accelerating sol-
vent release. A comparison of t-butyl phenolics
with other resins in Neoprene AD and AH ad-
Resins
hesives is shown in Tables 10 and 11.
The choice of which resin to use in a given sol- The t-butyl phenolic resins are generally used
vent adhesive application is of great impor- at levels between 35 and 50 phr. The optimum
tance. Resins serve to improve specific level for most adhesive applications is 40-45
adhesion and autohesion, obtain longer tack re- phr, which provides a good balance of tack and
tention and increase hot cohesive strength. The heat resistance. Lower levels are useful when
most widely used family of resins are the para- the required level of adhesion is relatively low
tertiary butyl phenolics. These resins give much and a soft glueline is desirable. Higher levels
higher heat resistance than other types of resins of resin are used when the demand for good
with similar melting points. This high heat re- adhesion is high, such as in metal-to-metal
sistance is due to their reactivity with the mag- bonding. The variation in open tack time and
nesium oxide present in Neoprene adhesive hot bond strength with increasing t-butyl phe-
systems. The magnesium oxide resinate or resin nolic resin content is shown in Pig. 4.

Table 10. Effect of Resin Type on Heat Resistance.

Base Compound Parts
Neoprene AD-20 (10 min breakdown) 100
Magnesium oxide 4
Zinc oxide 5
Antioxidant 2
Resin as shown
Water
Hexane 100
Toluene 400

Resin Selection A B C D E F G H

t-Butyl phenolic resin' 46 33 33 33 33

Hydrocarbon resin 25 22
Rosin ester 22
Terpene 65 22
Terpene phenolic 65 22
Solids content, % 24 21 25 25 26 25 26 25
Canvas/canvas bond
strength at R. T. ,
plib
After I day at R. T. 31 A lOC 12 C 14 C lOC 18 C 16 C 32 C
After 7 days at 46A 25 A 36 A 42 A 4F 23 A 30A 40A
R.T.
Canvas/canvas bond
strengtb at 80°C
(176°F), pli
After 7 days at 5.5 0.5 0.5 0.5 0.5 0.5 0.5 2.0
R.T.
'Magnesium oxide reacted.
bA = adhesive failure, C = cohesive failure, F = failure between films.
 294 HANDBOOK OF ADHESIVES

Table 11. Effect of Resin Type on Neoprene AH Hot Bond Strength. a

t-Butyl Phenolic Resin
Rosin Terpene Low High
Adhesive Propenies Ester Phenolic Reactivity Reactivity
Bond strength after 1 day
at R.T., pli
Tested at R.T. 5.4 C 9C 20C 21 C
Bond strength after 7 days
at R.T., pli
Tested at R.T. 8C 21 C 34A 42 A
Tested at 60°C (140°F) 18 C 28 C
Tested at 80°C (176°F) 6C 16 C
Tested at 100°C 0.3 C 0.8 C 2.5 C 7C
(212°F)
Open tack time, paper to 60 16 10-14 4-8
steel, min. •
'Based on fonnulation in Table 9 with 40 phr of resin.
e = cohesive failure, A = adhesive failure

Approximately 10 parts of magnesium oxide vents the reaction proceeds more slowly, as
are required to react completely with 100 parts shown in Table 12. In cases where the solvent
of resin. This is equivalent to 4 parts of mag- system contains a high percentage of polar sol-
nesium oxide in a solution containing 100 parts vents, it may be advisable to prereact the resin
of Neoprene and 40 of resin. The reaction takes in the nonoxygen-containing component of the
place at room temperature and requires the blend to ensure the reaction reaches comple-
presence of water as a catalyst. Although there tion.
is generally enough waterin the solvent system The use of t-butyl phenolic resins is essential
to ensure reactivity, it is common practice to in compounding Neoprene AF for maximum
add 1-2 parts of water by weight of resin to the viscosity stability and the best balance of adhe-
formulation. sion properties. This class of resins helps sta-
The solvent system used has a strong effect bilize the carboxyl functionality of Neoprene
on the rate of the magnesium oxide and resin AF in solution. The magnesia-tertiary butyl
reaction. In toluene the reaction is very fast, phenolic resin complex reacts with the polymer
reaching completion in one hour. In polar sol- carboxyl groups as shown in Fig. 5, preventing
gelation of the polymer with the metal oxide
....,
,. '\
16
alone.
fective
Increased resin levels are particularly ef-
in stabilizing compounds which are for:
12
mulated for maximum heat resistance and
,
2.4 6 10
t
contain high levels of magnesium oxide.
~ 2.0 5 i Neoprene adhesives containing metal oxides
"c;,i 1.6 4 i
and t-butyl phenolic resins may separate on
Di i\ ,
'0
g 1.2 3 " .,. Bond s1renglh
standing into a clear upper layer and a lower
In • I al BO'C 1176'F] layer of flocculated metal oxides. This separa-
O.S 2 / '.
0.4 1
)If,I'
".
~
I

"" ... _Tack 0.33

tion, called phasing, may occur in days or
months. Once an adhesive has phased, it must
, '-.-. be agitated before use to obtain full utility of
20 40 60 so the metal oxides.
t-Butyl Ph800ic Resin. phr
It is theorized that phasing is due to insuffi-
• A1SO'C 1176'FI
•• AI2O'C[68'FI cient dispersion stability of the metal oxides,
Fig. 4. Effect of t-butyl phenolic resin level on open tack resulting from low molecular weight portions
time and heat resistance. in commercial resins which are not large
 NEOPRENE (POLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 295

Table 12. Effect of Solvent Blend on the Rate of the Magnesium

Oxide/Resin Reaction. a
Ash Content Melt or Decomp.
Reaction of Reacted Temp. of Reacted
Solvent Time, hr Resin, %b Resin, °C (oF)
Toluene 6.5 250 (482) DC
24 6.8 258 (496) D
96 6.7 252 (486) D
Tol/ethyl acetatelhexane 24 6.9 255 (491) D
(1/1/1 by weight) 96 7.1 255 (491) D
Toluenelhexane 24 6.9 264 (507) D
(1/1 by weight)

Hexane 24 7.0 252 (486) D

Acetone 24 0.4 181 (358) M
Hexane/MEK 24 0.4 125 (257) M
(111 by weight) 48 2.9 130 (266) M
72 6.1 226 (439) M
96 6.2 224 (435) M
'Formulations contained I phr water and about 10 phr MgO per 100 phr resin.
'>6% ash and decomp. temp >250°C (48ZOF) indicates the reaction has gone to completion.
'0 = decomposed, M = melted.

enough to prevent particle attraction and ag- and Hitachi work led to the development of so-
glomeration when adsorbed on the metal oxide called nonphasing resins (Le., Schenectady's
surface. Commercial t-butyl phenolic resins SP-154, and Union Carbide's CK-1636). In
with a number average weight of 900-1200 can addition to resin choice, the formulator inter-
contain as much as 10-15 % by weight of ma- ested in minimizing phasing must also consider
terial having a molecular weight less than 500. the type of Neoprene, solvent system, solids
By increasing the average molecular weight of content, milling time, etc.
commercial t-butyl phenolic resins from 900 to Terpene phenolic resins, such as Schenecta-
1600 and fractionating out the low molecular dy's SP-560 or Occidental's Durez 12603, are
weight portion, DuPont workers were able to also often used in Neoprene adhesives. They
produce cements that did not phase. A series of are nonreactive and thermoplastic in nature and
experiments conducted by a team of workers at so provide longer open tack time and a softer
Hitachi Chemical Co. 4 confirmed this and glue line than the t-butyl phenolics, but offer
demonstrated further that phasing was caused less hot cohesive strength. Terpene phenolic
primarily by various dialcohols such as p-tert- resins are often used in combination with a
butyl phenol dialcohol (BPDA). The DuPont polyisocyanate curing agent, such as Bayer's
Desmodur RF, in a two-part adhesive system
to obtain better hot bond strength.
Other resins which find use as tackifiers for
~ - COOH Hooc-5 Polymer

J MgO& Resin Neoprene include poly terpene resins, hydro-

~ - COO - M g - Res;n - Mg - OOC -~ Gelled
genated wood rosins, rosin esters, and couma-
rone-indene resins. Chlorinated rubber is used
j MgO & Resin
Solution"
Additional

to promote metal adhesion and as an ingredient

2 ~ -COO-Mg-Resin --MgOH
Resin
Reacted
Polymer
of two-component adhesives. Poly-alpha-
methyl styrene is used to obtain better specific
Fig. 5. Magnesia and tertiary butyl phenolic interaction
with polymer acid. (The resin should be added before or adhesion to thermoplastic rubber. The compat-
at the same time as the MgO to prevent gelation during ibility of Neoprene with resins and other
mixing.) polymeric materials is detailed in Ref. 11.
296 HANDBOOK OF ADHESIVES

Fillers boxyl functionality is stable in solution; thus

one-part curing cements are possible.
Fillers find limited use in Neoprene adhesives.
They are included primarily to reduce cost in
high solids mastics. Conventional fillers such Solvents
as clay and calcium carbonate are used effec-
Solvent choice affects adhesive viscosity, bond
tively at levels as high as 250 phr in some mas-
strength development, open time, cost, and to
tic applications.
some degree ultimate strength. Trisolvent
The optimum filler concentration in Neo-
blends are generally used, consisting of vary-
prene AG based mastics depends on the filler
ing amounts of aromatic, aliphatic and oxygen-
used. Maximum bond strength is obtained with
ated solvents such as ketones and esters. In
fillers of low particle size ( - 5 micron) and in-
cases where nonflammable systems are re-
termediate oil absorption (30 g/l00 g filler);
quired, chlorinated solvents such as 1,1,1-
mastic extrusion rate and slump increase with
trichloroethane are employed.
decreasing filler absorption, almost indepen-
A graphical method can be used to predict
dently of filler particle size. 6 Increasing the
the utility of solvent blends in adhesives based
level of the treated calcium carbonate in Table
on Neoprene. It is based on using the solubility
7 above 100 phr causes the mastic to slump and
parameter (0) and the hydrogen bonding index
the impact resistance to decrease.
('Y) of each constituent solvent to predict that
In general, fillers reduce the specific adhe-
of the blend. The 0 and 'Y of blends are additive
sion and cohesive strength of adhesive films.
according to their volume proportions.
For these reasons, they are rarely used in low
Once the solubility parameter and hydrogen
solids contact adhesives. In some formulations,
bonding index of the blend has been deter-
e.g., Neoprene-terpene phenolics, the inclu-
mined, the blend can be positioned on the chart
sion of a fine particle size reinforcing silica such
shown in Fig. 6. Solvents or blends which fall
as HiSil233 (PPG Industries) will increase film
within the kidney shaped area will yield
strength. This effect is lost in formulations
smooth, free-flowing solutions with all solvent
using reacted magnesium resinate systems.
grade types except Neoprene AH. Those which
fall outside the kidney shape will not dissolve
Curing Agents
Neoprene. If a particular solvent blend falls in
The heat resistance of Neoprene cements can the shady area it mayor may not be suitable
be increased by compounding with a variety of depending on the amount of true solvent (e.g.,
curing agents such as thiocarbanilide, mixtures toluene) in the blend.
of sulfur with Vanax 808 or 833 (R.T. Van- Current regulations governing the use of sol-
derbilt), triethyl trimethylene triamine, and vents in adhesives vary from state to state and
monomeric or polymeric isocyanates. Room the adhesive formulator will need to assure
temperature cure rates with these curing agents himself that his products comply with both fed-
are slower with the A-types of Neoprene than eral and local regulations. Table 13 indicates
with the G-types. Such systems are not gener- the restrictions imposed by Rule 66.
ally employed in the U.S. because heat-reac- The evaporation rates of common solvents
tive t-butyl phenolic resins provide equivalent are also shown in Table 13. Because the open
or better heat resistance. Solutions containing tack time of an adhesive is partially dependent
curing agents are also relatively unstable and on the evaporation rate of the solvent system,
hence two-package systems are required. In this property can be controlled to some degree
other countries, however, isocyanate-cured through solvent selection. Small percentages of
Neoprene systems are popUlar, particularly in xylene « 5 %) are often added to increase open
the shoe industry. time, particularly in consumer products. In ad-
In Neoprene AF systems, metal oxides act as dition, the evaporation rates of the various
rapid room temperature curatives because of components of a blend must be taken into ac-
their reactivity with the polymer carboxyl func- count. If the better solvent is the slowest to
tionality. When properly compounded, the car- evaporate, the adhesive will retain tack longer.
 10
.. PPlICABLE 10 I
NEOPRENE AC . "D. WHV · A. .I. CAR:TOL " 1- -
W. WRI. WO. ISO~MYL
RAW POLYMER UNMillED
9 3% (Vo l. ) . Room Tllmp.ratuf. ALCOHOL
~.
• ISOPROPYL
I • I
ALCOHOL
SOLVENT STRENGTH
Z
m
8 + METHYL o
0 ~
"CELLOSOLVE"
• 21
- r--- I m
- r::-- Z
m
-~ .
7 3 ;:;
>< TYPE OF
w
-- ~ or-
0 rs SOLUTION oo(
~ -r-- (')
%
~
-~ r-
z 6
- r-- "' 1
is
o21
Z - ..L.- ACEtON E IN~fMPLrE o
0
co a ETHYL ~
r - .. 21
Z r-- ACETATE -" .":- -,:1. - - m
w 9
M~K ..... .
'1CLOUDY Z
~
, J. -
0 S .!!!
c<
0 10
>- DIBK I
-"'" Ci
:I: . n·PROPYL ACETATE ~
• .1 CLEAR m
,..I . 1 ANILINE C
I f I
4 r--- r- TURPENTINE en
• o
XYL~NE <
m
Z
CCI. T1L~ENE O~B -I
3 .. ~
BENZENE NITROtENZENE Z
j j .. C
t- "0.
n·PENTANE
' I. ! ~
2 -I
m
I'-n.H EXANE
\ YCLOrXAT
1 NITROPROPANE• X
n·HEPTANE j
1 ~
C
%
m
en
7 8 9 10 11 12 <:
m
5-S 0LUBILITY PARAMETER en
Fig. 6. Solvent strength chart (Ref. 9). N
ID
-..I
 298 HANDBOOK OF ADHESIVES

Table 13. Properties of Commonly Used Neoprene Solvents. d

Hydrogen Relative Flash Max. Allowable
Molecular Solubility Bonding Evaporation Point Concentration Viscosity, Restriction
Solvent Wt Parameter Index (HB) Rate" °Fb ppm" cps at 20°C (68°F) Rule 66
Acetone 58.08 10.0 5.9 1160 15 1000 0.35 None
Cyclohexane 84.16 8.2 2.2 720 40 300 1.06 None
Ethy I acetate 88.10 9.1 5.2 615 45 400 0.44 None
Heptane 100.20 7.4 2.2 386 25 500 0.42 None
Hexane 86.17 7.3 2.1 1000 -25 500 0.29 None
Isopropyl alcohol 60.09 11.5 8.7 300 . 70 400 2.41 None
Methyl ethyl ke- 72.10 9.3 5.4 572 35 200 0.42 None
tone
Pentane 72.15 7.0 2.2 2860 <-50 500 0.24 None
Toluene 92.13 8.9 3.3 240 44 100 0.59 20%
Xylene 106.16 8.8 3.5 63 80 100 0.69 8%
V.M. & P Naphtha * 7.6 2.5 275 48 500 * None
'n-Butyl acetate = 100.
·Cleveland Open Cup Method.
'Maximum allowable concentration in air where men work 8 hr/day "Dangerous Properties of Industrial Materials", 4th ed., N. (. Sax, Van Nostrand
Reinhold, New York, 1975.)
dRef. 10.
*Mixture of various hydrocart)()Ds-no definable molecular weight or viscosity.

If, on the other hand, it evaporates the most plus high shear refining. A brief description of
quickly, cohesive strength will develop more each follows.
rapidly.
Solvent choice also affects application prop-
Milling. The polymer is broken down on a
erties. True solvents, such as toluene or 1,1,1-
two-roll rubber mill prior to dissolution. To be
trichloroethane, give stronger solutions which
effective, milling should be carried out on a
tend to be more stringy and cobweb when
tight, cool mill-tight to increase the rate of
sprayed. Improved application properties are
shear, cool for the greatest degree of chain scis-
obtained by using a blend which falls closer to
sion. Neoprene can go through three phases on
the shady area of the kidney shaped solvent
a mill depending upon its temperature: elastic
diagram. For example, sprayable adhesives are
phase <71°C (160°F), granular phase 71-
generally based on fast-evaporating solvent
93°C (160-200°F), plastic phase >93°C
blends which fall in the upper left quadrant of
(200°F). Optimum breakdown and dispersion
Fig. 6.
occur in the elastic phase.
A small amount of water, about 1 phr, is
The metal oxides and antioxidant may be
often added to catalyze formation of the mag-
added to the polymer as it is being broken down
nesium oxide/resin reaction product and to im-
on a mill. The masterbatch is then dissolved
prove the viscosity stability of Neoprene AF
with any other compounding ingredients. This
adhesives. However, excess water reduces the
procedure provides better dispersion of the
hot cohesive strength of the adhesive. There-
metal oxides, which improves resistance to
fore, levels less than 3 phr are generally used.
phasing in the final adhesive. The antioxidant
and magnesium oxide should be incorporated
Adhesive Processing
before the zinc oxide to retard scorch during
The procedures used to prepare Neoprene ad- processing.
hesive cements can affect end use properties Milling aids in producing smooth, non-
such as hot cohesive strength and sprayability. stringy cements by selectively breaking down
Techniques used to prepare cements include the high molecular weight fraction of the poly-
milling, direct dissolving, and direct dissolving mer. In applications requiring sprayable adhe-
 NEOPRENE IPOLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 299

sives, milling is recommended in order to ob- Direct Dissolving. The polymer chips are
tain the best application properties. Milling also dissolved with the other compounding ingre-
increases penetration into porous substrates and dients in either high or low shear mixing equip-
decreases solution viscosity and early hot bond ment. This method is more economical than the
strength. previous one because milling equipment and the
For example, milling Neoprene AC for 5 min manpower required to operate it are not re-
[stock temperature - 50°C (122 °F)] reduces quired. Direct addition of dry ingredients to
initial 100°C (212°F) peel strength from 7 lb/ solvent or to a solution of Neoprene is not rec-
in. to less than lIb/in. After a bond aging pe- ommended, however, unless the blending
riod of one month, both have 12 lb/in. peel equipment is capable of creating a smooth dis-
strength at 100°C (212°F) as a result of partial persion of these materials. With a slow-speed
curing with zinc oxide. chum, it may be necessary to make a separate
The effect of milling on the Mooney viscos- dispersion of dry ingredients in solvent by ball
ity of Neoprene AC, Neoprene AD and Neo- milling before adding them to the Neoprene so-
prene AF is shown in Fig. 7. Neoprene AF does lution-hence this technique is often referred to
not break down to the same extent as the fast as the slurry method.
crystallizing types. Milling, therefore, does not Dissolvers can be classified as slow-speed
have as large an effect on the solution viscosity chums, high-speed chums, or heavy-duty mix-
of Neoprene AF cements. Because the bond ers, depending on their relative rates of solu-
strength development of Neoprene AF is tion of stock or their energy input. Slow-speed
largely due to reaction with zinc oxide, it is not chums may be mounted either vertically or hor-
significantly affected by milling. izontally. Typical solution time ranges from 24
The granulators, dicers, and shredders used to 48 hours. Those mounted horizontally may
in the rubber industry are also employed in the contain an agitator or they may be agitated
preparation of mill-mixed adhesive stocks. through rotation of the chum. Horizontal chums
They are used to precut mill stock prior to are well suited for the production of low vis-
charging it to the chum to increase the rate of cosity adhesives. Vertical chums are jacketed
solution. vessels which are agitated by paddles on a ver-
tical shaft. Vertical chums can be used for all
types of cements but are especially suited for
Stock Temperature 122DF. [SODC.)
high viscosity cements.
100 ,.----r-----r-----,r-------.
High-speed chums are designed to speed up
the preparation of smooth cements. Because of
their shearing action, they provide some poly-
i~ ~~---~~--_r---~---~
mer breakdown and resultant viscosity reduc-
tion. They generate considerable heat, so a
.~
ill jacketed vessel is preferred to control heat his-
~
u tory. The heat build-up increases the rate of so-
~ lution, particularly with the crystalline types
~ 50 1-----P"-....:::----'H"......,---1---"==-;
OJ
OJ ---'--AD because in addition to the simple temperature
;;
:ii! AF effect on solubility, heating decrystallizes the
polymer.
(251----+------+-----1--= AC
High-speed chums may be shearing disk type
or propeller type. The latter, typified by the
~ Struthers Wells chum, consists of two opposed
propellers positioned in the sides of a closed
cylindrical vessel, slightly off horizontal, one
o 10 15 20
on top of the chum, the other at the bottom.
Milling Time, Minutes
Shearing disk chums usually have variable
Fig. 7. Effect of milling on Mooney viscosity. speed control and differ from one another in the
300 HANDBOOK OF ADHESIVES

design of the flat disk at the end of the shaft. viscosity obtained using this procedure is inter-
Examples of such dissolvers include the Hock- mediate between that of milled and unmilled
emeyer Disperser and the Cowles Dissolver. adhesives.
Solution time for high-speed chums ranges In the past 8-10 years, many adhesive man-
from 3 to 12 hours. ufacturers have turned to high shear processing
Heavy duty mixers or kneaders are adapted as a means of attaining adhesives with a
to the manufacture of heavy doughs or trowel- smooth, mill-like consistency without the re-
ing compounds which have viscosities too high quired investment in capital and manpower.
for practical processing in the equipment dis- Some use a high shear refining step as de-
cussed above. These are high-energy internal scribed here while others speed up mixing time
mixers utilizing counter-rotating rotors like a by charging all ingredients directly to the mixer
Banbury, with sigma- or Z-shaped blades. By emulsifier unit. A comparison of milling, direct
careful addition of solvent, a smooth cement dissolving, and dissolving plus high shear re-
can be prepared in two hours or less. Too rapid fining is shown in Table 14.
addition of solvent will cause the compound to
"liver" and an abnormally long period of time
End Uses
will be required for solution.
Areas where Neoprene solvent cement is pop-
Direct Dissolving plus High Shear Refin- ular include adhesives for bonding high pres-
ing. This procedure combines many of the sure plastic laminates, automotive adhesives,
attractive features of milling and nonmilling. It adhesives for the construction industry and shoe
involves subjecting a previously dissolved ad- adhesives.
hesive to high shear for several minutes in Shoe adhesives have traditionally been a large
equipment such as a Ross mixer emulsifier. The market for Neoprene, particularly for the per-
high shear refining step breaks down the high manent attachment of shoe soles. However,
molecular weight fraction of the polymer, traditional Neoprene contact cements do not
yielding nonstringy adhesives and better metal give adequate adhesion to plasticized PVC, a
oxide dispersion without the sacrifice in hot synthetic material for shoe uppers which has
strength associated with milling. The adhesive grown in significance in recent years, because

Table 14. Effect of Adhesive Processing on Viscosity and

Creep Resistance of Neoprene AD Adhesive. a • b
5 min Mill Chum Chum Mix
Processing Breakdown Mix Plus High Shear"
Brookfield Viscosity, cps 220 1220 1050
Creep at 50°C (122°F) after
120 min with 5 lb weight,
Canvas/canvas Bonds,
Inches separationd
1 day bond aging 1.7 C 0.8 C 0.7 C
5 days bond aging 0.5 C 0.3 C 0.3 C
Open time, chipboard to for-
mica Bonds Assembled
After"
30 min 4 5 5
60 min 2 5 3
90 min 0 5 0
120 min 0 5 0
180 min 0 0 0
'Ref. 12
"Neoprene AD-30 adhesive with 40 phr t-butyl phenolic resin.
e3 min in homogenizer.
dC = Cohesive failure.
<Values 1 through 5 correspond to increasing bond strength.
 NEOPRENE (POLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 301

of plasticizer migration into the bond line. In hesive and minimizes drying time. The basic
response to a need for better adhesion, Neo- physical characteristics required of Neoprene
prene AD-G was developed. As was discussed adhesives for these application techniques are
earlier, it is designed for grafting with methyl summarized below.
methacrylate at the adhesive manufacturer's fa-
1. Spraying. A low Mooney, low nerve
cilities. The resulting graft polymer solution
Neoprene is preferred. Milling is re-
gives good adhesion to PVC without further
quired for the best spray characteristics.
compounding. For sole attachment, it is used
The viscosity should be below 250 cps.
as a two-part adhesive in combination with a
The solvent blend should contain pre-
poly isocyanate. The graft system also gives
dominantly fast-evaporating solvents
good adhesion to other hard to bond substrates
which individually could not dissolve
such as EV A sponge, thermoplastic rubber and
Neoprene.
SBR. In some of these cases, small amounts of
2. Curtain coating. A low Mooney, low
resins are used to increase specific adhesion.
nerve Neoprene is preferred. Milling or
AutomotiYe uses for Neoprene adhesives also
high shear refining improves curtain coat-
go back many years and include such things as
ing characteristics by reducing nerve.
adhering sponge insulation strips to doors and
Viscosity should be 200-300 cps utiliz-
trunk and hood lids. Other applications include
ing relatively slow evaporating solvents.
attachment of vinyl trim in panels and adhering
3. Roller coating. Milling or high shear re-
vinyl landau tops to roofs. Traditional Neo-
fining is recommended to reduce stringi-
prene/resin contact cements are used to bond
ness. The viscosity should be 500-1000
plasticized PVC in these applications because
cps using relatively slow evaporating sol-
the required adhesion level is not as great as in
vents. The slowest evaporating solvents
the shoe industry and/or a barrier film is em-
should be true solvents, either individ-
ployed.
ually or as a blend, in order to reduce
Another large market for Neoprene adhe-
"snap-back. "
sives is the bonding of high-pressure plastic
4. Brushing. The viscosity should be around
laminates to substrates such as wood, metal,
1000 cps. Solvent system, beneficial ef-
stone, etc. The contact cement enables con-
fect of milling, etc., depends on individ-
struction personnel to make kitchen cabinets in
ual application requirements.
place. Neoprene's rapid bond strength devel-
5. Extrusion. A high gel, low viscosity thix-
opment and high ultimate strength make it fea-
otropic Neoprene is best. The ideal can-
sible to install rolled edges for splash panels at
didate is Neoprene AG, by itself or in
the back of counters, etc. Greater and greater
blends with AC, AD or WHV-A. The
use of contact adhesives is also being found in
solvent blend should contain predomi-
factory manufactured plastic laminated panels.
nantly fast-evaporating solvents which
In the construction industry, Neoprene finds
individually could not dissolve Neo-
use in a variety of jobs. Some of the larger vol-
prene.
ume applications include: adhering gypsum dry
walls (wallboard) to itself in double dry wall
construction, adhering faces to paper and wood NEOPRENE LATEX-BASED ADHESIVES
core materials in flush doors and curtain wall
panels, and mastics for bonding plywood floor- Neoprene latexes can be categorized as anionic
ing to joists. or nonionic. The one nonionic latex available,
Latex 115, is stabilized with polyvinyl alcohol
and sold at a pH of about 7.0. Ten other latexes
Application Methods
are available which are stabilized with anionic
Neoprene adhesives are conventionally applied emulsifier systems. Seven of these are com-
by spraying, curtain coating, roller coating, monly used in adhesives. The properties of the
brushing, or extrusion (i.e., by a caulking gun). Neoprene latexes used in adhesive applications
Spraying is by far the most important industrial are summarized in Table 15 and in the follow-
technique, as it permits rapid laydown of ad- ing text.
Col
0
N

Table 15. Properties of Neoprene Latex Polymers.

Latex: Type 400 571 654 671A 735A 750 842A 115
Primary monomer chloroprene chloroprene chloroprene chloroprene chloroprene chloroprene chloroprene chloroprene
Comonomer 2,3-dichloro-l,3- sulfur 2,3-dichloro-l,3- methacrylic acid
butadiene butadiene
Emulsifier type potassium salt of principally so- potassium salt of potassium salt of sodium salt of dis- potassium salt of principally so- polyvinyl alcohol
disproportion- dium salts of disproportion- disproportion- proportionated disproportion- dium salts of
ated resin acids resin acids ated resin acids ated resin acids resins acids ated resin acids resin acids
Class anionic anionic anionic anionic anionic anionic anionic nonionic

Latex chamcteristics:
Percent solids 50 50 59 59 45 50 50 47
Initial pH at 25°C 12.5 12.0 12.0 12.5 12.0 12.5 12.0 7.0
(77°F), minimum
Viscosity, cps
Spindle 1 at 6 rpm 9 15 75 60 5 10 15
Spindle 1 at 30 rpm 9 15 55 45 5 10 15
Spindle 2 at 6 rpm 500
Spindle 2 at 30 rpm 350
Gel content medium high low medium very low medium high low

Film properties:
Modulus at 100%
elongation, MPa 1.8 0.6 0.2 0.6 0.2 0.4 0.4 0.2
Modulus at 300%
elongation, MPa 3.8 0.8 0.2 0.6 0.2 0.4 0.4 0.4
Crystallization mte very fast med. to fast medium slow to med. fast very slow slow does not crystal-
lize

Main features high chlorine con- high tensile good tack and ex- good balance of best open tack excellent extensi- low cost, fast cur- mechanical, elec-
tent and fast strength tensibility tack and hot time and good bility ing trolytic stabil-
crystallization strength adhesion ity, and
carboxyl func-
tionality
 NEOPRENE (POLYCHLOROPRENEI-BASED SOLVENT AND LATEX ADHESIVES 303

Anionic Types alcohol. For many adhesive applications, La-

tex 115 offers two major advantages over the
Latex 400 contains a fast-crystallizing polymer
other Neoprene latexes:
which yields the highest uncured strength of all
the Neoprene latexes, but the shortest dry open 1. Excellent colloidal stability.
tack time. Successful use requires that sub- 2. Carboxyl functionality.
strates either be bonded wet, heat reactivated
The excellent colloidal stability of Latex 115
or bonded under high pressure. Adhesives
gives it exceptional resistance to shear and a
based on Latex 400 have good resistance to
broad tolerance to a variety of materials that
weather, water, heat, and ozone. The polymer
would destabilize the anionic Neoprene la-
in Latex 400 also possesses the highest chlorine
texes.
content of the Neoprene latexes and is often
The carboxyl functionality of Latex 115 gives
used in applications which require good resis-
it much better specific adhesion to a variety of
tance to degradation by flame.
nonporous substrates. In addition, it offers a
Latex 571 contains a very high gel polymer
means of room temperature cure through cross-
which offers high strength films with low per-
linking with metal oxides. Zinc oxide is gen-
manent set. Latex 571 is primarily used in
erally used at two to five parts, although other
combination with other latexes and resorcinol-
metal oxides are effective. Crosslinking can
formaldehyde resins for bonding elastomers to
also be achieved with organic crosslinking
fibers and fabrics.
agents such as methylol ureas, methylol me-
Latex 654 is a high solids, low viscosity la-
larnines, and epoxies.
tex containing a very low gel polymer which
Latex 115 is used primarily in industrial con-
offers good tack and flexibility. It is generally
tact bond applications. Formulations based on
used in wet laminating applications, for ex-
Latex 115, such as the one shown in Table 17,
ample, to adhere various facing materials to a
come the closest to matching the performance
variety of fiberglass batts and boards.
of Neoprene solvent-based contact cements.
Latex 671A is a high solids, low viscosity
Neoprene Latex 115 reacts slowly with zinc
latex containing a medium-high gel polymer
oxide in adhesive form, causing a gradual in-
which offers high uncured cohesive strength
crease in the adhesive gel content. In contact
combined with good open tack time. It is used
bonding, where gel content directly affects the
in both contact bond and wet laminating appli-
contactability of dry films, it is suggested that
cations. It offers better hot strength than Latex
adhesives be used within six months.
654 with a sacrifice in contactability.
Latex 750 a contains medium gel, slow crys-
tallizing polymer which gives an excellent
combination of flexibility, dry tack, heat-reac- Compounding
tivity and cohesive strength. It is used primar- Antioxidants. The presence of a good an-
ily in contact bond adhesives., . tioxidant in Neoprene compounds is essential
Latex 735A contains a sol polymer WhICh for adequate protection against oxidation.
gives the longest dry open tack time of all the Hindered bis-phenols, such as Wing stay L or
latexes. Its films are also the most readily heat Antioxidant 2246, are usually used where min-
reactivated. Latex 735A is generally used in imum discoloration and/or minimum staining
adhesives for wet laminating. is desired. Where discoloration ,is unimportant,
Latex 842A contains a very high gel polymer amine type antioxidants are used.
which crystallizes more slowly than the poly-
mer in Latex 571. It is used primarily in foil
Metal Oxides. Zinc oxide is the most effec-
laminating applications.
tive metal oxide. French-process-type zinc ox-
ide, which is low in lead content, is
Nonionic Type
incorporated into the latex as a dispersion. Zinc
Latex 115 contains a copolymer of chloroprene oxide serves three main functions: (1) pro-
and methacrylic acid, stabilized with polyvinyl motes cure; (2) improves aging, heat, and
304 HANDBOOK OF ADHESIVES

weather resistance; and (3) serves as an acid level. However, terpene phenolic resins are less
acceptor. tacky than many of the softer synthetic resins.
For most adhesive applications, 2 phr of an- They are frequently used in blends with other
tioxidant, and from 2 to 5 phr of zinc oxide are resins to achieve a better balance of hot strength
adequate to provide the desired performance. and open time.
In some more demanding applications, it may Resins are incorporated in Neoprene latex as
be beneficial to increase the amount of antiox- solvent-cut emulsions, solventless pebble-
idant and/or zinc oxide. Accelerated aging milled dispersions, or sometimes as solvent-
tests, simulating as close as possible the antic- free emulsions prepared using invert emulsifi-
ipated exposure the adhesive will encounter, cation techniques. In the latter case a resin with
should be conducted to be sure the amounts and a melting point of 80°C (176°F) or lower is
types of ingredients added to the Neoprene will melted. Water and surfactants are added to the
yield the performance required. molten resin and the temperature of the mixture
is decreased. Upon reaching a certain temper-
Resins. Because of colloidal incompatibil- ature, known as the phase inversion tempera-
ity, the metal oxide/t-butyl phenolic resin com- ture, the water in molten resin emulsion
plex which in solvent adhesives provides spontaneously inverts to form a resin in water
improved adhesion largely and hot strength is emulsion suitable for use in latex adhesives. A
ineffective in latex systems. Of the types of res- resin dispersion which can be prepared in this
ins which are commonly used in Neoprene la- manner is shown in Table 16. This particular
tex adhesives, only the terpene phenolics such resin dispersion can be used to produce adhe-
as Durez 12603 (Occidental) and SP-560 sives with moderate hot strength and good open
(Schenectady) do not cause an appreciable loss time using the following recipe:
in hot strength as the resin content is increased.
Others such as coumarone indene resins, liquid % Solids Dry Parts
terpene resins and rosin esters are valuable from Neoprene latex 671A 60 100
a standpoint of increasing adhesion and open Antioxidant 33 2
time, but decrease cohesive strength at elevated Zinc oxide 50 5
temperatures. This is illustrated in Fig. 8, Resin dispersion 50 30
where canvas-to-canvas peel strength at 70°C
(158°F) is plotted against resin level with sev-
Table 16. Resin Dispersion Made from
eral different classes of resins in Neoprene La-
Invert Emulsification Process.
tex 750. Only the terpene phenolic systems
provided adhesive failure, even at the 50 phr Resin Suspension Parts
Arizona Zonester 65 Resina 100
Witcomul 4089 b 3
20 rorp. Phon. ~50'C)
Igepal CO-970c 3
Deionized water 94
"". failure
Procedure:
"
1. Melt the resin and emulsifiers in a 100°C (212°P)
circulating air oven.
2. Add resin mixture to temperature controlled vessel
Coum.lnd.
~10'C) 85-90°C (l85-194°P), and stir until mixture cools
Rosin Ester
to 90-95°C (194-203°P).
(B3'C) 3. Add 6 g of 85°C (l85°P) water.
Penta. Ester 4. Cool mixture to 85°C (185°F). Slowly add 6 g of
(132'C)
85°C (l85°P) water. Mixture will become thick as
Phen. Coum.
Ind.~O'C)
it inverts.
rorl. Butyl Phon. (90'CI2OO+ 'C) 5. Add remaining water with thorough mixing. Cool to
room temperature without stirring. Particle size
o 10 20 30 40 50 75 should be 1-3 I'm.
Resin,Phr
'Rosin ester, Arizona Chemical Corp.
Pig. 8. Effect of resin type in neoprene Latex 750 adhe- "Rosin diethanol amide, Witco Chemical Corp.
sives. Bonds aged 7 days at R. T. 'Ethoxylated nonyl phenol, GAF Corporation.
 NEOPRENE (POLYCHLOROPRENE)-BASED SOLVENT AND LATEX ADHESIVES 305

The solvent-free systems offer several advan- or Latex 750 provide a good starting point in
tages over emulsions which utilize solvent to this formulation. The latter provides better
dissolve the resin: contactability at the expense of hot cohesive
strength.
1. Ability to produce lower viscosity adhe-
The second formulation is a contact bond ad-
sives, as one avoids the thickening action
hesive based on Neoprene Latex 115. It pro-
of the solvent;
vides good cohesive strength development
2. Higher resin content;
because of the reactivity of Latex 115. For best
3. Addition of flammable solvents IS
results, it should be used within six months
averted; and
after formulation.
4. Greater latitude in controlling rheology
The third and fourth formulations are de-
with synthetic thickeners is gained by
signed for high-speed lamination of aluminum
omission or reduction of the amounts of
foil to kraft and other papers. Neoprene Latex
solvent, soap, and casein usually present
654 is a suitable choice in the anionic recipe
in the emulsions.
because it can tolerate high filler loadings while
Fillers. The Neoprene latexes are not signif- retaining adequate "wet grab" performance.
icantly reinforced by the addition of fillers. Neoprene Latex 115 is also a good choice for
Fillers are used to reduce cost and control this application because of its excellent shear
rheology, solids content, and modulus. Both stability and adhesion. The fourth formulation
tend to reduce cohesion and adhesion. Hy- provides a suitable starting point for evalua-
drated alumina is often used when resistance to tion.
degradation by flame is important. In other
cases, calcium carbonate, clay, silica, and feld-
spar are commonly used. BIBLIOGRAPHY

1. Anon., "Neoprene Solvent Adhesives," DuPont

Typical Formulations Elastomers Bulletin.
2. Cuervo, C.R., and Maldonado, A.J., "Solution Ad-
Typical adhesives based on Neoprene latex are hesives Based on Graft Polymers of Neoprene and
presented in Table 17. The first is a general- Methyl Methacrylate," DuPont Elastomers Infonnal
purpose contact adhesive. Either Latex 671A Bulletin, October 1984.

Table 17. Neoprene Latex Starting-Point Adhesive Formulations.

Dry Pans
Foil to Foil to
Contact Paper Paper
Ingredient Contact Bond Banda Laminating Laminatinl
Anionic Neoprene latex polymer 100 100
Neoprene Latex 115 100 100
Antifoam as required X X
Surfactants as required X X X X
Zinc oxide 5 2 5 5
Antioxidant 2 2 2 2
Terpene phenolic resin 50
Liquid polyterpene resin 25
(low melting point)
Hydrogenated wood rosin or 30 20
rosin ester
Filler 100 100
Resimene 717< 5
Ammonium chloride 0.2
Thickener as required X X X X
'Adhesive should be used within 6 months.
bRef. 15.
'Melamine fonnaldehyde resin, Monsanto.
306 HANDBOOK OF ADHESIVES

3. Hennes, M.E., "Neoprene AF Handling Guide," prene-Solvent Systems," DuPont Elastomers Bulle-
DuPont Elastomers Infonna! Bulletin, September tin.
1972. 10. Anon., "Solvent Systems for Neoprene-Predicting
4. Tanno, T., and Shibuya, I., "Special Behavior of p- Solvent Strength, " DuPont Elastomers Bulletin.
tert-Butylphenol Dialcohol in Polychloroprene Sol- 11. Kelly, D.l., and McDonald, I.W., "Solution Com-
vent Adhesives," Adhesives and Sealants Council- patibility of Neoprene with Elastomers and Resins,"
Spring meeting 1967. DuPont Elastomers Bulletin, Oct. 1963.
5. Keown, R.W., and McDonald, I.W., "Factors Af- 12. McDonald, I.W., "Neoprene Adhesive Processing-
fecting Phasing of Neoprene Solvent Adhesives," High Shear Refining," DuPont Elastomers Informal
DuPont Elastomers Bulletin. Bulletin.
6. Crenshaw, L.E., "Neoprene AG-Effect of Filler 13. Doherty, F.W., "Neoprene Latex Adhesives,"
Type in High Viscosity Mastics," DuPont Elastomers DuPont Elastomers Infonna! Bulletin.
Report, Feb. 19, 1968. 14. Gelbert, C.H., "A Selection Guide for Neoprene La-
7. Megill, R.W., "Adhesives Based on Neoprene AG," texes, " DuPont Elastomers Bulletin.
Adhesives and Sealant Council-Spring Meeting 1968. 15. Gelbert, C.H. "Aluminum Foil to Paper Laminating
8. Nyce, I.L., "Neoprene AH-Aliphatic Hydrocarbon Adhesives Based on Neoprene Latex 115," DuPont
Dispersible Neoprene," DuPont Elastomers Infonna! Elastomers Infonnal Bulletin.
Bulletin, October 1973. 16. Gelbert, C.H., "Compounding Neoprene Latex for
9. Anon., "Factors Affecting Solution Viscosity in Neo- Colloidal Properties," DuPont Elastomers Bulletin.
 16
Polysulfide Sealants and Adhesives
JULIAN R. PANEK
Sealant Consultant
Yardley, Pennsylvania

The tenn polysulfide polymers referred at one potting compounds, caulks for wooden flight
time exclusively to the high-sulfur-containing decks which were designed as a stop gap in the
polymers as manufactured by the Thiokol early days of aircraft carriers, sealing and ad-
Chemical Corp. From 1928 to 1960 they were hering methacrylate bubbles on aircraft, seal-
the only high-sulfur polymers available. The ing cocoons in the mothball fleets, adhering
solid poly sulfide polymers contained 37-82 % aluminum strips on wings for reducing air tur-
bound sulfur, while the liquid polymers contain bulence during flight, and many others. Most
approximately 37 %, which gives them their of these were emergency measures adopted for
unique chemical properties. immediate use during the early 1940s and cov-
Between 1960 and 1976 several new mercap- ered by quick-issue military specifications.
tan tenninated polymers having varied polymer Use of poly sulfides is at present largely re-
backbones were introduced. These are covered stricted to sealants and insulating glass. Where
in the section entitled "Other Mercaptan Ter- these polymers were dominant in the 1960s and
minated Polymers." The chemical resistance early 1970s, they are now a poor third as build-
of these various polymers can vary depending ing sealants, giving way to silicones and ure-
upon their backbone structure and, on this ba- thanes. The decline of poly sulfide sealants in
sis, should be evaluated on their own relative the U. S. has been due in part to a price war
merits. which resulted in inferior-quality building seal-
ants, causing many suppliers to switch to ure-
thane. Some companies made their own
POL YSULFIDE SEALANTS
urethane-base polymers while others bought a
Sealants based on poly sulfide liquid polymers prepolymer from several sources. Another rea-
originally found wide acceptance for applica- son for the decline was the better perfonnance
tions requiring a flexible, adhering, chemically available with urethane and silicone sealants.
resistant composition of matter. Since they In Europe, the polysulfide sealants have a bet-
were the first liquid polymers available that ter market because of more rigid control of per-
could be cured at room temperature, they were fonnance, application, and specification.
soon specified for a number of military appli- One continuing large application for poly sul-
cations. Their use as aircraft sealants for fuel fide sealants is as a glass adhesive for making
tanks still remains as a major outlet. Other mil- insulating glass units. This application started
itary applications included a quick hose repair out in a small way in the early 1940s using a
compound, a sealant for bolted steel tanks for plasticized solid poly sulfide polymer; but this
quick assembly on the battle front, electrical was quickly replaced by the more versatile liq-

307
308 HANDBOOK OF ADHESIVES

uid polymer. In recent years, poly sulfide seal- Areas where the polysulfide sealants are still
ant, while still first, has been steadily giving used include dental impression compounds,
ground to other systems including butyl hot cast printing rolls, casting compounds for flex-
melt and the dual system of silicone/polyiso- ible molds, electrical potting, and miscella-
butylene. The hot melts are cheaper, and lend neous adhesives.
themselves to automation and lower labor costs. Poly sulfide sealants are excellent adhesives
The polysulfide systems are ending up as lower and adhere to a wide variety of surfaces; but
quality units for public housing and the home price inevitably plays a major role in the final
repair market which are not greatly affected or selection of material used for high-volume ap-
controlled by specifications. The high quality plications.
market for industrial and high rise buildings is
now using some poly sulfide, but the best units
are made using a dual system of silicone/poly- Chemistry
isobutylene. The trend will continue, with Many of the sealants have been prepared using
polysulfide losing out where high quality and Thiokol® LP®-2, LP®-32 or LP®-31 as the base
good performance specification will prevail. poly sulfide liquid polymer; the chemistry, cure
Another large market in the past was the use mechanisms, reinforcement, and applications
of poly sulfide sealant as a glass adhesive for will thus be restricted to these polymers. The
installing automotive windshields. In the orig- chemistry and applications of polysulfide poly-
inal process, the glass was attached by metal mers, crudes, water dispersions, and various
trim on the assembly line. General Motors de- liquid polymers are covered completely in ex-
signed a three-part mixer which was made by tensive bibliographies by Berenbaum and Pa-
Pyles Industries, and the use of the very fast- nek. 21
curing poly sulfide actually lowered total costs. The general preparation of polysulfide liquid
Thus poly sulfide was adopted by General Mo- polymers, as discussed by Patrick and
tors for many of their models; later, Chrysler Ferguson22 involves first the reaction of bis-
joined. This market lasted for approximately chloroethyl formal with a sodium poly sulfide
five years; but eventualty the polysulfide was solution containing specific emulsifying and
replaced by a simpler system consisting of a nucleating agents as shown below:
one-part urethane activated by mixing water
into the sealant just before use. Here again, cost
savings dictated the final selection.
The replacement market started out using a
two-part poly sulfide which was difficult to han-
dle. This was quickly replaced by the one-part The sulfur is present as a mixture of disulfide
silicone, which was more expensive but more and trisulfide.
foolproof. In the replacement market, labor
In the next step, the high molecular weight
costs were less important. polymer is split into segments which are simul-
Another large market which htld sway for taneously terminated by mercaptan groups as
approximately 6 years in the early 1960s was shown below:
the use of the sealant for military runway ex-
pansion joints. These sealants were highly ex- RSSR + NaSH + NaHS0 -------------------.
3
tended with filler and coal tar, and used
specialty polymers to meet the required low
cost. The bubble burst when the sealants hard-
ened with time, lost adhesion, and had to be
The concentration of splitting salts controls
replaced. The new system was a hot melt of
the average molecular weight of the LF®2 and
plasticized PVC, which has done an admirable
job with a simpler system and was eventually
covered by ASTM specifications. @Registered trademark of Thiokol Chemical Corp.
 POLYSULFIDE SEALANTS AND ADHESIVES 309

LF®32, which have the following average for- 2. Building sealants. In practice, polymer
mula: ratios have been observed to be lower.
3. Insulating glass sealants; the lower plas-
HS( -C2H40CH20C2~SS- b ticizer content and higher filler content
give the higher hardness which is needed
-C2~OCH20C2H4SH
for this application.
Both polymers are prepared at an average 4. Aircraft sealants, where plasticizer con-
molecular weight of 4000, and they differ only tent is kept at a minimum to reduce ex-
in the mole percentage of crosslinking agent traction by jet fuels.
(trichloropropane) used in the initial reaction. 5. General purpose casting compound with
LP-2 is made using 2 mole % of trichloropro- high plasticizer and good flow properties.
pane, whereas LP-32 is prepared with 0.5 %. The various groups of compounding ingredi-
Decreasing the crosslinking agent gives lower ents are discussed separately.
modulus and higher elongation desirable in ap-
plications involving greater movement. In some Curing Agents
instances LP-31 is used in sealant applications;
it differs from LP-32 in that it has a higher mo- While a large number of curing agents have
lecular weight and viscosity. The physical been tried, only a few have been found satis-
factory. A technical grade of lead dioxide is
properties of the three polymers used in sealant
applications are compared in Table 1. used for most two-part building sealants and
casting compounds. Stearic acid is used as a
Compounding retarder which is incorporated in the curing
agent paste. The paste is usually 50% lead
Poly sulfide sealants are formulated using rein- dioxide, 45% plasticizer, and 5% stearic acid.
forcing fillers, plasticizers, adhesive additives, A technical grade of manganese dioxide is
and curing agents. Table 2 illustrates five types used as a curing agent for insulating glass seal-
of compounds for use in several industries: ants since the cured compounds have better UV
1. One-part sealants, which generally use a resistance through glass and retain adhesion for
lower polymer content for better package extended periods of time. A base serves to ac-
stability. celerate the manganese dioxide to give about

Table 1. The Physical Properties of LJl® Polysulfide Liquid

Polymers.
LP-3J LP-2 LP-32
Viscosity at 25°F (poises) 800-1400 375-425 375-425
Average molecular weight 8000 4000 4000
Specific gravity 1.29 1.29 1.29
Refractive index 1.5728 1.5689 1.5689
Pour point (OF) 50 45 45
Flash point, (open cup)OF 455 450 455
Fire point, (open cup)OF 475 475 485
Crosslinking agent (%) 0.5 2.0 0.5

Table 2. Good Formulations for Several Applications, by Weight

J 2 3 4 5
polysulfide polymer 20 35 30 65 35
fillers 50 40 50 25 35
plasticizers 25 20 15 5 27
adhesion additive 2 2 2 2
curing agents 3 3 3 3 3
310 HANDBOOK OF ADHESIVES

30 minutes of work life and a cure in approxi- trusion properties; but it is kept at a minimum.
mately 8 hours. The compounds are adjusted to Insulating glass sealants would require less vol-
work with proper equipment. atile plasticizers in order to eliminate any fog-
One-part sealants use calcium peroxide as a ging within the unit.
curing agent since it is inert in an anhydrous
environment. In this sealant, barium oxide is Adhesion
incorporated as a dehydrating agent which is
Where adhesion is required, all sealants need
added last, but just before the addition of the
an adhesion additive. For two-part building
calcium peroxide paste. The barium peroxide
sealants, a selected phenolic resin (Methylon
picks up 6 molecules of water of hydration and
AP-108, General Electric) has been very sat-
is very effective in making the sealant package
isfactory. A silane monomer is used for the one-
stable.
part sealants. Aircraft sealants have used a se-
Other curing agents have included inorganic
lected phenolic resin which is more resistant to
chromates in aircraft sealants requiring better
the jet fuels. A Durez resin, #10694 (Occiden-
heat resistance. Some manganese has also been
tal Chemical Corporation) has been most sat-
used for aircraft sealants. Cumene hydroperox-
isfactory.
ide has found a place in a few casting com-
pounds; but in building sealants, it interferes
Primers
with adhesion.
All building sealants contain adhesion addi-
tives, but many times this is not enough. For
Fillers
bare metals, a dilute silane based primer is rec-
Some reinforcement is required for poly sulfide ommended. For porous surfaces, a film-fonn-
sealants. For aircraft compounds, some carbon ing primer is needed to seal off any water that
black is needed for higher physicals. For all might migrate to the interface. Primers have
other applications the chief fillers are the cal- also been used to seal off any gases that might
cium carbonates, which are available as ground penneate through the substrate. For unusual
marble dust or a precipitated grade. The cheap- building surfaces, all sealant manufacturers
est sealants use mostly marble dust, but some have additional primers in their bags of tricks.
precipitated grade is needed for thixotropy con- The masonry primers generally contain a chlo-
trol. rinated rubber or a modified phenolic resin or
For insulating glass sealants, some titanium both, along with some plasticizer. The primer
dioxide serves to make the base white, while a is very specific for the sealant, and is supplied
small amount of carbon black is added to the by the sealant manufacturer. The low-solids
catalyst. Since the components are mixed by silane primers provide monomolecular films
pumping metered amounts of both components which result in adhesion to metals, glass, and
through a patented static tube, any streaking ceramincs.
will indicate incomplete mixing. A thorough
mix gives a unifonn light gray color. Some cal- Specifications
cined clay has been used in building sealants to
Specifications for building sealants include the
neutralize the alkalinity from the carbonates.
Federal specifications TT-S-00227E for multi-
Lithopone and zinc sulfide have been used in
place of titanium dioxide. part and TT -S-00230C for one-part, as well as
ASTM C-920 for both parts. This specification
has been selected in 1972 by the National Bu-
Plasticizers reau of Standards to replace the Federal speci-
At one time the chlorinated diphenyls were fications. Other military specifications which
widely used in poly sulfide sealants; but be- are still being used are:
cause of their toxicity they were replaced by 1. MIL-S-7502C-aircraft fuel tank sealing.
phthalate, phosphate, and glycolate esters. 2. MIL-S-8802C-high temperature resist-
Some toluol solvent is used to improve the ex- ant fuel tank sealing.
 POLYSULFIDE SEALANTS AND ADHESIVES 311

3. MIL-S-8516C-electrical potting. been studied. The most widely used resins are
4. MIL-C-15705A-seam sealer for air- found in the viscosity range of 80 to 200 poises
craft. and have an epoxy equivalent of 175 to 210.
Examples of epoxy resins within this classifi-
ADHESIVES FROM POLYSULFIDE cation are Epon* 820 and Epon* 828 (Shell
LIQUID POLYMER-EPOXY RESIN Chemical Co.), ERL-3794 (Union Carbide),
REACTIONS and Araldite* 6020 (Ciba Co.,).
The epoxy resins, which are reaction prod-
The first reactions of poly sulfide liquid poly-
ucts of bisphenol A and epichlorohydrin, have
mers with epoxy resins were studied by Fettes
the following idealized formula:

and Gannon. 23 It immediately became apparent This reaction between polysulfide liquid poly-
that the reaction between these two classes of mers and epoxy resins is catalyzed or promoted
polymeric compounds gave reaction products by organic amine compounds. Although a con-
which could be considered in compositions for siderable number have been evaluated, final se-
applications involving castings, coatings, lam- lection has narrowed the list down to a few
inates, potting, adhesives, etc. The complete practical catalysts among which are: DMP-30®,
treatment of this extremely versatile class of re- Rohm and Haas) (tri-dimethylamino-
action compounds is given by Berenbaum and methyl phenol), DET (diethylenetriamine), and
Panek. 21 BDA (benzyldimethylamine). The amine cata-
This discussion will be limited to adhesive lysts are used in a fairly high ratio, in most
compounds. In formulations developed for ad- cases 10% based on weight of the epoxy resin.
hesives, the epoxy resin is the major compo- Because of the coreaction of primary amines
nent. However, modification of the epoxy resin such as DET, they are more properly classified
with polysulfide liquid polymers gives compo- as reactive hardeners. The general reaction of
sitions which in many cases have unique phys- a poly sulfide liquid polymer, an epoxy resin,
ical and chemical properties. and a primary amine hardener is:

Chemistry -RSH + C-C-R'-C-C + -R"NH --+

~O/ ~O/ 2
Of the several poly sulfide liquid polymers -RS-C-C-R'-C-CN-R"-
which have been studied, LP-3 has been used I I I
most extensively. The average formula for this o 0 H
H H
polymer is:

HS( C2H40CH20C2H4SS)8 Physical Properties

C2~OCH20C2H4SH LF®-3 polymer, when used to modify a liquid
epoxy resin cured with DMP-30, accelerates
This polymer has an average molecular the cure and increases the maximum tempera-
weight of 1000 and a viscosity of7 to 12 poises. ture due to reaction exotherm. The use of LP-
It is prepared using 2 mole % of trichloropro- 3 with epoxy resins gives compositions which
pane, which gives a measurable amount of have higher elongation, greater impact resis-
crosslinking when cured alone; this, however, tance, and less brittleness. The effect of in-
is not readily apparent when cured with epoxy creasing amounts of LP-3 on the physical
resins.
A number of liquid epoxy resins as well as
blends of liquid and solid epoxy resins have iIIRegistered trademark, u.s. Patent Office.
312 HANDBOOK OF ADHESIVES

properties of a liquid polymer epoxy resin is The data compare compositions after an oven
given in Table 3. cure of 1 hr at 250°F, which is considered op-
It is interesting to note the increase in tensile timum. Shear bond strengths of LP-3-modified
properties of the epoxy resin by adding up to compositions are appreciably higher than
50% LP-3. The straight epoxy-resin cured straight epoxy compositions in various envi-
compound theoretically has higher tensile, but ronments involving changes in temperature or
due to its low elongation, breaks before its ul- immersion media.
timate tensile may be realized. The combina- Similar improvement is obtained in peel and
tion of increased flexibility, tensile strength, bend strengths, a result of improved flexural
and elongation is very desirable in adhesives. properties through the use of LP-3.
The improved impact resistance of compo-
sitions containing LP-3 is apparent as well as
very desirable in certain adhesive formulations.
Applications
The heat distortion temperature is only
slightly affected by the incorporation of 20% One very practical application for the LP-3
LP-3, but at 1: 1 ratio the drop may become epoxy adhesives is in bonding old-to-old con-
significant. This is illustrated by the fact that a crete and new-to-old concrete. These adhesives
straight epoxy resin cured with DET has a heat have definite applications in the construction
distortion temperature of 55°C which is re- and maintenance of concrete structures such as
duced to 54°C when the LF®3/epoxy resin ra- highways, bridges, buildings, dams, airport
tio is 1: 4, to 50°C at a 1: 2 ratio; and to 40°C runways, sidewalks, driveways, commercial
at a 1 : 1 ratio. These specific properties prevent and industrial floors for patching, overlaying,
the use of such compositions at elevated tem- surface sealing, and skid proofing, as well as a
perature adhesives but do not deter their use number of other operations. Table 5 illustrates
when proper temperature limitations are main- the improved adhesive properties obtained
tained. using an LP/EP concrete adhesive as compared
The electrical properties of LP-3 epoxy resin to a straight epoxy resin compound. The LP/
compounds are only slightly lower than those EP compounds show considerably improved
of unmodified epoxies, even when a 1: 1 ratio bond strengths that, in almost all cases are lim-
is used.· These compounds thus can be used in ited only by the strengths of the concrete. These
electrical potting. compositions are unique in applications involv-
The adhesive properties of LP-3/epoxy com- ing adhering new freshly poured concrete to old
pounds are better than those of the epoxy alone, concrete. Bonds based on these assemblies ex-
as is illustrated in Table 4. hibit the same adhesive values.

Table 3. The Effect of Li'®3 Polymer on the Physical Properties of Liquid Epoxy
Resin.
Epoxy resina 100 100 100 100 100 100 100
LP-3 25 33 50 75 100 200
DMP-30 10 10 10 10 10 10 10
Physical Properties on Sheets Cured for 7 days at 77°F.
Tensile (psi) 3500 5500 6500 7200 3075 2350 150
Elongation (%) 0 1 2 5 7 10 300
Shore 0 Hardness 80 80 80 80 76 76 15
Coefficient of linear expansion
(in./in.fC x 10 5) 4.5 5.5 6.0 7.5 10.0 13.5 15.0
Impact resistance (ft-lb) 2 3 5 27 70 100

a Liquid epoxy resin, epoxy equivalent 175 to 210.

* Registered trademark u.s. Patent Office.
® Registered trademark of Thiokol Chemical Corp.
 POLYSULFIDE SEALANTS AND ADHESIVES 313

Table 4. Comparison of Adhesive Table 5. Comparison of Concrete

Values on Aluminum. Adhesive Values.
Straight Epoxy LP/EP Straight LP/EP
Control Adhesive Epoxy Concrete
Control Adhesive
A B A B A B A B
Thiokol® LP-3 100 Thiokol® LP-3 100
Liquid epoxy resina 100 100 Silica Filler 50 80
Calcium carbonate 100 71 179 DMP-30 7.5 20
EH-330 15 15 Liquid epoxy resina 100 200
AlB ratio 1/120 1/1
A/B ratio 1/13.3 1/1.5
Cure (considered
optimum) 1 hr at 250°F 1 hr at 250°F Tensile Adhesion Values, psi
Tested at room
Tensile shear bond strengths psi tested at 0.05 in.lmin temperature and
Tested at room after 7 days cure 0-150 345
temperature 1700 4500 Tested at room
Tested at 180°F 2000 1500 temperature and
Tested at _67° F 1400 2500 after 7 days
Peel Strength lb/in. 8 18 water immersion 0-150 335
Bend Bond Strengths Ib 100 140 Verticle Bond-Flexural Strength Ib/sq in
Tested at room
Shear Bond Strengths after 30 Days Drop Immersion
in Various Media at 80°F. temperature and
after 7 days cure 35 335
Water 1000 1700
Seawater 0 1100 Note: Values are practically identical whether bonding old-
JP-4 fuel 1800 3200 to-old concrete or new-to-old concrete. Concrete was pre-
Isopropyl alcohol 2000 3200 pared using ASTM Designation C-185. Tensile adhesion
Ethylene gylcol 1600 3700 assemblies and tests complied with ASTM Designation C-
Engine oil 1700 3200 190, whereas flexural assemblies and tests complied with
Methyl ethyl ketone 1600 500 ASTM Designation C-348.
Dibutylphthalate 1800 3400 Comparison of Shear Strength at Various
Temperatures (psi)
a Liquid epoxy resin epoxide equivalent 175 to 210.
Straight LP/EP
Epoxy Concrete
OTHER MERCAPTAN-TERMINATED Control Adhesive
POLYMERS
Tested at room
In recent years three classes of mercaptan-ter- temperature and
minated polymers have been introduced to in- after 7 days cure at:
dustry. In the 1960s Diamond Alkali offered ("F)
several polymers having a polyether backbone 150 400 4200
terminated with mercaptan groups.1.2 These 212 300 4300
350 100 100
polymers were cured in the same manner as the
Thiokol poly sulfide polymers, but were with- "Liquid epoxy resin, epoxide equivalent 175-210.
drawn after several years, since their properties
were generally poorer and offered no advan- Hooker Chemical introduced pilot plant batches
tages. Products Research came out with poly- of still another commercial venture. These poly-
mers having a urethane backbone but with mers had a polyethylene backbone and mercap-
mercaptan terminals; however, they sold only tan terminals, but the polymer had a very high
finished sealants, mainly for the insulating glass sulfur content of 55 %. The venture was
industry. These polymers are still being man- dropped when again the polymers had poorer
ufactured by PRC. 4 ,19,2o In the early 1970s properties than the Thiokol poly sulfide poly-
314 HANDBOOK OF ADHESIVES

mers. The References cite a number of patents These polymers are cured using Pb02 and other
covering various mercaptan-terminated poly- oxidizing agents.
mers of academic interest. In the summary be-
low, the literature is grouped into similar Urethanes
polymeric backbone structures wherever pos-
sible. Bertozzi8 synthesized a class of polythiopoly-
mercaptan-polyurethane polymers by reacting
disulfide-containing polyols, diisocyanates,
Polyethers and dimercaptans. These polymers were read-
Several patents are cited which involve a poly- ily cured with oxidizing agents. Gobran9 caps
ether backbone. LeFave and Hayashi prepared urethane prepolymers with nonpolymeric
polymers having a poly (oxyalkalene) polyol polymercaptans to yield mercaptan terminated
backbone terminated with mercaptan groups by ureas, thio-urethane linked polyesters, or poly-
esterifying the polyol with thio-substituted or- ether polyurethanes. Bertozzi reacted mer-
lO

ganic acids. These polymers were cured with captoalcohols with organic polyisocyanates to
tetramethy-thiuramdisulfide and Mn02' Le- yield mercaptan-containing polyurethane com-
Fave and others2 also prepared similar poly- positions which were easily cured with Pb02
mers by reacting the polyols with an and Lh02.19 Smithll prepared mercaptan-ter-
epihalohydrin and then reacting the intermedi- minated urethane-linked polyethers by reacting
ate with sodium sulfhydrate. These polymers a polyether glycol with an epihalohydrin, then
are cured with Pb02, Mn02' Zn02 and Ti02 to reacting with a polyisocyanate. This polymer
give rubbery products. was then treated with an alkali metal sulfhy-
Ephraim3 prepared thiol-terminated poly- drate to remove the chlorine terminals and yield
ethers by polymerizing a halogen-containing the desired polymers.
epoxide alone or in combination with an alky-
lene oxide and then converting the halo groups Olefin
to thiol groups using an alkali hydrosulfide. Noll and McCarthyl2 prepared branched chain
Morris and others4 reacted a poly (oxyalky- mercaptan-terminated polybutadiene by poly-
lene) glycol with an alkali metal in dispersion, merizing the polybutadiene with a xanthogen
and treated the alcoholate with a halogenated disulfide and pyrolyzing the ester. Weinstein
organic compound, and then reacting further and others 13 reacted a conjugated diene with
with a sulfur containing compound and, fi- sulfur which is then hydrogenated to produce
nally, hydrolyzing with an alkali metal to yield polymers of low molecular weight containing
the mercaptan terminated polyether. mercaptan groups. Wamer l4 and Franz l5 re-
Nummy5 prepared intermediates by reacting acted conjugated dienes with H 2S to yield mer-
the divinyl ether of diethylene glycol with H2S captan derivatives of polybutadiene, alone or in
to yield the bis(2-mercaptoethyl) ether of di- combination with other coreactants.
ethylene glycol, then oxidized this monomer to
give a range of mercaptan-terminated liquid Miscellaneous
polyether polymers.
Jones l6 prepared polyether-polyester polymer-
captans by reacting polyols with mercaptoor-
Polyesters
ganic acids and oxidized the resulting
Erickson6 reacted diacrylate-terminated esters prepolymers to give higher molecular weight
with H2S to obtain mercaptan-terminated poly- polymercaptans which were easily cured with
mers. These polymers can be cured using di- Pb02. Warner I7 irradiated mixtures of ethyl-
cumyl peroxide and MgO to give rubbery com- cyclohexyl-dimercaptan and vinyl cyclohexene
pounds. Cameron and Duke7 disclosed to yield thiol-terminated polymers.
mercaptan-terminated polyesters made by re- Bertozzi 18 prepared polymercaptan polymers
acting glycols with mercapto-organic acids. by reacting polymers containing geminal di-
 POLYSULFIDE SEALANTS AND ADHESIVES 315

thioether linkages with water in the presence of 12. Noll, R. F., and McCarthy, W. T. (to B. F. Goodrich
a strong nonoxidizing acid. Co.), British Patent 1,139,655 (Jan. 8, 1969); U.S.
Patent 3,449,301 (June 10, 1969).
13. Weinstein, A. H., Constanza, A. J., Coleman, R. J.,
and Meyer, G. F., French Patent 1,434,167 (April 8,
REFERENCES
1966).
14. Warner, P. F. (to Phillips Petroleum), U.S. Patent
1. LeFave, G. M., and Hayashi, F. Y. (to Diamond Al- 3,234,188 (Feb. 8, 1966) and 3,051,695 (Aug. 28,
kali Co.), U.S. Patent 3,278,496 (Oct. 11, 1966). 1962).
2. LeFave, G. M., Hayashi, F. Y., and Fradkin, A. W. 15. Warner, P. F., and Franz, R. J. (to Phillips Petro-
(to Diamond Alkali Co.), U.S. Patent 3,258,495 (June leum), U.S. Patent 3,282,901 (Nov. 16, 1961).
28, 1966). 16. Jones, F. B. (to Phillips Petroleum), U.S. Patent
3. Ephraim, S. N. (to Synergy Chemicals), U.S. Patent 3,475,389 (Oct. 31, 1966).
3,361,723. 17. Warner, P. F. (to Phillips Petroleum), U.S. Patent
4. Morris, L., Thompson, R. E., and Seegman, I. P. (to 3,484,355 (Nov. 10, 1966).
Pmducts Research and Chemical Corp.), French Pat- 18. Bertozzi, E. R. (to Thiokol Chemical Corp.), U.S.
ent 1,474,343 (Mar. 24, 1967); U.S. Patent 3,431,239 Patent 3,413,265 (Nov. 26, 1968).
(Mar. 4, 1969). 19. Seegman, I. P., Morris, L., and Mallard, P. (to Prod-
5. Nummy, W. R. (to Dow Chemical Co.), U.S. Patent ucts Research Corp.), U.S. Patent 3,255,017 (Dec.
2,866,766 (Dec. 30, 1958). 21, 1965).
6. Erickson, J. G. (to Minnesota Mining & Mfg. Co.), 20. Seegman, I. P., Morris, L., and Thompson, R. E. (to
U.S. Patent 3,397,189 (Aug. 13, 1968). Products Research Corp.), U.S. Patent 3,431,239
7. Cameron, G. M., and Duke, A. J. (to Ciba Ltd.), U.S. (March 4, 1969).
Patent 3,465,057 (Sept. 2, 1969). 21. Berenbaum, M. B., and Panek, J. R., in "Polyethers,
8. Bertozzi, E. R. (to Thiokol Chemical Corp.), U.S. Part III, V (Polyalkylene Sulfides and Other Poly-
Patent 3,440,273 (Apr. 22, 1969). thioethers)", pp. 43-224, N. G. Gaylord, ed., Inter-
9. Gobran, R. (to Thiokol Chemical Corp.), U.S. Patent science Publishers, New York, 1962.
3,114,734 (Dec. 17, 1963). 22. Patrick, J. C., and Ferguson, H. R. (to Thiokol
10. Bertozzi, E. R. (to Thiokol Chemical Corp.), U.S. Chemical Corp.), U.S. Patent 2,466,963 (Apr. 12,
Patent 3,446,780 (May 27, 1969). 1946).
11. Smith, M. B. (to Teledyne, Inc.), U.S. Patent 23. Fettes, E. M., and Gannon, J. A. (to Thiokol Chem-
3,547,896 (Dec. 15, 1970). ical Corp.), U.S. Patent 2,789,958 (Apr. 23, 1957).
 17
Phenolic Resin Adhesives
FRED L. TOBIASON
Department of Chemistry
Pacific Lutheran University
Tacoma, Washington

Phenolic resins have played an important role plastics as well as to economic factors. Since
in industrial advancement for over 80 years. new phenolic composites show excellent ther-
The tenn phenolic is applied to those materials mal stability and flame retardant characteris-
fonned during the condensation reaction be- tics, considerable development and growth are
tween phenol or substituted phenols and for- expected in many specialty areas. Sections are
maldehyde. Although Adolph Baeyerl first included in this chapter on molding compounds
reacted phenol and an aldehyde in 1872 to pro- and coatings to examine some of the special
duce a resinous material, and Arthur Smith was ahdhesive binding properties of phenolic resins
issued the first phenolic resin patent in 1899, 2 when used in other than thin films.
it is Leo H. Baekeland who is considered the Scientific activity continues to grow in both
creator of the phenolic resin industry. He pub- basic research and applications. It is interesting
lished a series of papers3 ,4 beginning in 1905, to look at the patents6 issued by country during
and established the Bakelite Company in the the years 1981-1987. The results in Table 2
U.S. in 1910. This eventually became a divi- show substantial commercial development in
sion of the Union Carbide Company in 1939. 2 the phenolic field and also illustrate the large
Over the years many scientists have helped contribution from Japan to the patent literature.
make phenolic resin products an integral part In 1982-1986 alone6 there were 4620 articles,
of modem life. excluding patents, pertaining specifically to
The basic production dataS shown in Table 1 phenolic chemistry and technology.
illustrate the large quantity of phenolic resins
used in United States markets from 1983 to
CHEMISTRY
1987 as well as the important product lines. The
total resin output has grown from 2.54 to 2.76 Building upon the early work in phenolic resins
billion lb during those five years. However, which was summarized in several excellent
from examining the table it is apparent that ply- books,7-1O considerable advancement has been
wood adhesives and related housing markets made in understanding the chemistry, molecu-
consume the largest quantity of resin and con- lar structure and application properties of phe-
tinue growing, but that product lines such as nolics. Much of this new insight parallels the
abrasives, foundry, and molding resins have enonnous growth in instrumentation and new
been decreasing. Some of these reversed trends techniques such as superconducting Fourier
are due to competition from other engineering Transfonn nuclear magnetic resonance

316
 PHENOLIC RESIN ADHESIVES 317

Table 1. Phenolic Resins Consumption, millions of Ib. 5

Market 1983' 1984a •b 1985 1986 1987
Bonding and adhesive resins for:
Coated and bonded 29 26 16 17 18
abrasives
Fibrous and granu- 179 183 217 235 226
lated wood
Friction materials 33 37 26 27 29
Foundry and shell 71 79 77 41 41
moldings
Insulation materials 355 353 419 420 421
Laminating:
Building 40 37 32 40 48
Electricallelectronics 31 33 20 22 25
Furniture 20 20 20 22 25
Other 75 73 70 83 95
Plywood 1312 1323 1255 1270 1346
Molding compounds 231 245 209 195 197
Protective coatings 18 20 23 22 . 23
Export 22 26 21 18 20
Other 121 128 235 250 250
TOTAL 2537 2583 2640 2662 2764
'Converted from metric tons.
bSome slightly different values were given in Mod. Plast., 63, 62 (1986).

Table 2. 1981-1987 Patent Activity in Phenolics by Country.a

Total
Patentl' Years USA Canada Japan West Germany France Britain Sweden USSR
2,205 1980-81 162 14 1,199 211 50'" 56 105 279
6,688 1982-86 590 31 4,217 822 506 495 475 536
1,818 1987 110 5 1,287 248 157 155 72 53
10,711 1980-87 862 50 6,703 1,281 713 706 652 868
'Patents documented as given by the country. This includes some multiple single patent entries to countries from the EPO and WIPO.
"The primary phenolics patents (single entry)-all countries.
'Estimated value.

(FTNMR) and advanced chromatographic sep- oils derived from cashew nutshell liquid are
arations. Several recent treatises on phenolics also used. Because the catalyst, mole ratio of
are available. 11-15 phenol to fonnaldehyde, reaction conditions,
Phenolics which are fonned when the molar addition sequence, and solvent conditions can
ratio of formaldehyde to phenol is greater than be varied, an enonnous variety of products can
one are called resoles. The phenol moieties are be tailored for specific end uses. When phe-
tenninated with reactive hydroxymethyl groups nolic resins are involved in composites, the va-
(-CH20H), known as methylol groups. If the riety of properties becomes even richer. The
mole ratio of fonnaldehyde to phenol is less majority of the syntheses rely on formalde-
than one, the polymer becomes phenol termi- hyde, so it is important to examine the nature
nated and is called a novolak. All phenolic of this structure in solution.
chemistry today revolves about these two basic
chemistry strategies. Although phenol is most
Formaldehyde
commonly involved in phenolics, resins con-
taining p-t-butylphenol, p-t-amylphenol, p- The reaction mechanism for the fonnation of
nonylphenol, mixed cresols, and substituted phenolic resins under acidic or basic catalysis
318 HANDBOOK OF ADHESIVES

conditions depends on the molecular nature of stems from an early trademark named by
the formaldehyde in the reaction medium. For- Baekeland22 in 1909. This original shellac sub-
maldehyde is found in aqueous solution as a stitute became known in its generic form as no-
series of oligomeric poly(methylene) gly- volac. In general, the novolak resins are called
COIS,16,17 two-step resins, since in order to effect a cure
another reactive component needs to be added
to the system. This can be a resole, an amino-
phenol, or more commonly, hexamethylene-
The most concentrated component in this tetramine (HMTA).
complex equilibrium is methylene glycol 16 (n Novolak materials do not contain active
= 1) with a formation equilibrium constant, K methylol groups as do resoles, and conse-
= 5 X 102 at 60 o e. Studies on the l3e NMR quently are relatively stable to molecular weight
spectra of the glycol 0ligomers l8 ,19 and the re- advancement. They are amorphous thermo-
action mechanisms under acidic and basic con- plastics that can be stored easily as powdered
ditions have been done. 2o In an acidic medium or flaked materials. According to Vansheidt,
the unique formaldehyde molecule takes the number average molecular weights varied in
form of a carbonium ion, whereas in a basic parabolic form from 200 at an F/P = 0.1 ratio
medium it reacts through an ionic species gen- to 1000 at a 0.8 ratio. 23 Others have found
erated from the diglycol molecular form. It was number average molecular weights of 950 by
shown in an early NMR study by Woodbrey21 VPO at a mole ratio of 0.83 24 and 900 by GPe
that if other hydroxyl groups are present, like at a mole ratio of 0.80 15 . Molecular weights of
on phenol or methanol, hemiacetals are formed. fractionated F/P = 0.83 novolaks range from
Raman and infrared spectra and other specific 200 to 8,000. 25 ,26 Glass transition temperatures
reactions are covered in Meyerl6 and Walker. 17 Tg range from 50 0 e uncured27 ,28 to 287°e
when fully cured in composites. 29
Novolaks
Strong Acid Reactions
Resins that are made using acid catalysis and
mole ratios of formaldehyde to phenol less than The reaction mechanism in a strong acid me-
one are called novolaks. The word novolak dium with pH < 4 is shown in Eqs. (2)-(5).

HO~CH 2~OH • H' --.

~
'CH 2--OH • H 2 O
(2)

© 0"
OH OH OH

©~",O"
alow f.a.
+ 'CH 2 OH --.-
L-
CH 2 0H --.-
L-
• H' (3)
~.

©r";
OH

(4)

(5)
 PHENOLIC RESIN ADHESIVES 319

The rearrangement to methylol phenol as shown hance the cure rate of these resins when com-
in Eq. (3) is very fast in a strong acid medium. pared to the mixed isomeric and branched
The methylol group is then converted to a car- resins. The high-ortho resins are generally pre-
bonium ion which readily reacts with a neutral pared in aqueous solutions containing Ca, Mg,
phenol molecule to form a dihydroxydiphen- Zn, Cd, Co, Ni, Cu, or Pb divalent salts in a
ylmethane, Eq. (5).12 Consequently, with mole pH range of 4-6. One of the preferred catalysts
ratios of formaldehyde to phenol less than one, is zinc acetate. The novolak processes make use
no methylol groups are found in these struc- of large molar excesses of phenol, with final
tures. 11 The reaction kinetics for systems con- postreaction temperatures at 150-160°C to
taining an excess of phenol are first order in promote condensation of the hydroxymethyl
formaldehyde and independent of the chemical groups. 11 The reaction mechanism thought re-
nature of the formaldehyde when added. Acid sponsible for this pathway is the metal ion
catalysts employed in novolak syntheses in- complexation in the ortho position of the 0-
clude hydrochloric, sulfuric, oxalic, p-toluene- methylolphenol.
sulfonic, and phosphoric acids. The pH in the
synthesis is commonly in the range of 0.5-1.5 Resoles
and the formaldehyde used is typically 37-50
Resoles contain methylol end groups and are
wt% in aqueous solutions. There are three basic
very dynamic resins, always advancing toward
isomers formed in the reaction that depend on
a cured state. The resole resin is a one-stage or
pH. The 2,4'- and 4,4'-dihydroxydiphenylme-
one-step thermosetting resin. That is, it can be
thanes are formed under strong acid conditions,
irreversibly cured with temperature and pres-
whereas the 2,2' -dihydroxydiphenyl-
sure. Many resoles are reacted in strongly basic
methane is favored in the 4-6 pH range. 30
media. The primary reaction pathway depends
on both the nature of the formaldehyde and the
Weak Acid Reactions
phenol in a basic medium.
The weak acid area, pH 4-7, allows the prep- The reaction mechanism steps are depicted in
aration of the important high-ortho novolak Eq. (6)-(10). The formaldehyde reacts as a
resins. These resins can be prepared as solid species generated from methylene glycol or oli-
novolaks or liquid resoles depending on the gomeric methylene glycol. The phenate ion is
formaldehyde/phenol mole ratio. It has been formed in a basic medium, and this hybrid of
recognized that having free para positions en- several resonance structures is an ideal nucleo-
phile.

HO-CHZ-OH - .
'"-- CHzO • HzO (6)

@ ~[~ -- 6~6]
OH

• OH- .&--
• HzO (7)

6
0-

a·
+ CHz
-4. ...-
---a.
I &~r4 ...- @r~
A
H
---a. (8)

6 ¢ ~-
OH

•
..CH a-4. ---a.
...- ...-
---a. (9)

H CHa-O
 320 HANDBOOK OF ADHESIVES

HO

-~,OH -+ ~ )=co, - HO@rH:@ (10)

Ho@
The reaction mechanism for the basic catal- 2,4-HMP, and phenol would be left in a cook
ysis of phenolics is not completely understood. even as condensation advances. Several com-
However, the reaction kinetics are known to be puter studies predicting the buildup of resin in-
first order in methylene glycol and in phenol. termediates have been made. 32 ,33 Table 4
A complete comparison of the relative reaction highlights some major differences between re-
rates of producing the seven possible methylol soles and novolaks.
phenols is given by Knopll and pizzi. 12 Table The variety of cooks and formulations using
3 shows the rate constants,31 the relative rate resoles is enormous. Consequently, it is im-
constants compared to 4-hydroxymethyl phenol portant to understand that it makes a difference
(4-HMP) and the relative rate constants after how the cook is formulated as to whether the
allowing for the statistical weighting of the two resin is going into a wood bonding adhesive, a
ortho positions in both phenol and 4-hydroxy- resole varnish, an impregnating resin, or a
methylphenol. Comparison of kinetic rate con- foundry resin application. Although many
stants for formaldehyde addition in the ortho cooks are run with a formaldehyde-to-phenol
positions relative to the kinetic rate constant for mole ratio of 1.2-1.8, a wider range is possi-
the addition of formaldehyde to phenol in the ble. For example, if branching is desired, then
para position shows that the formation of 2- an initial low temperature cook with a high FI
hydroxybenzyl alcohol is favored over 4-hy- P mole ratio will generate the largest concen-
droxybenzyl alcohol 1.7: 1. The formation of tration of trifunctional methylol monomers, es-
the 2,4-dihydroxymethylphenol (2,4-HMP) is pecially if the initial cooking temperature is
1.2: 1 compared to the formation of 2,6-dihy- near 6Q°C or lower. This naturally leads to a
droxymethylphenol at 1.40: 1. Interestingly, three-dimensional crosslinked structure which
the 2,4,6-trihydroxymethylpheno1 (2,4,6- implies solution instability in storage due to
HMP) forms at a ratio of 6.73 : 1 from the 2,6- rapid viscosity buildUp.
dihydroxymethyl phenol, but only 1.5: 1 from Resins that are primarily in the polymethylol
the 2,4-HMP relative to formation of 4-HMP. noncondensed form are called A-stage resins
Since two pathways lead to 2,4-HMP, it still and are easily soluble in water, alcohols and
becomes an effective route for producing 2,4,6- ketones. Further into the condensation, when
HMP. These relative rates show the dynamics dimers, trimers, and higher oligomers are
in resole resins toward forming trifunctional formed, resins are labeled B-stage; and finally,
polyalcohols and consequently toward branch- when curing, they are called C-stage resins.
ing and gelling. It is also clear that 4-HMP, Resoles are insoluble and intractable resins

Table 3. Resole Kinetic Parameters for Formaldehyde Addition at 30 o C. a

Reaction b k X 10- 6 , I mor1s- 1 Relative Formation C Relative Ratesd
Phenol-2-HMP 10.5 1.69 0.84
Phenol-4-HMP 6.2 1.00 1.00
2-HMP-2,6-HMP 8.7 1.40 1.40
2-HMP-2,4-HMP 7.3 1.18 1.18
4-HMP-2,4-HMP 7.5 1.21 0.60
2,4-HMP-2,4,6-HMP 9.1 1.47 1.47
2,2-HMP-2,4,6-HMP 41.7 6.73 6.73
'Freeman and Lewis ref. 31.
bFonnaldehyde addition reactions.
'Values are relative to fonnation of 4-HMP.
"Reactions with phenol and 4-HMP have two ortho sites.
 PHENOLIC RESIN ADHESIVES 321

Table 4. Summary of the Table 5. The comparison of Phenolic

Characteristics of Resole and Novolak Thermospheres (PTS) to Bulk Resole
Resins. Stability. a
Characteristic Novolak Resole Rate Constant, day-I
Mole ratio PIP > 1 < 1 Resin 25°C 40°C 60°C
P H/catalyst acidic basic
Addition reaction slow
PTS 0.003 0.029 0.67
fast
Bulk resole O.QlS 0.097 1.5
Condensation fast slow
Reaction rate second order second order 'Based on resin flow on a 60 degree inclined plane.
End groups phenol methylol
Chain structure linear branched
Molecular 200-S000 200-30,000 sensitive phenolic resins using a suspension po-
weight lymerization has been described by Brode. 27 ,28
Molecular narrower broader These materials are reacted using phenol,
wt. dist. aqueous formaldehyde, HMTA, and a suspen-
sion component such as gum arabic. A solid
when cured. Number average molecular material results that has good thermal stability
weights as high as 10,000 have been found in and is not so sensitive to water.
fractionated resole resins. 34 GPC studies indicate that a higher molecular
A method of obtaining high ortho resole weight material with a controllable narrow
structures has been reported in a patent issued spherical particle distribution can be formed.
to Monsanto. 35 Toluene or xylene is used to Table 6 compares the Tg of a particulate resole
form an azeotropic solvent with the high ortho to a bulk resole and a novolak. The particulate
content promoted by the continuous removal of Tg is 4S-54°C. Typical solid resoles have Tg
the water by distillation. These materials have around 40°C. The microstructure determined
important applications as binders and molding from \3C NMR showed less methylol function-
resins. ality and increased benzylamine and methylene
bridges as compared to conventional bulk re-
Dispersion Resoles soles.
In many cases resoles are prepared as solutions
Resin Cure
since they are water or solvent soluble in the
hydroxymethyl form. However, they are dy- The novolak resins are cured with hexamethy-
namic and typically must be of low molecular lenetetramine (HMT A) or with the addition of
weight in order to have some solution stability . resoles, or in many applications are modified
New methods of preparing one-step phenolics with epoxy resins to promote special properties
in dispersion form have been described. 36- 39 In and an alternate mechanism for curing. HMT A
the general reaction sequence, a two-stage re- is the most widely added curing agent and is
action scheme is employed. Using alkali or al- used in the 5-15% range. With heat and mois-
kaline earth metal hydroxide catalysts, the ture, HMT A breaks down stoichiometrically
resole is first brought to a molecular weight near into ammonia and formaldehyde. The methyl-
its water insolubility point. Then a polysac- ene bridge is the predominant linkage that is
charide such as gum arabic, gum ghatti, hy- formed from the formaldehyde, and although
droxyalkyl guars, or poly (vinyl chloride) is most of the ammonia gas escapes, there are
added as a protective colloid coating which studies showing the formation of benzoxazines
controls the particle size and distribution. The and azomethines. 12 These are thought to be re-
reaction is then advanced to a high molecular sponsible for the yellow color of HMTA-cured
weight. Dispersions have been carried out from novolak resins.
weight average molecular weights of SOO to The resole resins are thermoset materials that
46000. 36 Stability improvement data are given are cured with the addition of heat and pres-
in Table 5. sure. The rate of curing these typically low
The preparation of special particulate, heat number average molecular weight resins de-
322 HANDBOOK OF ADHESIVES

Table 6. Comparison of Phenolic Thermospheres (PTS)

Glass Transition Temperature to Other Phenolics.
Resin Tg.oC Wt% Gain. 22°C Form
PTS 48-54 2.5-3.5 slightly
sintered
Bulk resole 33-43 7.2-8.4 fused
Novolak 58-74 5.7-6.5 fused

pends on the temperature and on the distribu- 13e NMR studies include spectral assignments
tion of polyols present. In fact, depending on in PF resins,45-47 benzylphenols48 and cresol
which cooking program and what initial mole novolaks,49 reaction curing, 50 and phenolic
ratio is used, considerable variation in molec- precursors. 51 Several very useful chemical
ular weight and molecular weight distribution shifts for novolaks dissolved in pyridine are for
can be achieved in a controlled manner. This the methylene protons, p-p' at 3.8 ppm, 0-0' at
in tum influences the curing properties. The 4.1 ppm, and the o-p' substitution at 4.5 ppm.
crosslinking reactions proceed primarily The areas under the absorption peaks allow the
through the condensation of methylol groups percentage distribution of isomers to be evalu-
and the splitting out of formaldehyde and water. ated. The analogous 13e signals are in the re-
Resoles that are catalyzed by ammonia will gions of 41.0, 30.8-31.4, and 35.5-35.9 ppm,
have nitrogen built into the bonding along with respectively.
the methylene groups. 15 Gel permeation chromatography (GPC)
measures flow retention volumes through a col-
umn packed with material of given pore sizes.
Resin Analysis
Results proportional to molecular volume can
In recent years progress has been made in the be correlated to number average and weight av-
quality control and molecular understanding of erage molecular weights, thereby allowing
phenolic products through the use. of modem comparisons of molecular weight distributions
instrumentation. Several tools that have been and molecular weights. 52-55 These molecular
especially helpful in correlating structure and weights are valid to the extent that a standard
general properties are high and low field 13e calibration curve represents the hydrodynamic
and IH FTNMR, gel permeation chromatog- volume characteristics of the polymer in ques-
raphy, differential scanning calorimetry, ther- tion. Most laboratories have used polystyrene
mal gravimetric analysis, and dynamic standards, which present some problems in ar-
mechanical analysis. In addition, Fourier riving at reliable molecular weights for phe-
Transform infrared spectroscopy (FTIR) is nolics, especially resoles. The GPe methods
coming into much use. 40 ,41 using laser light scattering detection show
Nuclear magnetic resonance (NMR) mea- promise for arriving at more accurate molecu-
sures changes in the electronic environment of lar weights and molecular weight distribution
a nucleus and consequently is related to the na- in phenolics. 54
ture of the atom grouping and bonding in a Differential thermal analysis or differential
molecule. The results are reported as chemical scanning calorimetry (dsc) measures the tem-
shifts 0 relative to a standard like tetramethyl- perature change in a sample cell, generally rel-
silane. Integrated areas under absorption peaks ative to some inert standard, and can be run at
can be related to reaction advancement and dis- fixed temperature versus time or as a function
tribution of substitution. Early work done by oftemperature. Samples can be run under pres-
NMR21 ,42 has been followed by solid 13e sure. The areas under an exotherm or endo-
FTNMR studies making use of the magic angle therm can be related to heat change, and con-
technique on the thermal decomposition of sequently, in addition to melting points and Tg
cured resole phenolics43 and the HMTA curing values, parameters such as heats of fusion can
of phenolic resins. 44 Additional normal field be evaluated. The characterization of reaction
 PHENOLIC RESIN ADHESIVES 323

properties with dsc 56- 59 and the importance of kept below 105°C for resins used outside the
mechanical properties and glass transition tem- wood adhesives industry. Low molecular
peratures can be obtained from dynamic me- weight water-soluble resins must be finished at
chanical analysis. 60 ,61 Solution dipole moments low temperatures, 50-60°C, whereas less re-
have also been used to examine novolak con- active p-substituted phenols can be finished at
formational properties. 62 ,63 These values fol- temperatures as high as 120°C.2 Solid resoles
low a systematic function from a molecular are discharged from the reactor under rapid
weight of 200-6000. cooling.
In the manufacture of resole resins for the
MANUFACTURE wood industry, the cooking procedure may
have several loading steps for adding the for-
Phenolic resins are typically made by the batch
maldehyde or the base. Likewise, the temper-
process in a stainless steel reaction kettle that
ature can be programmed to bring about
is jacketed for steam or cooling water and
different molecular weight and substitution
equipped with a turbine blade or an agitator for
characteristics. Since the materials are always
stirring and a condenser. Molten phenol and
shipped in liquid form, reaction conditions are
formalin, typically 37-50 wt% formaldehyde,
carefully controlled to balance resin advance-
are charged into the kettle and agitation begun.
ment with resin stability. That is, the resin must
In novolak production an acid catalysis is
have high reactivity for good press times, and
added, and steam is applied to bring the reac-
yet have reasonable storage stability. It is easy
tion to a 100°C atmospheric reflux for 3-6
for resins to be too reactive and to set up in
hours. The reaction time depends upon the ca-
shipping or in storage.
talysis, pH, and phenol mole ratio. At the end
If substituted phenols are used, such as p+
of the reaction time the load is dehydrated un-
butylphenol, the synthesis may call for the ad-
der atmospheric and then vacuum conditions.
dition of an aromatic solvent and neutralization
The final temperature reached under 25-27
of the water layer.
inches vacuum is 140-160°C, which allows the
residue phenol to be removed. The solid resin
is discharged to pans or to a resin flaker. The ABRASIVES
resin can be sold in lump, powder, or flake
Phenolics are used in two main categories of
form. Most resins sold in solid form are blended
abrasives. Bonded abrasives are three-dimen-
with HMT A before packaging.
sional structures such as grinding wheels and
In the manufacture of solid and liquid resole
snagging wheels, and coated abrasives include
resins, the reaction procedure makes use of the
sandpaper, sanding discs, and belts. According
exothermic nature for heat production and vac-
to the data reported in Table 1, the markets for
uum dehydration for temperature control. After
abrasives have decreased by 11 million lb dur-
the alkaline catalyst (which is usually sodium
ing the years from 1983 to 1987.
hydroxide, but sometimes calcium hydroxide,
barium hydroxide or ammonia) is added to the
Bonded Abrasives
phenol and formaldehyde, the mixture is al-
lowed to heat at 80-100°C for 1-3 hours. The Although the ceramic binders in bonded abra-
size of the kettle batch, for example, 60,000- sives are generally harder and can be used in
135,000 lb, is controlled by the exothermic na- close tolerance work, the phenolic binders are
ture of the reaction, which has been tougher and can better withstand thermal and
measured64 •65 at 81.1 and 82.3 kJ /mole, the mechanical shock. The two main abrasives that
design of the reactor and the condenser cooling are used in grinding wheels are aluminum ox-
capacity. ide and silicon carbide. However, titanium ox-
Resole resins can set up in the kettle, so care ide can be added to aluminum oxide for
must be taken to control the reaction. Reaction toughness enhancement, and an alloy of zir-
temperatures below 100°C are controlled by conium oxide and aluminum oxide developed
vacuum, and final dehydration temperatures are by the Norton Company is important in heavy
324 HANDBOOK OF ADHESIVES

duty grinding. The invention of silicon carbide Z, extra hard. A hard wheel will have a larger
by Dr. Edward Acheson in 1891 and the for- amount of resin present, and more complete
mation of the Carborundum Company gave curing. The ratio of wet to dry resin is very
birth to the modern abrasives industry. Now critical and must be carefully controlled in or-
manufactured abrasives can be produced with der to handle the material as it is placed in the
selective uniformity from sizes 6000 fine to 6 steel mold. It is important to preserve uniform-
coarse. 66.67 ity in the mixture and to prevent agglomeration
The phenolic resin binder consists of a pow- in the mold. Wheels can be cold pressed, which
dered two-step novolak resin. The amount of is most economical, or hot pressed at temper-
HMTA added (5-14%) depends on the final atures generally between 175 and 205°C.
application of the grinding wheel. The resin can
be used alone but is more frequently combined
Coated Abrasives
with a liquid resole or a furfural resin which
sets the abrasives in place. Phenolics can be Phenolic resins are the primary adhesive used
modified with epoxy resins and formulated in in coated abrasives, more commonly called
wheels to soften the grinding action. Modifi- sandpapers, found in the form of papers, belts,
cation with polyvinyl acetate and polyvinyl bu- discs and drums. The resins used are typically
tyral can give a grinding action similar to formulated as one-step phenolic resoles made
shellac-bonded wheels which are useful in roll with a range of F/P ratios > 1. If the mole
grinding.68 Fillers such as cryolite (Na3AlF6), ratio is high, the resin will have high methylol
potassium fluoroborate (KBF4) or iron disul- content, enormous water solubility, allowing
fide (FeS2) melt at the grinding interface and 50-75% solutions prepared with pH 8 and
act as lubricating agents. The phenolics used above, and fast cure at temperatures around 93-
are fully cured at 150-200°C, so there is no 104°C. The resins in the intermediate mole ra-
danger of resin-filler interaction. The design of tio area, pH 6-8, run at 75-88 % solids, have
the phenolic, both in terms of molecular weight low water miscibility, and cure in the 135-
and the amount of HMTA that would be used, 149°C range. The lower mole ratio resins pre-
depends on the final application of the grinding pared near pH 8 have much less methylol con-
or snagging wheel. High molecular weight tent and therefore cure more slowly and require
phenolics used in conjunction with larger relatively high curing temperatures, e.g., 115-
amounts of HMTA are needed for high speed 130°C. A recent pateneo describes a binder that
or tough grinding applications where high heat is fast curing at a low temperature of 130°C.
resistance is needed2 to withstand wheel sur- This binder contains a phenolic resole in con-
face temperatures that can reach 1200°C. On junction with mixed condensates of mono and
the other hand, if a lower molecular weight polyhydric phenols and formaldehyde reacted
resin and lower HMTA content are important, in an F/P mole ratio typically in the 1.3-1.8
a better wetting of the abrasive grain is needed. range at lower temperature, e.g., 40-80°C. The
This also gives a grinding tool with better water binder is said to have low free formaldehyde
resistance. The use of siloxane-coated abra- present and excellent resin storage stability.
sives can help water resistance, too. The selection of resin type or blend of resins
The manufacture typically begins by first depends on the type of paper being coated, the
wetting each abrasive grain with a liquid resole kind and size of the abrasive grit used, and the
resin. This will allow the powdered phenolic parameters for the optimization of production
resin to coat and adhere to each grain. In some time.
cases the abrasive can be coated with furfural, The abrasives used for coatings are diamond,
and the amount of HMTA added to the phe- aluminum oxide (corundum), silicon carbide,
nolic will depend on the amount of furfural boron carbide, boron nitride, emery, flint
used. 69 (quartz), and garnet. These range in hardness
The grading of the grinding wheel is very im- and cost. Typically the superabrasives, syn-
portant. The grade of a wheel is designated by thetic diamond and cubic boron nitride, do not
letters, ranging from A, a very soft grade, to compete easily with the standard abrasives,
 PHENOLIC RESIN ADHESIVES 325

aluminum oxide and silicon carbide. 71 Flint is Table 7. Formulation for Electronic
a quartz material and found throughout the Encapsulation.
United States, but the high quality forms are Constituent Parts by Weight
mostly from New Hampshire and Maryland.
Epoxidized novolak 20
Garnets are silicates of varying color and qual- Phenolic resin 10
ity. They are harder and tougher than flint. Silica flour 70
Other specialty abrasives are chromium oxide Lubricant (stearate)
used to polish stainless steel, and zirconium Catalyst 0.4-2
oxide used for glass polishing.
Testing of coated abrasives must be done pri-
react with higher molecular weight epoxides
marily by running plant trials and examining
that contain both epoxide and hydroxyl func-
the end-use performance. However, some stan-
tionality. Here, fast reactions requiring only
dard tests include hot and cold tensile and flex-
heat occur through both the phenol hydroxyl
ural strength, resistance to water or coolant,
and methylol moieties. These resole formula-
maximum speed characteristics, and grinding
tions are excellent for container coatings and
efficiency ratio, i.e., metal removal versus
primers where a high degree of flexibility is
wheel wear.
needed. A typical baking primer coating for-
mulation is given in Table 8, and a primer for-
COATINGS mulation is shown in Table 9.
Rosin-modified phenolic resins are very use-
Phenolic resins play an important role in the
ful in printing ink, oil lacquers, and in alkyd
coatings industry because of their ability to
paint applications. A commonly used material
react with epoxy, alkyd, natural resins and
consisting of rosin acids is colophonium that is
maleinized oils for tailored protective coating
applications. Modified phenolics are important
as water, moisture, or solvent vapor barriers Table 8. Baking Primer Coating
and they can generally protect metals from a Formulation. a
corrosive environment. Unmodified phenolics Constituent Weight %
are not good for coatings because of inherent UCAR Phenolic Resin BKR-2620 9.01
tendencies for discoloration as well as the stiff- UCAR Phenoxy Resin PKHH 3.15
ness resulting from the rigid, three-dimensional Iron oxide, synthetic 12.16
structure in the cured state. However, when Barytes 13.51
they are combined with, e.g., an epoxy resin, Zinc oxide 1.35
Methyl ethyl ketone 24.33
a good balance of properties is obtained. They Cellosolve acetateb 24.33
are used mostly for undercoatings or coatings Toluene 12.16
that are colored. A good review of phenolic 'Ref. 73.
coatings is given by Richardson and Wertz. 72 bUnion Carbide Corp. Trademark; the acetate of ethylene glycol
monoethy lether.
The area of protective coatings has grown 27 %
since 1983, although it has been relatively con-
stant the last three years. See Table 1. Table 9. Epoxy/Phenolic Coating
Phenolics such as novolaks can easily react Primer. a
with epoxides through the phenol hydroxyl Constituent Weight %
group, using only heat and a base catalyst. The 37.5
Synthetic iron oxide
degree of crosslinking and flexibility intro- Epon-l007 (Shell Chemical) 17.5
duced into the resin is controlled by the nature UCAR phenolic resin BKR-2620 11.0
of the epoxide. In this reaction no water is re- Toluene 15.7
leased, and relatively thick films can be formed Methyl propasol" 7.5
MEK 4.5
without blistering or voids. Applications are in Methyl propasol acetate" 2.3
pipe linings and electrical insulation. An ex- n-Butanol 4.0
ample of an electrical encapSUlation formula- 'Union Carbide Corporation Tech. Bull.
tion is given in Table 7. Resole materials can bUnion Carbide Corporation Trademark.
326 HANDBOOK OF ADHESIVES

generally reacted with a resole phenolic in the Silica sands of very high purity are primarily
molten state between 110 and 140°C. The re- used in sand molding operations. However,
action is finished at temperatures near 250°C. 11 other materials can be added to control thermal
Oleoresinous varnishes and alkyd-modified expansion characteristics. Additional factors
phenolics can be formulated that cure at room that are very important in forming the character
temperature and are relatively clear. 73 of the mold are the sand grain and the size dis-
Cresol-, xylenol-, and phenol-formaldehyde tribution. The shapes of silica sands, for ex-
resoles find importance in the electronics field ample, are round, sub-angular, and angular.
application. These materials are made flexible Round sands have more strength in the com-
with PVB, PVF and alkyds. They are used in posite per resin content, but angular sands re-
impregnating, dynamo sheet, and wire varnish sist cracking. The rounded, low thermal
applications. expansion zircon is often added to silica sands
to balance properties. 74 Sand properties are
listed in Table 10.
FOUNDRY
Five basic fabrication processes are used by
Phenolic resins have been an important part of the foundry industry. These are the no-bake,
the foundry industry for many years. However, cold-box, hot-box or warm-box, oven bake,
as can be seen in Table 1, the drop from 77 and shell processes. 74
million Ib in 1985 to 41 million Ib in 1987 has
followed economic changes in that industry. 5 No Bake Process. In this process the sand
Phenolic resins are used for binding the sand and binder components are in a curing state at
used in manufacturing shell molds and cores. room temperature. Shortly after the cure is un-
The castings can be done either in permanent derway, the core box is filled with the sand mix
molds or lost molds. Permanent molds are typ- and as soon as the core becomes stable it is re-
ically made of metal or ceramics and are used moved from the box. This may take only a few
primarily to cast low melting metals. Lost minutes or several hours.
molds, used to cast ferrous metals, are made
from sand and an inorganic binder such as clay Cold-Box Process. In the cold-box process
and water or an organic binder such as a no- which takes place at room temperature, a gas
volak two-step resin. catalyst is passed through the sand to promote
Although molds made with clay or sodium curing. The catalysts are triethylamine or meth-
silicate binders are inexpensive, they have low ylethylamine for phenolic isocyanate binders,
dimensional tolerance and low stability. Phe- sulfur dioxide for vinyl-unsaturated urethane
nolic resins used as binders have mariy good binders, and methyl formate for an alkali metal
properties such as excellent dimensional stabil- salt of a phenolic resole binder. High-ortho res-
ity, fast curing times, and excellent storage of ins have been developed for the phenolic com-
cores and shells. In some applications furfuryl ponent by using water-free systems and salts of
alcohol and urea formaldehyde resins are also divalent metals as catalysts. A recent patent de-
used. 74 •75 scribes improvements in the two-package phe-

Table 10. Properties of Inorganic Sands. a

Sands
Property Silica Chromite Zircon Olivine
Composition Si02 Cr203 FeO ZrSiO. (Mg, FehSiO.
Specific gravity 2.64 4.5 4.6 3.2
Thermal Exp., in.lin. 0.018 0.005 0.003 0.0083
Heat transfer ave. very high high low
AFS grainb 25-180 50-90 95-160 40-160
'W. Rossbacher. Ref. 74.
bAmerican Foundry Society Standards.
 PHENOLIC RESIN ADHESIVES 327

nolic polyisocyanate process where the novolak ally speaking, the hot tensile strength continues
or resole A-stage is water free and the solvent to increase parabolically with the HMT A con-
is nonpolar. 76 tent up to 18 %. In order to reduce some of the
common shell problems such as mold cracking,
Hot-Box and Warm-Box Processes. In peel back, soft mold, or low hot-tensile
these two processes the sand mixture is coated strength, other additives such as Vinsol (Her-
with a liquid thermosetting binder which is cules, Inc.-thermoplastic resin .derived from
thoroughly combined with the dry sand and a pinewood), potassium fluoroborate or zircon
latent acid catalyst. This mixture is blown into are used. The variables of resin content, length
the core box at a temperature from 100 to of cure, percentage of HMT A, and mix of
260°C. Upon heating, the catalyst releases the sands must all be controlled to optimize the
acid which induces a rapid cure of the core. process.
The core can be removed from the box in 10-
30 seconds and the cure continues under the FRICTION COMPOSITES
exothermic reaction. The hot-box method typ-
ically requires post-curing in an oven. Phenolic resins are the primary binder for a va-
riety of materials in the production of friction
Oven-Bake Process. The oven-bake pro- products used mainly in the automotive indus-
cess is one of the oldest in the industry, and is try such as brake linings, brake blocks, disk
least used. The resins used are made from un- pads, clutch facings, and automatic transmis-
saturated hydrocarbons and heavy oils. sion blades. Phenolic resins are important in
these composites due to their thermal stability,
Shell Molding Process. The process for resistance to solvents and nonflammability.
combining resins and sand into a shell mold was After some decline, the phenolic resins friction
invented in Germany and patented in 1944 by elements market has been increasing over the
Johannes Croning. In the beginning 7-8% resin past three years and is now at 29 million lb.
was mixed with the dry sand, but over the years See Table 1.
this has been reduced to 1-4 %. Novolaks are
the main binder used in shell molding and are Fillers. In past years asbestos, especially
available in powder, flakes, granules, or as sol- chrysotile asbestos, was the main wearing filler
vent- or water-borne materials. High-ortho no- for friction products. It gave an even, pow-
volak resins have wide application in this dered breakdown of the friction element and
process because of their rapid curing rate. 77 The had even friction properties with increasing
shell lubricant, usually calcium stearate, is temperature. However, with the clear physio-
added at 4-6 % of resin weight and HMT A runs logical and carcinogenic hazards of all four
between 10-17 %.78 Initially, the sand is treated asbestoses-chrysotile, crocidolite, amosite,
by one of several methods. It can be: (1) dry and anthophyllite-work has been accelerated
mixed with the powdered resin, HTMA and lu- to find substitutes. 79-81 This has proven to be
bricant; (2) cold-coated with a powdered or an challenging and costly since no one material has
alcohol solution of novolak, HMTA, and lu- all the same properties as did asbestos, so in
bricant; (3) warm-coated using warm air near many cases a mixture of materials is needed. 79
121°C and sand around 66°C; or (4) the hot- Mineral, carbon, aramid, and metal fibers are
coated method where the sand is preheated to increasingly being used as replacements for as-
140°C and then cooled to under 93°C with a bestos. A newer material developed by Jim
water-borne novolak applied. The coated mix Walters Resources 79 is a processed mineral fi-
is then dumped on a hot pattern, forming the ber called PMF. PMF is a single-strand, fi-
investment. After going through a short cure, brous material that has shown considerable
the investment is inverted to remove excess promise in this area. Many brake linings using
sand, and then turned over and cured for an ad- the DuPont aromatic amide called Kevlar are
ditional 1-3 minutes at 345-540°C. The mold in use. A recent patent82 discloses a friction
shell is then stripped from the pattern. Gener- material composed of 5-70% by weight of
328 HANDBOOK OF ADHESIVES

pulplike particles from heat-resistant polymeric Testing. Although there are no industry
aromatic amides. Other nonreinforcing fillers product standards for brake linings and each
used are barium sulfate (barytes), rottenstone, company establishes its own specifications for
and brass particles. particular markets, the Society of Automotive
Engineers (SAE) has set standard test methods.
Resins. The phenolic resins used are varied. Performance tests determine friction and wear
They are novolak, resole, novolaklresole com- parameters. There is an SAE J-661 Brake Lin-
binations, cresol resins, and rubber-modified ing Test Control Procedure which uses a stan-
and oil-modified novolaks. Tung oil, cashew dard Chase-type friction testing machine.
nut shell liquid (CNSL), linseed oil, and soya However, modem analytical methods using
bean oil are reacted with phenolics. The value electron microscopy, differential scanning ca-
of oil-modified phenolics is the quieter perfor- lorimetry, thermal gravimetric analysis and
mance of the braking action, and the reduction· measurement of the coefficient of thermal ex-
of cracking in components. Oil-modified no- pansion, heat capacity and modulus of elastic-
volak resins are supplied in viscous liquid or ity are found to be important. A recent article
powdered forms. The flexibility in the cured by Lambla and Vo on optimizing friction ma-
resin can be controlled by the percentage and terials is of interest here. 84
type of oil introduced into the resin.
Cresylic acid, which is a mixture of cresols,
MOLDING COMPOUNDS
phenol, and xylenols, is also used in resins.
This material can be purchased from technical All phenolic molding compounds are resins that
grades with 80-85 % of a particular constituent are reinforced with minerals, glass fibers, ar-
to 98% single component purity. A typical oil- amid fibers or carbon materials. The binding
soluble phenolic resin can be made from p-t- and adhesive nature of the phenolic with the
amylphenol employing an acid catalyst. Both fillers plays an important role in the final struc-
p-t-butylphenol and p-t-octylphenol have ap- tural properties. These composites when fully
plications here, too. If these materials are first crosslinked can withstand high temperatures
reacted with an alkaline catalyst, then the ini- under high load for long periods of time; see
tial resole formulation can be modified with un- Table 11. 85 ,86 Phenolics as a class are non-
saturated compounds such as drying oils, flammable, and when burning give off very lit-
rosins, and rubber. tle smoke. Applications range from electrical
and electronic components such as electrical
Manufacturing. Several of the main pro- sockets and printed circuit boards to automo-
cesses include impregnation of the asbestos or tive, such as distributor caps, relays and brake
glass fabric for linings and clutch facings, the pistons; to housewares, such as utensil handles
wet mix dough process for drum brake linings, and appliance parts; and to sheet molding ma-
and finally the dry mix process for disk brakes terials such as those used for instrument panels
and drum linings. In the impregnation process, and airplane interiors.
a B-stage resin is pressure-driven into the fab- The amount of phenolics used in molding
ric. The dry mix process is the most heat-re- processes has declined; but there is substantial
sistant type and is made for heavy duty truck interest in the electrical/electronics market87
applications. The powdered phenolic novolak since phenolics can form matricies to withstand
resin as well as liquid and powdered resoles are considerable mechanical stress while retaining
mechanically mixed with the fiber (asbestos or thermal stability.
Kevlar) along with the other fillers and friction The novolak phenolic is the most commonly
components. It is first cold pressed and finally used in these applications because of its longer
hot pressed at higher pressures and tempera- shelf-life. Resole resins, however, have the ad-
tures of 125-135°C. Details of processing are vantage of not emitting ammonia during mold-
found in Barth. 2 A two-binder friction compo- ing or operation in a closed, high-temperature
sition has recently been patented. 83 environment. They also retain their dimen-
 PHENOLIC RESIN ADHESIVES 329

Table 11. Load and Heat Deflection for Engineering Plastics.

Deflection,
Maximum Stress degrees, 4
Material Load, psi Temp.,oC hr
Polysulfone, 30% glass 1,050 175 5
Polybutylene terephthalate, 30% 525 200 9
glass
Polybutylene terephthalate, glass/ 525 200 9
mineral
Polyethylene terephthalate, 30% 1,050 210 8
glass
Polyether-imide, 10% glass 1,050 210 8
Polyether-imide, 20% mineral 275 210 5
Polyether sulfone, 30% glass 275 205 7
Polyphenylene sulfide, 30% glass 275 260 4
Polyphenylene sulfide, glass/ 275 260 4
mineral
Phenolic, mineral filled 2,100 210 4
Thermoset polyester glass/min- 2,100 230 3
eral
Thermoset polyester BMC 30% 2,100 260 2
glass
Phenolic, 20% glass' 2,100 270
'Deflection of 4 at 285 after 500 hr, Plenco 06582.
0 0

sional stability during vapor-phase soldering Great effort is continuing to extend the tem-
conditions, and expansion and swelling at perature range of phenolics. When compared to
higher temperature are minimal. 88 Novolak most engineering plastics, phenolics have a
phenolics also do well here if the entrapped significa.ntly higher glass transition tempera-
gases are driven off by post-curing. ture, e.g., around 200°C. It appears that the Tg
can be increased to as high as 244°C by an-
Resins. Novolaks cured with HMT A are the nealing molded parts. 88
principal resins used in composites. The resin A phenolic resin which is modified with a
and the curing agent make up between 30 and thermoplastic elastomer89- 91 can function at
50 % of the composition. Sometimes the resin 180° for 1600 hr with minimal weight loss,
is modified with as much as 10% melamines. whereas a mineral-filled phenolic will show
Resins are typically cured with oxalic acid, al- considerable weight loss.
though hydrochloric or sulfuric acids are used,
too. High-ortho novolaks find use in a number Fillers. Fillers used in molding compounds
of applications. One-step resoles or resole/no- are glass fibers, aromatic polyamide fibers (like
volak combinations also find use in specialty Kevlar and Arenka), mineral flour (mica, sil-
applications such as glass fiber compounds or ica, wollastonite, talcum, and calcium carbon-
compounds that need to adhere to copper sub- ate), wood flour, cellulose, and carbon fibers.
strates in electrical products. In this latter case, Fillers reduce shrinkage during cure, give
the use of non-ammonia-producing cures is es- higher compressive strength and stiffness, and
sential, since ammonia attacks the copper. No- improve thermal resistance, electrical proper-
volaks cured with epoxide resins are important ties, and flame retardancy.
where gas generation cannot be tolerated. The Calcium-aluminum silicate is the most used
inherent discoloring in the phenolic resins lim- mineral filler because it is economical. Mica
its the possibility of making clear molded prod- imparts high dielectric strength and thermal re-
ucts; however, a variety of colored products are sistance, and also has low thermal conduct-
now being developed. ance. II The high temperature and strength
330 HANDBOOK OF ADHESIVES

characteristics of aramid fibers are bringing parts from preformed glass mats were compa-
them into specialty markets. Fillers ranging rable to "vinyl esters" (epoxyl acrylates) and
from wollastonite to glass spheres, modified polyester materials, and displayed better ther-
with silanes, titanates, and wetting agents,92 are mal stability. 98
available from NyCo, a division of Processed Coefficients of thermal expansion are sum-
Minerals Corp. Asbestos, because of its health marized by Merserear. 99 Coefficients for phe-
hazards, is being phased out of the industry. nolics filled with carbon are similar to steel over
A typical mixture of a general molding com- the range of temperatures from 20 to 160 0 C .99
pound is shown in Table 12, and a sheet mold-
ing formulation is given in Table 13. Sheet Post-Treatment. A post-bake (post-curing)
molding compounds are in increasing demand can have a beneficial effect on the thermal sta-
in automotive, transportation, construction and bility and dimensional stability of phenolic
appliance markets. These phenolics are non- molded parts. Early work showed that the glass
flammable and give off little smoke, unlike transition temperature (Tg) increases with cure
polyesters. 93 Substituted novolak structure- in phenolics. 99- 101 More recently it has become
property relationships and flammability have apparent that the Tg of an as-molded phenolic
been examined by Pearce. 94 novolak part strongly influences the post-bake
conditions to be used. If parts are molded above
Manufacturing. Phenolic resins are molded the T, an unacceptable expansion can oc-
mainly by injection, compression, and transfer cur. 101,103 The Tg continues to increase during
molding. Injection molding is the dominant the post-baking. Table 14 gives data showing
method. A new technique is reaction injection the changes of Tg with curing time and post-
molding (RIM). In this method two or more cure. This data suggests that the post-baking
reactive components are brought together un- operation is best done in a series of pro-
der low pressure into a mixing stream and then grammed steps where the oven temperature is
forced into a hot mold. A phenolic RIM system always a prescribed value below the glass tran-
developed by Brode, Chow and Michn095 em- sition temperature. 102,103 A computer model of
ploys a high-ortho, high-solids, liquid resole post-baking has been put forth by Landi. 104
resin that is combined with a latent acid cata- Some new applications include the work the
lyst like phenyl hydrogen maleate, phenyl tri- Rogers company is doing with Polimotor Re-
fluoroacetate, or butadiene sulfone. 96 ,97 Molded search to build a totally plastic car engine based
on a moldable phenolic composite. A plastic
Table 12. A Typical Compression engine is in operation. Also, a compression
Molding Compound Formulation. molded military helmet has been made91 ,105
Component Weight % from a catalyzed resin system composed of
Phenol novolak 40
equal parts of phenolic and polyvinyl butyl
HMTA 6 resin impregnated into 19 layers of Kevlar
MgO I aramid fiber. Composites made of Novoloid
Wood flour 50 phenolic fibers in polypropylene, examined by
Lubricant and release agents Broutman,I06 showed an increased heat deflec-
Coolant and pigments 2
tion temperature with only a small reduction in
impact strength.
Table 13. A General Sheet Molding
Compound Formulation. PHOTORESISTS AND CARBONlESS
PAPER
Constituent Weight %

Phenolic resin content 35-50 Resists. Photoresists are light- or other en-
E-glass 25-40 ergy-sensitive resins that can be applied as films
Calcite (CaC03 ) 10-20 and patterned to protect some and expose other
Other Additives 2-10 areas of silicon wafers for doping, etching, or
Lubricants and release 1-3 plating, using either positive or negative im-
 PHENOLIC RESIN ADHESIVES 331

Table 14. The Change of Tg with Cure Temperature and

. Time.
T•• °C
Cure Temp .• °C 30 sec 60 sec 90 sec 180 sec 300 sec 1800 sec
132.2 87 98 115 122
154.4 116 132 142 150 161 188
196.1 180 186 186 217
218.3 207 214 242
Post-bake (I32.2"C) Schedule 90° to 232°, T, = 287°C.

aging. In commercial microlithogmphy, posi- creased the molecular weight or crosslinking

tive resists make use of the photofunctional through hydrogen abstmction. III A resorcinol-
change in diazonaphthoquinones in novolak based novolak resin containing silicon as part
resins since novolaks exhibit less swelling and of an alkyl ether linkage gave submicrometer
image distortion during the development of the images. \07 A positive resist incorporating as
image than do negative materials. The novolak much as 50% trimethylsilylnitrile into a phenol-
plays the role of the binder, holding the pho- formaldehyde resin has also been described. I \0
toactive substance in place. Commercial posi- In many cases phenolic resists have poly(p-
tive resists usually are cresol-based. Molecular vinyl phenol) as the matrix. 112 They are easily
weight, molecular weight distribution and sam- prepared from p-vinyl phenol and can be po-
ple purity are very carefully controlled. lymerized under free radical conditions and
An improvement in photo resists for inte- crosslinked with HMT A 113 or epoxide res-
gmted circuit chips is the use of a multilayering ins. 114 They can also be used in combination
effect to increase the resolution of smaller and with epoxide resins in the production of mul-
smaller features. The top film layer receives tilayer circuit boards.
the image to be tmnsmitted through the
other layers to the substmte surface. One ap- Carbon less Paper. Novolaks based on p-
plication is to cover a film of conventional phenylphenol and other p-alkyl phenol copol-
phenolic novolak photoresist with a second ymers have proven to be valuable in the man-
film of polystyrene doped with a nitrone ufacture of carbonless paper. In order to keep
[R ~CH=N(O)- R]. The nitrone is opaque to the oxidation and yellowing of the papers low,
light wavelengths from 315 nm well into the highly hindered substituted alkyl phenolics are
visible and is photolyzed at a shorter wave- incorpomted as antioxidants. New formula-
length to a tmnsparent compound. Light can tions also incorporate the phenolics as zinc and
then pass through the tmnsparent areas to pho- aluminum salts.
tolyze a 2-diazonaphthoquinone dispersed in The process that occurs arises from an elec-
the novolak to 1-indane carboxylic acid. The tron tmnsfer between an electron donating or-
contmst-enhancing top film is stripped off with ganic compound and a color developing
toluene-anisole solvent, and the image in the material such as crystal violet lactone or ben-
novolak is developed with aqueous alkali. \08 A zoylleucoaummine dyes. The phenolics act as
t-butylphenol or phenylphenol novolak is used coating materials.
as the alkali soluble resin along with quinone-
diazide or poly(2-methylpentane-1-sulfone) to
LAMINATING
make a positive resist with special radiation re-
sistant crosslinking properties. 109 Phenolic resins have been successfully applied
Phenolic resin has been used to replace bis- in the manufacturing of electronics materials,
azide-cyclized polyisoprene through the incor- decomtive laminates, filters, and tubes. The
poration of a variety of azides, giving a resin easily penetmtes papers of various kinds
negative resist that is sensitive to broad areas because of the hydrophilic nature of the resins.
of visible and UV light. A monoazide in- Most laminating processes make use of resole
332 HANDBOOK OF ADHESIVES

type materials with high percentages of meth- characterize the phenol formaldehyde resin
ylol groups present. properties. I 18

Electrical and Industrial. The l~rge de- Resins. For economic reasons, the one-step
mand for electrical components that have high impregnation of material is preferred. How-
heat resistance under load, excellent flame re- ever, with kraft papers, for example, a two-step
tardance, and good mechanical properties along resin impregnation is needed if the machine line
with an attractive price, have brought growth is not long enough. The resins are all resoles
to industrial laminates made with phenolics. A typically composed of phenol-, cresol-, or xy-
Vits high-speed saturated paper treater is shown lenol-formaldehydes with p-t-butyl- or p-non-
in Fig. 1. The impregnation of papers, cloth ylphenol inserted to enhance flexibility. Phenol
fabrics such as cotton, glass, and carbon fiber resins can even be modified with other syn-
mats has standards documented in the LI-l thetic flexibilizers, e.g., polyethers, polyes-
NEMA code (National Electrical Manufactur- ters, or polyurethanes. The resins must be
ers Association) 115,116 in the United States, the carefully controlled in molecular weight and
DIN 7735 code in West Germany and the NF molecular weight distribution. Metal ions must
in France. Some of the NEMA standards for be kept at minute concentrations, which dic-
paper and glass are given in Table 15. The tates that cations from basic catalysis must be
NEMA code was revised in 1983 and is again precipitated at the end of the reaction. Thus it
undergoing revision, to be -released in Novem- is convenient to use calcium, barium, or mag-
ber, 1988.117 Since people in the marketplace nesium hydroxides for the resole preparation
are always looking for better materials and which allow the cation to be eliminated as an
higher performance, the higher standard grades insoluble sulfate. In a two-step impregnation
are always in a state of change. A study has such as would be required for a kraft paper, the
been done on carbon laminates by NASA to first step requires a low molecular weight resin

Fig. 1. The sheeter and roll winding stations on a Vits (W. Germany) high-speed phenolic saturated paper treater.
(Courtesy of Reichhold Chemicals, Inc.).
 PHENOLIC RESIN ADHESIVES 333

Table 15. NEMA U-1 Laminated Thermoset Sheet Grades. a

Resin
NEMA Grade Description Reinforcementb Content, %
X mechanical kraft paper 33-36
XP hot punching kraft paper 33-38
XPC cold punching, weaker kraft, acp, clp 34-40
than grade XP
XX normal electrical clp, acp, bp 45-50
XXP hot punching, better than clp and acp 45-50
XX in electrical prop.
XXX radio frequency work, rag pap, acp, clp 55-60
moisture resistance
XXXP good electrical, good in- rag, acp, clp 57-60
sulation, and low di-
electric loss under high
humidity
XXXPC same as XXXP except rag, acp, clp 57-60
suitable for cold punch-
ing
XXXPC/FR-2 class I flame resist. rag, acp, clp 57-60
C gear stock and high im- cotton fabric 46-50
pact applications
CE electrical properties cotton fabric 50-55
nearly equal to XX
L fine machining props cotton fabric 46-50
G-3 high impact and flex continuous fil. 55-60
strength, good electri- glass fabric
cal
N-I excellent electrical nylon fabric 55-60
aAdapted and revised from Ref. 2.
"Legend: acp = alpha = cellulose paper; clp = cotton linter paper; bp = bleached kraft.

with high solids. The second resin application NMR is shown in Table 16. A phenolic resin
must introduce the flexibilizers into the paper. composition patented by Hitachi 120, based on a
Tung oil is a good material for modifying the brominated cresol novolak, meets UL V-I fire
resin since it brings in flexibility and tough- resistance ratings. Another area where consid-
ness. The final board has good punchability and erable development has taken place is in mod-
is solvent resistant. ifying phenolics with epoxy resins for use in
The production of a low-colored laminating items ranging from circuit boards to recrea-
resin is described in a patent issued to Weyer- tional equipment.
haeuser.1I9 The resin is made with an F/P mole
ratio in the range of 1.9-5.0 using citric acid Decorative Laminates. The main applica-
to neutralize the mixture. The distribution of tion here is in the furniture and cabinet mar-
formaldehyde in this material as determined by kets. As can be seen in examining the

Table 16. Distribution of Formaldehyde in Uncured Resin

Intermediate.
Distribution of Formaldehyde, Mole %
FIP Li2 C03' -CH2 OCH2 OH -CH2 OCH2 - -CH2 OH -CH2 - H2 CO
2.00 0.55 32.S 6.6 3S.3 1O.S 1l.5
2.65 0.76 36.2 S.4 20.5 16.9 IS. I
3.14 1.12 34.4 7.S 27.7 15.9 14.6
5.00 1.47 37.4 5.1 9.4 10.1 3S.0
'Moles to moles phenol.
334 HANDBOOK OF ADHESIVES

laminating products shown in Table 1, these tannin structures. 122 The lignin structures are
markets have been strong and are growing. The composed of a variety of phenolic units based
high pressure laminating processes are applied on coniferyl and sinapyl moieties.
in furniture production, and the low pressure The exact ratios of the main tree components
process for decorative papers, wood veneers, vary among the tree species and from hard-
and vinyl facings that are used in the lamina- wood to softwood. The structure of the lignin
tion of particle board. The laminate in a paper also varies. Although the exact nature of the
application is produced by impregnating the bonds formed between the wood and the resin
paper with an A-stage resin, and then bringing are not clearly proven, it is thought that there
it to the B-stage in cure with heat treatment as are several operating variables. These are the
the solvent is removed. The final standard for degree of penetration of the resin into the wood
these laminates is NEMA LD-3, 1985. 121 Gen- structure, the potential for hydrogen bonding
erally NaOH-catalyzed phenol-formaldehyde interaction, and the reaction of reactive meth-
resins are used, although some cresols can also ylol groups with active functionalities within
be incorporated. The resin solids pickup is typ- the lignin structures. In gluing operations the
ically 32-35% based on dry paper. Melamine moisture content of the wood and the surface
resins are used to impregnate the overlay pa- properties, such as porosity and coarseness,
pers (50%) and decorative top papers (67%). play an important role in the final bond for-
Some industrial applications include impreg- mation. These factors can lead to the necessity
nated kraft papers used for overlay plywood, of varying the glue mixes during the different
and fiber boards for use outdoors where protec- seasons of the year.
tion from weather and abrasion is needed. Con-
crete forms are one example. Plywood. Plywood is a laminated structure
that is composed of a minimum of three sheets
Filters and Separators. Impregnated phe- of veneer layered cross-grain. It is used for
nolic resin papers have important application in construction siding, concrete forms, kitchen
making oil, fuel, and air filters for the trans- and bathroom cabinets, flooring, and roofing.
portation industry. Generally novolak pheno- The plywood resins must be tailored to the par-
lics are used in a volatile solvent like acetone ticular wood species being glued. For example,
or methanol. The HMTA is a constituent in the a formulation for exterior grade plywood based
resin. The solution consists of around 65 % on douglas fir or hemlock is shown in Table 17.
resin solids and the material is applied in the The resin is almost always based on phenol
amount of 20-30% by weight of paper. An- using a mole ratio of 1.5-2.5 F/P with a so-
other area of importance is the production of dium hydroxide catalyst. Wheat flour is com-
battery separators. These materials are impreg- monly used for a filler and walnut shell as an
nated papers that are cured to a designated po- extender that helps control moisture dissipation
rosity. The resole resins used are prepared with from the glue line. Sometimes borax and blood
a relatively high F/P mole ratio and are applied are added for prepressing properties. The resins
in the low molecular weight A-stage. are generally 40-45 % nonvolatiles and range
from 25 to 31 % solid weight in the final glue
mix. Soda ash is included as a curing rate ad-
WOOD BONDING
ditive. Resins are currently made with very low
The area of phenolic use that is by far the larg- free formaldehyde or free phenol present.
est deals with wood bonding, for example, in However, much formaldehyde may be tied up
producing plywood, finger joints, wafer board, as hemiformals. Glue mixes for other wood
chip board, and laminated beams. This is illus- species must be formulated in very specific
trated by the data in Table 1. In understanding ways. If formulated, for example, for u.S.
the wood-glue bond, the wood structure must southern pine, variations of resole mole ratio,
be taken into account. Wood is composed of pH, fillers, and extender would be tried until
40-45% cellulose, 20-30% hemicellulose, and the wood-glue bond was maximized in that
20-30% lignin, along with natural resins and wood species.
 PHENOLIC RESIN ADHESIVES 335

Table 17. Exterior Plywood Glue Mix Formulation.

Constituent Mix 1, Wt% Mix 2, Wt%
Resole resin 58.3 (43% NV) 62.5 (40% NV)
Water 21.2 19.5
Glufil HLa 11.0
Bohemia l00b 11.6
Wheat flour 4.7 6.3
50% Caustic 4.7
Soda ash 4.7
Brookfield viscosity 4,100 4,800
pH 12.5 12.5
Veneer temp., of 70 70
Wood failure %, 95 93
6.25 min press
time @ 150°C
8Agrashell, Inc. Tradename for walnut shell flour.
'Bohemia, Inc. Tradename for fractionated douglas fir hark.

When plywood is laid up in a 5-ply construc- wafer weight. The mixture is then molded un-
tion, first the back is placed down with the grain der high pressure to achieve satisfactory
parallel to the long axis. The next veneer, called weather-resistant bond strength. A recent pat-
the cross band, has adhesive on both sides and ent has perfected the spray-drying process with
is placed with the grain perpendicular to the good dry resin particle size control. 124 When
back. Then the next veneer is placed with the the wood wafers are oriented by using a scat-
grain parallel with the back, followed by an- tering grid or have chips with greater length
other cross band with adhesive on both sides. than width, the product is called a strand board.
The final top piece, like the back, has the grain These materials are made with higher resin
parallel with the long axis. Then follows a stand content through use of liquid resoles, and have
time or a prepressing time to bring the glue into properties approaching those of plywood. In the
intimate contact with the surfaces before the hot United States, particle board is generally made
pressing that will take place-5-7 min at 140°C with urea or urea melamine resins. However,
and 175-200 psi for softwood plywood. Con- because of the formaldehyde release problem
trol of molecular weight of the resin, mix vis- with particle board, considerable work has been
cosity, and moisture in the wood are all done with diisocyanates. These materials have
important in setting a good glue line. A number excellent water resistant properties as com-
of methods for extending the phenolic resin in pared to nitrogen resins.
wood bonding have been explored; for exam-
ple, bark extender phenolic with the finely
ground wood bark treated with aqueous alka- Laminated Beams. Laminated beams or
line phenol-aldehyde resin. 123 timbers are made using three or more pieces of
sawed lumber with the grains laid nearly par-
allel. The adhesives are generally phenol-re-
Composition Board. In this class of mate- sorcinol- or resorcinol-formaldehyde mixes.
rials are strand board, wafer board, chip board, These resins have rapid curing characteristics,
particle board, and fiber board. As large-di- excellent water resistance, and can be used in
mensional trees have become more scarce, a hot pressing or in cold curing. Mechanical sys-
momentum toward research in developing and tems allow the continuous spreading of the glue
using composition board has increased. Wafer mix on sized, sawed lumber with the beams
board is a construction that is competitive with formed by stacking and clamping the timbers
plywood in many applications. It is made by until room temperature cure has been achieved.
spraying large wood particles with a resole resin Timbers can be treated with moisture and heat
in a rotating drum, usually at 2.5-3.0% of dry to be shaped into arches, for example. 125
336 HANDBOOK OF ADHESIVES

End Joints and Finger Joints. Another end nature of the crosslinking reaction. Blowing
use for fast curing resin is in end joints and agents can be chlorofluorohydrocarbons like
finger joints. These are designed to build larger trichlorotrifluoroethane or lower alkanes like
beams or to join pieces of lumber together with pentane. With atmospheric ozone depletion be-
a strength that is greater than the wood strength. coming an international problem, fluorochlo-
Resins have been developed that are two-com- rohydrocarbons will need to be replaced. 127
ponent and very fast reacting when brought in Foam can be made in a cellular form which has
contact with each other. 126 One component is a great structural strength, or in an open, water
normal phenol-resorcinol-formaldehyde with a absorbing form used in floral arrangements.
hardener like paraformaldehyde, and the sec- With stricter flammability standards being for-
ond mixture contains a fast-reacting phenol-m- mulated, interest will increase in phenolics. 128
aminophenol-formaldehyde resin. When the Phenolic microballoons are useful in making
components are brought together, for example, foams and other lightweight material. They can
in mating two ends, a bond sets up in minutes, be molded with phenolics to form rigid syntac-
and is fully cured in 30 minutes at 25°CY tic foams that reduce weight, increase stiffness
A number of adhesives have been formulated and improve crack resistance. They are used in
by using either lignins or tannins in combina- floating devices, ablative heat shields for reen-
tion with phenolics for applications from ply- try vehicles, and cores for wall panels. 129 Hon-
wood to composites. 12 Pretreatment of the eycomb materials can now be made that have
lignin or tannin is a requisite to success in al- all the inherent strength of natural construc-
most all cases. Generally it has been difficult tion. 130
to obtain consistent results. In addition, the
products are not as water resistant as when pre- GENERAL ADHESIVES
pared with PF resins.
Contact Adhesives. Phenolic resins are
widely used in neoprene and nitrile contact ad-
INSULATION AND FOAM
hesives mainly as tackifiers and adhesion pro-
Insulation. Resole resins are sprayed on hot moters. That is, they are needed to help hold
fibers with the. matted fibers then heated until the material together while the main adhesion
cured. The resins are generally phenol based process takes place. Contact adhesives must
and prepared at high F/P mole ratios, e.g., 2.5- have high green strength and high peel strength.
3.5, and cooked at low temperatures. These Applications for these materials are in leather,
conditions produce primarily uncondensed cloth, plastic, and rubber adhesion, upholstery,
polymethylolated phenols. The catalysts are weather stripping, and counter and desk tops.
commonly alkaline earth hydroxides. The resin Phenolics used in neoprene contact adhesives
is applied in 10-15% aqueous solutions. 11 The are either substituted novolak or resole resins,
PF resin imparts good dimensional quality to whereas the nonsubstituted resole is primarily
the glass wool mats and provides its important used with nitrile rubbers. A neoprene/phenolic
nonflammability characteristics. formulation 2 is given in Table 18. A nitrile rub-
ber contact adhesive could have 15 % high mo-
Foams. Resins used in foam are made as re- lecular weight acrylonitrile rubber, 15 %
soles with an F/P mole ratio of 1.5-3.0 using phenolic, and 70% of an oxy-solvent such as
either sodium or alkaline earth hydroxides. acetone. At 60°C this could have a canvas/can-
Formulations are made to contain approxi- vas peel strength of 17 lb / in. after pressing for
mately 80% resin solids. Foam density is reg- 15 min at 300 psi and 121°C. Other phenolic
ulated by the amount of surfactant, blowing formulations are found in this book in the neo-
agent, temperature and the acid-activity of the prene chapter. A good review of this subject
resin. Crosslinking is promoted by acids like p- was given by Barth. 2
toluenesulfonic or sulfonic acid. The foam
blowing agent is typically a high-vapor-pres- Structural Adhesives. Phenolic resins have
sure liquid that is volatile under the exothermic had wide use in structural adhesives for their
 PHENOLIC RESIN ADHESIVES 337

Table 18. A Neoprene/Phenolic ENVIRONMENTAL AND

Adhesive Test Formulation. 2 TOXICOLOGICAL CONSIDERATIONS
Parts
When a phenol-formaldehyde resin is fully
Component by Weight
cured, there are few hazards connected with the
Two-roll mill blend material, although dermatitis has been re-
Neoprene AC 100
ported. 131 ,132 However, the starting materials,
Neozone A antioxidant 2
MgO 4 phenol, substituted phenols, and formalde-
ZnO 5 hyde, are hazardous. Consequently, when
Phenolic resin 45 dealing with an A-stage or B-stage resin, there
MgO 4 will be free formaldehyde and free phenol pres-
Water
ent in the mixture, and proper safety precau-
Toluene 115
Hexane 115 tions should be taken, Phenols are highly toxic
Ethyl acetate 115 and can cause protein degeneration. Mono-
TOTAL 506 meric phenols can be quickly absorbed through
SOLIDS = 31.6% by weight the skin and cause a burning sensation and, in
fact, considerable damage. The oral LDso for
rats is 530 mg/kg. All phenolic resins contain-
strength properties with impervious substrates ing more than 5 % free phenol must be marked
as well as with wood. They are combined with as poisonous, and those containing 1-5 % as
thermoplastic polymers to provide both metal- detrimental to health.
to-metal or metal-to-paper or plastic bonding. Although test results are not conclusive re-
It is postulated that the phenolic crosslinks to garding the carcinogenic character of formal-
rubber through quinone methide intermediates II dehyde, it is known that many people are highly
by a 1-4 addition across the vinyl double bonds. sensitive to this compound. The current stan-
Some of the main materials are NBR with 15- dard in the United States for formaldehyde ex-
40% acrylonitrile in nitrile/phenolic resins and posure on an 8-hr basis is 1 ppm time weighted
polyvinylacetal in vinyl/phenolic blends. In all average (TWA), 2 ppm short term exposure
cases the phenolic gives inherent strength, sol- (STEL), and 0.5 ppm as the level where the
vent resistance, and thermal stability to the ad- company must take action. 133 In West Ger-
hesive. many and Scandinavia the threshold limit value
(TLV) is 1 ppm. Thermal oxidative breakdown
products generated from phenolic resins have
been examined by Waitkus and Lepeska. 134

PHENOLIC RESIN COMPANIES

Ashland Chemical Co. Fiberite Corp.

Columbus, OH 43200 Winona, MN 55987

BTL, Ltd. General Electric Co.

Niagara Falls, NY 14302 Pittsfield, MA 01201

Borden, Inc. Georgia Pacific Corporation

Salem OR 97300 Atlanta, GA 30348

CHEMBOND, Inc. Monsanto Co.

Springfield, OR 97477 St Louis, MO 63167

DuPont & Co., Inc. Occidental Corp.

Wilmington, DE 19898 North Tonawanda, NY 14120
338 HANDBOOK OF ADHESIVES

Plaslok COrp. Rogue Valley Polymer

Buffalo, NY 14200 San Francisco, CA 94111

Plastics Engineering Company Schenectady Chemicals, Inc.

Sheboygan, WI 53081 Schenectady, NY 12301

Resinoid Union Carbide Corporation

Skokie, IL 60076 Danbury, CT 06817

Rogers Corporation Westinghouse Electric Co.

Rogers, CT 06263 Hampton, SC 29924

ACKNOWLEDGMENTS
It is with appreciation that I give special thanks 15. Kopf, P. W., "Phenolic Resins," in "Encyclopedia
of Polymer Science and Engineering," Vol. 11, J.
to Ralph Moir and Jack Baush of Georgia Pa- Kroschutz, ed., New York, Wiley-Interscience,
cific Corporation, Jack Blanchard and Tino 1988, pp. 45-95.
Maccarrone of Reichhold Chemicals, Inc., 16. Meyer, B., "Urea-Formaldehyde Resins," Reading,
Vince Landi of the Rogers Corporation, the MA, Addison-Wesley, 1979, pp. 26-58.
Plastics Engineering Company, and the Union 17. Walker, J. F., "Formaldehyde," ACS Monogmph
159, 3rd Ed., New York, Reinhold Publishing Corp.,
Carbide Corporation for providing special in- 1964.
formation for this review. Their help is grate- 18. Le Bodan, D. J., Mechin, B. G., and Martin, G. J.,
fully acknowledged. Anal. Chem., 55, 587 (1983).
19. Tomita, B., Hirose, Y., J. Polym. Sci., Chem. Ed.,
14, 387 (1976).
REFERENCES 20. Funderburk, L. H., Aldwin, L., and Jencks, W. P.,
J. Am. Chem. Soc., 100 (Aug. 1978).
1. Baeyer, A., Ber. 5,25 (1872). 21. Woodbrey, J. C., Higginbottom, H. P., Culbertson,
2. Barth, B. P., "Phenolic Resin Adhesives," in H. M., J. Polym. Sci. Part. A, 3, 1079 (1965).
"Handbook of Adhesives," 2nd Ed., I. Skeist, Ed., 22. Baekeland, L. H., J. Ind. Eng. Chem., 1,545 (1909).
New York, Van Nostrand Reinhold, 1977, Ch 23. 23. Vansheidt, A. A., Itenberg, A., and Andreeva, T.,
3. Baekeland, L. H., U.S. Patent 942,699 (July 13, Chem. Ber., 69B, 1900 (1936); Prom. Org. Khim.,
1907). 3, 385 (1937).
4. Baekeland, L. H., J. Ind. Eng. Chem., 1, 149 (1909). 24. Tobiason, F. L., unpublished results.
5. "Materials," Modem Plastics, 62, 67 (1985); 64, 25. Tobiason, F. L., Chandler, C., and Schwarz, F. E.,
55 (1987); 65, 98 (1988). Macromolecules, 5, 321 (1972).
6. Pacific Luthemn University, DIALOG Search, 1988. 26. Gardikes, J. J., and Konmd, F. M., Am. Chem. Soc.
7. Martin, R. W., "The Chemistry of Phenolic Res- Div. Org. Coatings and Plastics, 26(1), 131 (1966).
ins," New York, John Wiley and Sons, 1956. 27. Brode, G. L., Kopf, P. W., and Chow, S. W., Ind.
8. Megson, N. J. L., "Phenolic Resin Chemistry," Eng. Chem. Prod. Res. Dev., 21, 142 (1982).
London, Butterworths, 1958. 28. Regina-Mazzuca, A. M., Ark, W. F., and Jones, T.
9. Whitehouse, A., Pritchett, E., and Barnett, G., R., Ind. Eng. Chem. Prod. Res. Dev., 21, 139
"Phenolic Resins," New York, Elsevier, 1968. (1982).
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14. Brode, G., "Phenolic Resins" in "Kirk-Othmer En- 34. Tobiason, F. L., Chandler, C., Negstad, P., and
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125, Washington, D.C., American Chemical Soci- 60. Christiansen, A. W., and Gollob, L., J. Appl.
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38. Harding, J. (to Union Carbide), U.S. Pat. 3,823,103 63. Tobiason, F. L., Houglum, K., Shanafelt, A.,
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Polym. Chem. Ed., 11,939 (1973). Polymer Science and Engineering," 2nd ed., New
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45. de Breet, A. J., Dankelman, W., Huymans, W. G., 68. "Phenolic Resins as a Bonding Agent for Grinding
and de Wit, J., Angew. Makromol. Chemie, 62, 7 Wheels," Technical Bulletin 1503, Reichhold
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46. Kim, M. G., Tiedeman, G. T., and Amos, L. W., 69. Narayanan, K. S., and Hickory, E. (to Norton Co.),
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Tompkins, T. J., Appl. Polym. Sci., 27, 3449 (1982). Dekker, 1972, Chapter 3.
50. Sojka, S. A., Wolfe, R. A., and Guenther, G. D., 73. "Durable Coatings Based on UCAR Phenolic Res-
Macromolecules, 14, 1539 (1981). ins," Technical Report, Union Carbide Corp., 1987.
51. Lamartine, R., Plastics and Rubber Process. and 74. Rossbacher, W., AFS Midwest Foundry Confer-
Appl., 6, 3\3 (1986). ence, South Bend, IN, Nov 1972.
52. Schulz, G., Gnauck, R., and Ziebarth, G., Plaste 75. "Shell Process Foundry Practice," 2nd Ed., Des
und Kautschuk, 29,401 (1982). Plaines, IL, American Foundryman's Society, 1963.
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294, 130 (1979). 4,590,229 (May 20, 1986).
54. Wellons, J. D., and Gollob, L., "Determining Mo- 77. McDonald, R. A. (to Georgia-Pacific Corporation),
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55. Sebenik, A., J. Chromat., 160, 205 (1978). York, Wiley-Interscience, 1987, p. 290.
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 18
Amino Resin Adhesives
IVOR H. UPDEGRAFF
Consultant Synthetic Resins and Plastics
Stamford, Connecticut

Amino resins are prepared by reacting fonnal- The principal attractions of amino resins are:
dehyde with a compound containing the amino water solubility before curing (which allows
group -NH2 • The amino compounds most easy application to many substrates and with
commonly used are urea and melamine: many other materials), colorlessness (which
pennits a colorless glue line as well as unlim-
ited colorability with dyes and pigments), good
solvent resistance, hardness, and heat resis-
tance, as well as low cost. A limitation of
urea
amino resins is the release of fonnaldehyde
during curing and in some cases after curing.
Outdoor weatherability is poor for products
melamine
made with urea-fonnaldehyde resins, but prod-
Urea-fonnaldehyde accounts for about 80% ucts made with melamine-fonnaldehyde resins
of production; melamine-fonnaldehyde consti- have good water resistance and outdoor weath-
tutes most of the remainder. A few other amino erability.
compounds are used to a very minor extent. Some amino resins are used to modify the
Amino resins are manufactured throughout properties of other materials. For example, a
the industrialized world for a variety of appli- small amount of an amino resin added to textile
cations. Adhesives represent by far the largest fabric imparts the familiar pennanent press or
market. Large amounts of simple urea-formal- wash-and-wear qualities. A small amount of an
dehyde resin adhesives are used to bond ply- amino resin added to paper can improve the tear
wood and particleboard, also known as strength even when the paper is wet. Textile
chipboard, flakeboard, or waferboard. More treating uses a low molecular weight soluble
complex adhesive fonnulations are used to resin, whereas for paper treatment the resin is
make laminated wood beams, parquet flooring advanced to fonn a colloidal dispersion so that
and interior flush doors, and for furniture as- it will attach to the cellulose fibers as the paper
sembly. is being made. The amino resin adhesive reacts
Several large chemical companies manufac- with the primary hydroxyls of the cellulose,
ture a full line of amino resins. This may re- thereby replacing weak hydrogen bonds with
quire as many as 75 different fonnulations to strong covalent bonds. The hydrogen bonds are
meet all application needs. Large particleboard released when the paper or cotton fabric is wet,
manufacturers may prepare a simple urea-for- but the covalent bonds remain in effect so that
maldehyde adhesive resin at the plant. the paper will retain strength and the cotton

341
342 HANDBOOK OF ADHESIVES

fabric will return to the original creased or flat cost basis. It is interesting that in today's pat-
condition when dried. tern of consumption, amino resin adhesives are
by far the largest segment of the amino resin
HISTORY market. Reconstituted wood products such as
plywood, chipboard, etc. represent the major
Urea-fonnaldehyde reaction products were de-
use. Lack of water resistance and slow release
scribed as early as 1908,1 but the first useful
of formaldehyde has been a deterrent to some
commercial product, a molding compound in-
applications.
vented in England by Edmond C. Rossiter,2 did
The future of amino resins and plastics seems
not arrive until almost 20 years later. It was a
to be secure since they can provide qualities not
fairly complex fonnulation using purified cel-
easily obtained in other ways. New develop-
lulose fiber as reinforcement. The amino resin
ments will probably be in more highly special-
contained equimolar amounts of urea and thi-
ized fonnulations for specific applications.
ourea. The new product could be supplied in
light translucent colors. The molded products
RAW MATERIALS
had a hard, stain resistant surface, and there
was no objectionable phenolic odor. In short, Formaldehyde is a highly reactive, pungent
the product was unique for its time. smelling, poisonous gas. It is made by passing
Although the use of thiourea gave the mold- air and methanol vapors through a heated cop-
ings a better gloss and improved water resis- per or platinum gauze. The resulting formal-
tance, it had the disadvantage of staining the dehyde is dissolved in water. It is highly
steel molds. As the technology advanced it was reactive and can fonn methylene glycol:
found that the amount of thiourea could be re-
duced and finally eliminated. Today's urea-for- HCHO + H 20 ~ HO-CH2-OH
maldehyde molding compounds contain no
thiourea. HO-CH2-OH + n HCHO
Melamine-formaldehyde resins were intro- - HO-CH 2 -O(CH2-O)nH
duced about ten years after the urea-fonnalde-
hyde products came on the market. The Henkel The reaction can continue to produce chains of
Company was granted patents for products polyoxymethylene glycol. To prevent precipi-
based on melamine in 1936 and 1937. 3 The tation of the fonnaldehyde polymer, known as
products made with melamine-fonnaldehyde parafonnaldehyde, the solution can be stabi-
resin were very similar to those based on urea lized by adding methyl alcohol. A 37 % solu-
but with some important superiority. Molded tion of fonnaldehyde must be maintained at a
plastics based on melamine-fonnaldehyde resin temperature of at least 32 ° C to prevent precip-
had much better water resistance and outdoor itation of the polymer. By adding 5-10% meth-
weatherability than moldings made with urea- anol, the solution will remain clear if stored at
fonnaldehyde resin. The combination of hard- room temperature.
ness, water resistance, and unlimited colora- Higher concentrations of fonnaldehyde are
bility made melamine-fonnaldehyde ideal for often supplied to customers using large quan-
molded plastic dinnerware and this remains the tities of the chemical, to reduce shipping costs
major application. The good stability of the and improve manufacturing efficiency. Heated
symmetrical triazine ring makes the melamine- storage tanks are required. For example, at
formaldehyde polymers very resistant to chem- 50 % fonnaldehyde the solution must be kept at
ical change once the resin has been cured to the 55°C to avoid precipitation. A very highly con-
insoluble cross-linked state. centrated fonn of fonnaldehyde stabilized with
The use ofurea-fonnaldehyde resin as an ad- urea is also available. It is manufactured by Al-
hesive was suggested as early as 1918,4 but lied Chemical Co. and is known as UF Con-
since it offered no new desirable properties the centrate 85. 5 The product contains 4.6 moles
commercial development was delayed until the of fonnaldehyde for each mole of urea and is
amino-fonnaldehyde resin could compete on a concentrated to 85% solids. It is convenient for
 AMINO RESIN ADHESIVES 343

the manufacture of urea-formaldehyde adhe-

sives, since the user need only add urea to give
the desired urea-formaldehyde ratio, adjust the
pH to the desired level, and react the resin to
the desired state of cure before use in his spe-
cific application.
Paraformaldehyde is available as a solid in
the form of flakes or powder. It is an unstable
polymer and can easily release formaldehyde
when dissolved in water. Formaldehyde also
exists in the form of a cyclic trimer, trioxane. melamine
It is a fairly stable compound and is not used
in the manufacture of amino resin adhesives. CHEMISTRY
Urea is the most important building block for
amino resins and plastics-first, because urea- Two major chemical reactions are involved in
formaldehyde is the largest selling amino resin, the bonding of amino compounds together with
and second because urea is used to make me- formaldehyde to produce and cure an amino
lamine, the amino compound in the second resin. The first is the addition of formaldehyde
largest selling amino resin. Urea is also in- to the amino group to introduce the hydroxy-
volved in the manufacture of a variety of other methyl group, also known as the methylol
amino compounds that are also used to make group:
amino resins.
Urea is a colorless, odorless solid, mp.
133°C. It is generally recognized as the first
organic compound to be synthesized from in- The second reaction is the combination of the
organic raw materials; Wohler synthesized it in methylol group with an active hydrogen to re-
1828 by heating ammonium cyanate. Urea is lease a molecule of water forming a dimer, a
now made in immense quantities for use as a polymer chain, or a vast three-dimensional pol-
fertilizer and cattle feed supplement. It is made ymer network. This reaction is known as meth-
by reacting carbon dioxide with ammonia un- ylene bridge formation, polymerization, or
der high pressure. Ammonium carbamate is simply cure. It is illustrated in the equation be-
first formed but releases a molecule of water to low:
form urea:
RNH -CH20H + H2NR
CO2 + 2 NH3 - NH 2CONH2
-+ RNH-CH 2-NHR + H20
+ H20 ~ H2NCOONH4
Melamine was synthesized early in the his- Success in making and using amino resins
tory of organic chemistry but remained a chem- depends on the precise control of these two re-
ical curiosity until it was found to react with actions. The first is primarily concerned with
formaldehyde to form a useful amino resin. the manufacture of the resin, while the second
Melamine was first manufactured from dicyan- is most important for the application in which
diamide, but it is now made from urea, a much the resin is used. The reaction of formaldehyde
lower-cost starting material. In this process the with an amino group will take place under
urea is dehydrated to cyanamid which termi- either acidic or basic conditions. The second
nates to melamine. The reaction is carried out reaction, however is catalyzed by acid. It is
at high pressure in the presence of ammonia to common practice to prepare the resin under
suppress the formation of deamination prod- fairly neutral conditions. Both reactions can
ucts. Ammonium carbamate is also formed in proceed slowly to form the methylol deriva-
the reaction and must be recycled to convert it tives and advance the polymerization to the de-
back to urea. sired degree. Some polymerization is needed to
344 HANDBOOK OF ADHESIVES

prevent crystallization of the monomeric meth- amino compound with formaldehyde and ad-
ylol compounds. A possible side reaction is for vance the polymerization to the desired degree.
two methylol compounds to combine forming The excess water may then be removed by vac-
a dimethylene ether linkage and releasing a uum distillation to give the desired viscosity.
molecule of water: Continuous processes have been described in
patents and may be in use for making simple
2 RNH-CH 20H amino resin adhesives. 6
+:t RNH-CH2 -O-CH2 -HNR END USES
+ H 20 Particleboard

The dimethylene ether so formed is not as Chips and shavings from scrap logs or from the
stable as the diaminomethylene bridge and may processing of lumber are screened to the de-
rearrange to form a methylene ether linkage and sired size. After drying to a moisture content
release a molecule of formaldehyde: of about 7 %, the chips are coated with the resin
adhesive, usually to about 7-9%, solids basis.
RNH-CH2 -O-CH2 -HNR The adhesive can be sprayed onto the chips as
they tumble in a blender. A wax emulsion may
~ RNH-CH2 -HNR + HCHO also be applied to reduce the water absorption
of the finished board. Total moisture content of
The methylol groups of amino resins may the resin coated chips should be in the range of
also react with the primary hydroxyl groups of 8-12 %. Too much moisture can cause blisters
cellulose. This reaction is of great importance when the cured board is removed from the
in the use of amino resins to improve the wet heated press. After application of the resin, the
strength of paper and to impart wash and wear treated flakes are spread onto trays and formed
qualities to garments made from cotton fabric. into a mat which may be prepressed, and then
This reactivity of methylol groups may be of loaded into a multiplaten heated press for cur-
significance for the application of amino resin ing. Cure time will depend on the thickness of
adhesives in the bonding of plywood and par- the board and may be in the range of 10-20
ticleboard because it allows the formation of minutes at a temperature of 125-175°C.
chemical bonds directly between the adhesive Three-layer chipboard is also produced, using
and the primary hydroxyl groups of the cellu- fine particles treated with a higher resin content
lose. on the face layers, with larger chips in the core
The usual catalysts or curing agents are am- layer. The resulting chipboard may be 75 %
monium salts, for example ammonium chlo- core and 25% surface layers.
ride. It may be mixed with wood flour or walnut Particle board made with urea formaldehyde
shell flour and mixed with the amino resin just resin adhesive is restricted to applications
before application. A buffer may also be in- where it is protected from water. It may not be
cluded with the catalyst. This could be calcium used in outdoor applications.
phosphate. It is slow in reacting but will com- It is not uncommon to use a urea-formalde-
bine with the acid released by the ammonium hyde resin of lower formaldehyde content in the
chloride and thus reduce the damage that the manufacture of particle board. For example, the
acid might cause to the wood. Such catalyst particle board adhesive might be 1 mol of urea
systems may be used with urea resins or urea- to 1.8 mol of formaldehyde, while the plywood
melamine resins to provide full cure at room adhesive might contain 2 mol of formaldehyde
temperature for furniture assembly. Resins for for each mol of urea.
plywood and chipboard applications are usu- A variety of formaldehyde scavengers have
ally hot pressed without any external catalyst. been suggested for use in urea-formaldehyde
Amino resins are usually made by a batch resins for particle board. The addition of free
process. The ingredients are charged to a ket- urea or melamine just prior to curing the resin
tle, adjusted for pH, and heated to combine the has been suggested. When the particle board is
 AMINO RESIN ADHESIVES 345

subjected to hot weather and high humidity, the Miscellaneous Applications

fonnaldehyde that is released might combine
Fiberglass insulation that is bonded with a phe-
with these free amino compounds. However,
nolic resin is made more fire resistant by add-
the methylol compounds so produced might
ing an amino resin. An amino resin adhesive
also undergo hydrolysis as hot and humid con-
may be used to bond a fire retardant to flam-
ditions are continued. Polyacrylamide has been
mable draperies.
suggested as an efficient scavening agent for use
Amino resin adhesives may also be used to
in urea-fonnaldehyde adhesives. 7
improve bonding between other materials. For
example, tire cord is nonnally treated with a
Plywood rubber latex to improve adhesion to the vulcan-
ized rubber. The latex dip solution may also
Plywood is an assembly of three or more layers
contain a resorcinol-formaldehyde resin or an
of wood (veneers) joined together with an ad-
amino resin to improve the bonding. Both urea
hesive. Hardwood plywood has an outside layer
and melamine resins are mentioned in patents,
of decorative wood such as walnut, oak, ma-
but melamine-fonnaldehyde is said to be most
ple, etc. with interior or support layers of
cheaper softwood such as pine. Ordinary ply- effective.
Regenerated cellulose film does not have
wood is 100% softwood and is used for struc-
good water resistance but may be made much
tural applications only. It is usuany made with
more water resistant by coating it with a film
phenolic resin adhesive to provide good water
of nitrocellulose or polyvinylidine chloride.
resistance. Hardwood plywood is made in both
outdoor and indoor grades. The water resistant The cellophane film is first passed through a
type is made with a melamine-formaldehyde dip tank containing about 1 % of a melamine-
fonnaldehyde acid colloid resin. This type of
adhesive that will not discolor a light decora-
tive surface veneer. Phenolic resin can be used resin is called an anchoring agent. It improves
to provide good water resistance with dark col- the adhesion between the waterproofing coat-
ored veneers. ing and the cellophane film.
The adhesive is applied to both sides of the Urea-fonnaldehyde resin is also commonly
alternate ply veneers. They are passed through used to bind the sand together to make the cores
that are placed in molds for casting hollow
a glue spreader and then stacked between the
metal shapes. The amino resin is mixed with
uncoated veneers to fonn the plywood assem-
bly. A product made with urea-fonnaldehyde the moist sand and fonned into the desired
adhesive might be pressed at 125°C and a pres- shape. After drying and curing, the core is as-
sembled into the mold. The sand core is stable
sure of 150-300 pounds per square inch for 5-
10 minutes to achieve a satisfactory cure. enough to hold the molten metal to the desired
shape until the metal solidifies. The continued
heating of the sand core breaks down the resin
High-Pressure Decorative Laminates so that the loose sand may be poured out by the
Melamine-fonnaldehyde resin provides both time that the molding has cooled down and so-
adhesive and functional properties in Formica lidified to the desired shape.
decorative laminates. To prepare a decorative A rapidly growing market for urea-formal-
laminate, a melamine resin-impregnated deco- dehyde adhesive resin is in use as a binder for
rative sheet is sandwiched between a melamine the glass fiber mats used in the manufacture of
resin-treated protective overlay layer and a shingles and built-up roofing. It is expected that
number of phenolic resin-treated support lay- this market will have an annual growth rate of
ers. The resulting combination provides the re- 10 % per year for the next few years.
markable properties of the decorative appear-
TOXICITY
ance of the printed pattern protected by the
hard, stain-resistant, and abrasion resistant sur- Urea and melamine are considered nontoxic.
face provided by the melamine-fonnaldehyde Urea is used as a feed supplement for ruminant
resin. animals such as cattle and sheep. The rumen
346 HANDBOOK OF ADHESIVES

microorganisms convert the urea to protein that Henkel Corporation.

can be used as food by the animal. Melamine Monsanto Chemical Company.
has caused no ill effects in rats even when they Monomer-Polymer and Dajac Labs. Inc.
are fed high concentrations. Fully cured amino Reichhold Chemicals, Inc.
plastics, such as urea-formaldehyde bottle caps T. R. America Chemicals, Inc.
and molded melamine-formaldehyde plastic
dinnerware are also considered nontoxic.
REFERENCES
Formaldehyde is a toxic gas and may be re-
leased from some amino-formaldehyde resins 1. Einhorn, A. and Hamburger, A., Ber. Dtsh. Ges., 41,
even after curing. This is true for urea-formal- 24 (1908).
dehyde foam insulation and for urea-formal- 2. Rossiter, E. C. British Patents. 248,477 (Dec. 5, 1924)
dehyde adhesives used in plywood and particle 258,950 (July 1, 1925) and 266,028 (Nov. 5, 1925).
(to British Cyanides Co., Ltd.)
board. Formaldehyde can irritate the eyes,
3. Hentrich, W. and Kohler, R. German Patent 647,303
nose, and throat. In some cases an allergic re- (July 6, 1937) and British Patent 455,008 (Oct. 12,
action develops so that complete removal from 1936). (to Henkel and Co. GmbH).
formaldehyde vapors is required. Formalde- 4. John, H., British Patent 151,016 (Sept. 14, 1920) and
hyde has also been found to cause cancer in U.S. Patent 1,355,834 (Oct. 19, 1920).
5. U. F. Concentrate-85, Technical Bulletin, Allied
laboratory animals. It is not uncommon for ad-
Chemical Corp., New York.
hesives based on urea-formaldehyde resin to 6. Elbel, K. British Patent 829,953 (Mar. 9, 1960).
contain some additive to react with the formal- 7. Dutkiewicz, J., J. Appl. Polym. Sci., 29, 45-55
dehyde that might be released in the curing re- (1984).
action. Many countries have adopted restrictive 8. Calve, L. R., and Brunette, G. G., Adhesives Age, 27,
39 (Aug. 1984).
standards limiting the amount of formaldehyde
9. Bowtell, M., Adhesives Age, 28, 42 (May, 1985).
that may be released from particleboard that is
used in the construction of residential housing.
General Literature
West Germany is reported to have one of the
most stringent formaldehyde regulations. 8,9 10. Vale, C. P., and Taylor, W. G. K., "Amino Plastics,
London, Iliffe Books, Ltd., 1964. A very comprehen-
sive review of amino resin chemistry and technology.
AMINO RESIN PRODUCTION 11. Williams, L. L., Updegraff, I. H., and Petropoulos,
J. C., "Applied Polymer Science," 2nd Ed., Wash-
American suppliers of amino resins include: ington, DC, Organic Coatings and Plastics Chemistry
American Cyanamid Company, Chemicals Division of the American Chemical Society, 1985,
Chapter 45.
Group. 12. Updegraff, I. H., "Encyclopedia of Polymer Science
Borden, Inc., Chemical Division. and Engineering, Vol. 1, 2nd Ed., New York, John
Chembond Corporation. Wiley & Sons, 1985.
 19
Epoxy Resin Adhesives
ALLAN R. MEATH
Dow Chemical U.S.A.
Freeport, Texas

INTRODUCTION Bisphenol A epoxy resins are difunctional, with

epoxide groups on the ends of the chain. As the
Structural adhesives based on epoxy resins were
molecular weight is increased, the resin retains
first introduced in 1950 and their use has grown
its epoxide difunctionality while adding n re-
steadily since. Epoxy resins are reactive with a
peating groups as shown above. The epoxide
number of different curing agents and yield a
equivalent weight (EEW) is one-half of the mo-
wide variety of products with different cure re-
lecular weight:
quirements and end-use performance. Epoxy
resins cure with no evolution of byproducts,
Epoxide Equivalent Weight (EEW)
have low shrinkage and adhere to many differ-
Molecular Weight
ent substrates. Although epoxy adhesives rep-
resent only a small part of the total adhesives 2
market, they are unequalled in performance
where high strength and endurance propertiesCommercial liquid resins such as D.E.R. 331
are critical. (Dow), Epon 828 (Shell), Araldite 6010 (Ciba-
Geigy), Epi-Rez 510 (Interez), and Epotuf 37-
1410 (Reichhold) range in viscosity from
EPOXY RESINS USED IN ADHESIVES
10,000 to 16,000 cps at 25°C and have an av-
erage n value of 0.15. Above n = 2, epoxy
Bisphenol A Based Epoxy Resins resins become nonsintering solids character-
ized by high molecular weights, high viscosi-
The most widely used epoxy resins are based ties, and low weight percent epoxide contents.
on Bisphenol A and epichlorohydrin. The Fig. 1 shows various relationships which exist
chemical structure is: between the liquid and solid Bisphenol A based
epoxy resins.

Epoxy Novolac Resins

Epoxy novolac resins are produced by reacting
a novolac resin with epichlorohydrin to obtain
epoxy functionality. Unlike the Bisphenol A
based resins, the epoxy novolac resins have an

347
348 HANDBOOK OF ADHESIVES

. . . .
% Epaxlde
. . High Performance Epoxy Resins
0 2.5 5 10 15 20
;~ With the increased demand for high tempera-
.
1720 860
.
430
EEW
287
. .
215
.
172
II
iii
u;
ture and high humidity resistance, new resins
have been developed which have higher epox-
ii ide and aromatic content. Three resins which
N Value .;
>- fit the category are TACTIX 742 (Dow), Ar-
f
•• • • I •

10.9 4.9 1.8 0.8 0.3 0 aldite MY 720 (Ciba-Geigy), and Epon 1031
(Shell). Their idealized structures are:
"I+-- Solid __ 1..... S::~:lid+ 1- LiqUid---+lJ
l\
Resin Cure
--=:l .. C~:CH-~ ~rCH_C~
i High Temperature
14-- Room Temperature
II

lQJ~
u
e
CL
~
Epoxlde. :::J
IHydroxyl1 & I +-Cured through Epoxide-+! 0
Hydroxyl --.J

~
Fig. 1. Comparative physical and curing properties for
liquid and solid Bis-A based resins.

epoxide group on each repeating unit as shown

in the following structure: TACTIX* 742
PI
O-CH2-CH-CH2

o 0
/\ /\
CH,-CH_~ ~H,-CH-CH'

H ----r.

The increased functionality YIelds cured ad-

hesives with higher crosslink densities result- l\
CH2'CH-CH2-O
ing in higher temperature performance and Epon* 1031
increased chemical resistance. The functional-
ity of commercially available, phenol based l\ l\
epoxy novolac resins varies from 2.3 to 6.0.
CH;-CH_~H,-CH_C~
Epoxy novolac resins can also be produced
from substituted phenols like creosol and po-
lyhydroxy phenols such as resorcinol. In the
United States, Dow Chemical and Ciba-Geigy

~
supply both phenol and cresol based epoxy no-
volac resins.
Epoxy novolac resins are normally used as
modifiers for Bisphenol A based epoxy resins
in adhesives. When used alone, the epoxy no-
volac resins tend to yield adhesives which are
PI PI
CHrCH-CH2'N-CH2'CH-CH2
too brittle for most applications. Araldite* MY 720
 EPOXY RESIN ADHESIVES 349

These high perfonnance resins can be cross- The types and number of curing agents avail-
linked with either an aromatic amine or a cat- able continues to grow rapidly. The chart in
alytic curing agent to induce epoxy-to-epoxy Table 2, taken from Dow Chemical's "General
homopolymerization. High temperatures are Guide to Formulating with Dow Epoxy Res-
required for these reactions to occur. ins," summarizes the applications and advan-
tages/disadvantages of different types of curing
Flexible Epoxy Resins agents.
A brief description of various curing agents
Long chain aliphatic epoxy resins based on a
is provided to aid in the selection of an appro-
polyglycol or a vegetable oil fatty acid, when
priate curing agent for a variety of adhesive ap-
reacted with epicblorohydrin, are used as ad-
plications.
ditives to flexibilize epoxy resin adhesives.
They are not used alone because of their water
Polysulfides
sensitivity and overall lack of toughness. They
serve as modifiers for Bisphenol A based epoxy An example of a typical poly sulfide and its re-
resins. An idealized structure for flexible epoxy action sequence with an epoxide group is shown
resins is shown below: below:
REACTION SEQUENCE

MERCAPTAN
R • AN ORGANIC GROUP OR HYDROGEN
o
J
e • / \
Examples of typical aliphatic epoxy resins HS-A-SH + RaN- HS-A-S + RaN H+ CHfCH -AM"-
based on polyol propylene glycol are D.E.R.

HS-A-S-CH,J~~+R3N
732 and D.E.R. 736 (Dow). Epi-Rez 505 (In-
terez) and Heloxy WC-85 (Wilmington Chem-
ical) are typical flexible epoxy resins based on [
a vegetable oil fatty acid.
A compilation of commercial epoxy resins
used in adhesives is shown in Table 1. A= (C 2H40 C2H40 C2H4SS) N

R= ALIPHATIC
CURING AGENTS USED IN CYCLOALIPHATIC
ADHESIVES AROMATIC

The selection of an appropriate curing agent is The reaction between the terminal mercaptan
as important as selecting the proper epoxy and epoxide group proceeds very slowly at am-
resin. The type of curing agent will determine bient temperature. However, the introduction
the rate of reactivity, degree of exotherm, for- of a basic material such as a tertiary amine
mulation viscosity, gel time, and the heat re- greatly accelerates the cure. Poly sulfides are
quirement during the cure cycle. In addition, typically used at ratios of 1: 1 or less with
application technique, pot life requirements, epoxy resins, and can be used as co-curing
and the desired performance properties of the agents with aliphatic amines. Stoichiometric
cured adhesive must be considered when se- quantities of aliphatic amine and 25 to 50 parts
lecting an epoxy curative. Curing agents deter- by weight of poly sulfide will react with 100
mine the type of chemical bonds formed and parts by weight of epoxy resin.
the degree of crosslinking which occur with the Poly sulfide/epoxy systems accelerated with
epoxy resin. These factors, in tum, affect the tertiary amines exhibit good flexibility and ten-
chemical resistance, electrical and physical sile strength at ambient temperature. The ali-
properties, and the heat resistance of the cured phatic amine/polysulfide co-curing agent
adhesive. systems yield improved initial elevated tem-
350 HANDBOOK OF ADHESIVES

Table 1. Epoxy Resins Used in Adhesives.

Viscosity @ 25°C,
cps or Epoxide
Durran's softening Equivalent Commercial
Type point Weight Products Remarks
Bisphenol A resins 4000-6500 172-180 D.E.R.332 Virtually pure
low viscosity (Dow) diglycidyl
Epon 825 ether of
(Shell); Araldite Bisphenol
GY 6004 (Ciba A
Geigy); Epo-Tuf
37-15 (Reich-
hold)
medium viscosity 7000-10 ,000 176-190 D.E.R.330, Undiluted
D.E.R.383, resins with
Araldite viscosity
GY 6008, lower than
Epon 826, standard
Epi-Rez 509 resins.
(Interez)
standard liquid 11 ,000-14,000 182-195 D.E.R.331, Standard un-
Araldite diluted
GY 6010, epoxy res-
Epon 828, ins
Epi-Rez 510,
Epo-Tuf 37-140
high viscosity 16,000-25,000 200-250 D.E.R.317,
D.E.R.337,
Araldite GY
6020,
Epon 834,
Epo-Tuf 37-141
solid 75-85°C, Durrans 500-575 D.E.R.661, Low melting
softening points Epon 1001, solid resin
Epi-Rez 520°C,
Epo-Tuf 37-001,
Araldite GT 7071
Epoxy novolac resins 1100-1700 @ 52°C 172-179 D.E.N.431 Phenolic no-
volac
20,000-50,000 @ 52°C 176-181 D.E.N. 438, Ar- Phenolic no-
aldite EPN volac
1138, D.E.N.
444
Epoxy cresol novo- 175-350 @ 150°C 180-220 Quatrex 3310 High-purity
lac resins (Dow) electronic
350-700 @ 150°C 180-230 Quatrex 3410 grades
700-1300 @ 150°C 190-230 Quatrex 3710
73°C SP 215-230 Araldite 1273
80°C SP 235 Max. Araldite 1280
99°C SP 220-245 Araldite 1299

perature perfonnance. Both systems, however, molecule. A primary amine group (nitrogen
lose some flexibility on aging. with two hydrogens bound to it) will react with
two epoxide groups. A secondary amine group
Amines (nitrogen with only one hydrogen bound to it)
The functionality of an amine is detennined by will react with one epoxide group. A tertiary
the number of amine hydrogens present on the amine group (nitrogen with no hydrogens
 EPOXY RESIN ADHESIVES 351

Table 2. Applications and Characteristics of Epoxy Curing Agents.

Type Advantage Disadvantage Application
Poly sulfides Moisture insensitive, quick Odor, poor elevated tem- Adhesives, sealants
set time, flexible perature performance
Aliphatic amines Convenience, room tempera- Critical mix ratios, strong Civil engineering, adhesives,
ture cure, low viscosity, skin irritant, high vapor grouts, casting and electrical
low formulation cost pressure, blushes encapsulation
Polyamides Convenience, room tempera- Higher formulation cost, Civil engineering, adhesives,
ture cure, low toxicity, high viscosity, low heat grouts, castings, coatings
good flexibility or resili- resistance, low vapor
ence, good toughness pressure
Amidoamines Reduced volatility, conve- Poor elevated temperature Construction adhesives, con-
nient mix ratios, good performance, some in- crete bonding, troweling
toughness compatibility with compounds
epoxy resin
Aromatic amines Moderate heat resistance, Solids at room tempera- Filament wound pipe, electrical
good chemical resistance ture, long elevated-tem- encapsulation, adhesives
perature cure schedules
Dicyandiamide Latent cure, good elevated Long elevated-temperature Powder coatings, electrical
temperature properties, cure, insoluble in resin laminates, one-component
good electrical properties adhesives
Catalytic Extremely long pot life, high Long elevated-temperature Adhesives, electrical, encapsu-
heat resistance cure schedules, poor lation, powder coatings,
moisture resistance electric laminates
Anhydrides Good heat resistance, good Long elevated-temperature Filament wound pipe, electrical
chemical resistance cure schedules, critical encapSUlation and adhesives
mix ratios
Melamine/formalde- Good hardness and flexibil- Elevated temperature cure Waterborne coatings, container
hyde ity, one-package stability, and deco finishes
solvent-free systems
Urea/formaldehyde Good film color, one-pack- Elevated temperature cure Fast bake enamels, primers and
age stability, good inter- topcoats
coat adhesion
Phenol/formaldehyde Good elevated temperature Solid, poor weatherability Powder coatings, molding com-
properties, good chemical pounds
resistance, good hardness
and flexibility

bound to it) will not react readily with an epox- Theoretically, the hydroxyl groups generated
ide group, but will act as a catalyst to acceler- in the above reaction sequence are capable of
ate epoxy reactions. A typical amine reaction reacting with other epoxide groups, thus form-
sequence is shown below: ing an ether linkage. This reaction can be cat-
PATH OF REACTION alyzed by tertiary amines.

Aliphatic Amines
The liquid aliphatic polyamines and their ad-
ducts are convenient to handle and give good
cured resin physical properties, including ex-
cellent chemical and solvent resistance. Mix
OH ratios are critical for optimum performance.
I
/ CH f CH 4IV'- Aliphatic amines offer fast curing at ambient
RN COMPLETELY
CROSSLINKED temperatures. Pot life is short and high exo-
R= ALIPHATIC OH
1
" CHf H4IV'- SYSTEM therm in thick sections or large masses can lead
CYCLOALIPHATIC to thermal decomposition. Good long-term re-
AROMATIC tention of properties is possible at temperatures
352 HANDBOOK OF ADHESIVES

up to 100°C (212°F). Short-term exposure to polyamide to epoxy is more forgiving (less crit-
higher temperatures can be tolerated. Epoxy ical) than with low molecular weight polyam-
resin formulations containing aliphatic amines ines. Polyamides also offer the advantages of
will blush under very humid conditions. curing without blushing, and improved adhe-
Adducted aliphatic polyamines such as D. E. sion. However, they are much darker in color
H. 52 (Dow) epoxy hardener and D. E. H. 58 than polyamines.
(Dow) epoxy hardener offer the advantages of The various molecular weight polyamides
lower vapor pressure, reduced tendency to exhibit different degrees of compatibility with
blush, and less critical mix ratios. epoxy resins. To ensure optimum properties,
the polyamide/epoxy mixture must be allowed
Cycloaliphatic Amines to react partially before being used. The partial
reaction assures compatibility and is known as
When compared to aliphatic polyamines, cy-
the induction period. Because polyamides have
cloaliphatic amines produce cured resins hav-
a long pot life, the induction time does not sig-
ing improved thermal resistance and toughness.
nificantly shorten the usable time of the sys-
Glass transition temperatures approach those of
tem.
aromatic amines while percent elongation can
Polyamide-cured epoxides lose structural
be doubled. Because cycloaliphatic amines are
strength rapidly with increasing temperature.
less reactive than aliphatic polyamines, their
This limits their use to adhesive applications
use results in a longer pot life and in the ability
which will not be subjected to temperatures
to cast larger masses.
above 65°C (148°F).
Aromatic Amines
Amidoamines
Aromatic amines are solids at room tempera-
Amidoamines are derivatives of monobasic
ture. These hardeners are routinely melted at
carboxylic acids (such as ricinoleic acid) and
elevated temperatures and blended with
an aliphatic polyamine. Like the polyamides,
warmed resin. Eutectic mixtures of metaphen-
amidoamines can be used over a range of ad-
ylene diamine and methylene dianiline exhibit
ditive levels to enhance a specific property. The
a depressed melting point resulting in an aro-
reactivity of amidoamines with epoxies is sim-
matic hardener that remains a liquid over short
ilar to that of polyamides. However, amidoam-
periods of time. The pot life is considerably
ines offer several advantages over aliphatic
longer than that achieved with aliphatic po-
amines and polyamines: more convenient mix
lyamines. Elevated temperature cures are re-
ratios, increased flexibility, better moisture re-
quired to develop optimum properties which are
sistance than aliphatic polyamines, and lower
maintained at temperatures up to 150°C
viscosity and color than polyamides.
(300°F). Aromatic amines have improved
chemical and thermal resistance when com-
Dicyandiamide
pared to aliphatic polyamines.
NH
Polyamides II
H2N-C-NH-C=N
The most commonly used polyamides are the
condensation products of dimerized fatty acids Dicyandiamide (Dicy) is a solid curing agent
and aliphatic amines such as diethylene tria- which, when ball milled into liquid epoxy res-
mine. A range of molecular weights are avail- ins, provides one-package stability for up to six
able making polyamide curing agents versatile months at ambient temperature. Cures occur
in a variety of adhesive applications. The po- with heating to 150°C (300°F). A tertiary
lyamides react with epoxide groups through the amine accelerator is necessary for rapid cures.
unreacted amine functional groups in the po- Dicy offer Ute advantage of being latent (reacts
lyamide backbone. As a result of their rela- with epoxy resins upon heating, and stops re-
tively large molecular weight, the ratio of acting when the heat is removed). This par-
 EPOXY RESIN ADHESIVES 353

tially cured or "B-staged" state is ideal for pre- temperature performance. The optimum con-
pregs for supported film adhesives. Typically, centration of accelerator should be determined
dicyandiamide is used at levels of 5-7 parts per experimentally. Eutectic mixtures to depress
100 parts liquid epoxy resin, and at levels of melting points may be prepared.
3-4 parts per 100 parts solid epoxy resin. The reaction of anhydrides with epoxide
groups is complex, with several competing re-
Catalytic Curing Agents actions capable of taking place. The three most
important are:
Catalytic curing agents are a group of com-
pounds which promote epoxy to epoxy reac- 1. The opening of the anhydride ring with
tions without being consumed in the process. an alcoholic hydroxyl to form the mon-
A typical epoxy homopolymerization using a oester.
tertiary amine is shown below: 2. Subsequent to the opening of the ring, the
nascent carboxylic groups react with the
o Oe epoxide to give an ester linkage.
/ \ • I
R3N+ CHr CH-1W'- ~ R3N-CHrCH-AM"- J 3. The epoxide groups react with nascent or

Ll\
existing hydroxyl groups, catalyzed by
the acid, producing an ether linkage.
·
CHrCH-1W'- --» R3N-C HrC H-1W'-
At low elevated temperature cures, the ether
I
O-CH-CH-1W'- and ester reactions take place at about the same
Ie
o frequency. At higher temperatures, the ester
linkage occurs more frequently and this prob-
Stable, one-package systems can be devel- ably accounts for the reduced elevated temper-
oped with many catalytic curing agents such as ature performance of systems gelled at initially
the boron trifluoride complexes. Tertiary high temperatures. Because reaction 3 can take
amines and amine salts have pot lives generally place independently in the acid medium, the ra-
ranging from 2 to 24 hours. The latent catalysts tio of anyhydride to epoxy is less critical than
are activated by heat and cause a disassociation with an amine. It can vary from 0.5 to 0.9
of the active catalyst from the blocking group. equivalents of epoxy and is determined exper-
The amount of catalyst used may vary from
imentally to achieve desired properties.
2 to 10 parts per 100 parts resin. To determine Compared to aliphatic amine cures, the pot
the best ratio of catalyst to resin, several dif-
life of epoxy-anhydride formulations is usually
ferent catalyst levels should be evaluated to de-
long and exotherm is low. Elevated tempera-
termine which level provides maximum ture cures (up to 200°C) are necessary and long
properties. Several common catalytic curing
post-cures are required to develop ultimate
agents are benzyldimethylamine (BDMA), bo-
properties. Electrical and physical strength
ron trifluoride monoethylamine (BF3 . MEA), properties are good over a wide temperature
and 2-methylimidazole (2-MI).
range. Compared to amine-cured systems, an-
hydride-cured systems offer better chemical re-
Anhydrides
sistance to aqueous acids and less chemical
Liquid and solid anhydrides are used exten- resistance to some reagents.
sively to cure epoxy resins. The reactivity of
some anhydrides with epoxies is slow, there-
SUMMARY
fore an accelerator, usually a tertiary amine, is
often used at 0.5-3 % to speed gel time and The most commonly used curing agents for
cure. The optimum amount is usually critical, ambient cured adhesives are polyamides, ali-
and is dependent on the anhydride, the resin phatic amines, cycloaliphatic amines and ami-
used, and cure schedules. The amount of ac- doamines. The choice of hardener is dependent
celerator above or below the "optimum" con- on the performance requirements of the adhe-
centration can result in reduced high sive. For high performance, high temperature
354 HANDBOOK OF ADHESIVES

Table 3. Curing Agents for Epoxy Resins Adhesives.

Recommended Curing
Partsll {)() parts Temperature Curing agent
Curing agent Liquid resin ·C Suppliers and Trade Names
Aliphatic amines
diethylene triamine 8-10 R.T.-150 D.E.H. (The Dow Chemi-
(DETA) cal Company)
triethy lene tetramine 10-13 R.T.-150 Amicure (Pacific Anchor
(TETA) Chemical Co.)
Aminoethyl piperazine 20-23 R.T.-150 Epo-Tuf (Reichhold Chem-
(AEP) ical)

Aromatic amines
methylene dianiline 51-55 175 (2 hr) Curithane (Dow)
4,4-diaminodiphenyl sul- 30-34 175 (2hr)
fone
MDA/MPDA eutectics Amicure (Air Products and
Chemicals, Inc.)
Ancamine (Pacific Anchor)
Epon (Shell Chemical
Company)

Cyc10aliphatic amines
wide variety of modified R.T.-150 Amicure (Air Products)
products from major Ancamine (Pacific Anchor)
curing agent suppliers Azamine (SHEREX)
Epo-Tuf (Reichhold)
Versamine (Henkel Corpo-
ration)

Polyamides
wide variety of polyam- R.T. to 2 hr All major curing agent sup-
ide curing agent with @100 pliers listed above offer
range of molecular Polyamide curing agents.
weights.

Heat activated curing

agents and catalysts
benzyl dimethylamine 2-4 150 (2 hr) Air Products and Chemi-
(BDMA) cal, Inc.
dicyandiamide (DICY) 2-4 150 (2 hr) Pacific Anchor Chemical
Corp.
boron trifluoride amine 2-4 150 (2 hr) Allied Chemical, Ciba-
complexes Geigy, Sylvachem (Sub.
of Arizona Chem.)

resistant adhesives, the aromatic amines, di- of large amounts of filler. Both reactive and
cyandiamide, and catalytic curing agents are nonreactive diluents are used. Reactive di-
used. luents are low viscosity mono or difunctional
Table 3 contains a list of curing agents used epoxy materials. Table 4 lists reactive epoxy
in adhesives and their manufacturers. diluents in descending order of viscosity .
Nonreactive diluents are not as widely used
as reactive diluents in epoxy resin adhesives
DILUENTS
because they decrease the cured properties more
Diluents are used in epoxy adhesive formula- than a reactive diluent and have a tendency to
tions to reduce viscosity and to allow the use migrate to the surface of the adhesive bond. The
 EPOXY RESIN ADHESIVES 355

Table 4. Reactive Diluents For Epoxy hesive. Organotitanates, zircoaluminates, or

Adhesives. silanes can be added to formulations to im-
Diluents cps at 25°C prove filler wetting, enabling higher filler load-
ings without increasing the viscosity.
Butyl glycidyl ether 2 max.
2-Ethylhexyl glycidyl ether 1-4
Table 6 contains a compilation of the effect
t-Butyl glycidyl ether 2-5 of various fillers on the physical properties of
Phenyl glycidyl ether 4-7 cured epoxy resin systems.
o-Cresyl glycidyl ether 2-10
C I2-C 14 alkyl glycidyl ether 6-10
Diglycidyl ether of 1,4 butanediol 14-18 ELASTOMERIC MODIFIERS

Elastomeric modifiers are used to increase the

advantage of non-reactive diluents is their lower peel strength (toughness) of epoxy resin adhe-
cost compared to reactive diluents. Table 5 sives. The most commonly used elastomeric
contains a list of non-reactive diluents used in materials are functionally terminated polybu-
epoxy resin adhesives. tadiene resins made by the B. F. Goodrich
Company, Chemical Group under the trade
FILLERS name of Hycar Reactive Liquid Polymers. Ini-
Fillers are incorporated in epoxy resin adhesive tially, carboxyl-terminated butadiene acryloni-
formulations to enhance or obtain specific de- trile (CTBN) resins were introduced; the
sired properties and to reduce cost. The amount carboxyl terminated materials are usually ad-
and type of filler used are determined by the ducted with the epoxy resin to improve com-
specific properties desired. patibility and to increase the toughness.
The amount of filler by weight that can be The latest addition to reactive liquid poly-
incorporated into an epoxy adhesive will de- mers are amine-terminated butadiene acryloni-
pend on the filler's particle size, shape, density trile rubbers. These amine-terminated polymers
and oil absorption properties. Porous, high-oil- are added to the hardener side of two-compo-
absorption fillers such as diatomaceous silicas nent epoxy resin adhesives. The carboxyl or
and chopped glass will greatly increase the vis- amine terminated polymers may be used at rel-
cosity of an epoxy adhesive with low filler atively low concentrations, about 3-30 parts of
loadings of 20-50 parts per hundred resin (phr). rubber per 100 parts resin, to produce tough-
Oil absorbent, granular fillers of medium ened epoxy resins. These toughened epoxy res-
weight, such as powdered aluminum and alu- ins provide greatly improved impact resistance
mina, may be used at loadings up to 200 phr. and fracture surface energies with little loss of
Nonporous, lower oil absorbent fillers like alu- modulus and hot strength. Higher concentra-
minum oxide, silica, and calcium carbonates tions of rubber (30-100 phr) produce epoxy ad-
can be incorporated at levels of 700-800 phr hesives with large increases in tensile
without producing an unusable formulation. elongation, and resistance to thermal shock, but
Filler loadings can be increased by using a with lower room temperature strength, stiff-
diluent, although diluents will usually detract ness, and hot strength.
from the physical properties of the cured ad-
TYPICAL ADHESIVE FORMULATIONS
Table 5. Non-reactive Diluents For
Epoxy Adhesives. The following are examples of typical epoxy
Nonyl phenol
resin adhesive systems. One of the advantages
Diocty I phthalate of epoxy based adhesives is the wide choice of
Dibutyl phthalate available curing agents, allowing the formula-
Furfuryl alcohol tor to produce adhesives with either fast am-
Pine oil bient cures, high temperature cures, or one
Coal tar
package systems with extended shelf life.
356 HANDBOOK OF ADHESIVES

Table 6. Effects of Fillers on Properties of Cured Epoxy Systems. 8

Im-
Improved Improved Improved proved Improved Improved
Therrtull Machina- Abrasion Impact Electrical Thixotrop
Conductivity bility Resistance Strength Conductivity Response
Additives Calcium car- Alumina, Chopped Mica, Metallic ·fill- Colloidal
bonate, flint pow- glass silica, ers, or al- silica,
calcium der, carbo- pow- umina Benton-
silicate, rundum, dered ite clay
powdered silica, or or
aluminum, molybde- flaked
or copper num disul- glass
fide
Cost D D N D D
Exothenn D D D D D D
Thennal con- I D
ductivity
Heat deflection N
temp.
Machinability D D D
Abrasion resis- N D D
tance
Impact strength D D D D N
Tensile strength D N D N N
Flexural D N D N N
strength
Compressive D N D N N
strength
Dielectric con- N
stant
Thixotropy N N N N N
'D, decrease; I, increase; N, essentially no effect.

Epoxy Concrete Adhesive Room Temperature Cure General Use

Part A Adhesive
Thiokol LP-3 100
Hydrite Clay 121 140 Part A
Trimethylaminomethyl 20 Liquid Epoxy Resin (EEW 70
phenol 190)
Toluene 65 D.E.R. 732 Aliphatic Epoxy 30
Resin
Part B Alumina T -60 50
D.E.R.331 200
Hydrite Clay 121 105 Part B
Toluene 5 Triethylene Tetramine 13
The following test results are reported by
Thiokol when the formulation is used to bond Tensile Shear Strengths (psi)
new to old concrete after 7 days aging at 80°F: Substrate Cured 7 Days Cured 2 hrs
@ 75°F @ 200°F
Tensile strength, psi 450
Aluminum, 16 1150 1600
Flexural strength, psi 345
gauge
Compressive shear strength, psi 4350
Stainless steel, 1400 1730
All failures were in the concrete. 16 gauge
 EPOXY RESIN ADHESIVES 357

General Purpose Adhesive • More uniform application of the adhesive

for Temperatures Up to 150°C bead results in higher quality finished
products.
Part A
• Decreased adhesive or sealant material
D.E.N.438 90
costs. Material use can be decreased by as
D.E.R.736 10
much as 30%.
Atomized Aluminum Powder 40
• Better utilization of people and machinery
Part B plus increased process flexibility.
Cycloaliphatic Amine 28 • Improved working environment because
the operator is not in constant contact with
Supported Epoxy Film Adhesive volatile components released from the ad-
hesive or sealant.
D.E.R.331 100
D.E.N. 438-A85 100 Industries leading in the use of robotics are
until desired the appliance, automotive, and furniture man-
Solvent
viscosity reached ufacturing.
Dicyandiamide 16
Benzyldimethyl 2-4
Induction Curing
amine (BDMA)
The expanded use of adhesives for bonding ad-
• Mix resins and solvent. Ball mill curing
vanced composites and metallic structures to-
agent into varnish.
gether could be restricted by the need for jigs
• Varnish is then B-staged on desired film
or spot welding to hold the components to-
backing (e.g., glass cloth or graphite) and
gether until the adhesive cures to the extent of
heat cure in place.
providing structural strength. Reaching this
Unsupported Film Adhesive point can require heating to high temperatures
Cast From Solvent Solution (300-400°F) the part being produced and the
jigging equipment. Induction heating tech-
. D.E.R. 684 EK 40 212
niques can eliminate these needs by providing
D.E.N. 438 EK 85 37.5
heat directly to the bond line and/or adherends
Dicyandiamide 12
without heating the entire structure, supports
Benzyldimethylamine 1.0
and fixtures of a bonding assembly. Bonding
Solvent removal 1 hr @ 180°F times for specimens can be cut by a factor of
Dry film thickness 0.002 10-100 compared to standard press bonding.
Cure schedule 1 hr@ 175°C Induction heating is produced when a current
Pressure 120 psi passing through a conductive coil produces a
magnetic flux inside and around the coil. When
COMPLEMENTARY TECHNOLOGIES a mass of conducting metal (susceptor) is
moved into the magnetic field or is subjected
New technologies which will impact the growth
to a changing flux, induced currents called eddy
of adhesives in assembly line applications are
currents circulate in the susceptor producing
robotics and induction curing.
heat. Susceptors can be incorporated into the
adhesive bond line by using magnetic iron ox-
Robotics
ide, iron filings or carbon as· a filler in the ad-
The use of robots is fast growing in prominence hesive formulation or imbedding a steel screen
in the field of material dispensing, especially in or perforated steel foil in the adhesive bond
the application of adhesive and sealants. Com- line. The heat produced will cause the epoxy
panies who have installed robots to dispense adhesive to cure. Ideal induction cure adhe-
adhesives or sealants have realized rapid pay- sives will have a broad cure temperature of
back of their capital investment because of the 275-425°F and no adverse affect by overheat-
following benefits: ing.
358 HANDBOOK OF ADHESIVES

APPLICATIONS AND SUMMARY Adhesives based on epoxy resins find use in

the consumer, furniture, construction, auto-
Adhesives based on epoxy resins can be for-
motive, aircraft/aerospace, electrical/elec-
mulated to bond to a variety of substrates and
tronic and industrial tool maintenance industries
perform over a broad range of conditions. They
where they provide both protective and load
are used in one- or two-component pastes or
bearing properties.
films which are curable under ambient or ele-
vated temperatures. Film adhesives, most com-
REFERENCES
monly formulated with Bisphenol A and/or no-
volac epoxy resins and latent curing agents and 1. "Fonnulating With Dow Epoxy Resins," Midland,
impregnated on glass cloth or other mediums, Michigan, The Dow Chemical Company.
can be stored for prolonged time periods prior 2. Lee, H., and Neville, K., "Handbook of Epoxy Res-
ins," New York, McGraw-Hill Book Co., 1967.
to cutting and heat curing.
3. Flick, E. W., "Adhesive and Sealant Compound For-
When compared to other polymeric adhe- mulations," Park Ridge, NJ, Noyes Publications, 1984.
sives, epoxy adhesives have the following ad- 4. Bruins, P. F., "Epoxy Resin Technology," New York,
vantages: Interscience Publishers, 1968.
5. Torrey, S., "Adhesive Technology Developments Since
1977," Park Ridge, NJ, Noyes Publications, 1980.
• Excellent tensile shear strength. 6. Wake, w. C., "Developments in Adhesives," Lon-
• Good moisture, humidity, chemical, and don, Applied Science Publishers, Ltd., 1980.
high temperature resistance. 7. Dueweke, N., "Robotics and Adhesives: An Over-
• No evolution of volatiles and low shrink- view," Adhesives Age, April, 1983.
8. Buckley, J. D., et aI., "Equipment and Techniques in
age during cure.
Rapid Bonding of Composites," NASA Langley Re-
• Good surface wetting ability. search Center, April, 1984.
• Low creep under prolonged stress condi- 9. "New I-Part Epoxy Adhesive Join Auto Parts Swiftly,"
tions. Metalworking News, April, 1987.
 20
Polyurethane- and
Isocyanate-Based Adhesives
C.S. SCHOLLENBERGER
Polyurethane Specialist and Consultant
Hudson. Ohio

The most important polyurethane adhesive Market Sales, $MM Applications

components continue to be toluene diisocyan- Film and foil
Food packaging 20
ate (TOl) (1)*, diphenylmethane-4,4' -diiso- lamination
cyanate (MOl) (VIII), polymethylene
Footwear 15 Vinyl-to-Ieather
polyphenyl isocyanate (PAPI) (XV), and tri-
and canvas
phenylmethane triisocyanate (Desmodur R)
Consumer 3.5 Do-it-yourself
(III) together with various polyester and poly-
products
ether glycols. One review points out that po-
Construction 10 Film lamination
lyester based polyurethanes have emerged as
for wall
the forerunner over polyether systems because
panel, out-
of their inherently higher cohesive and adhe- door carpet
sive properties. 54 Nevertheless, poly(ether-ur-
Furniture 20 Lamination to
ethane) adhesive compositions unquestionably
particle board
have useful adhesive properties. 78
Automotive 8 SMC to SMC,
The use of polyurethane- and isocyanate- interior trim
based adhesives in the United States is esti-
Aircraft 0.5 Interior plastics
mated to have grown from a level of less than
Total 97
100,000 lb in 1960 to 10-12 million pounds in
1972. 1 Although substantial, this growth was Their multiple use-forms (e.g., in in situ-re-
considered by many to be unimpressive for the acting, neat, liquid systems; solutions; aqueous
time span involved. 2• 3 However, existing as dispersions; films; webs; powders) and other
well as new high-performance polyurethane valuable attributes (e.g., adhesion to a variety
adhesive systems for specialized industrial ap- of substrates; VI'b ratlOn-
. dampmg . bonds,.4.13
plications generated a 97 million dollar busi- gasoline, oil, and solvent resistance; etc.) con-
ness by 1981, distributed as follows: 81
tinue to make polyurethane- and isocyanate-
1981 Polyurethane Adhesives Market based adhesives the materials of choice in many
adhesive applications.
Market Sales, $MM Applications
The practical basis for polyurethane adhesive
Textile 20 Fabric tie-coats, use is abundantly evident, for example, in fast
flocking sole-to-upper bonding in footwear; strong,
*Roman numerals refer to structural formulas at end of flexible adhesion with high pigment loadings in
chapter. magnetic oxide binders for magnetic tape; dis-

359
360 HANDBOOK OF ADHESIVES

similar material bonding in film laminates; oratories about 1940. In the course of
strong, flexible, solvent-resistant urethane attempting to vulcanize hydroxylated buna (po-
foam-fabric bonds in apparel; toughness in lybutadiene) rubbers and hydroxyl-bearing
abrasion devices; application ease in electrical buna copolymer rubbers with diisocyanates (to
systems; etc. replace a sulfur cure) they discovered that
A special polyester glycol type, polycapro- Buna-S and natural rubber both undergo dis-
lactone glycol (XXVI), has become well estab- tinct vulcanization effects with diisocyanates.
lished as a polyurethane adhesive component. 54 Of greater importance to the present subject was
And still another macroglycol type, polybuta- their observation that such stocks adhered
diene glycol (Poly BD glycol) (XXVII) has strongly to the metal parts of the vulcanization
gained use in polyurethane adhesive systems. 79 press after the cure. This effect was studied
Thermoplastic polyurethanes continue to hold more thoroughly in cooperation with the Cen-
the imposing inroads they have made in adhe- tral Rubber Laboratory of I. G. Farbenindus-
sive applications. And ecological considera- trie. Such studies led to "the long-sought
tions direct growing attention to nonpolluting adhesive for applying buna to various sup-
urethane adhesive forms, e.g., powders, films, ports. "
aqueous dispersions, and 100% solids reactive Heat-stable bonds of normal buna-sulfur
systems. mixtures to iron, light metals, porcelain, etc.,
This chapter builds on an earlier one. 5 It in- with strengths up to 1138 psi (stock failure)
cludes what are considered to be some of the were realized using toluene diisocyanate (I) and
more important developments and considera- hexamethylene diisocyanate (II). Still, some
tions in the field of polyurethane- and isocyan- problems in the use of isocyanates in adhesive
ate-based adhesives. In addition, it includes systems were encountered. Thus, "Desmodur
information from other areas of polyurethane R (III) had shown outstanding adhesion in
technology and chemistry such as polymer sta- bonding rubber tank treads to steel. It still gave
bility and stabilization, since these are relevant erratic performance, however, and needed fur-
to adhesive applications. The reader may also ther development. ,,12 These studies apparently
wish to consult other references 2 ,6a, 7 ,8,82a,b, represented the beginning of the diverse appli-
which review information on the present sub- cation of isocyanates in adhesive systems in
ject. Germany.
One could easily conclude that the above de-
velopment was related to the use of diisocyan-
DEVELOPMENT OF THE USE OF
ates as coupling agents in the preparation of
POLYURETHANES AND ISOCYANATES
polyurethane plastics and elastomers, whose
IN ADHESIVES
intense study was in progress in Germany at
Allied interrogation teams, who were assigned about the same time. At any rate, German ex-
the task of studying the state of development of ploitation of di- and polyisocyanates ("Des-
the German plastics and rubber industries at the modurs") in adhesive systems centered for the
end of World War II, reported substantial ac- most part on their use in admixture with reac-
complishments in the preparation and use of tive, low molecular weight, hydroxyl-termi-
isocyanates in Germany during the war. Not nated polyesters ("Desmophens"). Combin-
among the least of these was their use in ad- ations of certain "Desmodurs" and "Desmo-
hesive systems. phens" comprised the "Polystal" line of ad-
A translation of a portion of a German tech- hesives. Concerning these it is stated: "The
nical paper appearing in a CIOS Report, 9 the Desmodur-Desmophen systems were reported
section later appearing in essence in a German to give some of the best adhesives yet devel-
scientific publication IO and referred to in a oped. They were said to stick "anything to
monograph on polyurethanes II indicates that anything." The advantages were: curing at low
the exceptional and useful adhesive properties temperatures, good bond strength, versatility,
of the isocyanates became apparent to investi- good water resistance, and good low tempera-
gators of the I. G. Farbenindustrie, A. G., lab- ture flexibility. ,,12
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 361

In somewhat greater detail: "the varieties polyurethanes which wet, intimately con-
sold in small amounts as "Polystal" were tact, and show strong attraction for a va-
tough, resistant combinations of a flexible alkyd riety of surfaces.
such as "Desmophen 1200" (IV) with an iso- 5. Isocyanates provide elastomer-metal
cyanate such as "Desmodur TH" (V) and an bonds whose favorable gradation in phys-
auxiliary such as an amine or anything which ical properties between elastomer and
would change the pH. Cures were immensely metal affords superior fatigue life. 13
speeded by acid, alkali, or a little triethylam- 6. Isocyanates "react even with hydrated
ine. For a tough, cold-curing wood adhesive, oxide layers on metal surfaces, thus pro-
to be used where vibration was bad, they pro- ducing a clean surface, and therein, most
posed 40 parts of a 70% ethyl acetate solution probably allowing the urea groups of the
of "Desmophen 900" (VI) and 100 parts of a adhesive to form chemical bonds with the
75 % ethyl acetate solution of "Desmodur TH" residual valencies of the metal lat-
(V).9,12 tice. ,,9,10
German enthusiasm for isocyanate-based ad-
Let's look more closely at the foregoing fea-
hesive systems proves to have been justified.
tures of isocyanates which contribute to their
Buist and Naunton were later to conclude the
effectiveness as adhesives.
following concerning rubber-metal adhesion:
I. Reaction of isocyanates with other func-
"On the whole, when tested by a discriminat-
tional groups. In considering the likelihood of
ing method (by impact) isocyanate-based ce-
adhering two objects with an adhesive, one is
ments give higher strength than do other
more inclined to expect strong adhesion if the
cements. The bonds are fast to heat and sol-
development of chemical bonds linking adher-
vents, and are better able to withstand contin-
end to adhesive is a possibility. The ready re-
ued fatigue. The polyisocyanates suffer from
action of the isocyanate group with a large
the disadvantage that they are highly reactive
number of other functional groups would, on
chemicals and must be treated as such by
this basis, favor the success of isocyanate-based
avoiding their contact with moisture and the
compositions as adhesives.
skin. For many uses, the better results justify
Organic isocyanates tend to react, in many
the extra care necessary in using them. ,,13
cases quite readily, with substances containing
active hydrogen atoms, that is, with hydrogen
REASONS· FOR THE EFFECTIVENESS
atoms reactive enough to be replaced in their
OF POLYURETHANE AND
compounds by alkali metals 10 or by the Zere-
ISOCYANATE-BASED ADHESIVES
witinoff reagent, methyl magnesium iodide. 14
The effectiveness of isocyanate-based adhe- In the case of alcohols, for example ethyl al-
sives involves a combination of several fea- cohol, the hydrogen on the oxygen atom is an
tures which are characteristic of the materials: active hydrogen atom:
I. Isocyanates react readily with a variety of
other functional groups. CH3CH20H + CH3MgI -
Ethyl alcohol Methyl magne-
2. Di- and polyisocyanates can undergo self sium iodide

polymerization to form three dimensional CH4 + CH3CH20MgI

Methane Ethoxy magnesio-
resins in situ. 9 ,IO iodide
3. Isocyanates are quite soluble in many or-
ganic substances, and due to their small Functional groups containing active hydro-
molecular size readily permeate insoluble gen atoms and, therefore, the ability to react
porous structures. 10 with isocyanates, include: -OH (hydroxyl),
4. The reaction of di- and polyisocyanates -SH (sultbydryl), -NH- (imino) -NH2
with hydroxyl-bearing polyesters and (amino), - NHR (substituted amino),
polyethers, co-reactants in many isocyan- -NHCO-O- (carbamate), -NHCONH-
ate adhesive applications, produces the (carbamide), -C02H (carboxyl), -CONH2
strong, polar, hydrogen-bonded, flexible (carbonamide), -CONHR (substituted car-
362 HANDBOOK OF ADHESIVES

bonamide), -CSNH2 (thioamide), -S020H A quantitative indication of the readiness

(sulfonic), etc. with which isocyanates react with certain ac-
The reaction of isocyanates with some of tive hydrogen groups is provided by Morton,
these groups is illustrated below. For simplic- Diesz, and Ohta. 15 •6b They found phenyl iso-
ity's sake, monoisocyanates are used in the cyanate to react with the followin~ compounds
equations to illustrate the chemistry. In actual at the indicated rates at 80°C in dioxane solu-
adhesive applications, di- or polyisocyanates tion:
are used; therefore, the reader must realize that
the reactions shown below occur in more than Active Hydrogen K x 10 4 Relative
one position and concurrently in each isocyan- Compound l/Mole Sec Rate
ate molecule.
For example, isocyanates react with alcohols n-Butyl phenyl 0.02 ± 0.02
to produce urethanes (carbamates): carbamate
n- Butyranilide 0.28 ± 0.05 14
NCO Diphenyl urea 1.48 ± 0.06 74
CH3CH20H + '- -
o I --+ n-Butyric acid 1.56 ± 0.33 78
Water 5.89 3 295 3
Ethyl alcohol Phenyl isocyanate n-Butanol 27.5 a 1375 a

CH3CH20-CO-NH-D a Calculated from rate data obtained at lower

temperatures.
Ethyl phenyl urethane

with amines to produce substituted ureas (crab- 2. Reaction with other isocyanate groups.
mides): Aromatic and aliphatic isocyanates can undergo
self-reaction to form stable resinous trimer
o-NH2 + o-NCO --+ structures. The reaction is catalyzed by many
materials including calcium acetate, potassium
Aniline Phenyl isocyanate acetate, sodium formate, sodium carbonate,
sodium methoxide, triethylamine, oxalic acid,
o-NH-CO-NH~ sodium benzoate in dimethyl formamide, and a
large number of soluble metal compounds of
sym.· Diphenyl urea iron, sodium, potassium, magnesium, mer-
with carboxyl groups to produce substituted cury, nickel, copper, zinc, aluminum, tin, vana-
ureas, acid anhydrides, and carbon dioxide: dium, titanium, and chromium, titanium tetra-
butyrate, oxygen, and Friedel-Crafts type cat-
alystS. 6b Strong heating can also promote this
2CH 3C0 2 H + 2 o-NCO - - - +
change, which can be represented in the case
Acetic Phenyl isocyanate
of phenyl isocyanate as follows:
acid

NH-CO-NH-o
" I
o-
" I + (CH:}COhO + C~ I 'NCO
30- --+
sym. Diphenyl Acetic Carbon "'-
urea anhydride dioxide

Aliphatic isocyanates yield substituted amides

and carbon dioxide on reaction with carboxylic
acids. Phenyl isocyanatt Phenyl isocyanatt trimtr
For some time the hydroxyl groups of raw
cellulose (but not of its derivatives such as ni- Some isocyanates also react with themselves
tro, sec. acetyl, ethyl, benzyl, etc.) were con- to form thermally reversible dimer structures,
sidered to probably not react with isocyanate. 10 the so-called uretidinediones. Such self reac-
But this reaction has also been achieved. 80 tion is apparently confined to aromatic
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 363

isocyanates6b and is illustrated with phenyl iso- provide intimate contact if not actual chemical
cyanate: bonds between adhesive and adherend.
/CO, DeBell, Goggin, and Gloor12 cite a striking
example of the adhesion ofisocyanates to glass:
2o-NCO~ o-N'CO/N-o "One ingenious soul had patented a process for
etching designs on glass by cementing on a
Phenyl Phenyl isocyanote dimer
isocyanote (phenyl uretidinedione) metal stamping (carried on a mesh), and then
tearing the mesh loose, whereby the surface of
The dimerization reaction is catalyzed vig-
the glass pulled off."
orously by trialkyl phosphines and less by ter-
tiary amines such as pyridine.
TYPES AND USE OF POLYURETHANE
3. Solubility characteristics. Baye~·lO noted
AND ISOCYANATE BASED ADHESIVE
the excellent solubility of the isocyanates in
SYSTEMS
practically every organic substance, and their
small molecular size, which allows ready dif- Polyurethanes and isocyanates are used in ad-
fusion. These characteristics promote adhesion hesives systems in several ways. The general
by allowing the isocyanates to penetrate the ad- use methods and systems, which include for-
herend. There they may undergo the foregoing mulations containing both free or reacted iso-
multiple reactions all of which' enlarge the mol- cyanate, are now reviewed.
ecule, presumably entangling it in or attaching
it to the adherend. Method A (isocyanate primer)
Good strength and ft.exibility characteristics A di- or polyisocyanate, usually in solution, is
in the boundary film formed between the ad- applied to the surface of an adherend prior to
herend members by the isocyanate-based ad- its contact with other adherend member(s) sim-
hesives are also considered to be favorable ilarly coated.
contributions to good adhesion. Ex. 1. Buna-sulfur mixtures which are to be
4. Polarity. The reaction of di- and poly- cemented are brushed with a solution of Des-
isocyanates with various polyester and poly- modur R (III) and then vulcanized. In this way,
ether glycols, their co-reactants in many adhe- bond strengths of up to 1138 psi are real-
sive applications, produces the relatively polar, ized. 9 •10
highly hydrogen-bonded polyurethanes which Ex. 2 MOl-50 (VII) affords heat-, fatigue-,
wet, intimately contact, and show strong at- impact-, oil-, and solvent-resistant bonds be-
traction for a variety of surfaces. tween metals and elastomers by press or hot air
5. Step-off characteristics. Buist and curing the green freshly milled or calendered
Naunton 13 state that "polyisocyanate cements stock against the metal which previously has
not only give a stronger (rubber-metal) bond been roughened (light sandblasting), solvent
but produce, possibly by a gradation of physi- washed, thinly coated with MOl-50 and
cal properties from the immovable rubber in dried. 16 Humidity is an important factor in the
contact with metal to the soft mass of the rub- degree of adhesion obtained. The following
ber, a condition in the rubber capable of with- demonstrates the adhesion possible using this
standing greater fatigue." system with various elastomers and metals:
6. Reaction with impervious surfaces. To
explain the adhesion of isocyanate-based ad- Adherend Members Bond Strength (psi)
hesives to impervious, apparently unreactive Neoprene W to steel
1100
surfaces such as glass and metals, BayerlO sug- Neoprene W to brass 1050
gested the reaction of isocyanate groups with Neoprene W to stainless steel 1200
the molecular film of tightly absorbed water al- Neoprene W to aluminum 1325
ways present on such surfaces, the reaction of Neoprene W to copper 950
Natural rubber (smoked sheet)
the isocyanate groups with the oxyhydrate layer to steel 1200
on metal surfaces, and isocyanate polymeriza- Butadiene-acrylonitrile rubber
tion on (alkaline) glass. All of these processes to steel 850
364 HANDBOOK OF ADHESIVES

Ex. 3. Elastomer coatings may be adhered to The above cements applied at 10 to 15 % of

synthetic fiber fabrics and other materials by the fabric weight are excellent primers for the
Hylene M(VIII) or Hylene M-50 (IX) which adhesion of elastomers to fabric. The cements
are applied to the fabric as a 2 % solution in can be applied to fabric by any of the conven-
toluene by dipping or spraying, drying, then tional methods, and the primed fabric used after
applying the elastomer coating. 17 solvent removal or stored in a dry place until
Ex. 4. Degreased, sandblasted steel plates are needed. The composite product may be cured
coated by dipping in Leukonat adhesive (X). by the methods conventionally used for curing
Green, filled stocks of Nairit, SKN-26 (buta- rubber (press, oven, air pressure vulcanizers).
diene-acrylonitrile), natural, and SKS-30 (bu- High pressures are unnecessary and the good
tadiene-styrene) rubbers are freshened with contact between the two surfaces is sufficient
solvent. Freshened rubber and coated metal are to produce a strong bond. 21
contacted and heated in a press. IS Table 1 demonstrates the degree of adhesion
obtained on the platen press curing of rubber-
Method B (conventional plastic or rubber ized 10 oz cotton duck to square woven fabric
vehicle + isocyanate) samples made from rayon, cotton, and nylon.
The duck had been skim-coated 90 mils with
A di- or polyisocyanate is mixed with a con-
some typical tire carcass stocks made from
ventional elastomericor plastic vehicle, usu-
neoprene GR-M, SBR, and natural rubber. The
ally in a dry, inert solvent. The combination is
other fabrics were precoated with 20 % by
spread over the surfaces to be adhered which
weight of the MDI-50 adhesive primers. 21
are then air-dried and contacted. Curing is at
Ex. 2. The adhesion of "Terylene," a po-
room or elevated temperatures.
lyester fiber, to rubber is greatly improved by
DuPont l6 points out some special advantages
in elastomer-to-metal adhesion which result
from the use of an elastomeric vehicle with Table 1. The Adhesion of Fibers to
MDI-50 bonding cements. First, the elasto- Elastomers via MOl-50 Priming
meric vehicle (usually the same as the adherend Cement. 21
elastomer) covers the diisocyanate component
Adhesive Primer
in applied coatings, protecting it from moisture
and providing longer but not unlimited * useful Neoprene Natural
life of cement-primed parts. Second, the elas- GR-M/ Rubber/ SBR/
MDI-50 MDI-50 MDI-50
tomeric vehicle affords greater building tack .
and helps hold the adherend members in the de- A B A B A B
Rayon to natural 35 24 19 30 19
sired assembly position.
rubber
Ex. 1. Natural rubber (pale crepe or smoked Rayon to neoprene 30 21 39 33 12
sheet), SBR, or neoprene Types GN, GR-M, GR-M
or GR-MIO are broken down in Banbury mix- Rayon to SBR 37 26 28 35 17
ers or on mills. Dry aromatic solvents such as Cotton to natural 25* 16* 25* 16*
xylene, toluene, or chlorobenzene (900 parts) rubber
Cotton to neoprene 24* 16* 35* 21*
are added and agitated to dissolve 100 parts of GR-M
elastomer. Forty parts of MDI-50 (VII) are Cotton to SBR 29* 15* 27* 15*
added to the elastomer solution with agitation. Nylon to natural 20* 11* 15* 8*
The cements are stored at room temperature: rubber
Nylon to neoprene 18* 9* 23* 12*
the rubber cement keeps 7 days, the SBR keeps
GR-M
3 to 4 days, and the neoprene cement keeps 3 Nylon to SBR 22* 10* 20* 11*
days.
A = adhesion at 28°C (lb pull/in. )
width) Strip adhesion test
*MDI-50 elastomer cements slowly increase in viscosity B = adhesion at 95°C in water (lb (ASTM D413-39)
with time, eventually gelling on prolonged storage at room pull/in. width)
temperature. 16 • = Greater adhesion realized with more adhesive primer .
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 365

the addition of "Vulcabond" TX* (XIII), a di- The Relative Effectiven_ of "Vulcabond" T and
isocyanate. Thus, a natural rubber stock con- TX in Rayon Cord-to-Natural Rubber Adhesion. 13
taining all pigments (curing, reinforcing, Load (lb) to Pull out a
processing agents) was made into a dough using Single Cord
Pool Rubber Solvent. Twenty-five percent by
weight of "Vulcabond" TX was blended into Not After 4 days
this dough, and the mixture was spread onto Fatigued Fatigue at 80°C
"Terylene" fabric, topped with rubber stock "Vulcabond" TX cement 12.5 11.0
on a calender, doubled, and finally platen press- "Vulcabond" T cement 11. 3 9.6
cured (200 psi) for 30 min at 141°C. Peel tests
on I-in. wide strips of this construction 24 hr
later showed adhesions of 30.S lb/in. (to initi- Ex. 5. For metal adhesion, polyisocyanates
ate) and 22.0 lb/in. (average to maintain peel- are best mixed into a solution of a synthetic or
ing). The control, minus "Vulcabond" TX, chlorinated rubber. The following table com-
showed only 3.5 lb/in. adhesion in this test. pares the adhesion of natural rubber tire tread
Triphenylmethane-p,p', p "-triisocyanate (III, to mild steel using a polyisocyanate priming
X, XII) was similarly effective at the same con- cement ("Vulcabond" TX) with that obtained
centration. 22a using a chlorinated rubber cement. 13
Ex. 3. Natural, "Hycar," "Paracril," and "Vuleabond" TX Versus Chlorinated Rubber in
butyl and neoprene rubbers are bonded to seven Natural Rubber-Steel Adhesion. 13
metals/alloys with an adhesive comprising 50
parts of a chlorinated rubber ("Alloprene" B) Strength
Straight Impact After
and 100 parts of "Vulcabond" TX (XIII) dis- Pull Strength Fatigue
solved in 150 parts of ethylene dichloride. (psi) (ft Ib) (%)
Bonds to copper and "Monel" metal were in-
ferior. Information is provided on the effect on "Vulcabond" TX
bond strength of accelerator, loading types cement 835 220 90
Chlorinated rubber
(carbon blacks, white fillers) in the bonded cement 785 116 20
stocks, and the age of the fully formulated ad-
hesive. 22b
Ex. 4. A 3 % rubber solution of a standard Ex. 6. A priming cement for the high level
tire carcass compound was supplemented with adhesion (ca 2Slb/in.) of vinyl plastisol or film
50% of "Vulcabond" TX (XIII) on the weight to nylon, "Dacron," rayon, or glass fabric is
of rubber. Rayon cord dried for 1 hr at 100°C prepared from "Geon" 400 x 100* (100 parts)
was then dipped into this cement, squeezed be- or certain other polyvinyl chloride resins, dioc-
tween glass rods, air-dried overnight, and tyl phthalate (60 parts), methyl ethyl ketone
baked 30 min at 100°C. This pretreated cord, (3S0 parts) and DAD!, dianisidine disocyan-
carefully positioned in a metal jig to provide a ate, (XIV) (10 parts). The adhesion is reported
concentration of 24 cords per in, was cured into to be surprisingly independent of fabric con-
a strip of rubber compound, which was then struction and is obtained with a minimal effect
fatigued 4 days/SO°C in a modified Roelig ma- on the fabric properties. The bond is reported
chine and finally tested for cord adhesion to the to have been submitted to one million "S"
rubber. The following table shows how rayon flexes with no reduction in bond strength. The
cord primed with the "Vulcabond" TX-rubber fabric is coated via normal solution-coating
cement outperformed a latex-resorcinol-for- methods to about O.S oz/sq yd (dry weight) and
maldehyde priming cement, ("Vulcabond" is cured against PVC film or plastisol at 300 to
T)Y 400°F for maximum adhesion (optimum adhe-
sion 2 min/3600p).
*Imperial Chemical Industries, Ltd., Manchester, En-
gland. *B. F. Goodrich Chemical Company, Cleveland, Ohio.
366 HANDBOOK OF ADHESIVES

The primed fabric is stable for at least 60 ature such a cement has a pot life of 1-2 days
days, and probably indefinitely; therefore, it and with accelerator 3 hr. The setting time of
need not be laminated to PVC film or coated this cement, containing accelerators, in wood
with plastisol immediately. 23 adhesion is 4-5 hr at 10°C, 7 hours at O°C,
Ex. 7. The incorporation of PAPI, a poly- overnight at less than O°C.lO
isocyanate (XV), in specially compounded rub- Ex. 4. The M/M (Mondur/Multron) adhe-
ber-coating compositions has provided im- sive formulations are further examples of type
proved adhesion of rubber to nylon and (b) two component polyurethane adhesive sys-
polyester cord. 24 terns. They are used for bonding metals such
as steel, soft iron, aluminum, and magnesium
to themselves and to each other. A recom-
Method C (in situ polyurethane mended formulation for room temperature cures
polymerization) consists of 100 parts by weight of Multron R-
12 (the polyester glycol resin component in
A di- or polyisocyanate is mixed with di- or 80% solids ethyl acetate solution) which is
polyhydroxy materials and the combination is mixed with 120 parts of Mondur CB-75
(a) partially prereacted, or (b) allowed to react (XXIX). Thus, Mondur CB-75 is a similar MI
largely in situ, to form polyurethanes which M counterpart of Desmodur HH in Polystal U-
contain free isocyanate groups capable of re- II. The full strength of steel bonds formed with
acting with the adherend upon application. Dry this room temperature curing M/M system is
solvents free of alcohols, carboxylic acids, etc. 6800 psi and is achieved in 8 days. A recom-
are used with these systems. mended formulation for elevated temperature
Ex. 1. Windemuth 19 teaches the practice of cures uses 200 parts of Mondur CB-75 per 100
(a), a one part system. An isocyanate-termi- parts of the Multron R-12 solution. Steel bond
nated, viscous (in the melt), linear prepolymer strengths of about 7800 psi are achieved in 3 hr
is prepared from 2 moles of hexamethylene di- at 195°P, 2 hr at 265°P, or 1 hr at 355°P. MI
isocyanate (II) and 1 mole of hydroxyl-termi- M adhesive gels 24 hr after mixing and cannot
nated, linear polyester prepared from diethylene be reconstituted. 2o
glycol and adipic acid. Two percent of hexa- Ex 5. "Tyrite" polyurethane structural ad-
hydrodimethyl aniline (a basic catalyst) is hesives are applied to adherends, then react or
added to this prepolymer dissolved in dry ben- finish reacting in situ to form adhesive bonds.
zene. The solution is applied to adherend mem- "Tyrite 7500" is two-part, 100% solids, pot
bers (e.g., the two ends of a leather drive belt) life 6-10 min or 20-30 min depending on for-
and dried. Subsequent brief exposure of the mulation, curing at room or elevated (e.g.,
coated parts to moist air, followed by their con- 2oo-240 0 P) temperatures, for bonding rigid
tact under light pressure, results in a tough, plastics, e.g., polycarbonate auto headlamps
flexible, rubbery bond in 2 to 3 hr. and RIM (reaction injection molded) urethane
Ex. 2. Liquid, isocyanate-terminated prepo- auto body panels. 88a Three two-part moisture-
lymers prepared from diisocyanates such as curing systems have good storage life in the ab-
TDI (I) and Poly B-D glycol (XXVII), a po- sence of moisture. In the presence of moisture,
lybutadiene glycol, may be placed on an ad- assembled objects are handleable in 4-6 hr, and
herend directly or from solution and permitted have full cure in 1-10 days, depending on the
to cure via the action of moisture in the air. particular system and the ambient relative hu-
Useful as rubber-fabric adhesive. 79 midity. "Tyrite 7411" is 100% solids, applied
Ex. 3. System (b), a two-part adhesive sys- hot, for fabric and rigid plastics;88b, "Tyrite
tem, is exemplified in the following. One part 7602 is 64% solids, for general purpose use;88c
of Polystal U-I [a 70% solution of Desmophen and "Tyrite 7650" is 60% solids, with good
900 (VI) in ethyl acetate] is mixed with 2-2.5 initial grab, works well with polyethylene,
parts of Polystal UII [Desmodur HH (XI) in polystyrene, and polyurethane foams as well as
75% ethyl acetate solution]. At room temper- plastics, fabrics, rubber, prepared metals. 88d
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 367

Method 0 (polyurethane elastomer hydroperoxide is then added to such interme-

without or with added polyisocyanate) diates and the formulation is packaged in oxy-
gen-permeable containers (e.g., polyethylene)
Method D appears to be possibly the most im- with the deliberate inclusion of air. The reason
portant type of isocyanate-based adhesive sys- for this is that oxygen prevents the free radical-
tem. It is similar to Method B in that a initiated polymerization of such unsaturated
preformed, fully reacted, high molecular products. This preserves the adhesive on stor-
weight polymer is employed as a vehicle in the age and after application on exposed substrate
adhesive formulation. The strength of the ve- surfaces. But contact of the coated adherend
hicle holds adherend members in exact position surfaces buries the adhesive, excluding oxygen
after assembly until the full bond has formed. and allowing polymerization of the acrylate
Method D differs from Method B in that its ve- function with bond formation. 68
hicle polymer is a polyurethane. A further dif- Let's examine some representative examples
ference is that the inherent adhesive character of Method D adhesion. Examples 1-3 involve
and strength of the polyurethane vehicle fre- thermoplastic polyurethane elastomer vehicles.
quently enables its use without added di- or po- Examples 4-7 involve polyurethane gums.
lyisocyanate. This strength may be realized in Ex. 1. A solution of Estane 5703F2 (11.25
essentially amorphous compositions such as the parts), Geon Resin 202 (3.75 parts), and te-
thermoplastic polyurethane elastomers25 or trahydrofuran (85 parts) is prepared and
millable gums. 26a ,b Or it may be achieved with brushed onto vinyl shoe sole and leather upper.
crystallizing urethane adhesive polymers. 27 ,28 After 1 min air drying the coated adherend sur-
In the practice of Method D the high molec- faces are contacted under 20 psi pressure. Bond
ular weight polyurethane gum or thermoplastic peel strength is 8.9 lb/in. after 15 min aging,
resin is dissolved in a suitable dry, isocyanate- and 29.0 lb/in. after 60 min aging. Good adhe-
inert solvent. In the case of the polyurethane sion to other substrates including rubber, fab-
gums free di- or poly isocyanate is added to the rics, and metal is claimed. 27a
solution. This is also sometimes done in the Ex. 2. Estane 5711, 5712, and 5713 resins
case of the thermoplastic polyurethane resins are thermoplastic polyurethanes specifically
but frequently is unnecessary, in which case the designed for adhesive applications with a va-
use of dry isocyanate-inert solvents is also un- riety of substrates (e.g., wood, vinyl, leather,
necessary. metal, rubber, fabrics, etc.) They are highly
Such cements are applied to adherend and al- crystalline resins, soluble in practical solvents
lowed to dry to the desired degree of tackiness and characterized by high strength and tough-
before contacting the adherend coated surfaces. ness. At about 125, 140, and 160°F, respec-
Or, as in the case of the crystallizing thermo- tively, these resins decrystallize to the
plastic polyurethane resins, the adhesive coat- amorphous state whereupon they become soft
ing may be allowed to fully dry and crystallize. and rubbery with excellent wetting of a variety
Subsequent heat activation of the coated adher- of substrates and a high degree of tack. At
end surfaces, then contact with each other, rap- 75°F, the amorphous forms recrystallize in
idly produces a strong bond. about 114, 2, and 24 hr, respectively, and be-
So-called "anaerobic" polyurethane adhe- come tackfree, very strong (3000, 5000, 9800
sives also appear to belong in the Method D psi tensile, respectively), very extensible (790,
category. This system combines urethane poly- 790, 730% ultimate elongation, respectively),
addition chemistry with free radical-initiated and hard yet flexible. Suitable solvents for the
addition polymerization to provide an interest- various types include benzene, MEK, cyclo-
ing adhesive class. In practice, a polymerizable hexanone, DMF, THF.
alcohol such as ,8-hydroxyethyl methacrylate is Estane 5712 applied from MEK cement be-
reacted with an equivalent amount of a diiso- tween vinyl shoe sole and vinyl shoe upper
cyanate such as TDI (I) or with an isocyanate stocks gave a peel bond strength of 40 Ib/in. 27b
terminated urethane prepolymer. An organic Ex. 3. Desmocolll76,28a 400,28b and 42028c
 368 HANDBOOK OF ADHESIVES

are primarily linear, thermoplastic polyure- Ex. 4. Royal M6482 and S-5210 adhesives
thane elastomer resins of "medium," "high," can be applied to adherend surfaces from ke-
and "high" crystallization rates, respectively. tone solution and after drying may be heat or
They are supplied as small, light brown, talc- solvent activated. M6482 activates at 180-
covered, pieces. The polymers have a density 240°F and is a good adhesive for vinyl and for
of 1.2-1.23 g/cc. This density and their sta- wood. S-521O activates at 135-155°F and was
bilization by the hydrolysis stabilizer, Stabaxol designed for bonding man-made shoe upper
1, suggests that they are poly (ester-urethanes). stocks, leather, vinyl, etc. 29
They show outstanding adhesion to numerous Ex. 5. One hundred parts of Daltoftex A-I0
materials including plastics, rubber, leather, (XVill) is mixed with 20 parts of Suprasec GA
fabrics, wood, metals, etc. (XIX), 4.5 parts of Daltorol PRI (XX), and 25
The following solvents dissolve some if not parts of MEK solvent to provide a basic adhe-
all of the foregoing Desmocoll adhesive poly- sive formulation. The Daltorol PRI increases
mers: methyl, ethyl, and butyl acetates, ace- open tack time while the Suprasec GA cross-
tone, methyl ethyl ketone, methylene chloride, links the system and improves its stability to
propylene dichloride, trichloroethylene, the steam, providing a vulcanizate of 2200 psi ten-
monomethyl ether-acetates of ethylene glycol sile strength, 200% elongation, and 1800 psi
and 1,3-butylene glycol, etc. Toluene may be elastic modulus.
used as a dilution solvent. The Daltoftex A-1O system is recommended
Desmocoll 176 is compatible with such plas- as an air-curing (2-7 day /25 °C, < 1 day /
ticizers as benzyl butyl phthalate (Unimoll BB), 100°C) adhesive for textile applications (fab-
diphenyl cresylphosphate (Disftamoll DPK) , ric-fabric, fabric-foam) since it affords good
and trichloroethyl phosphate (Disftamoll TCA). green strength and good hand, and for film-film
It has slight or no compatibility with dibutyl lamination since it produces clear laminates
phthalate (Unimoll DB), dioctyl phthalate, tri- which resist separation due to mechanical and
phenyl phosphate (Disftamoll TP), tridresyl thermal stresS. 3D
phosphate (Disftamoll TKP) , dibutyl adipate Ex. 6 Multranil 176 polyurethane elastomer
(Adimoll DB), benzyl octyl adipate (Adimoll is dissolved at 20% by weight in a mixture of
BO), phenyl and cresyl alkyl sulfonates (Mes- dry ethyl acetate and acetone, and 8.3 phr of
amoll, Dellatol MMA, Sintol T). Mondur TM (XII) (for natural and synthetic
The foregoing Desmacoll polymers show rubber adhesion) or 5 phr of Mondur CB-75
compatibility with some or all of the following (XXIX) (for non rubber adhesion) is added.
polymers to the extent that they give clear so- These combinations are versatile adhesives for
lutions and films: phthalic resins (Soft Resin bonding vulcanized rubber (natural and syn-
MM, Alkydal BG), xylene-formaldehyde resin, thetic) to itself, leather, urethane, PVC, cork,
cyclohexanone-formaldehyde resin (Synthetic wood, etc. Cure occurs at room temperature,
Resin AFS), highly chlorinated terphenyl (Clo- and faster at elevated temperatures. At room
phen Resin A60), terpene-phenolic resin (Durez temperature bond strengths (peel) are (imme-
12603), acetyl cellulose (Cellit BL700), nitro- diate/after 3 days): rubber-to-rubber, 5.5-9.0/
cellulose, Desmocolls 12 and 22, nitrile rubber 25; rubber-to-shoe sole leather, 5.5-7.3/24;
(Perbunan N), post chlorinated PVC (Rheno- shoe sole leather-to-shoe sole leather, 7.3-9.0/
ftex) , vinyl chloride-vinyl acetate copolymer 24; rubber-to-shoe sole leather, 9.5/24 lb/in.
(Vinnol), rosin esters (Pentalin A, Stabelite Es- width. 3l
ter 10), and coumarone resin. Ex. 7. "Bostik 7070" (100 parts) with
In bonding strong substrates, and if solvent "Boscodur No.1" (5 parts) appears to be an-
and greater heat-resistance are required in the other example of a two part millable polyure-
adhesive bond, then the Desmocolls may be thane gum adhesive system. It is recommended
mixed with appropriate amounts of isocyanates by the manufacturer as a laundering and dry
such as Desmodur L (XVI), Desmodur R (ill), cleaning resistant cement for bonding urethane
and Desmodur RF (XVII). sponge and urethane rubber. It is also recom-
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 369

mended as an adhesive which provides strong including water and alcohols. But usually the
elastic bonds with leather, natural and synthetic reactive medium must be removed by evapo-
fabrics, cork, wood, Masonite, and a wide va- ration before the blocked isocyanate is heated
riety of porous materials. to its decomposition temperature. Otherwise the
The combination of Bostik 7070 and Bos- generated isocyanate would be consumed by
codur No.1 is reported to have a working life reaction with the medium before undergoing the
of about 18 hr. Although a hot bonding method intended reactions with adherend and reactive
(4 min at 130°F) is optional, the cement will vehicle (if present). This may not be necessary
cure at room temperature, developing maxi- if the isocyanate is more reactive with the ad-
mum adhesion in 6 daysY herend or vehicle than it is with the medium.
Commercially available blocked isocyanates
Method E (blocked di- or polyisocyanate) have included: Hylene MP from duPont
(XXI)34 which is phenol-blocked MDI: Mon-
A stable, blocked di- or poly isocyanate in sus- dur S (XXII),35.36 a phenol-blocked TDI ad-
pension, including aqueous suspension, or so- duct; Mondur SH (XXill),36,37 a cresol-blocked
lution is applied alone (as in Method A), in TDI trimer; and Experimental E-320 blocked
combination with a conventional plastic or rub- isocyanate (XXIV), 36,38,39 a ketoxime-blocked
ber vehicle (as in Method B), in combination tetraisocyanate, all from Mobay; and Isonate
with a di- or polyhydroxy material (as in 123P (XXV)40 which is f-caprolactam-blocked
Method C), or in combination with a pre- PAPI from the Upjohn Company. The Ashland
formed polyurethane vehicle (as in Method D) Chemical Company has marketed a commer-
to adherend surfaces. The coating is dried, the cial chemical class called "aminimides" which
coated adherend surfaces contacted, and the as- act as isocyanate precursors, eliminating the
sembly heated to decompose the blocked iso- problem of by-product phenol from the use of
cyanate. This generates free di- or poly- phenol-blocked isocyanates. 65a ,b Their chem-
isocyanate which proceeds to bond the adher- istry relevant to this use, is as follows:
end directly and through reaction with the ve-
hicle which may be a pre- or in situ-formed
polyurethane. The cleaved blocking agent dif-
o
(I) e II
•

fuses into the surrounding matrix or escapes R 3-N : N-C-R'

into the air. ~ R'NCO + R3N
The formation and thermal cleavage of (isocyanate) (tertiary
blocked isocyanates can be represented as fol- amine)
lows:
formation (mono) aminimide in
resonance forms
R(NCO)n + nBH IE ..
thermal cleavage
(isocyanate) (blocking agent)
Aminimides are useful in a variety of adhe-
H 0
I II sive systems for bonding tire cord and indus-
R(N-C-B)n trial fabrics, wire, and glass. They act as
(blocked isocyanate) adhesive applicators in bonding rubber to tire
cord. Considerable interest has developed in
where n is usually 2, 3 and sometimes more. polyester cord dips, and the aminimide systems
Cleavage temperatures range from ca 60 to show great promise in bonding a variety of fab-
200°C depending on the compound. 6b .33 ,62 rics as well as wire such as stainless and carbon
"Blocked," "masked," or "pseudo" diiso- steel. Adhesion promoters for polyester fabric/
cyanates date back to German work of the rubber composites can be prepared from di-
1940s. 33 The stability of blocked isocyanates functional aminimides that react through polym-
toward active hydrogen substances enables their erization with selective poly functional epox-
formulation and application in reactive media, ides. Aminimides, functioning as isocyanate
370 HANDBOOK OF ADHESIVES

precursors, offer many advantages over the any time thereafter. When the sheet rubber is
usual phenol-blocked isocyanates, because applied it should be held under moderate pres-
these aminimides rearrange to isocyanates by sure of about 30 psi to provide intimate contact
simple thermolysis without yielding phenol as with the treated fabric and to prevent lifting if
a by-product. This affords a safer industrial ap- any gases are emitted during cure. Press cures
plication of the tire cord adhesive. of 20 to 40 min at 284 OF are sufficient to cure
Aminimides also offer processing advantages the adhesive and most elastomer compositions
because of their water solubility. Aminimide being adhered. If a latex film is applied to the
pre-dips are easily prepared in water, so a va- treated fabric, the assembly can be cured in a
riety of water-soluble surfactants, both anionic hot air oven at 250°F. Bonds strengths of 50 to
and cationic, can be used to enhance perfor- 52 lb (nylon to neoprene, SBR), and 30 to 35
mance. lb (Dacron to neoprene, SBR) are claimed. A
Polymers containing the pendant dipolar chemical bond allegedly results between nylon
aminimide functional groups adhere strongly to and the diphenylmethane-p,p' -diisocyanate
glass. Low mole percents of aminimide mon- generated on the thermal cleavage of "Hylene
omers incorporated into polymethylmethacry- MP. ,,41
late significantly increase adhesion to glass. Ex. 2. A typical, excellent processing, ami-
This property is valuable in polymers for bond- nimide rubber-to-fiber adhesive formulation
ing glass to glass or to other solid sub- recommended for pre-dipping polyester, ny-
strates. ,,65a lon, and other polyamides comprises the fol-
The blocked isocyanate function of aminim- 10wing: 65b
ides also allows their use as polyurethane ad-
hesives. Thus, "bis (aminimides) crosslink
with polyester or polyether diols to yield a Dip Bath Concentration 7.5%
(parts by wt)
range of elastomers, dependent upon the struc-
ture of the bis (aminimide) and the coreactant Aminimide 2.0
chosen. For example, bis (aminimides) mixed Epoxy Resina 1.0
with polyhydroxyl components can provide Surfactant b 0.112
stable, single package prepolymer composi- Water 42.0
tions which yield polyurethanes on heating66
a XD-7160 (Dow Chemical Co.) or Epon 812 (Shell
without the problem of isocyanate moisture Chemical Co.).
sensitivity which can plague polyurethane ap- b Aerosol OT (American Cyanamid Co.) or Aminimide
plications. Suggested applications include ad- 56203 (Ashland Chemical Co.).
hesives ... ,,67
Ex. 1. Vulcanized neoprene and SBR can be The dip is prepared by dissolving the ami-
adhered strongly to nylon and "Dacron" po- nimide and surfactant in water with moderate
lyester fiber fabric by means of the following stirring. The epoxy resin is then added with
aqueous adhesive system: rapid stirring. The dip is ready for use and sta-
ble for 10-14 days. It is applied to the cord in
a 1-3 sec dip. This is followed by drying in an
"Hylene MP" dispersion (40%) 27.5 parts oven at about 450°F (depending on cord type
Neoprene latex Type 635 173.0
and desired properties) for about 45-60 sec. A
Zinc oxide dispersion (50%) 15.0
Zalba emulsion (50%)* 6.0 second "cover dip" of conventional resorci-
nol-formaldehyde-latex emulsion is then ap-
* A hindered phenolic antioxidant - duPont Elastomer plied followed by 45 sec drying at 450°F.
Chemicals Dept. Following the foregoing procedure an Ash-
land Aminimide AL-X-3oo (XXVill) formu-
This combination is spread or roller coated lation yielded 3/8 in. H adhesion value for
onto the fabric which is then allowed to dry. polyester cord (1300/39 X 9 twist) ranging
Bonds to sheet rubber stock can be made im- from 46.3 lb (120 sec dwell at 405°F) to 58.7
mediately after the treated fabric is dried or at lb (60 sec dwell at 465°F).65
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 371

Method F (aqueous dispersion) Deterrents to the more widespread use of ur-

ethane latices appear to include their higher
Most isocyanate- and polyurethane-based ad- cost, as well as an inferior property level, rel-
hesive systems are now applied from solution ative to solution-applied polyurethanes, in those
in volatile organic solvents. But some day, per- polymers that can be successfully made and
haps not too far off, such systems may be im- used as aqueous dispersions. In addition, iso-
practical to use due to restrictions. Growing cyanate-curing aqueous polyurethane disper-
concern by ecologists for atmospheric pollu- sions for the most part require the use of the
tion, and by safety agencies for worker welfare more expensive blocked isocyanates as well as
(explosion, fire, and toxicity) are factors to be substantial heat activation in place of the
increasingly reckoned with in all manufactur- cheaper unmodified di- and polyisocyanates
ing processes which involve the use of large which cure effectively with little or no heating.
amounts of volatile organic solvent in open Moreover, more energy and longer times are
systems. One way around the problem would required to dry systems applied from water than
seem to be the use of aqueous polyurethane la- those applied from volatile organic solvent. A
tex adhesives. change to water medium may require some un-
The preparation of polyurethane aqueous dis- welcome cycle modifications and line altera-
persions can be accomplished in several ways. 83 tions. So, the motivation for polyurethane
The procedure claimed to yield at present the adhesive users to use aqueous latex forms has
highest quality products82a ,b involves the reac- not been overwhelming, and unless a compel-
tion of an isocyanate-terminated prepolymer in ling situation develops or cheaper latices be-
a water-miscible solvent, e.g., acetone, with a come available, the matter may remain that
diamine carboxylate or sulfonate. The resultant way. Whatever the outcome, several suppliers
polyurethane ionomer solution is mixed with are now vigorously marketing aqueous ure-
water which forms the dispersion and further thane latex products. Let's examine some.
chain-extends the polymer. Finally, the or- Ex. 1. BASF Wyandotte supplies a family of
ganic solvent is removed by distillation and can nonionic and ionic, stable, 50% solids, water
be recycled.84 As in the case of the thermo- dispersions of high molecular weight poly
plastic polyurethane elastomer adhesives, dis- (ether-urethane) polymers. 44 These products
persions can also be prepared with different de- reportedly contain some solvent in very low
grees of crystallinity in the polyurethanes concentration, presumably toluene. They form
depending on the nature of the prepolymer. 82a,b continuous films when dried at room tempera-
Alternatively, a linear, isocyanate-termi- ture, but film strength, abrasion resistance, and
nated, urethane prepolymer is prepared, some- adhesion to substrates all improve when films
times with added solvent, from excess or coatings are dried for several minutes at
diisocyanate, macroglycol, dimethylolpro- 250°F to 350°F.
pionic acid, and a tertiary amine. This product The outstanding properties of coatings and
is dispersed in water and the prepolymer is then adhesives based on these latices are claimed to
chain-extended with added diamine to produce be: wide range of flexibility or rigidity, flexi-
an anionic aqueous latex comprising a high bility retention to -40°F, excellent wear resis-
molecular weight poly(ester or ether-urethane- tance, good adhesion to substrates, excellent
urea) with pendant, tertiary amine-neutralized film strength (540 to 4550 psi tensile strength)
carboxyl groups, dispersed in water. and elongation (300 to 750%), good color sta-
Or thermoplastic polyurethanes made in so- bility except in white and pastel shades, low
lution or dissolved in solvents are emulsified in toxicity, and low air pollution.
water, then solvent is removed. Or an isocya- Ex. 2. Dainippon Ink and Chemicals, Inc.,
nate-terminated urethane prepolymer, possibly supplies Vondic 10 lOC , 1030, and 1310 high
with hydrophilic branches, is blocked with an molecular weight poly (ether-urethane), 40%
appropriate isocyanate-blocking agent, and solids, aqueous dispersions. 45 Each product
emulsified in water together with a crosslinking contains a small portion of toluene and the fol-
agent. lowing features are claimed: 6 months stability
372 HANDBOOK OF ADHESIVES

at room temperature; drying yields film of good selected acrylic dispersions and vinyl copoly-
physical properties (tensile strength after 16 hr mers. It can be compounded with various col-
at 25°C then 3 min at 100°C, 4900 psi, or 3 orants, pigments, and fillers.
min at 140°C, 5300 psi; elongation, 480 to Uncompounded 0.1 mm film shows 3550 psi
530%; excellent abrasion resistance, flexibil- tensile strength, 270 psi 100% modulus, and
ity, and tear strength; good retention of color 700% ultimate elongation. Tensile strength
and physical properties; fairly good solvent and drops to 565 psi after 400 hr of ultraviolet ex-
water resistance). posure (Xeno test) and to 2400 psi after hy-
Ex. 3 Verona (Bayer) supplies Impranil4496 drolysis exposure (14 days at 70°C(100%
(DLN) color stable, 40% solids, thermoplastic, R.H.).
aliphatic poly (ester-urethane), anionic, Ex. 4. American Cyanamid supplies 10
aqueous dispersion. 46 ,47 Samples have ap- Cyanabond textile adhesives48 which are de-
peared to contain a trace of solvent (acetone, scribed as nontoxic, water-based, 30 or 40%
MEK?). Presumably Impranil 4496 (DLN) solids, prereacted, polyurethane emulsions that
contains a polyurethane ionomer and is pre- provide highly durable bonds when applied to
pared without added emulsifier, the polyure- woven, knitted, or nonwoven fabrics. They
thane itself having its own emulsifier function. have an acetic acid-type odor. They may be
The incorporation of this function in the poly- used on a wide variety of cellulosic and syn-
urethane chains as sodium (A) sulfonate or (B) thetic textile substrates. When applied by es-
carboxylate groups is seen in the following tablished processing techniques they form
equations: 47 bonds of cloth-to-cloth and foam-to-fabric that

This product is recommended for textile are highly resistant to the effects of dry clean-
coating (skin, adhesive) via transfer coating. It ing and machine washing.
is also claimed to be suitable for use as an ad- Types include Cyanabond Textile Adhesive
hesive in laminating woven materials to knitted U-270, U-271, U-251, U-253, U-273, U-274,
goods or in laminating woven or knitted goods U-255, and U-275 whose viscosities vary from
with polyurethane foam. Bondings are said to water-thin liquids to mobile pastes of 90,000-
exhibit high elasticity, excellent cold flexibil- 95,000 cps viscosity (Brookfield LVF viscom-
ity, and good fastness properties. The supplier eter, No.4 spindle, 6 rpm, nOF). Storage sta-
points out that the thermoplastic nature of Im- bility is good for at least 6 months at nOF.
pranil4496 allows it to be heat sealed and post- In use Cyanabond Textile Adhesives, lami-
embossed. nant fabrics, and foam must be completely
Impranil 4496 particle size is 0.1-0.2 mi- dried and the laminated assembly then heated
crometers. Storage life is at least 6 months, but to 220°F for 5-10 sec for long term dry clean-
prolonged exposure above 140°F and cooling ing performance, or to 260°F for 15-30 sec for
to less than 38°F must be avoided. Viscosity is long term washability.
220 cps at 20°C (Brookfield, No.1 spindle, 12 Stress-strain testing of Cyanabond Textile
rpm). The latex yields continuous film with Adhesive U-270 at 30 in./min showed film to
programmed drying (200°F, 230°F, 265- exhibit 1900 psi tensile strength, 655 % ulti-
290°F) but adhesive applications accommo- mate elongation, and 730 psi 100% modulus.
date 265-290°F directly. Ex. 5. Refined Onyx Division, Millmaster
Adhesion level may be increased by an ad- Onyx Corporation supplies Karathanes 5A and
ditive, and Impranil 4496 is compatible with 5HS, 50% solids, stable, aqueous, cationic
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 373

emulsions of fully reacted polyurethane. 49 The also marketed such products in its "Hi-Tuff"
5HS product is reportedly a slight modification line. 53 Thermoplastic polyurethane elastomer
of the 5A product with much higher hydrolytic film and sheet are especially well suited for ad-
stability. Viscosity of Karathane 5A is typi- hesive applications.
cally 10,000 cps (Brookfield Model LVF, No. Ex. 1. "Tuftane" film is ideally suited for
4 spindle, 12 rpm). Karathane 5A films form bonding emblems, numerals, and letters to
on evaporating the emulsion water at ambient many fabrics by heat and pressure alone. It also
or elevated temperatures. They pass a flexibil- flame-bonds well to both polyester- and poly-
ity test at -40°C, and show 1500 psi tensile ether-urethane foams at commercial bonding
strength and 800% ultimate elongation. Kara- speeds. Since it contains no volatiles it does not
thane can be compounded (diluted, thickened, require cure times as do solvent- or water-based
and pigmented). It must not be allowed to adhesive systems. All "Tuftane" films can be
freeze. adhered thermally by hot bar, thermal impulse,
Nopco Chemical, a Division of the Diamond ultrasonic, or dielectric methods over a wide
Shamrock Corporation, also supplies polyure- range of temperatures. Adhesive lamination to
thane aqueous latices, as does the Witco Cor- many substrates is possible by the heated drum,
poration. curing oven, or multiple can methods. Fabric
bonds made with "Tuftane" are strong and
withstand laundering and dry cleaning.
Method G (film and tape)
"Tuftane" film is available in several grades:
According to one article, tape and film adhe- as aromatic poly(ester-urethanes)-TF310,
sives are viewed as the "Cadillacs" of the ad- 312, 330, 360, 800, 840; aromatic poly(ether-
hesive industry in spite of their application in urethanes) TF41O, 420; aliphatic poly(ester-ur-
products of low overall cost. 50 By generally ac- ethanes) TFI00; aliphatic poly(ether-ure-
cepted definition, tape adhesives are those thanes) TFII0; low melt polymers TF260, 270;
backed with a reinforcement or carrier while and special polyesters TF700, 710. It can be
film adhesives are self supporting. Five reasons made in 1-90 mil thickness and !-80 in.
are advanced for their increasing acceptance, widths. 86,87
namely: very high reliability in use, very high Ex. 2. Hi-Tuff HT-2000 series polyurethane
degree .of chemical and physical uniformity, thin-gauge sheeting and film "outperforms all
ease of handling (which results in manufactur- other plastic film and thin gauge rubber sheet-
ing cost reduction), significant waste reduction ings where product applications require supe-
(since unused material can be stored for sub- rior toughness, abrasion resistance, tear
sequent use), absence of mixing limitations strength, flex life, low temperature flexibility,
(which allows realization of adhesive maxi- oil and gasoline resistance, and longer aging
mum physical properties).50 To these can be properties. Hi-Tuff sheeting can be vacuum
added the same arguments advanced in favor formed, dielectrically sealed, and solvent or
of aqueous polyurethane latex adhesives over heat-bonded to substrates. ,,53
polyurethane cement adhesives in organic sol-
vents-health, safety, and pollution abatement.
Method H (powder)
Varlous polyurethane types can be fabricated
as elastomeric film and sheet. 51 The B.F. Powdered forms of plastics and rubbers are of
Goodrich Chemical Company supplies a family worldwide interest. They allow the economi-
of thermoplastic polyurethane elastomers cal, low energy mixing of polymers with ad-
("Estane") suitable for making such prod- ditives such as colorants, plasticizers,
ucts,85 and formerly marketed "Tuftane" film stabilizers, curatives, etc. The gentleness of
and sheet made from these polymers. 52 Cur- powder mixing preserves polymer integrity,
rently, the Lord Corporation continues the properties, and thus subsequent performance
manufacture and marketing of "Tuftane" film characteristics.
and sheet. 86,87 Stevens Molded Products has The fluidity of powders is another asset. It
374 HANDBOOK OF ADHESIVES

permits conveyance, distribution, and applica- eration in applications which involve long term
tion without benefit of other media such as or- continuous immersion in water. They undergo
ganic solvents or water which must finally be autoxidation on thermal or ultraviolet activa-
removed and disposed. It obviates the need for tion. 59 ,60 Poly (ester-urethanes) are subject to
melting the polymer to convey and distribute microbiological degradation. 61, 76, 77
it. The urethane linkage has a very practical de-
The elimination of organic solvents in the ap- gree of thermal stability but nevertheless it is
plication of coatings, saturants, sealants, and not outstanding in this regard. Thermal disso-
adhesives and its importance in environmental ciation at high temperatures is an inherent char-
pollution abatement and worker health and acteristic of the urethane linkage. It can be
safety has already been discussed in connection minimized by the exclusion of catalyst residues
with aqueous polyurethane latex and polyure- from the polymer. And to a degree by proper
thane film adhesives. The absence of trouble- tailoring of the polyurethane structure. 56
some and expensive solvents in their The addition of carbodiimides, e.g., Sta-
application must rank near the top in the list of baxol 1, and particularly Stabaxol P (formerly
advantages associated with the use of pow- Antioxidant PCD, Stabaxol PCD) which are
dered polymers, including adhesives. supplied by Farbenfabriken Bayer, to poly (es-
Of the available polyurethane types, the ter-urethanes) is one of the most effective ways
"virtually crosslinked" thermoplastic polyu- to stabilize them against hydrolysis. 58 ,71,72
rethane elastomers would seem to be best and Also, polyurethane structure can be tailored for
ideally suited for supply and use in powdered better hydrolysis resistance. 58
form. Their uses include adhesive applications Satrastab, developed by SATRA (Shoe and
which exploit the advantages of the powder Allied Trades Research Association, Kettering
form. England), is also claimed to be an effective hy-
Farbenfabriken Bayer (Ultramoll) and Dai- drolysis stabilizer for formulated polyurethanes
nippon Ink and Chemical Company (Pandel) in poromeric footwear materials. 63 ,64
supply powdered polyurethane. And duPont has The response of polyurethanes to thermally
explored these materials. activated autoxidation depends on polymer
Ex. 1. Ultramoll PU is a highly flexible po- structure. In general, polyurethane degradation
lyurethane based polymeric plasticizer in the by this mechanism is suppressed by the addi-
form of a colorless and odorless powder of tion of antioxidant to the polymer_ But in one
< 1000 micrometer particle size. It contains 5 study with a poly (ether-urethane) this was not
± 3 % of PVC and was especially designed for true. 57 Ultraviolet initiated autoxidation is sup-
combination with PVC. It has 72 ± 3 degrees pressed by a suitable screen (e.g., carbon black,
Shore A hardness. Ultramoll PU yields im- titanium dioxide) or a combination of antioxi-
proved adhesion strength in comparison with dant and ultraviolet absorber. 59 Irganox 1010
plasticized PVC in its injection molding as sole and Tinuvin P (Ciba-Geigy) are particularly
stock against shoe upper material. 55 suitable antioxidant and ultraviolet absorbers,
respectively, for polyurethanes. The polymer
chemist can tailor polyurethane structures with
POLYURETHANE STABILIZATION
enhanced resistance to ultraviolet-initiated au-
Although polyurethanes are very extensively toxidation. 6o
and successfully used polymeric materials with Inclusion of an effective fungicide in poly
an excellent overall record of serviceability, (ester-urethanes) prevents their degradation by
sometimes they are misapplied or improperly microbiological action. Effective agents of this
formulated and their performance is disap- type include copper-8-quinolinolate (' 'Cuni-
pointing. They are not high temperature poly- late," Scientific Chemicals, "Quindex"-
mers;56,57 continuous service applications at Nuodex Division, Heyden Newport) and N-
more than about 120°C are not recommended. (trichloromethylthio) phthalimide (" Fungitrol
They are subject to hydrolysis; 58,61,63,64,70-75 11"-Nuodex). 69 Poly (ether-urethanes) resist
other materials should be included for consid- microbiological degradation.
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 375

HANDLING ISOCYANATE BASED (III) Desmodur R - triphenylmethane-

ADHESIVES p,p I,p "-triisocyanate - a 20% solution in
methylene chloride. 2.28e
Isocyanates unquestionably are highly reactive
chemicals, which to a considerable degree ex-

¢
plains their effectiveness in adhesive applica-
tions. Consequently, adhesive formulations
containing isocyanates must have reasonable
protection from contact with agents that com-

¢-
bine with the isocyanate group, thus neutraliz- HC-o-NCO
ing it before it is able to react via
polymerization or with the adherend. This dic-
tates the use of essentially dry solvents which
are nonreactive and free of reactive impurities, NCO
as well as avoiding exposure of isocyanate-
containing adhesives to moisture during stor- (IV) Desmophen 1200-a polyester prepared
age and excessive moisture during use. from adipic acid (3.00 moles), trimethylol pro-
Reasonable caution in the use of materials pane or glycerine (1.00 mole) and 1,3-butylene
containing free isocyanate including adequate glycol (3.00 moles). 10
ventilation in use areas and the prompt cleans- (V) Desmodur TH-adduct from 2,4-toluene
ing of body areas contacted is recommended by diisocyanate (3.00 moles) and 3-methylol pen-
all isocyanate suppliers. tylene glycol-2,4 (1.00 mole); 10

-b-
CH 3
NCO

f "'
-
?H3
NH-CO-O-CH-CH-CH-O-CO-NH
I
CH:z
fH 3 -{j-NCO
f "'
-
CH 3

I
o
I

;;
CO
I

YNCOCH 3

(VI) Desmophen 900-a polyester prepared

IDENTIFICATION OF ADHESIVE from adipic acid (3.00 moles), trimethylol pro-
COMPONENTS pane (4.2 moles).9.12
(I) Toluene diisocyanate (VII) MDI-50-diphenylmethane-p,p'-diiso-

J: cyanate-50 parts, orthodichlorobenzene-50

parts. 16
Q-NCO"", OCNDNCO
CH 3
(VIII) Hylene M-diphenylmethane-p,p di- I

isocyanate. 17

NCO
2.4·isomer 2.6·isomer

(II) Hexamethylene diisocyanate (IX) Hylene M-50-Hylene M-50 parts, or-

OCN-(CH2)6- NCO thodichlorobenzene-50 parts. 17
376 HANDBOOK OF ADHESIVES

(X) Leukonat adhesive-triphenylmethane-p,p 'p "-triisocyanate-a 20% solution in di-

chloroethane. 18
(XI) Desmodur HH-adduct from 1,6-hexamethylene diisocyanate (3.00 moles) and 3-meth-
ylol pentylene glycol-2,4 (1.00 mole): 10
CH 3 CH 3
I I
OCN-(CH1)6-NH-CO-O-CH-CH-CH-O-CO-NH-(CH1)6-NCO
I
CH1
I
o
I
CO
I
NH
I
(CH 1 )6
I
NCO

(XII) Mondur TM-triphenylmethane-p,p I,p "-triisocyanate-a 20% solution in methylene

chloride. 42
A 50% solution of diphenylmethane-p,p I-diisocyanate in xylene or orthodichloro-benzene. 43
(XIII) Vulcabond TX-a polyisocyanate, principally a diisocyanate. 22c
(XIV) DAD!-dianisidine diisocyanate. 24

(XV) PAPI-polymethylene polyphenylisocyanate. 24

O
NCO k5iCO NCO

CH ' CHl-6
" 1" 0-3 "
(XVI)Desmodur L-equivalent to Mondur CB-75 (XXIX).28d
(XVII) Desmodur RF-a 20% solution of thiophosphoric acid tris (p-isocyanatophenyl ester)
in methylene chloride. 28f

(XVIII) Daltoflex A-lO-a viscous 45 % solution in methyl ethyl ketone of a stable poly-
urethane elastomer containing no unreacted isocyanate. 30
(XIX) Suprasec GA-A 75% solution in ethyl acetate of a resinous organic polyisocyanate
containing a small amount of volatile free isocyanate. 30
(XX) Daltrol PRI-a reactive liquid polyester. 3o
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 377

(XXI) Hylene MP-Methylene-bis-phenyl-(4-phenyl carbamate). 34

o-0-CO-NH-o-CH2-o-NH-COO-O ~ 2S0-284°F,

2 o-OH + OCN-o-CH2-o-NCO
Phenol MDI

(XXII) Mondur S-a phenol-blocked TDI adduct. 35,36

(XXIII) Mondur SH-a cresol-blocked TDI trimer,36,37 presumably

(XXIV) Experimental E-320 Blocked Isocyanate-a ketoxime-blocked tetraisocyanate. 36 ,38,39

(XXV) Isonate 123P-E-caprolactam-blocked PAPI. 4U

(;1\ .......>... co """ / ':

: H ::
.... ,.......... ---_ ............. .
\
"'+.-' :' /"'"" \ \.~j :' /CO \
N-CO\~- (CH2~~/ N-CO\~-{CH2).~j
~~~ . ~' .... ..
-fI---'cH;-"-'-II-+-

(XXVI) Poly (caprolactone) glyco1. 54

H -to(CH2 h-CO-t xO- R -0-tCO-

(CH 2h-O T yH
378 HANDBOOK OF ADHESIVES

(XXVII) Polybutadiene Glycol (Poly BD reprinted in Rubber Chem. ell: Technol., 23, (4) (Oct.-
Glycol). 79 Dec. 1950).
14. Kohler, E. P., Stone, Jr., J. F., and Fuson, R. C., J.
Poly BD R-I5M and R-45M are hydroxyl- Am. Chem. Soc., 49, 3181 (1927).
tenninated polymers comprised solely of buta- 15. Morton, M., Deisz, M. A., and Ohta, M., "Degra-
diene. Poly BD CS-I5 and CN-I5 are hy- dation Studies on Condensation Polymers," U.S. De-
droxyl-tenninated polymers with backbone partment of Commerce Report PB-131795 (Mar. 31,
structures comprised of butadiene-styrene and 1957).
16. Bonding Elastomers to Metals with MDI-50, Elasto-
butadiene-acrylonitrile, respectively. mers Division Bulletin, BL-241 (Apr. 30, 1951), E.
(XXVIII) Aminimide AL-X-300. 65b I. du Pont de Nemours & Co., Wilmington, Del.
17. Hylene M, Hylene M-50-0rganic Isocyanates, Elas-
CH 0 0 CH tomers Division Bulletin HR-5 (Dec. 1955), E. I.
3'EB e II II e EB/ 3 duPont de Nemours & Co., Wilmington, Del.
N-N-C-CH:zCH:zCH:zCH:z-C-N-N-CH3
/1 1 18. Medvedeva, A. M., Deryagin, B. V., and Zherebkov,
CH3 CH:z CH:z S. K., Colloid J. (USSR), 19, 417 (1958); reprinted
1 1 in Rubber Chem. ell: Technol., 32, (1), 67 (1959).
H-C-CH 3 H-C-CH 3 19. Windemuth, E., U.S. Patent 2,650,212 (Aug. 8,
1 1
OH OH 1953), to Farbenfabriken Bayer A. G., Leverkusen,
Germany.
(XXIX) Mondur CB-75 36-a TDl-trimethy- 20. Rigid Urethane Adhesives Evaluation Fonnulations,
Technical Data Bulletin S-IO, Revised 3/1165, Mobay
101 propane adduct, 75 % nonvolatiles in ethyl Chemical Co., Pittsburgh, Penna.
acetate solution. 21. Abernathy, H. H., and Radcliff, R. R., The Adhesion
of Fibers to Elastomers, Rubber Chemicals Division
Report No. 47-4 (May 1947), E. I. duPont de Nem-
REFERENCES ours & Co., Wilmington, Del.
22. Meyrick, T. J., and Watts, J. T., Polyisocyanates in
1. B. F. Goodrich Chemical Co. Bonding.
2. Eby, L. T., and Brown, H. P., Chap. 3, "Treatise on (a) Terylene Polyester Fiber to Rubber, India Rubber
Adhesion and Adhesives," R. L. Patrick (ed.), New J., 467 (Mar. 22, 1952).
York, Marcel Dekker, 1969. (b) Rubber to Metals, India Rubber J., 505 (March
3. Allen, G. D., and Fryer, C. W., RubberJoumal, 153, 29, 1952).
(1),31 (Jan. 1971) (c) Trans. InSf. Rubber Ind.• 25, (3) (1949).
4. Lewis, A: F., and Elder, G. B., Adhesives Age, 12, 23. Vinyl Adhesion to Synthetic Fabric, Technical Bulle-
(10), 31 (Oct. 1969). tin (June 1, 1959), Carwin Chemical Co. (now the
5. Schollenberger, C. S., Chap. 27, Isocyanate-Based Upjohn Co., Kalamazoo, Mich.).
Adhesives, "Handbook of Adhesives," 2nd Ed., I. 24. Product Catalog (1957). The Carwin Chemical Co.
Skeist (ed.), New York, Van Nostrand Reinhold, (now the Upjohn Co., Kalamazoo, Mich.).
1977. 25. Schollenberger, C. S., Scott, H., and Moore, G. R.,
6. Saunders, J. H., and Frisch, K. C., "Polyurethanes: Rubber World. 137, (4), 549 (Jan. 1958).
Chemistry and Technology. " 26. The General Tire and Rubber Co., Akron, Ohio,
(a) Part II, Technology, John Wiley (Interscience), (a) Genthane S, Technical Bulletin GT-S3.
1964. (b) Genthane SR, Technical Bulletin GT-SR1.
(b) Part I, Chemistry, John Wiley (Interscience), 27. Estane Polyurethane Materials Service Bulletins:
1962. (a) Estane Polyurethane Adhesive Systems (TSR 64-
7. DeLollis, N. J., "Adhesives for Metals: Theory and 14, TF116).
Technology," New York, Industrial Press 1970. (b) New "Open Tack" Estane Polyurethane Adhe-
8. Reegen, S. L., and Ilkka, G. A., "The Adhesion of sives (TSR64-20. TF116), B. F. Goodrich
Polyurethanes to Metals," Adhesion and Cohesion Chemical Co., Cleveland, Ohio.
Symposium, General Motors Research Laboratory, 28. (a) Desmocolll76 (Order No. KA4201e, Ed. 118/69,
Elsevier, 1962. USA 19-710/67421).
9. CIOS Report 29-12 (Appendix; Item 22), P. B. 46961 (b) Desmocoll 400 (Order No. KA4209USA, Ed. 11
(Feb. 1946). 2/69, USA 20-710/67 422).
10. Bayer, 0., Angew. Chem., 59, (9), 257 (Sept. 1947). (c) Desmoco1l420 (Order No. KA4241, Ed. 117169.
11. Dombrow, B. A., "Polyurethanes," New York, Van USA 25-710/67 427).
Nostrand Reinhold, 1957. (d) Desmodur L - information from Mobay Chemi-
12. DeBell, J. M., Goggin, W. C., and Gloor, W. E., cal Co.
"Gennan Plastics Practice," DeBell and Richardson, (e) Desmodur R (Order No. KA4217 USA, Ed. 1121
Springfield, Mass., 1946. 69, USA 93-710/67 407).
13. Buist, J. M., and Naunton, W. J. S., Rubber Bonding, (f) Desmodur RF (Order No. KA4218 USA, Ed. 11
Trans. Inst. Rubber Ind., 25, (6), 378 (April 1950); 2/69, USA 94-710/67 408).
 POLYURETHANE-AND ISOCYANATE-BASED ADHESIVES 379

Technical Bulletins, Farbenfabriken Bayer AG, Lev- 49. Karathane 5A, Technical Bulletin, Refined-Onyx Di-
erkusen, Germany (via Mobay Chemical Co.). vision, Millmaster Onyx Corp., Lyndhurst, N.J.
29. U.S. Royal Adhesive Technical Data Bulletin, Uni- 50. King, H. A., Adhesives Age, IS, (2), 22 (Feb. 1972).
royal, Inc., Mishawaka, Ind. 51. Schollenberger, C. S., and Esarove, D., Chap. 12,
30. Urethane Adhesives Based on Daltoftex A-IO, Tech- "Polyurethanes, The Science and Technology of Pol-
nical Bulletin 287, I.C.1. Organics, Inc., Stamford, ymer Films," Volume II, O. J. Sweeting, (ed.), New
Conn. York, John Wiley (lnterscience), 1971.
31. Flexible Urethane Adhesives Evaluation Formula- 52. Tuftane Polyurethane Film and Sheet, Bulletin T-5,
tions, Technical Data Bulletin, Mobay Chemical Co., The B. F. Goodrich Chemical Co., Cleveland, Ohio.
Pittsburgh, Penna. 53. Hi-Tuff Precision Elastomeric Sheeting, Technical
32. Bostik 7070 with Boscodur No. I, Bostik Data Sheet, Bulletin, Stevens Molded Products-a Department of
B. B. Chemical Co., Cambridge, Mass. (July 25, J. P. Stevens Co., Inc., Easthampton, Mass.
1958). 54. Ward, R. J., Adhesives Age, 26 (Oct. 1970).
33. Petersen, S., Ann. Chem., 562, 205 (1949). 55. Polymeric Plasticizers, Technical Bulletin 6.3.1 (Ul-
34. Hylene MP Water Stable Diisocyanate Generator, tramoll PU), edition 1.4.1972e, Farbenfabriken Bayer
Elastomer Chemicals Department Bulletin HR-25, G. A. G., Leverkusen, Germany.
E. Owen, Jr., E. I. duPont de Nemours Co., Wil- 56. Singh, Ajaib, "Advances in Urethane Science and
mington, Del. (July 1957). Technology," Vol. 1, Chap. 5, K. C. Frisch, and S.
35. Mondur S (Mobay Stablized Polyisocyanate Adduct). L. Reegen (eds.), Technomic, Stamford, Conn., 1971.
Data Sheet 8/1163, Mobay Chemical Co., Pittsburgh, 57. Singh, A., Weissbein, L., and Mollica, J. C., Rubber
Penna. Age (New York), 98, (12), 77 (Dec. 1966).
36. Chemicals for Coatings, Surfaces, Sealants, Binders, 58. Schollenberger, C. S., and Stewart, F. D., J. Elas-
Adhesives, Elastomers, and Chemical Intermediates, toplastics, 3, 28 (Jan. 1971); and, "Advances in Ur-
Bulletin, Mobay Chemical Co. Pittsburgh, Penna. ethane Science and Technology," Vol. 1, K. C.
37. Mondur SH (Mobay Stabilized Polyisocyanate Ad- Frisch, and S. L. Reegen, (eds.), Technomic, Stam-
duct), Data Sheet 2/1159, Mobay Chemical Co., Pitts- ford, Conn., 1972.
burgh, Penna. 59. Schollenberger, C. S., and Dinbergs, K., SPE Trans-
38. Experimental Product E-320, Data Sheet, April 1969, actions, 1, (1), 31 (Jan. 1961).
Mobay Chemical Co., Pittsburgh, Penna. 60. Schollenberger, C. S., and Stewart, F. D., J. Elas-
39. Hill, H. E., Pietras, C. S., and Damico, D. J., J. topiastics, 4, 294 (Oct. 1972), and "Advances in Ur-
Paint Techno!., 43, (553), 55 (Feb. 1971). ethane Science and Technology," Vol. 2, K. C. Frisch
40. Isonate 123P (Caprolactam-blocked PAPI), Bulletin and S. L. Reegen, (eds.), Technomic, Stamford,
CD 1217 (June 1971); Product Report (September 1, Conn., 1973.
1969), The Upjohn Co. Kalamazoo, Mich. 61. Ossefort, Z. T., and Testroet, F. B., "Hydrolytic Sta-
41. An Aqueous Adhesive System for Bonding Elastomers bility of Urethane Elastomers," 89th Meeting, Rub-
to Synthetic Fibers, C. H. Gelbert, G. E. Owen, Jr., ber Division, American Chemical Society, San
Elastomer Chemicals Department Report BL-338, E. Francisco, Calif. May 4, 1966. Also, Rubber Chem-
I. duPont de Nemours & Co., Wilmington, Del. istry and Technol., 39, (4), Part 2, 1308 (September
42. Mondur TM (Data Sheet, 3/15/64) Mobay Chemical 1966).
Co., Pittsburgh, Penna. 62. Griffith, G. R., and Willwerth, L. J., Industrial and
43. Buchan, S., Rubber to Metal Bonding, London, Engineering Chemistry Product Research and Devel-
Crosby, Lockwood and Son, Ltd., 1959. opment, 1,265 (1962).
44. Technical Data Bulletins on Urethane Latices (D-14, 63. Hole, L. G., Kann, G., and Dawkins, P. J., The De-
-15, -16, -17, -18, -120, -121), BASF Wyandotte terioration of Polyurethanes by Hydrolysis, Rubber-
Corp. Wyandotte, Mich. con, F3-1, International Rubber Conference, Brighton,
45. Crisvon and Vondic 1310; Vondic 1000C, Tech. Bul- England (May 1972).
letin CR 895002, Dainippon Ink and Chemicals, Inc., 64. Hole, L. G., and Abbott, S. G., The Chemical Sta-
Tokyo, Japan. bility of Polyurethane in Artificial Leather, paper at
46. Impranil4496 (DLN) Dispersion-Urethane Aqueous Inter-SAT '71, Imperial Hotel, Blackpool, England
Dispersion for Textile Coating. Technical Data Sheet (Apr. 20-22, 1971).
No. 1269 (Revised), Verona Division, Baychem 65. Ashland Chemical Co., a Division of Ashland Oil,
Corp., Union, N.J. Inc., Columbus, Ohio.
47. Neumaier, H. H., Aqueous Dispersions of Polyure- (a) Ashland Aminimides, a New Organic Functional
thane Ionomers for Coating and Laminating, Paper at Group, Sales Brochure (1972).
AATCC Symposium on Coated Fabrics Technology, (b) Ashland Aminimides for Tire Cord Dips, Tech-
Marriott Motor Inn, Newton, Mass. (Mar. 28-29, nical Bulletin 1238.
1973). 66. U.S. Patent 3,450,673, William J. McKillip assignor
48. Cyanabond Textile Adhesives for Bonding and Flock- to Ashland Oil Corp. (June 17, 1969).
ing. Technical Sales Bulletin No. 1031 (Revised 21 67. Rubber World, 168, (1), 13 (April 1973).
70), Cyanamid Dyes and Textile Chemicals Depart- 68. U.S. Patent 3,425,988, J. W. Gorman, and A. S. To-
ment, American Cyanamid Co., Bound Brook, N.J. back assignors to the Loctite Corp. (Feb. 4, 1969).
380 HANDBOOK OF ADHESIVES

69. Schollenberger, C. S., and Dinbergs, K., B. F. Good- sives", Technomic Publishing Co. Seminar on "Ad-
rich Co. (unpublished). vances in Polyurethanes," Ramada Inn Central,
70. Cooper, W., Pearson, R. W., and Darke, S., The In- Atlanta, GA (Nov. 10, 1987).
dustrial Chemist, 36, 121 (1960). 82. Dollhausen, M., and Warrach, W.,
71. Neumann, W., Peter, 1., Holtschmidt, H., and Kal- (a) "A Review of Polyurethane Adhesives Technol-
lert, W., Proc. of the 4th Rubber Technology Confer- ogy , " presented at Adhesive and Sealant Council
ence, London, Paper 59, 738 (1962). Fall Seminar, Philadelphia, PA (October 18-21,
72. Neuman, W., Holtschmidt, H., Peter, J., and Fischer, 1981 ).
P., U.S. Patent 3,193,522 (July 6, 1965). (b) Adhesives Age, 28 (June, 1982).
73. Athey, R. J., Rubber Age (New York), 96, (5), 705 83. Dieterich, D., and Rieck, J. N., Adhesives Age, 21(2),
(1965). . 24 (February 1978).
74. Gahimer, F. H., and Nieske, F. W., J. Elastoplastics, 84. Dieterich, D., and Reiff, H., Angew. Makromo!.
1,266 (Oct. 1969). Chem., 26, 85 (1972).
75. Magnus, G., Dunleavy, R. A., and Critchfield, F. E., 85. Estane Thermoplastic Polyurethane for Film and Sheet
Rubber Chem. & Techno!., 39 (4), Part 2, 1328 (Sept. Applications," Technical Bulletin ES-3, B. F. Good-
1966). rich Co. Chemical Group, Cleveland, OH, 1984.
76. Kaplan, A. M., Darby, R. T., Greenberger, M., and 86. Bartko, G. J., Jr., "State of the Art in Polyurethane
Rogers, M. R., Dev. Ind. Microbiol., 9201 (1968). Film Technology," Paper, Film, and Foil Convertor
77. Darby, R. T., and Kaplan, A. M., Appl. Microbiol, (February 1986).
900 (June 1968). 87. Tuftane Specialty Film and Sheet, Technical Bulletin
78. Reegen, S. L., Adhesion of Urethanes from Oxypro- DSlO-5000 A, Lord Corporation/Film Products Di-
pylene Polyols, "Advances in Urethane Science and vision, 1985.
Technology," Vol. 2, 56, K. C. Frisch and S. L. Ree- 88. Lord Corp. (Industrial Adhesives Div.) Technical
gen (eds.), Technomic, Stamford, Conn., 1973. Bulletins.
79. Hydroxyl-Terminated Poly B-D Resins in Urethane (a) "TYRITE 7500," #DSlO-3606C (1984).
Systems, Technical Bulletin, Arco Chemical Co. (b) "TYRITE 7411," #DSlO-3580B (1981).
80. Scheebeli, P., Compt. rend, 236, 1034 (1953). (c) "TYRITE 7602," #DSlO-3602C (1984).
81. Zalucha, D. J., Lecture, "Polyurethanes in Adhe- (d) "TYRITE 7650," #DSlO-3650 (1987).
 21
Polyvinyl Acetate Emulsions
for Adhesives
HAROLD L. JAFFE
Chemical Consultant
Millburn, New Jersey
and
FRANKLIN M. ROSENBLUM AND WILEY DANIELS
Air Products and Chemicals, Inc.
Allentown, Pennsylvania

Polyvinyl acetate has been available commer- ticated polymer and copolymer products have
cially in the United States since the 1930s. been commercialized to meet the needs of
Growth was slow until the 1940s, when poly- changing technology.
vinyl acetate emulsions were introduced. The The excellent adhesion of polyvinyl acetate
volume of resin consumed has since grown emulsions to cellulosic and other materials gave
from a negligible amount in 1945 to 1.7 billion rise to an abundance of applications, including
pounds currently. bookbinding, paper bags, milk cartons, drink-
The adhesive industry is one of the most im- ing straws, envelopes, gummed tapes, convo-
portant outlets for polyvinyl acetate. An esti- lute tubes, folding boxes, multiwall shipping
mated 500 million pounds was used bags, labels, foils, film and paper board decals,
domestically in adhesives in 1987. Polyvinyl cigarette tips, lagging compounds, wood as-
acetate also goes into surface coatings, caulks, sembly, padding, automobile upholstery, pen-
etc. cils, leather binding, and tile cements.
Polyvinyl acetate came into widespread use Because of their relatively low cost, ready
in adhesives in the 1940s as a synthetic resin availability, wide compatibility, and excellent
substitute for hide glue. Superior properties of adhesive characteristics, many polyvinyl ace-
the synthetic resins offset their higher price. tate resins, solutions, and emulsions are treated
Polyvinyl acetate adhesives were adaptable to as commodity items by the adhesives industry.
new high-speed machinery in the paper con- Among the many U.S. manufacturers of poly-
verting and packaging fields and were enthu- vinyl acetate based resins are the following ma-
siastically received. They found a place in jor producers: Air Products, H. B. Fuller,
wood adhesives and later were introduced in National Starch, Reichhold, Rohm and Haas,
the familiar household "white glue." Signifi- Union Carbide, Union Oil, and W. R.Grace.
cant advances have taken place in polyvinyl The resulting competition has benefited adhe-
acetate technology. A large number of sophis- sives formulators with low prices, good qual-

381
382 HANDBOOK OF ADHESIVES

ity, new improved products, and greater aqueous dispersions and (2) solid resins de-
technical service from the resin manufacturers. rived from aqueous dispersions.
Price variation is a common experience in this
competitive market. Grade of resin and volume Polymerization
are important factors in selling price.
Early studies of the polymerization of vinyl
Emphasis on the use of polyvinyl acetate in
acetate and the structure and properties of the
the adhesives industry alone gives a rather con-
polymer were made during the first quarter of
fining picture of the resin. Its use in other .in-
the century. 15,16 The first patents on polymeri-
dustries actually depends on its adhesive,
zation were also issued during that period. 17.18
binding, and film properties as much as it does
The real commercial development on the con-
in the adhesives industry. 1 Among the major
tinent began in 1925. Commercial polymeri-
outlets for polyvinyl acetate emulsions are in-
zation was underway by 1929. 19- 21 Since then,
terior and exterior flat paints, particularly for
a wealth of technical literature has been pub-
masonry surfaces. Leveling and color retention
lished dealing with polyvinyl acetate. 22 A par-
are the outstanding properties of these coat-
ticularly comprehensive article and bibliog-
ings. The textile industry utilizes polyvinyl
raphy on vinyl acetate polymerization and
acetates, mostly in emulsion fonn, for finishes
polymer properties is found in the "Encyclo-
that impart durability, strength, and "hand" to
pedia of Polymer Science and Technology." 12
woven cotton and other fabrics. Emulsions of
Vinyl acetate polymerizes by a free-radical
vinyl acetate and comonomers serve as binders
mechanism. Free radicals generated by the de-
for nonwoven or bonded fabrics. The paper in-
composition of organic peroxides such as ben-
dustry uses small particle size polyvinyl acetate
zoyl or hydrogen peroxide or of inorganic
emulsions as pigment binders for clays in paper
"per" salts such as potassium or ammonium
and paper board coatings.
persulfate are commonly used to initiate poly-
merization. Reactions ordinarily are accom-
Monomer
plished at temperatures above room temper-
Vinyl acetate is the most available and widely ature. Other techniques of polymerization have
used member of the vinyl ester family. This been used to make novel products; low tem-
colorless, flammable liquid was first prepared perature redox polymerization, irradiation, and
in 1912. Liquid-phase processes were com- ionic catalysis.
mercialized early in Germany and Canada, 3 but High molecular weight and essentially linear
these have been replaced generally by vapor- polymers, controlled particle size in the case of
phase processes. Earlier commercial processes emulsions, and even polymers with spatially
were based on the catalyzed reaction of acety- regulated structures are available. Vinyl acetate
lene with acetic acid. The more recent techni- copolymerizes with many other vinyl mono-
cal development is the production of vinyl mers. Acrylate esters; vinyl chloride and vi-
acetate monomer from ethylene and acetic acid. nylidene chloride; dibutyl and other dialkyl
Palladium catalyst is used for the vapor phase maleates and fumarates; crotonic, acrylic,
process. The ethylene route is the dominant methacrylic and itaconic acids; vinyl pyrroli-
route worldwide. done; and ethylene are commercially important
Vinyl acetate is manufactured in the U.S. by comonomers. 2 A monomer that does not com-
Borden, Celanese, duPont, Union Carbide, and bine with vinyl acetate alone may be combined
U.S.1. Chemicals. Its properties and reactions by use of a third monomer. "Grafting" can be
are reviewed in trade bulletins of the sup- used with monomers such as styrene that do not
pliers,6-9 and more extensive discussions are copolymerize with vinyl acetate.
presented in technical literature. 10-14 Laboratory processes for the polymerization
Domestic capacity for production of vinyl of vinyl acetate and some of the other vinyl es-
acetate in the U.S. was estimated to be 2.4 bil- ters are readily available from monomer sup-
lion pounds per year in 1987. pliers and in the patent literature. Commer-
The discussion that follows covers (1) cially, vinyl acetate polymers have been made
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 383

by all of the standard methods: bulk, suspen- hesives market is served by vinyl acetate and
sion, emulsion, and solution. 2 ,12 Manufactur- its copolymers.
ing processes are also available. 12

Emulsions ADVANTAGES OF POLYVINYL

ACETATE EMULSIONS
Polyvinyl acetate is most widely used in the
form of a dispersion of solid resin in water. Adhesion to a Wide Variety of Surfaces
These dispersions are produced by emulsion
Polyvinyl acetate resins adhere well to more
polymerization and are more commonly termed
surfaces than most other adhesive bases. Poly-
emulsions. In 1987, production volume was on
vinyl acetate homopolymers bond particularly
the order of 1.7 billion wet pounds for all uses
well to wood and paper substrates. Copolymers
and 500 million wet pounds for adhesives. Most
of polyvinyl acetates adhere to, or can be com-
products for adhesives are sold at 55 % solids
pounded to adhere to, a wide variety of plastic
at a sufficiently high viscosity level to facilitate
film and metal foils that are frequently lami-
use. These products are manufactured by one
nated or combined with paper and wood.
of several techniques23 - 26-batch, continuous,
or delay feed, depending on properties desired.
High Molecular Weight
The large volume usage depends not only on
the outstanding adhesive properties of the resin Polyvinyl acetate emulsions have the advan-
but also on the excellent compatibility of the tage of combining high molecular weight with
emulsions with many modifying agents. I low usable viscosity. Since the molecular
The properties, uses, and methods of for- weight of the polyvi~yl acetate does not affect
mulating emulsions are graphically and com- the viscosity of the emulsion, it is possible to
prehensively described in the trade literature, design adhesive bases which have high cohe-
which is an excellent source of information. sive strength and toughness, and yet also have
Most manufacturers specify properties of their viscosities that allow application by roller,
emulsions in terms of percent solids, emulsion spray, or extruder.
viscosity, pH, acid content, percent unreacted
monomer, and density. Other properties gen- High Solids
erally described are particle size, molecular
The emulsion form of polyvinyl acetate also al-
weight, film properties such as clarity, water
lows the production of high solids (55%) ad-
and grease resistance, and tolerance of the
hesives at low viscosities. It is possible,
emulsions to various organic and inorganic
therefore, to make rapid-setting, low shrinkage
chemicals.
adhesives at viscosities which permit them to
Although all components of an adhesive (film
be easily applied by roller, spray, or extruder.
formers, plasticizers, viscosity modifiers, tack-
Recent emulsions contain 65-66 % solids while
ifiers, solvents, fillers, and surfactants) have
maintaining low viscosity. 27
strong influence on the performance of the ad-
hesive, the film formers or polymer emulsions
Rapid Setting Speeds
are the most important. This is because the pol-
ymers, through molecular weight and struc- In the case of emulsion-based adhesives, the
ture, contribute such vital properties as tensile loss of a relatively small amount of water will
strength, toughness, flexibility, specific adhe- cause the inversion of the emulsion and rapid
sion, chemical resistance, mechanical stability, setting of the adhesive. This contrasts favora-
and compatibility with modifiers. bly to solution-based adhesives, both water and
The fundamental properties of the polymer organic solvent types, which require that most
background determine the suitability of a given of their solvent be lost to the atmosphere and/
type. of emulsion for a particular market. or absorbed into the substrate before they be-
Though styrene butadiene and acrylics are come tacky enough to hold the substrate to-
widely used, the largest portion of the U.S. ad- gether. In fact, even more solvent must be lost
384 HANDBOOK OF ADHESIVES

before strong, fiber-tearing bonds can be ob- Low Toxicity

tained.
Polyvinyl acetate adhesives have a low degree
of toxicity and have been used in food pack-
Easy Modification of Water and Solvent
aging for decades. They have been approved
Resistance
for this use by the Food and Drug Administra-
Polyvinyl acetate can be protected with colloid tion.
systems, surfactant systems, or a combination
of both. 12 By varying the protection system, it Minimal Environmental Impact
is possible to produce adhesive bases whose
Polyvinyl acetate emulsions, as a class, have a
relative water resistance will differ in range
low biological and chemical oxygen demand.
from water remoistenable to water resistant (24
hr) and even to boiling water resistant. The
HOMOPOLYMERS AND COPOLYMERS
choice of a protection system used in an adhe-
sive base will also affect the degree of solvent Homopolymers
resistance. 4o
The early polyvinyl acetate emulsions were ho-
mopolymers protected with partially hydro-
Good Machining Characteristics
lyzed polyvinyl alcohol. These high molecular
Polyvinyl acetate-based adhesives have a high weight polymers had great strength and set rap-
degree of mechanical stability and machine well idly to hard, horny films. Today, these homo-
in many different modes of application. At the polymers are the workhorses of the industry due
same time, they will set very rapidly. to their excellent adhesion to uncoated paper,
wood, concrete, ceramics, and glass. In addi-
Ease of Compounding tion, they exhibit a fair degree of water sensi-
tivity. This allows them to be easily cleaned
Polyvinyl acetate emulsion adhesives can be
from equipment and permits their use in re-
compounded using very basic mixing equip-
moistenable adhesives.
ment and procedures. Many resins, plasticiz-
ers, solvents, and fillers can be blended directly
Copolymers
into the emulsion without preemulsifying or
predispersing the additives. The ability to mod- Since polyvinyl acetate is a stiff material, the
ify polyvinyl acetate with a wide variety of ad- need for more flexible versions became appar-
ditives makes the adhesives more versatile and ent early in the development of the industry.
allows adhesion to a wider number of sub- The adhering of plastic films to paper and the
strates than adhesives made from other resin bonding of resin-coated paperboard in packag-
bases. ing applications are two examples of this need
for greater flexibility .
Resistance to Microorganisms Flexibility can be obtained either by com-
pounding with an external plasticizer or by co-
Dried polyvinyl acetate adhesive films are
polymerizing with a suitable monomer. When
highly resistant to attack by microorganisms.
a homopolymer adhesive is flexibilized with
The addition of biocides will prevent attack of
external plasticizers and/or solvents, the re-
microorganisms on a liquid emulsion or on a
sultant bonds frequently fail on aging because
dried adhesive film when animal or vegetable
of plasticizer migration. This may occur in any
modifying ingredients have been added to the
of three ways: (a) the plasticizer may migrate
emulsion.
into the plastic substrate, leaving a brittle ad-
hesive which loses its bond in as little as 7-10
Resistance to Oxidation and Ultraviolet
days; (b) if the substrate is plasticized PVC,
Radiation
the plasticizer in the substrate may migrate into
Polyvinyl acetate is a saturated molecule and is the adhesive, softening it to the point where it
therefore not subject to degradation by oxygen, has little cohesive strength; or (c) the plasti-
ozone, or ultraviolet radiation. cizer in the substrate may migrate to the inter-
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 385

face and, in effect, act as a release agent due to

incompatibility with the polyvinyl acetate.
When a polyvinyl acetate emulsion is fiexi-
bilized internally with a comonomer, the plas-
ticization is permanent and nonmigratory. This
is because the comonomers are part of the main
polymer chain, often with bulky side groups,
increasing the freedom of rotation of the chain.
The resulting softening and polymer mobility
allows better adhesion to plastic surfaces.
Monomers which are copolymerized with vi-
nyl acetate include alkylacrylates, alkylma-
leates, fumarates, and ethylene. The level of
comonomers may vary from a few weight per-
cent of the copolymer to as much as 70 weight -40+---'--r-r-"""T-""T"-'--~
percent. o 5 10 15 20 25 30 35
% COMONOMER

Ethylene vs. Ester Comonomers Fig. 1. Comonomer levels required to plasticize polyvi-
ny I acetate.
The early copolymers of vinyl acetate with di-
butyl maleate or acrylate esters offered distinct
advantages over the homopolymer in their abil-
ity to adhere to a vast number of difficult-to- 3.0 ......- - - - - - - - - - - - - ,
bond surfaces. However, they also had disad-
vantages, e.g., poor heat resistance, relatively
2.5
low strength, rather slow setting speed, and
·iii
comparatively poor machinability. The intro- a.
o
duction of vinyl acetate-ethylene copolymers ~ 2.0
changed this picture considerably. This class of I
~

emulsion had all the benefits of homopolymers Cl

a; 1.5
in strength, machinability and heat resistance II:
~

in addition to better adhesion characteristics rJ)

W
1.0
than those of the ester copolymers. ...J
iii
z
Ethylene is a much more effective internal w
~

plasticizer for polyvinyl acetate than are dibu- .5

tyl maleate and acrylate comonomers. Com-
pared with dibutyl maleate, smaller amounts of
ethylene are necessary to decrease the glass 30 20 10 0 -10 -20 -30
transition temperature of the homopolymer T9 (0C)
(Fig. 1). Vinyl acetate-ethylene copolymers
Fig. 2. Effect of Tg on vinyl acetate copolymer film ten-
also have much higher tensile strength than vi- sile strength.
nyl acetate-dibutyl maleate copolymers at
equivalent glass transition temperatures (Fig.
2). In fact, the ethylene copolymer emulsion
has a higher tensile strength than vinyl acetate-
Table 1. How Comonomers Affect
dibutyl maleate even though its glass transition
Copolymer Film Properties.
temperature is lower and its percent elongation
is about the same (Table 1). In addition, the VAclDibutyl
Property VAclEthylene Maleate
vinyl acetate-ethylene copolymer has the same
heat or creep resistance as the homopolymer Tensile Strength (psi) 960 618
and much better creep resistance than the vinyl Tg (0C) 0 6
Elongation (%) 1660 1550
acetate-dibutyl maleate type (Table 2). It should
386 HANDBOOK OF ADHESIVES

Table 2. Relative Creep Resistance of Effect of Accelerated Aging' on

Polyvinyl Acetate Copolymers
Polyvinyl Acetate Emulsions.
Emulsion Type Creep (mmlmin)
_ Belor. Aging
Homopolymer 0.02
DAfter Aging
VAc/ethylene 0.02
3
VAc/dibutyl maleate 7.6
.£
Homopolymer and 10% DBP" 0.6 0;
VAc/ethylene and 10% DBP" 0.6 Q)

-=
'DBP = Dibutyl phthalate. ".ci-=-
I 2
l-
t!)
Z
be noted that when it is plasticized with 10% W
II:
dibutyl phthalate, it still has less creep than the I-
en
neat vinyl acetate-dibutyl maleate and is equal ...J
w
W
to a homopolymer containing an equal amount 11.

of plasticizer.
VAE (vinyl acetate-ethylene) emulsions do
not require as much plasticizer to obtain a
strong bond to PVC as do vinyl acetate-dibutyl VAc/Ethylene' VAc/ VAc/Dlbutyl
maleate and vinyl acetate-acrylate (Fig. 3). Im- Acrylate' Maleate'
portantly, these copolymers do not soften I. Bonds aged one week at 120°F.
nearly as much as the other copolymers when 2. Prolective colloid: polyvinyl alcoh.ol.
plasticizer is added. This means that as lami- 3. Proteclive colloid: cellulosic.

nations of films to cellulosic substrates age, the Fig. 4. Peel strength of PVC to cloth bonds.
bond made by the VAE will not lose its cohe-
sive strength and weaken (Fig. 4).
Certain properties may best be explained by percent of dibutyl maleate may be visualized as
examining the molecular structure of polyvinyl a polyethylene chain with acetate groups on
acetate and some of its copolymers. Fig. 5 every other carbon atom for 16 atoms on the
compares polyethylene and polyvinyl acetate chain, and a butyl ester group on the 17th and
homopolymers. Polyethylene is, of course, a 18th carbon atoms (Fig. 6). These resins are
flexible polymer, whereas polyvinyl acetate flexible because the bulky pendant butyl ester
homopolymer is hard and brittle because steric groups allow intermolecular movement and also
hindrance between alternate acetate groups re- separate the chains of polymers so that they can
stricts movement of the molecules. A copoly- slip past one another rather easily. This ac-
mer of vinyl acetate containing 25 weight counts for the higher degree of creep in a vinyl

Effect of Plasticizer on Polyvinyl Acetate Copolymers

5
.5
-
0; VAc/Ethylene
Q) 4
~
-
.--------
-
g 3
I
l-
e> VAc/Dlbutyl Maleate
zw 2
II:
I-
en 0
VAcl Acrylate -
.
...J
W
W
11.

o 2
. .
4 6 8
,
10 12 14 16 18 20
•
PARTS OF PLASTICIZER (DIPROPYLENE GLYCOL DIBENZOATE) PER 100 PARTS OF EMULSION

Fig. 3. Peel strength of PVC to cloth bonds.

 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 387

copolymers is that they have greater resistance

to alkalis and acids than the older copolymers.
H, H. H. When acetate groups are present on alternate
carbons, the hydrolysis of one acetate group by
H. H. H. alkali exposes the next acetate group. The re-
/C~H/C~H/C~H/ action proceeds rapidly down the entire chain,
C C C unzipping the polymer. With vinyl acetate-eth-
I I I
000 ylene, the zipping is interrupted; therefore,
I I I rapid hydrolysis does not take place. In fact,
C-O C-O C-O
I I I test films of vinyl acetate-ethylene have been
CH, CH, CH, exposed to weak alkalis and acids for more than
Fig. 5. Polyethylene and polyvinyl acetate homopoly- a year without showing signs of deterioration.
mers.
Other Factors Affecting Adhesive
Properties
acetate-alkylmaleate or vinyl acetate-alkylacry-
late copolymer. In the case of vinyl acetate-eth- Polyvinyl acetate emulsions are among the most
ylene copolymers, the flexibility is achieved versatile bases for adhesives because they can
through much less steric hindrance, because the be modified during polymerization in many
acetate groups are not attached to alternate car- more ways than other resins used for adhesive
bons, and movement is not restricted along the compounding. Major changes can be made to
molecule (Fig. 7). Since the large, bulky side the adhesive properties of polyvinyl acetate by
chains are not present to achieve flexibility, changing the method of protecting the emul-
these polymers exhibit higher cohesive strength sion, by varying the glass transition tempera-
and much less creep. The use of polymer Tg as ture (Tg ), by modifying the degree of
a guide to latex specification for adhesive pur- branching, or by adding a variety of functional
poses has been described. 39 groups. These modifications may be made sin-
Another feature of the vinyl acetate-ethylene gly or in any combination of the above four.

H. H. H. H. H

/C~H/C~H/C~H/C~H/f~H/
C C C C c-o C
I I I I I I
o 0 0 0 0 c-o
I I I I I I
c-o c-o c-o c-o CH. 0
I I I I I I
CH, CH 3 CH 3 CH 3 CH. CH.
I I
CH. CH.
I I
CH 3 CH.
I
CH 3
Fig. 6. Vinyl acetate-dibutyl maleate copolymer.

H. H. H. H. H. H. H.

/C~H/C~H/C~H/C~H/C~H/C~H/C~
C C C C C C
I I I
0 0 0
I I I
C-O C-O c-o
I I I
CH, CH, CH,

Fig. 7. Vinyl acetate-ethylene copolymer.

 388 HANDBOOK OF ADHESIVES

As an indicator of the technical significance used with polyvinyl acetate) has a fine particle
to the adhesive industry of these emulsions, one size and a rather narrow particle size distribu-
finds 2,333 patents describing them and their tion.
uses listed in chemical abstracts from 1972 to Polyvinyl alcohol is a water-soluble mole-
the present. A total of 28 review articles have cule. It will therefore contribute a high degree
appeared worldwide in that time. 28 of wet tack to an emulsion that is not possible
with surfactant protection. Polyvinyl acetate
Protection by Colloids and/or Surfactants emulsions protected with partially hydrolyzed
polyvinyl alcohol have a combination of prop-
Polyvinyl acetate can be protected with colloid
erties usually described as "good machining, ' ,
systems, surfactant systems, or a combination
which include good flow, clean running, easy
of both. The type and amount of protection used
cleanup, and nonslinging or nonspitting. These
in the polymerization of polyvinyl acetate have
properties are generally not present in emul-
a great bearing on the physical properties of the
sions protected solely with surfactants. Surfac-
resin and on the working characteristics of the
tant-protected emulsions are much more
dispersion.
thixotropic than polyvinyl alcohol-protected
Table 3 compares emulsion and dried film
emulsions, and become thin under high-shear
properties controlled by the protection system.
conditions.
Since partially hydrolyzed polyvinyl alcohol is
Polyvinyl acetate emulsions set by losing
a poor emulsifier compared with a surfactant, a
water through evaporation into the air and also
polyvinyl acetate emulsion protected with this
by absorption into the porous substrates to
colloid would have a combination of large par-
which they are applied. 38 The polyvinyl acetate
ticles and a rather wide particle size distribu-
spheres in the emulsion pack together and form
tion. This combination of particle size and
capillaries which aid in the transport of the
distribution yields an emulsion that does not
water out of the film. The fine particles in an
change its viscosity very much as it experi-.
all-surfactant system form small capillaries
ences high shear conditions. On the other hand,
which drive water out at a rather rapid rate. In
an emulsion which is protected solely with a
a polyvinyl alcohol-protected system, the var-
surfactant (nonionic surfactants are generally
iously sized particles pack tighter and form
much finer capillaries, which drive the water
Table 3. How the Protection System out at a much more rapid rate. This causes the
Affects the Properties of an Adhesive emulsion to form a film and set more rapidly
Base. than an all-surfactant system.
Emulsion Properties- Emulsion Properties- The particles of polyvinyl acetate coated with
Colloid Protected Surfactant Protected partially hydrolyzed polyvinyl alcohol cannot
form a very tightly coalesced film. This is be-
Large particle size Fine particle size
Wide particle size dis- Narrow particle size cause polyvinyl alcohol has a higher Tg than,
tribution distribution and is not compatible with, polyvinyl acetate.
Strong wet tack Poor wet tack As a result, the dried film will have a hazy, flat
Good flow Poor flow appearance. This contrasts with a surfactant-
Good machining Relatively poor ma-
chining
protected acetate, which will coalesce more
Rapid setting Relatively slow set- tightly and will therefore form a clear, glossy
ting film. The dried film of a surfactant-protected
Near-Newtonian Thixotropic rheology emulsion will be much less water sensitive than
rheology (does not (thins with shear) that of a polyvinyl alcohol-protected emulsion.
shear thin)
This is attributable to the water solubility of
Film Properties- Film Properties- polyvinyl alcohol, and can be overcome to var-
Colloid Protected Surfactant Protected
ious degrees by crosslinking of the PVOH after
Hazy film Clear film film formation has occurred. 33 ,36,37
Flat film Glossy film Emulsions which combine surfactant and
Water sensitive Water resistant
colloid protection will display properties that
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 389

fall somewhere between those exhibited by col- The PVOH-protected emulsion has a greater
loid systems or surfactant systems alone. wet tack because of the water soluble polyvinyl
The effect of the protection system is illus- alcohol in its continuous phase. As discussed
trated in Table 4, which shows the properties earlier, polyvinyl alcohol protection contrib-
of three VAE copolymers with the same level utes to finer capillary formation and thereby
of ethylene and the same Tg • One is PVOH pro- promotes more rapid setting speed.
tected, one is surfactant protected, and the last The PVOH-protected emulsion and adhe-
is protected by a combination of surfactant and sives made with it spray very well in airless
cellulosic. spray systems, but relatively poorly in air spray
The first major difference among the three is systems.
that the PVOH-protected emulsion is incom- Table 4 further illustrates that the PVOH-
patible with borax and highly soluble dextrin, protected and the cellulosic emulsion are both
whereas the other two emulsions can accept excellent bases for adhesives to bond to poly-
these compounds without breaking. In addi- vinyl chloride. The PVOH-protected emulsion
tion, the PVOH-protected emulsion exhibits is usually chosen for wet laminations and the
less water resistance and more water spotting. cellulosic emulsion for heat-seal applications.
Water resistance denotes the ability of a lami- The surfactant emulsion shows much better
nation between two substrates, such as kraft adhesion to polystyrene than the other two
paper or cloth, to maintain its integrity or bond emulsions, but the other emulsions can be com-
strength after immersion in water for a speci- pounded with plasticizers and/or tackifier res-
fied time. Water spotting describes the appear- ins to make excellent polystyrene adhesive
ance of a dried film or emulsion after water is bases.
placed on that surface. A good or excellent film Though all three products exhibit the same
would not blush as rapidly as would the film glass transition temperature, the heat-seal tem-
indicated as fair. A lamination or bond made perature of the surfactant emulsion is below that
with the PVOH-protected emulsion has good of either the PVOH-protected or the cellulosic
water resistance, yet can be cleaned from ma- emulsions. Fig. 8 shows the difference between
chines more readily than the other two emul- the PVOH-protected and the surfactant emul-
sions. The water resistance of the PVOH- sion in laminating films of polyvinyl chloride
protected emulsion permits its use in glue laps, to each other, using a heat-seal technique. In
bag-seam adhesives, and polyvinyl chloride- this case, each emulsion was coated onto a PVC
laminating adhesives. film, allowed to dry, then heat sealed at the

Table 4. How Protection System Affects the Properties of

Three VAE Emulsions.
Protection System
Polyvinyl Nonionic Surfactant and
Propeny Alcohol Surfactant Cellulosic
Borax compatibility none good good
Dextrin compatibility poor good good
Water resistance good excellent very good
Water spotting fair excellent good
Wet tack excellent poor poor
Set speed rapid slower slower
Sprayability poor excellent excellent
PVC adhesion excellent fair excellent
Polystyrene adhesion fair excellent good
Heat sealability good fair excellent
Thickening response high moderate low
Solvent reactivation good fair excellent
Compatibility with rubber fair good excellent
Latices
390 HANDBOOK OF ADHESIVES

Effect of Heat-Sealing Temperature 60

on Two Types of Emulsions
10.5 .....--------~_ _
50

9
.5 ~
u
40
iii 0
e.
0
.~
<::
g >
l-
30
ii)
:I: 0
I- U
Cl 5 til
z :> 20
w
a:
I-
til
..J 10
W
W
11.
5
1.2
0.5 0 10 20 30
0~-r_~--,_~r__r-~_1
PARTS OF DIBUTYL PHTHALATE
o 80 90 100 110 120 130 140 (DBP)/l00 PARTS EMULSION
HEAT SEALING TEMPERATURE (OC)
Fig. 8. Peel strength of PVC-to-PVC bonds. 1. Brookfield Viscometer. Model RVF at 20 rpm. 2SoC.

Fig. 9. Thickening response of two Airflex emulsions to

plasticizer.
temperatures shown on the horizontal axis. The
laminations were then separated on an Instron®
tester. The measured resistance to delamination sive. This technique would be used if two non-
is shown on the vertical axis of the chart. It porous surfaces were to be joined together and
should be noted that the emulsions can be it was not possible to use heat to soften and
blended to obtain intennediate adhesion val- reactivate the adhesive. In this situation, small
ues. amounts of solvent could be used to reactivate
Plasticizer and solvent thickening response the adhesive, resulting in very low emissions.
are other important compounding properties This technique would also take advantage of
controlled by the protection system used in the much higher molecular weight, and there-
polymerization. Fig. 9 clearly shows that the fore greater tensile strength, of an emulsion-
polyvinyl alcohol-protected emulsion thickens polymerized adhesive resin compared with a
much more rapidly than the surfactant and cel- solvent-polymerized resin.
lulosic-protected emulsions. The rapid thick-
ening response of the PVOH-protected
emulsion is an economic advantage in com- Advantages of Polyvinyl Alcohol
pounding many packaging adhesives. There are Protection
times, however, when it is necessary to have a
high-solids, low-viscosity adhesive that con- As a protection system, polyvinyl alcohol con-
tains high amounts of either plasticizer or sol- fers unique properties on emulsions stabilized
vent. The surfactant emulsion would then have with it. Since polyvinyl alcohol enhances the
an advantage over the PVOH-protected emul- adhesive properties of polyvinyl acetate to such
sion; but again, it is possible to blend these two a great degree, a majority of adhesive emul-
emulsions to obtain intennediate properties. sions use this protection system. In addition to
The protection system used with polyvinyl the advantages listed in Table 5, polyvinyl al-
acetate emulsions also affects solvent reactiva- cohol-protected emulsions are easily modified
tion. Solvent reactivation describes the tech- to reinforce specific adhesive properties. Im-
nique whereby dried adhesive films are wet portantly, the resulting compounds exhibit ex-
with solvents in order to reactivate the adhe- cellent stability.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 391

Table 5. Advantages of Polyvinyl 45

Alcohol Protection
;35
Good machinability
Easy cleanup
Good wet tack 25
Rapid setting speed
Rapid thickening response
15
Good heat resistance ~ VAc Homopolymer
Low degree of blocking 01
I-
Crosslinkability 5

-5
POLYMER STRUCTURE AND
PROPERTIES -15

Glass Transition Temperature -25

0 5 10 15 20 25
As indicated in Table 6, the glass transition
PARTS OF DIBUTYL PHTHALATE
temperature (Tg) has notable effects on prop- (DBP)/100 PARTS EMULSION
erties of adhesive emulsions. Varying the
amount of ethylene incorporated into a copol- Fig. 10. Effect of plasticizer on Tg of two emulsion types.

ymer has a direct relationship to the Tg : the

more ethylene, the lower the Tg • The glass
transition temperature affects such properties as Measured in % Bond Retention
flexibility, water resistance, PVC adhesion, 15~--------------------~

paper adhesion, and setting speed. The three

emulsions in Table 6 are all protected with ~
z
polyvinyl alcohol. The major difference among 0 10
j:::
them is the ethylene content as illustrated by z
UJ
the Tg • It should be noted that water resistance I-
UJ
a::
and ease-of-cleanup are inversely related. 0 5
z
The glass transition temperatures of polyvi- 0
al
nyl acetate emulsions may be lowered further
by adding a plasticizer such as dibutyl phthal- O~~~----~--~--~--~
ate (Fig. 10). Plasticizer addition will, in turn, o 5 10 15 20 25
PARTS OF DIBUTYL PHTHALATE
increase water resistance (Fig. 11). (DBP)/100 PARTS EMULSION
1. Cloth to cloth bonds
Branching
Fig. 11. Effect of plasticizer on water resistance of two
The linearity of a polyvinyl acetate resin can emulsion types.
be controlled during the polymerization pro-

Table 6. Effect of Tg on the Properties of Three VAE

Emulsions
Propeny Tg (O°C) Tg (-20°C) Tg (-30°C)

Wt % -CH2 -CH2 - (approx.) 17% 25% 31%

Water resistance good fair poor
PVC adhesion excellent poor poor
Paper adhesion excellent good fair
(Clay-coated board)
Setting speed excellent good fair
 392 HANDBOOK OF ADHESIVES

cess. Conditions such as high temperature and Table 7. Peel Strengtha of Cloth-to-
high catalyst concentration can favor the for- Metal Bondsb (lbs./linear in.)-Effect of
mation of pendant or branched segments on the Carboxyl Functionality on Vinyl Acetate-
linear chain. 29 This branching will increase Ethylene Polymers
tensile strength and toughness of the polymer. Conventional Vinyl Carboxylated Vinyl
It will also increase the heat resistance (creep Acetate-Ethylene Acetate-Ethylene
resistance) and reduce the tackiness of the pol- Aluminum 0.4 . 1.8
ymer's dried film. A branched polyvinyl ace- Brass 0.8 4.5
tate emulsion will accept greater amounts of Copper 0.6 3.9
polar and water-miscible solvent without Galvanized steel 0.6 3.5
breaking (destabilizing) than will a linear type. Lead 0.7 1.4
Steel 1.3 4.1
Some effects of branching and chain structure
'T Peel (180 0 peel on Instron~ tester, 2 in.lmin).
on adhesion have been reported. 34 bCotton poplin cloth. Laminated wet. Dried 24 hours.

Functional Groups
acetate-ethylene polymer adheres much better
Polyvinyl acetate emulsions can be further to metal substrates.
modified by the incorporation of functional The incorporation of a carboxyl functionality
groups. These groups permit the design of pol- reduces the softening range of vinyl acetate-
ymers which have the ability to bond a wider ethylene resin while enhancing its adhesion.
spectrum of surfaces, including difficult-to- Fig. 12 shows the difference in adhesion be-
bond substrates. The addition of functional tween carboxylated vinyl acetate-ethylene and
groups also permits crosslinkability of the pol- conventional vinyl acetate-ethylene polymer
ymer in order to achieve a high degree of water, when each is used as a heat-seal adhesive for
solvent, or heat resistance. bonding two pieces of commercial polyvinyl
N-Methylolacrylamide is commonly used to chloride film. For test purposes, these emul-
manufacture self-crosslinking vinyl acetate
polymers. 12
Rigid polymers are available which can be
used to make highly water resistant wood ad- 11
hesives. Other copolymers are available which
.5 10
are flexible enough to be used as water or sol- :a
G>
vent resistant nonwoven binder or as flocking .S
:::;
9
adhesives. The N-methylolacrylamide copol- g,
8
ymer will usually require the addition of an acid J:
I-
C!l
salt and a heat cure to achieve the desired ef- z 7
w
fect. a:
I-
CIl 6
Carboxyl functionality in a vinyl acetate-eth-
ylene emulsion offers three advantages over
noncarboxylated products. They are; increased
adhesion to metals and polymeric surfaces; re-
active sites for crosslinking; and a means for
thickening. 150 160 170 180 190 200 210
Carboxyl functionality increases the adhe- HEAT SEAL TEMPERATURE (OF)
sion of vinyl acetate-ethylene to several metals 1. Adhesion of PVC to PVC film; heat-sealed
on a Sentinel Heat Sealer using constant
(Table 7). A conventional vinyl acetate-ethyl- pressure of 40 psi; 8 seconds dwell time.
ene and a carboxylated vinyl acetate-ethylene
Fig. 12. Effect of carboxyl functionality on heat-seal
polymer both may have the same glass transi- adhesion. Adhesion of PVC to PVC film. Heat sealed on
tion temperature and the same ratio of vinyl a sentinel heat sealer using constant pressure of 40 psi; 8
acetate to ethylene, but the carboxylated vinyl seconds dwell time.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 393

WITH UREA carboxylated vinyl acetate-ethylene with ami-

FORMALDEHYDE (AMINOPLASn RESIN
noplast increases the polymer's water and creep
o resistance, especially when the bond is heat-
II cured (Table.S).
o CH.OH /CH.o-c-a
II /
2R-C-OH + R, _R, 0 +2H;o
COMPOUNDING
\ \ II
CH.OH CH,O--C-R
Many polyvinyl acetate emulsions can be used
as adhesives without modification. However,
WITH PHENOLIC RESIN
an adhesive is usually compounded in order to
tailor the product for a particular application.
o

¢
o Compounding of adhesives facilitates applica-
II tion on equipment and bonding on specific sub-
2R--C-OH +
strates. It also imparts resistance to ambient
conditions. In addition to film formers, an ad-
CH.OH
hesive usually contains some of the following
WITH EPOXY RESIN
components; plasticizers, viscosity/rheology
modifiers, tackifiers/extenders, solvents, fill-
R, R, 0 ers, humectants, surfactants, and biocides.
I I II
o HC\ HC-O-C--R

2RJLOH + I 0- I ~ +H.O
Plasticizers
Copolymer emulsions are flexible and soft be-
HC/ HC-O-C-R
I I cause of bulky pendant groups or flexible back-
R, R,
bones. Polyvinyl acetate homopolymer
Fig. 13. Reactions of a carboxylated vinyl acetate-eth- emulsions series are hard and stiff due to the
ylene emulsion. steric hindrance of the acetate groups and the
strong intermolecular attraction. Any of these
sions were coated on one piece of film, allowed emulsion families may be compounded with
to dry, and then heat-sealed to the uncoated plasticizers to increase flexibility.
PVC film. Carboxylated vinyl acetate-ethylene Plasticizers are added to reduce the inter-
polymer will react with aminoplast, phenolic, molecular attraction of the polyvinyl acetate
and epoxy resins (Fig. 13). The reaction of the polymers. They cause the polyvinyl acetate

Table 8. How the Reaction of Carboxylated VAE Emulsion

with Urea Formaldehyde (Aminoplast) Resin Affects Water
and Creep Resistance. a
Peel Strength b (Ibs/linear inch)
Wet Wet Creep mm/minb
Pans UF Resin Dry (uncured) (cured)" (cured)"

0 13.0 3.0 5.8 0.96

3-Beetle 60 12.8 3.2 7.1 0.58
5-Beetle 60 12.6 3.4 7.4 0.23
10-Beetle 60 12.0 4.0 7.5 0.25
3-Beetle 65 12.0 2.9 8.3 0.36
5-Beetle 65 11.8 3.1 8.2 0.23
10-Beetle 65 11.0 3.6 7.9 0.01
Tests used cotton poplin to cotton poplin bonds. Cloth was laminated, then dried 7 days at room
temperature.
'T Peel (180° peel on Instron~ tester, 2 in.lmin).
~ Peel (500 g static load/linear/in., I70°F).
'Cured for 5 minutes at 275°F.
394 HANDBOOK OF ADHESIVES

particles to swell; this raises the viscosity of the 45

emulsion (Fig. 14) and destabilizes it for faster
breaking and setting speeds. In addition, the 35
resin particles in the emulsion gain mobility.
Increased mobility helps the resin to wet 25
smooth, nonporous surfaces, (e.g., films, foils,
and coated papers) and consequently to in- 15
crease its adhesion to these surfaces. More- E
over, softened polymer particles coalesce more ....C> 5
rapidly and more completely at lower temper-
atures. -5
When added to an emulsion, plasticizers will
also lower the glass transition temperature ( Tg) -15
of the polyvinyl acetate film, making it softer
and more flexible (Fig. 15). Finally, plasticiz-
25
ers will increase the tackiness of the film, re-
PARTS OF DIBUTYL PHTHALATE
duce its heat-sealing temperature, and improve (DBP)/l00 PARTS EMULSION
its water resistance (Fig. 16).30.31 Fig. 15. Effect of plasticizer on Tg of two emulsion types.
The general-purpose plasticizers listed in Ta-
ble 9 can be added to polyvinyl acetate homo-
polymer and copolymer emulsions. Fire- Viscosity IRheology Modifiers
retardant plasticizers, which are occasionally Adhesives are most commonly applied by ma-
needed, are also listed. chine. Each type of machine has its own vis-
cosity/rheology requirements. Most roll
applications use adhesives with a viscosity of
l00r---------------------~
1500-3000 cp and operate best with a slightly
thixotropic flow. Sprays require a more New-
tonian flow and use viscosities in the 200-800
cp range. Construction adhesives are applied
through a gun or trowel and use thixotropic or
pseudoplastic, high viscosity materials. The
proper choice of thickener will control viscos-
nu ity as well as rheology.

~ Measured in % Bond Retention

...>
8
Ul
;;;
15~--------------------~

~ 10
i=
z
w
....
w
a:
c 5
z
~ VAc Homopolymer

o 10 20 30 40 50 25
PARTS OF DIBUTYL PHTHALATE (DBP)I PARTS OF DIBUTYL PHTHALATE
100 PARTS EMULSION (DBP)/l00 PARTS EMULSION
Fig. 14. Thickening response of homopolymer emulsion Fig. 16. Effect of plasticizer on water resistance of two
to plasticizers. emulsion types.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 395

Table 9. Plasticizers. lulosic, and fumed silica will also confer

General Purpose Fire Retardant pseudoplasticity.
Thickeners that can be added to all homo-
Acetyl tributy I citrate Cresyl diphenyl phos-
*Butyl benzyl phthalate phate
polymer and copolymer polyvinyl acetate ad-
Butyl phthalyl butyl *Tricresyl phosphate hesive emulsions include those shown in Table
glycolate Triphenyl phosphate 10.
*Dibutyl phthalate
Dibutyl sebacate Tackifiers/Extenders
Diethyl phthalate
*Diethylene glycol diben- Tackifiers increase the tackiness and the setting
zoate speed of adhesives. They increase tackiness by
Dipropylene glycol
*Dipropylene glycol di-
softening the polyvinyl acetate polymer, both
benzoate in the wet and in the dry adhesive film. They
Ethyl phthalyl ethyl gly- accelerate setting speed by raising the total sol-
colate ids content of the emulsion. This action has the
Ethyl-p-toluene sulfona- twofold result of "crowding" the aqueous
mide
Hexylene glycol
phase and making the emulsion less mechani-
Methyl phthalyl ethyl gly- cally stable.
colate Tackifier resins often increase the affinity of
Polyoxyethylene aryl adhesives for specific surfaces such as plastics
ether and metal foils. They also lower the softening
Tributoxyethyl phthalate
and heat-sealing temperatures of adhesive
*Denotes most frequently used.
films.
Tackifiers are insoluble in the continuous
Thickeners added to an adhesive will raise (water) phase of the emulsion and must be dis-
viscosity and pennit dilution with water. This solved in organic solvents and/or plasticizer
reduces the total solids of the adhesive and thus before they can be added.
lowers its (wet) cost. Thickeners release water By virtue of adding to the adhesive properties
slowly, and when combined with lower solids, of the polyvinyl acetate emulsion, tackifiers are
they also slow the setting (prolong open time) also extenders. (Most are too brittle to act as
of the adhesive. Thickeners such as polyvinyl adhesives in their own right and need the
alcohol, starch, and hydroxyethyl cellulose will toughness of polyvinyl acetate in order to func-
improve adhesion to porous substrates by re- tion). By raising the total solids content of the
ducing penetration of an emulsion into the sub- emulsion, tackifiers accelerate the breaking and
strate and decreasing the likelihood of a setting speeds and may reduce the cost of the
"starved joint. " adhesives to the extent that the active (polyvi-
Some thickeners can prevent adhesives from
spitting and throwing during high-speed appli- Table 10. Thickeners
cations. They pennit them to transfer cleanly
Alginates
and break short rather than draw to fibers. Bentonite
Polyvinyl alcohol is a good example of this type Casein
of thickener. Polyvinyl alcohol is also recom- Fumed silica
mended for high speed roll application because Guar gum
it does not shear thin as do other thickeners. Gum tragacanth
*Hydroxyethylcellulose
Some other specific effects of polyvinyl alcohol Locust bean gum
on emulsion adhesive properties have been re- *Methylcellulose
ported. 32 Polyacrylic acid salts (ammonium, potassium, sodium)
Pseudoplastic (shear thinning) adhesives can **Polyvinyl alcohol
be prepared by adding polyacrylates such as so- *Sodium carboxymethyl cellulose
*Starches
dium or ammonium polyacrylate. Starch, cel-
396 HANDBOOK OF ADHESIVES

nyl acetate) solids can be diluted by adding 100~--------------------,

water.
Plasticizers, solvents, tackified (borated) and
untackified polyvinyl alcohol, and certain
polyvinyl emulsions impart wet tack to poly-
vinyl acetate emulsions. Those additives spe-
cifically designated as tackifiers are listed in
Table 11.
ii
u
10
Solvents ~
Because of their volatility, solvents perform
...iii>
0
like plasticizers oom temporary basis. Solvents 0

increase the viscosity over that of emulsions;

'"
:>

they also dissolve wax or resin coatings, accel- 1.1.1. Trichloroethane

erate setting speed, reduce film-forming tem-
perature, reduce adhesive (wet) cost, increase
wet tack, dissolve tackifiers, and lower the
freezing point.
Like plasticizers, solvents cause the polyvi-
nyl acetate particles to soften and swell, raising
10 20 30 40 50
the viscosity of the emulsion (Fig. 17). Higher PARTS SOLVENT PER
viscosity allows dilution of the adhesive with 100 PARTS EMULSION -

water, thus reducing the adhesive wet cost. 1. Brooklield Viscometer, Model RVF at 20 rpm,
2S·C
Swelling and softening also destabilize the Fig. 17. Thickening response of homopolymer emulsion
emulsion. This increases the setting speed and to two solvent types.
also allows the adhesive to coalesce into a film
more rapidly and at a lower temperature than impart the necessary speed to the wet adhesive,
the neat emulsion. The improved coalescence but because they are volatile, will not cause the
results in greater water resistance for the film. dried bond to creep.
Low-boiling solvents impart only wet tack to Solvents promote adhesion to solvent-sensi-
the adhesive film, whereas high-boiling sol- tive adherends (plastic films and reconstituted
vents confer both dry and wet tack and lower cellulose films) by swelling and partially dis-
the heat sealing temperatures. High-boiling solving them, thus allowing the adhesive to wet
solvents behave like plasticizer except for and/or penetrate the surface. Coated adherends
eventual evaporation from the film. This evap- that resist adhesion, such as printed, lacquered,
oration aids wood glue or packaging adhesives or waxed papers, may also be partially dis-
that require fast setting speeds. Solvents can solved by solvents to promote adhesion. (Chlo-
rinated solvents are particularly effective on
Table 11. Tackifiers waxed surfaces).
Tackifier resins are usually dissolved in a
*Coumarone-indene
Ester gum solvent or a blend of solvent and plasticizer be-
Gum rosin fore being added to a polyvinyl acetate emul-
*Hydrocarbon resins sion. The compounded solvent and resin has a
Hydrogenated rosin crowding effect on the emulsion, which results
Phenolic modified hydrocarbon resins
in destabilization and a rapid setting speed.
*Rosin esters
Tall oil rosins The choice of solvents used with polyvinyl
Terpene phenolic acetate homo and copolymer emulsions de-
Terpene resins pends on the nature of the individual emulsion,
Toluenesufonamide-formaldehyde resin and importantly, on the degree of branching of
Wood rosin
each emulsion. For instance, highly branched
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 397

emulsions are more compatible with water- cooked starch fillers, in particular, reduce the
miscible solvents than other lesser-branched cold flow in wood glues.
emulsions. Clays and other fillers impart stiffness to ad-
Table 12 classifies various solvent types as hesive films. Clays reduce the penetration of
water-miscible or water-immiscible. adhesives into porous substrates. Large-parti-
cle clays are better able to control penetration
and also impart more rapid setting speed. A
Fillers
highly plastic clay, bentonite, makes adhesives
Fillers are added to emulsion adhesives to re- thixotropic-fluid under high shear, thicker
duce cost by replacing resin solids without de- upon application. A study has been made 3l of
creasing total solids, to reduce penetration into the effect of various fillers on the adhesive
porous substrate, and to change the rheology of properties of polyvinyl acetate.
the compound. Depending on their individual Table 13 lists general purpose fillers than can
properties, fillers can also add stiffness and be added to all polyvinyl acetate homo- and co-
strength or decrease tack and blocking. Un- polymer adhesive emulsions.

Table 12. Water Miscibility of Various Solvent Types.

Solvents Water Miscible Water Immiscible
ALCOHOLS
Ethanol •
*Isopropanol •
Methanol •
Chlorinated Compounds
Ethylene dichloride •
Methylene chloride •
Perchlorethylene •
*1, 1, 1-Trichlorethane •
Trichloroethylene •
Esters
Ethy I acetate •
Methyl acetate •
n-Butyl acetate •
Glycols, Ethers, and Oxides
Diethylene glycol diethyl ether •
Diethylene glycol monobutyl ether •
Diethylene glycol monoethyl ether •
Diethylene glycol monomethyl ether •
Dioxane •
Ethylene glycol monoethyl ether •
Ethylene glycol monobutyl ether •
Lower glycol ethers •
Hydrocarbons
Mineral spirits •
Naphtha •
*Toluene •
Xylene •
Ketones
Acetone •
Cyclohexanone •
Diacetone alcohol •
Isophorone •
*Methyl ethyl ketone •
Methyl isobutyl ketone •
Miscellaneous
Tetrahydrofuran •
398 HANDBOOK OF ADHESIVES

Table 13. Fillers. Table 15. Wetting Agents.

Bentonite Nut shell flours Alkyloxyl polyether alcohols
*Calcium carbonate Silica Dodecyl benzene sodium sulfonate
Calcium silicate Talc Polyoxy ethylene sorbitan monooleate
*Clay *Uncooked starches *Sodium alkyl benzene sulfonate
Mica Wood flour *Sodium dioctylsulfosuccinate
Sodium tetradecyl sulfate
*Acetylenic glycols
Humectants Tetrasodium pyrophosphate

A humectant is a hygroscopic substance, one

that absorbs and retains moisture from the Therefore, these should be added in minimal
atmosphere. In. emulsion adhesives, humec- amounts.
tants prevent the surface of the compound from Wetting agents that can be used with poly-
skinning by keeping it wet. When polyvinyl al- vinyl acetate homo- and copolymer emulsions
cohol or starch is present, the humectant holds are listed in Table 15. The effect of various sur-
water, which plasticizes these materials and factants on PV Ac latex film structure and prop-
keeps them flexible after drying. By retarding erties has been studied. 33
drying, humectants also slow setting speed and
extend the open time of the adhesive. Foam Control Agents
Humectants suitable for use in polyvinyl ace-
Foam control agents include antifoam and de-
tate homo and copolymer adhesive emulsions
foamer compounds. Foam causes problems in
are shown in Table 14.
the manufacturing and the application of ad-
hesives. Air in the formulation increases vis-
Wetting Agents
cosity, which can be misleading when adding
The surface-active agents (surfactants) added ingredients. A misleading viscosity also pre-
to polyvinyl acetate form two classes: wetting vents accurate metering during application of
agents and foam control agents. the adhesive, thereby preventing the deposit of
Wetting agents aid the adhesive to wet the sufficient solids on the glue line.
surface of the adherend, thereby improving A small amount of foam control agent, 0.1-
adhesion. When a vinyl acetate-ethylene poly- 0.2 % of the adhesive, is usually sufficient to
mer is used to bond PVC, the secondary plas- prevent or break foam.
ticizers in the film may exude to the surface, A foam control agent should be pretested in
making the film very difficult to wet and bond. each new adhesive formulation and each time
The addition of a good wetting agent amelio- an ingredient is changed. Changing the amount
rates this situation. of an ingredient can change foam control re-
Wetting agents help water penetrate the sur- quirements. The adhesive sample should age 6-
face of an adherend. This allows the polymer 8 weeks before analysis of foam control effi-
particles to coalesce and set rapidly. These ciency. Some foam controllers may emulsify or
compounds also disperse solids throughout the separate upon aging.
adhesive, which reduce settling.
Many of the anionic wetting agents cause Biocide
foaming if used to excess, and may also in-
Biocides are required when animal or vegetable
crease the water sensitivity of the adhesive film.
substances or their derivatives (starches, casein
and other proteins, nut shell flours, sugar, and
Table 14. Humectants. cellulosic resins) are incorporated into polyvi-
Calcium chloride Sodium nitrate nyl acetate homo- or copolymer emulsion ad-
Diethylene glycol Sorbitol hesives. Growing microorganisms digest these
*G\ycerine *Sucrose substances and can generate foul odors, dis-
Hexylene glycol *Urea
*Propylene glycol
color the adhesive, lower its viscosity, and
weaken the bond.
 POLYVINYL ACETATE EMULSIONS FOR ADHESIVES 399

Table 16. Recommended Modifiers- Trademarks and Suppliers.

Plasticizers Thickeners
Abalyn® Hercules Inc. Natrosol® Hercules
Hercoflex® Hercules Inc. Cellosize® Union Carbide
Hercolyn® Hercules Inc. Methocel® Dow Chemical
Benzoflex® 2-45, 9-88, 50 Velsicol Chemical Corp. Polyco® 296W Borden Chemical
Pycal® 95 ICI Americas Polyoxy® WSRN 750 Union Carbide
Celluflex® CEF Stauffer Chemicals Carbopol® BF Goodrich Chemical
Resoflex® 296 Cambridge Industries Co.
Santicizerlll 8, 160, M17, Monsanto
140, 141 Solvents

Tackifiers-Extensing Resins Chlorothene® Dow Chemical Co.

Cellosolve® Union Carbide
Hercolyn® Hercules Carbitol® Union Carbide
Polpale® Resin Hercules
Stabelite® Ester 3, 10 Hercules Surfactants
Piccolite® Hercules
Surfynol® Air Products and Chemi-
Piccoflex® Hercules
cals, Inc.
Piccolastic® Hercules
Aerosol® OT American Cyanamid
Piccopale® Hercules
Nopcowet® 50 W. R. Grace and Co.
Foral® 85 Hercules
Foamasterlll JMY W. R. Grace and Co.
Vinsol® Hercules
Tween® ICI Americas
Santolite® MS Monsanto
Colloid® 682, 770 Colloid Inc.
MHP, MS80
Drew® 11250 Drew Chemical Corp.
Bakelite® CKM2400 Union Carbide
Bakelite® CKM2432 Union Carbide
Preservatives
Bakelite® CKROO36 Union Carbide
Bakelite® CKR2103 Union Carbide Dowicide® A, G Dow Chemical Corp.
Nevillac® Neville Chemical Co. Dowicil® 75 Dow Chemical Corp.
Proxcel® GXL ICI Americas
Thickeners
Merbac® 35 Merck and Co., Inc.
Cabosil® Cabot Corp. Kathon® LX Rohm and Haas

The inclusion of 0.1-0.2% of a biocide, The grade numbers indicated may not be ex-
based on the total wet weight of the formula- haustive of all those available; however, these
tion, prevents microbial growth. Nevertheless, are the most highly recommended.
microbes frequently adapt to a specific biocide
and flourish. Biocides should be changed reg- BIBLIOGRAPHY
ularly to prevent this occurrence.
1. Daniels, W. E., "Poly(Vinyl Acetate)" in "Kirk-
Polyvinyl Alcohol Othmer Encyclopedia of Chemical Technology," 3rd
Ed., pp. 817-847, New York, John Wiley and Sons,
Polyvinyl alcohol, a first class adhesive in its 1983.
2. Schildknecht, C. A., "Vinyl and Related Polymers,"
own right, also serves as an excellent additive
pp. 323, New York, John Wiley and Sons, 1952.
for modifying the properties of polyvinyl ace- 3. Skirrow, F. W., and Herzberg, O. W., U.S. Patent
tate emulsion adhesives. See Chapter 22 of this 1,638,713 (to Shawinigan Resins).
volume. 4. Hydrocarbon Processing, 46(4), 146 (1967).
5. Petroleum Refiner, 38, 304 (1959).
TRADEMARKS AND SUPPLIERS 6. Vinyl Acetate, Bulletin No. S-56-3, Celanese Chem-
ical Co., New York, 1969.
Table 16 lists the most commonly used modi- 7. Vinyl Acetate Monomer, F4l519, Union Carbide Co.,
New York, 1967.
fiers listed by their brand names and respective
8. Vinyl Acetate Monomer, BC-6, Borden Chemical Co.,
manufacturers. These modifiers are classified New York, 1969.
by functional uses, such as plasticizer, tacki- 9. Vinyl Acetate Monomer, Air Reduction Co., New
fiers, thickeners, solvents, and preservatives. York, 1969.
400 HANDBOOK OF ADHESIVES

10. Horsley, L. H., "Azeotropic Data II," Advances ogy," 1st Ed., pp. 691-709; 2nd Ed., pp. 317-353;
Chern. Ser. No. 35, Washington, DC, American 3rd Ed., pp. 817-847.
Chemical Society, 1962. 23. Mayne, J. E., and Warson, H., Brit. Patent 627,612.
11. Lindeman, M. K., in "Vinyl Polymerization," Vol. 24. Lenney, W. E., and Daniels, W. E., U.S. Patent
I, G. E. Ham (ed.), New York, Marcel Dekker Inc., 4,164,489 (1979) (to Air Products).
1967. 25. Kissipanides, C., MacGregor, J. P., and Hamiliec, A.
12. Lindeman, M. K., in "Encyclopedia of Polymer Sci- E., Can. J. Chem. Eng .• 58(1),48 (1980).
ence and Technology," Vol. 15, N. Bikales (ed.), 26. Elgasser, M., Vanderhott, J. W., Misra, S. C., and
New York, John Wiley and Sons, 1971. Pichot, C., J. Polym. Sci. Leu. Ed.• 17,567 (1979).
13. Rekusheua, A. F., Russ. Chem. Rev.• 37, 1009 27. Chem. Mark. Rep. 23(4),24 (1987).
(1968). 28. Chern. Abstracts On-Line: "PVAc and PVAc/E as
14. Swem, D., and Jordan, E., in "Organic Synthesis Adhesives. "
Coli." Vol. 4, N. Rabjohn (ed.), New York, John 29. Stein, D., and Schulz, G. V., Makromol. Chemie.
Wiley and Sons, 1963. 125,48 (1969).
15. Klatte, F., U.S. Patent 1,084,581 (1914) (to Chem- 30. Hommaner, A., Adhaesion. 28(3), 13-6 (1984).
ische Fabriken Griesheim). 31. Hommaner, A., Adhaesion. 28(5), 26-31 (1984).
16. Klatte, F., Dokumente Aus Hoeschster Archiven. 10, 32. Hommaner, A., Kunstharz-Nach. 21,30-2 (1984).
47 (1965). 33. Vijayendran, B. R., and Bone, T. J., Disp. Sci. Tech.
17. Hemnan, W.O., Deutsch, H., and Baum, E., U.S. 3(1), 81-97 (1982).
Patent 1,790,920 (1931) (to Wacker Chimie). 34. Cheng, J. T., CA 103(16): 124207u.
18. Klatte, F., and Rollet, A., U.S. Patent 1,241,738 35. Freiden, A. S. Derevoabrab. Prom. (9), 17-19 (1980);
(1914) (to Chemische Fabriken Griesheim). CA (94)18: 140786b.
19. Hermann, W.O., and Haehnel, W., U.S. Patent 36. Sedliacci, K. CA 96(10): 70039a.
1,710,825 (1928) (to Wacker Chimie). 37. Hommaner, A., Kunstharz-Nach., 18,26-34 (1982).
20. Skirrow, F. W., U.S. Patent 1,872,824 (to Shawini- 38. Inoue, M. Mitsuo, and Lepoutre, P., CA 100(4):
gan Resins). 23697e.
21. Hermann, W.O., and Baum, E., U.S. Patent 39. Fisher, K., ChemiefasernlTextile Ind .• 36(7-8), 589-
1,586,803 (to Wacker Chimie). 92 (1986).
22. "Kirk-Othmer Encyclopedia of Chemical Technol- 40. Rosenblum, F. M., Adhesives Age No.6, June 1972.
 22
PolyNinyl Alcohol) for Adhesives
HAROLD L. JAFFE
Chemical Consultant
Millburn, New Jersey
and
FRANKLIN M. ROSENBLUM
Air Products and Chemicals, Inc.
Allentown, Pennsylvania

Poly(vinyl alcohol) (PVOH) is a water-soluble Poly(vinyl alcohol) also contributes to emulsi-

synthetic resin. It is produced by the hydrolysis fication and stabilization of aqueous disper-
of poly(vinyl acetate); the theoretical mon- sions.
omer, CH2 =CHOH, does not exist. Discovery The main uses of PVOH in the United States
of PVOH was credited to German scientists W. are in textile and paper sizing, adhesives, and
O. Herrmann and W. Haehnel in 1924, and the emulsion polymerization. Significant volumes
polymer was commercially introduced into the are also used in such diverse applications as
United States in 1939. I joint cements for building construction, water-
Poly(vinyl alcohol), also known as polyvinyl soluble film for hospital laundry bags, emulsi-
alcohol, is a dry solid and is available in gran- fiers in cosmetics, temporary protective films
ular or powdered form. Grades include both the to prevent scratching of highly polished sur-
fully hydrolyzed form on poly(vinyl acetate) faces, and soil binding to control erosion.
and products containing residual, i.e., unhy- Poly(vinyl alcohol) is an intermediate in the
drolyzed, acetate groups. Resin properties vary production of poly(vinyl butyral), the adhesive
according to the molecular weight of the parent interlayer in laminated safety glass. Outside the
poly(vinyl acetate) and the degree of hydroly- United States, PVOH is also used for textile
sis. A wide range of grades is offered by PVOH fiber, although it must be chemically treated to
manufacturers . become water-insoluble. 2 Poly(vinyl alcohol)
The wide range of chemical and physical fiber is produced in Japan and the People's Re-
properties ofPVOH resins has led to their broad public of China for captive use.
industrial use. They are excellent adhesives and
highly resistant to solvents, oil, and grease.
PHYSICAL PROPERTIES
Poly(vinyl alcohol) forms tough, clear films
that have high tensile strength and abrasion re- The physical properties of PVOH are con-
sistance. Its oxygen-barrier qualities are supe- trolled by molecular weight and the degree of
rior to those of any known polymer; however, hydrolysis. The upper portion of Fig. 1 shows
PVOH must be protected from moisture, which the variation in properties with molecular
greatly increased its gas permeability. weight at a constant degree of hydrolysis. 3 Hy-

401
402 HANDBOOK OF ADHESIVES

given in the lower portion of the figure. Since

, _• • v'.coalty
hydrolysis and molecular weight can be inde-
'nc...... block re.'alenc. pendently controlled in the manufacturing pro-
'nc...... flexlbI'lty 'nc...... 1M.'" alrengI/I cess, a product matrix has evolved that provides
'nc...... Iftl• • en.lllvlty 'nc...... l1/li""re.,m_
the property balance needed for different appli-
'nc...." .... of .otv.1Jon 'nc.......he.1IIe aIrengI/I
Inc...... • ofvenI ,..,mnc. cations. The PVOH product matrix has four
'nc...... d'.per.'ng poww important molecular weight ranges and three
MoIecu'ar weight key hydrolysis levels, although intermediate
products are available (see Specifications).
Various physical properties are listed in Table
% Hydroly.'.
1.
'ncr. . . . flexlbl'lty 'ncr. . . . wal. re.'.lance
'nc...... d'.per.'ng poww 'ncr..... len.ne alreng!h
'nc...... block re.'alance
SOLUBILITY
'nc...... wa"" .en.lllvlty
'nc...... adhe.,on 10 'nc...." aofvenI ,..,mnce All commercial PVOH grades are soluble in
hydrophobic .urfac•• 'nc...... adhe.1on 10
hydrophilic surface.
water, the only practical solvent. The ease with
which PVOH can be dissolved is controlled
primarily by the degree of hydrolysis. Fig. 2
shows the effect of degree of hydrolysis on sol-
Fig. I. Properties of poly(vinyl alcohol).
ubility with other variables held constant. Fully
hydrolyzed products must be heated close to the
atmospheric boiling point of water to dissolve
Table 1. Physical Properties of
completely. Lower temperatures are required
Poly(Vinyl Alcohol).
as the degree of hydrolysis is decreased until
Property Value 75-80% hydrolysis is reached, at which point
Appearance
Specific gravity; White-to-cream granular
of solid powder
1.27-1.31
of 10 wt % solution at 1.02
25°C
Thennal stability Gradual discoloration
above 100°C; darkens
rapidly above 150°C; w
rapid decomposition ~
above 200°C g
en
Refractive index (film) at 1.55 is
20°C
12
Thennal conductivity,
W/(m . K)'
0.2 :g
Electrical resistivity,
ohm-cm
(3.1-3.8) X 107 8en
w
Specific heat, J / (g . K)b 1.5
Melting point (unplasti- 230 for fully hydrolyzed
cized), °C grades; 180-190 for
partially hydrolyzed
grades
Tg,OC 75-85
Storage stability (solid) Indefinite when protected
from moisture
Flammability Burns similarly to paper 30 40 50 60 70 60 90
Stability in sunlight Excellent
'To convert W/(m . K) to (Btu· in.)/(h . ft2 . OF), divide by TEMPERATURE,oC
0.1441.
"To convert J to cal. divide by 4.184. Fig. 2. Solubility of O.4-rnm poly(vinyl alcohol) cast film.
 POLY(VINYL ALCOHOL) FOR ADHESIVES 403

the product is fully cold-water soluble but pre- col, acetone, and methyl acetate. 5 It has limited
cipitates upon heating. The hydrolysis range of solubility in dimethyl sulfoxide; the solubility
87-89% is considered optimum for both cold is in proportion to the residual acetate content.
and hot water solubility. Products with this op- Although there are no good solvents for PVOH
timum degree of hydrolysis are commonly re- other than water, up to 50% of lower alcohols
ferred to as partially hydrolyzed poly(vinyl can be added to PVOH solutions without caus-
alcohol). Regardless of the degree of hydroly- ing precipitation.
sis, all commercial PVOH grades remain dis-
solved upon cooling. SOLUTION VISCOSITY
Solubility is also influenced by particle size,
The viscosity of a PVOH solution is controlled
i.e., surface area, molecular weight, and crys-
by molecular weight, concentration, and to
tallinity. Decreasing particle size and molecu-
lesser degree, temperature. Degree of hydrol-
lar weight improves the solubility weight.
ysis does not strongly affect viscosity, although
Crystallinity is induced by heat treatment and
the viscosity is proportional to degree of hy-
retards the solubility rate. 4 Because the pres-
drolysis at constant molecular weight. Viscos-
ence of residual acetate groups reduces the ex-
ity relationships for low, medium, and high
tent of crystallinity, low hydrolysis grades are
molecular weight grades are shown in Fig. 3.
much less sensitive to heat treatment.
Viscosity, rather than solubility, limits the con-
Poly(vinyl alcohol) solutions show a high
centration of PVOH solutions. With conven-
tolerance toward many electrolytes, as shown
tional batch-mixing equipment, the practical
in Table 2. Small additions of strong inorganic
concentration limits for low, medium and high
acids and bases do not precipitate PVOH from
molecular weight resins are ca 30 wt %, 20 wt
solution, but the hydrolysis reaction continues
%, and 15 wt %, respectively.
to completion at extreme pH.
Poly(vinyl alcohol) cannot be dissolved by
most common organic solvents, e.g., gasoline,
kerosene, benzene, xylene, trichloroethylene,
carbon tetrachloride, methanol, ethylene gly-

Table 2. Maximum Salt Concentration

in which PVA is Soluble, % in Water. B,b
A
PYA degree of
hydrolysis ,A
/
Electrolyte 95% 88% /
/
Na2S04 5 4 /
(NH4hS04 6 5 //
Na2HP04 . 7H 2O 8 5 /
Na3P04 . 12H2O 8 6 /
NA2HP04 . H2O 9 6 /
/
NaHC03 9 7
Alz{S04h . 16H2O 10 6
Na2S203 . 5H2O 10 8
ZnS04 . 7H 2O 13 10
NaCl; KCl 14 10
CUS04' 5H2O 15 10
CH 3COONa . 3H 2O 23 15
NaN0 3 24 20 Concentration in water. WI %
'Courtesy of Air Products and Chemicals, Inc. Degree of polymerization: A, 800; B. 2000; and C. 2400.
bDetermined by adding a 10% solution of PVA dropwise to 50 ml Solid line, at 20·C; broken line, at 65"C.
of the salt solution at increasing concentration until precipitation is
observed. Fig. 3. Solution viscosity of poly (vinyl alcohol).
404 HANDBOOK OF ADHESIVES

The viscosities of partially hydrolyzed PVOH forms as the poly (vinyl acetate) converts into
solutions remain stable if the solutions are PVOH. The product is then washed with meth-
stored at high temperatures over a wide range anol and is filtered and dried. A moving belt
of concentrations. However, viscosities of con- process allows the PVOH to form a gel and
centrated solutions of fully hydrolyzed PV A subsequently to be cut into granular form. II
gradually increase over a period of days when The alcoholysis process yields methyl ace-
stored at room temperature, and gelation oc- tate as a byproduct. The methyl acetate can be
curs in products that contains < 1 mol % ace- used as a solvent or it can be processed to re-
tate groups. This viscosity increase or gelation cover methanol and acetic acid. One such pro-
can be reversed by reheating. 6 Lower solution cess involves mixing the methyl acetate with
concentrations and lower degrees of hydrolysis water and passing them through a cation-ex-
eliminate viscosity instability associated with change resin to catalyze the hydrolysis reac-
long-term solution storage. tion. lo
Methanol recovered from this process can be
MANUFACTURE totally recycled to the methanolysis step, and
the acetic acid is sold as a byproduct.
All PVOH manufacture involves poly (vinyl
acetate) as the starting material. The theoretical
POLYVINYL ALCOHOL IN POLYVINYL
monomer, vinyl alcohol (CH2 =CHOH), does
ACETATE EMULSION ADHESIVES
not exist. Conversion of poly(vinyl acetate) to
PVOH is generally accomplished by base-cat- Polyvinyl alcohol is a first-class adhesive in its
alyzed methanolysis; 10 sodium hydroxide is the own right. It also serves as an excellent addi-
usual base. tive for modifying the properties of polyvinyl
Poly(vinyl acetate) polymerization is accom- acetate emulsion adhesives.
plished by conventional processes, e.g., solu- Polyvinyl alcohol adheres particularly well
tion, bulk, or emulsion polymerization. to cellulosic substrates such as wood or paper.
Solution polymerization is favored because the Adding it to a polyvinyl acetate emulsion will
subsequent alcoholysis reaction requires sol- increase the affinity as well as the tensile
vent addition. 10 The polymerization step deter- strength of the formulation.
mines the ultimate molecular weight of the Because it is a hydrophilic polymer, polyvi-
PVOH. Catalyst concentration, temperature, nyl alcohol functions as a humectant to retard
and solvent control the degree of polymeriza- the loss of water from the formulation and pro-
tion; acetaldehyde is an effective chain-transfer long open time of the adhesive film. Wet tack
agent. It is the agent commonly used. is increased and can be enhanced further by
The degree of hydrolysis of PVOH is con- adding tackified (borated) polyvinyl alcohols.
trolled during the alcoholysis and is indepen- Polyvinyl alcohol is used as a thickener to
dent of molecular-weight control. Fully increase viscosity and control the solids con-
hydrolyzed PVOH is obtained if methanolysis tent. When a high viscosity but low solids for-
is allowed to go to completion. The reaction mulation is needed, a small amount of a high
can be terminated by neutralizing or removing viscosity polyvinyl alcohol should be added.
the sodium hydroxide catalyst. The addition of When both high viscosity and high solids are
small amounts of water to the reactants pro- desired, a medium viscosity grade should be
motes saponification of poly(vinyl acetate), added. All grades impart smooth flow from ap-
which consumes sodium hydroxide. The extent plicator reservoirs and shear resistance at high
of hydrolysis is inversely proportional to the machine speeds. Polyvinyl alcohol affords the
amount of water added. A disadvantage of best means of balancing the viscosity and sol-
water addition is an increase in byproduct so- ids content of an emulsion adhesive.
dium acetate, which is present as ash in all Partially hydrolyzed polyvinyl alcohols in-
commercially available grades of PVOH. The crease the stability of emulsion adhesives by
alcoholysis reaction can be carried out in a functioning as emulsifiers and protective col-
highly agitated slurry process; a fine precipitate loids. 8 These alcohols increase water sensitiv-
 POLYIVINYL ALCOHOl) FOR ADHESIVES 405

ity of adhesive films, making them useful in and prolonged storage of the treated PVOH so-
emulsions designed for remoistenable adhe- lution should be avoided. Crosslinking can also
sives or in those requiring easy clean up. Par- be accomplished by simply heating dry PVOH
tially hydrolyzed resin types are also used to above 100°C; this dehydrates the polymer and
preemulsify organic solvent solutions before yields an unsaturated carbon backbone. Inter-
adding them to emulsions adhesives. Fully hy- molecular reactions between unsaturated groups
drolyzed polyvinyl alcohols, however, increase in adjacent polymer chains form permanent
the water resistance of adhesive films, partic- crosslinks. However, thermal crosslinking is
ularly the medium and high molecular weight not considered a practical reaction because it is
grades. 12 also accompanied by polymer decomposi-
All polyvinyl alcohols improve the machin- tion. 13
ability of emulsion adhesives; spitting and Although PVOH film can be rendered insol-
throwing are reduced on high speed equipment. uble by crosslinking, it swells in water and
All types have surface-active properties that loses strength upon extended exposure. Com-
promote thorough wetting of roller applicators plete water insensitivity cannot be achieved, al-
and adherends. Wetting and penetration into the though it improves with degree of hydrolysis.
adherend are improved by using polyvinyl al- Fiber-grade PVOH has a degree of hydrolysis
cohols with lower molecular weight and hy- of at least 99.9%; it exhibits negligible swell-
drolysis. Since polyvinyl alcohol has a higher ing in water, although it absorbs moisture, like
melting point (200°C) than the emulsion to many natural fibers.
which it is being added, it raises the heat-seal-
ing and blocking temperature of the film and GELATION
increases its overall heat resistance. All poly-
The controlled gelation of PVOH solutions is
vinyl alcohol resins facilitate the incorporation
important where penetration into a porous sub-
of water-immiscible substances into the for-
strate is undesirable, e.g., paper coatings and
mulation and stabilize the adhesive. In addi-
adhesives. Boric acid and borax react strongly
tion, solvent and oil resistance are increased
with PVOH and are widely used industrially as
and creep is decreased by polyvinyl alcohol. 12
gelling agents. Poly(vinyl alcohol) is extremely
sensitive to borax, which causes gelation by
CROSSLINKING
forming a bisdiol complex as shown below:
Poly(vinyl alcohol) can be readily crosslinked
for improved water resistance. 9 The most prac-
tical means of crosslinking PVOH is with
chemical additives, e.g., glyoxal, urea-formal-
dehydes, and melamine-formaldehyde. Tri-
methylolmelamine is often preferred if a low
temperature is required. An acid catalyst, e.g.,
ammonium sulfate or ammonium chloride, is
necessary with the formaldehyde crosslinkers. As little as 0.1 % borax, based on solution
Metal compounds can also be effective insolu- weight, can cause thermally irreversible gela-
bilizers for PVOH. These additives include tion. Boric acid forms a weaker monodiol com-
strongly chelating metal salts of copper and plex and is preferred for controlled, partial
nickel, e.g., cupric ammonium complexes, gelation of PVOH. 7 The reaction is very sen-
chromium complexes, organic titanates, and sitive to pH, and full gelation occurs above pH
dichromates. The heat treatment during drying 6.
of PVOH films or coating is generally sufficient Boration causes aqueous solutions of PVOH
to complete the crosslinking reaction, although to develop strong wet tack after cooking. Ad-
when dichromates are used the reaction is best hesives based on tackified (borated) poly (vinyl
catalyzed by ultraviolet light. Crosslinking alcohol) work particularly well where they can
slowly takes place even at room temperature, be applied as a very thin film and then the sub-
406 HANDBOOK OF ADHESIVES

strates mated using very high pressures. These The PVOH process is highly capital inten-
conditions are found in spiral tube winding and sive, requiring separate facilities for polymer-
solid fiber laminating. These adhesives are usu- ization, alcoholysis and recovery of acetic acid
ally prepared at solid content levels of 18-25 %. and methanol from the byproduct methyl ace-
The poly(vinyl alcohol) content varies from 5 tate.
to 9 %; the remainder of the solids is comprised Some major producers and announced capac-
of kaolin clay. The liquid adhesive is applied ities:
at rates of 40-45 grams per 1000 square me- Capacity (thousand
ters, which results in a dry application of 8-12 metric tons/yr)
grams per 1000 square feet. U.S.
The tackified polyvinyl alcohols, introduced Air Products and 48
in the early 1960s, rapidly replaced starch/urea Chemicals, Inc.
formaldehyde adhesives in solid fiber laminat- duPont 60
ing and dextrine, compounded polyvinyl ace- Japan
tate and sodium silicate adhesives in spiral tube Kuraray 110
winding. The new adhesives demonstrated su- Nippon Goshei 50
perior adhesion over silicates and dextrines to Denka 25
a wide variety of paper substrates. These ad- Unitiken 25
hesives reduce warp in solid fiber laminating Total Japan 210
and shrinkage in spiral tubes because of the low Europe
adhesive application rate and, thus, low amount Hoechst 30
of water added to the laminations. The low ap- Taiwan
plication rate and low resin level also made Chang Chun 34
these adhesives very economical.
Another advantage of these adhesives is that SPECIFICATIONS AND REGULATIONS
they permit rapid bond formation when applied Three important commercially available types
properly. Tubes and board bound with fully or of PVOH are distinguished by the mole percent
superhydrolyzed polyvinyl alcohol and clay ad- residual acetate groups in the resin: fully hy-
hesives also have excellent water resistance, drolyzed (1-2 mol % acetate), intermediately
and are used where the box or tube may be ex- hydrolyzed (3-7 mol %), and partially hydro-
posed to water for an extended period, as is the lyzed (10-15 mol %) PVOH. Poly(vinyl alco-
case with military packages and composite cans hol)s with other degrees of hydrolysis are
or dynamite tubes. produced, but collectively, they have a much
The adhesive properties of polyvinyl alcohol smaller market share than any of the three prin-
also appeared attractive for the manufacture of cipal grades. When no reference is made to the
corrugated board. Adhesives based on the su- degree of hydrolysis in describing PVOH, it is
perbydrolyzed grades of tackified polyvinyl al- generally assumed to be a fully hydrolyzed
cohol were demonstrated at both the single face grade.
and double backer sections of modem corru- Poly(vinyl alcohol) is produced in four gen-
gated machines which were run at full speed. eral molecular weight ranges, as shown in Ta-
The board had strong dry bonds, high water re- ble 3. Several other molecular weight resins are
sistance and showed excellent nonwarp prop-
erties. But while the polyvinyl alcohol Table 3. Molecular Weight of Main
adhesives were a technical success, they were Commercial Poly(Vinyl Alcohol) Grades. a
unable to compete economically against starch Nominal 4% solution viscosity,
adhesives. Viscosity grade Ma mPa . s (= CP)b

Low 25,000 5-7

PRODUCTION Intennediate 40,000 13-16
Medium 60,000 28-32
There are two producers of PVOH in the U.S., High 100,000 55-65
four in Japan, and several in Europe, where 'Courtesy of Air Products and Chemicals. Inc.
Hoechst is the dominant one. "Measured at 20·C with Brookfield viscometer.
 POL YIVINYL ALCOHOl) FOR ADHESIVES 407

Table 4. FDA Regulations Applicable to bution in molecular weight and degree of

Poly(Vinyl Alcohol) as an Indirect Food hydrolysis, which may be undesirable in some
Additive. applications.
Regulation Description FDA regulations applicable to the use of
PVOH as an indirect food additive are listed in
181.30 Prior sanctioned substances used in
manufacture of paper and paperboard Table 4.
products used in food packaging for
fatty foods only BIBLIOGRAPHY
175.105 Adhesives, no limitations
176.170 Components of paper and paperboard 1. Herrman, W.O., and Haehnel, W., U.S. Patent
in contact with aqueous and fatty 1,672,156 (1928) (to Wacker Chimie).
foods, extractive limitations 2. Ave, H., and Ono, Y., U.S. Patent 3,084,989 (1963)
176.180 Components of paper and paperboard (to Kuraray and Air Products).
in contact with dry food, no limita- 3. "Vinol" Product Handbook, Air Products and Chem-
tions icals, Inc., Allentown PA 1980.
177.1200 Cellophane coating, no limitations 4. Tubbs, R. K., Inskip, J. K., and Subramanian, P. M.,
177.1670 Poly(vinyl alcohol) film Soc. Chern. Ind., Monograph 30, London (1968) pp.
177.2260 Filters, resin-bonded where filter fiber 88-103.
is cellulose 5. Peirerls, E. S., Mod. Pfost., 18(6) (1941).
177.2600 Filters, resin-bonded; extractables must 6. Toyoshina, K., in "Polyvinyl Alcohol," C. A. Finch
be less than 0.08 mg/cm2 (0.5 mg/ (ed.), pp. 17-67, New York, John Wiley and Sons,
sq. in.) (1973).
175.300 Resinous and polymeric coatings 7. Hawkins, R. L., U.S. Patent 3,135,648 (1964) (to Air
175.320 Resinous and polymeric coatings for Products and Chemicals).
polyolefin films; net extractable less 8. Hulbekian, E. V., and Reynolds, O. E. D., in "Poly-
than 0.08 mg/cm2 (0.5 mg/sq. in.) vinyl Alcohol," C. A. Finch (ed.), pp. 427-461, New
177.2800 Textiles and textile fibers, for dry York, John Wiley & Sons, (1973).
foods only 9. Finch, C. A., in "Polyvinyl Alcohol," C. A. Finch
178.3910 Surface lubricants in the manufacture (ed.), pp. 183-302, New York, John Wiley and Sons,
of metallic articles (1973).
10. Chin, Y., "Polyvinyl Acetate and Polyvinyl Alco-
hoi," private report No. 57A by Process Economics
Program, Stanford Res. Inst., Menlo Park, CA (1970).
produced, but they have only a minor market 11. Demny, R., "Polyvinyl Acetate and Polyvinyl Alco-
share. Industry practice expresses the molecu- hoI," private report No. 57 by Process Economics
lar weight of a particular grade in terms of its Program, Stanford Res. Inst., Menlo Park, CA (1970).
4 % aqueous solution viscosity. Intermediate 12. Daniels, W. E., "Polyvinyl Acetate," in "Kirk-Oth-
viscosities can be achieved by blending. Prod- mer Encyclopedia of Chemical Technology," 3rd Ed.,
pp. 839-843, New York, John Wiley and Sons, 1983.
ucts of different degree of hydrolysis can also 13. Tubbs, R. K., and Wu, T. K., in "Polyvinyl Alco-
be blended to develop, e.g., intermediate sol- hol," C. A. Finch (ed.), pp. 167-183, New York,
ubility. Blended products have a broad distri- John Wiley and Sons, 1973.
 23
Polyolefin and Ethylene Copolymer-
based Hot Melt Adhesives
ERNEST F. EASTMAN,t AND LAWRENCE FULLHART, JR.*
E. I. du Pont de Nemours & Co., Inc.
Polymer Products Department
Wilmington, Delaware

The adhesive industry in the U.S. has had a • The elimination of solvent recovery or
remarkably steady growth over the past 15 disposal costs.
years. Hot melts, in particular, have grown • Elimination of hazardous chemicals (sol-
steadily from 100 million pounds in 1970 to vents).
over 400 million pounds in 1985. The annual • Smaller space requirements for both stor-
growth rate over this total period averages age and use.
above 10 %. It is rather obvious then that· hot • Reduced maintenance and cleanup costs.
melt adhesives have been the major growth • Wide formulating latitude to meet cost and
segment in the adhesive industry, with the performance needs for a variety of end
aqueous and solvent-based products showing a uses.
decline. The growth rate for polyolefin and eth-
The ability to speed up packaging lines to
ylene copolymer based hot melt adhesives has
achieve much greater productivity without in-
slowed down until currently it approximates the
creasing space requirements, by simply con-
growth in GNP. Emphasis in the adhesive in-
verting to hot melt adhesives from cold glues,
dustry, however, is still largely centered on the
was an economic bonus to many companies.
hot melt products, in particular those based on
Hot melt application equipment interchange-
new block copolymers. While it is obvious that
able with aqueous dispensers was developed by
in one sense the hot melt adhesive market is
several companies, permitting relatively inex-
maturing, there are still many new opportuni-
pensive conversions to the hot melt system.
ties opening up.
The use of solvents to produce quick setting
The rapid growth of hot melt adhesives was
adhesives came under pressure as environmen-
the result of several factors. First, they pro-
talists pushed to reduce the amount of solvent
vided many advantages, e.g.:
being released into the atmosphere. This effort
• Rapid set time produces an increase in was felt by both the adhesive manufacturer and
production rate. the user of the solvent-based adhesive. Hot melt
• Hot melt dispensing is easy to automate. adhesives were a logical alternative, since they
are 100% solid systems containing no solvent,
*Retired and have a very rapid set time.
tTechnical Consultant While this chapter will deal only with poly-

408
 POL YOLEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 409

olefin and ethylene copolymer based hot melts, fying resin contributes surface wetting and tack,
it should be pointed out that several other while petroleum wax is used to lower melt vis-
polymer compositions are used in hot melt ad- cosity, reduce cost, and control setting speed.
hesives. Many of these are in competition with Antioxidants, fillers, plasticizers and blowing
the polyolefins. agents can also be used to enhance certain
Early hot melt adhesives were based on ethyl properties.
cellulose and animal or hide glues. These were
later replaced by synthetic resins such as poly-
Polymers
amides and ethylene-vinyl acetate copolymers.
More recently a new class of compounds, re- The large production capacity for ethylene and
ferred to as block copolymers because of their vinyl acetate monomers during the 1960s and
unique chemical structure, have emerged. early 1970s made ethylene-vinyl acetate resins
These latter compounds are copolymers of sty- with 18-40% vinyl acetate content readily
rene and butadiene, isoprene, or ethylene-bu- available. In fact, with the exception of the pe-
tylene which tend to widen the flexibility riod of the oil embargo in 1974-1976, when
property range of hot melt adhesives. They prices escalated rapidly, the poly olefin resins
probably represent the fastest growing segment such as low molecular weight polyethylene,
of the hot melt adhesives market at the present ethylene copolymers, and polypropylene resins
time. Their primary application is in hot melt took on the characteristics of commodity prod-
pressure sensitive adhesives. Polymers based ucts. Each of these polymers is used exten-
on other than polyolefin resins are discussed insively in producing hot melt adhesives. The
other chapters in this handbook. ethylene-vinyl acetates were the most popular
The ethylene-vinyl acetate copolymers cover because of their superior adhesion to most sub-
a wide range of compositions and melt indices, strates and their ease of formulation. Thus,
as shown in Fig. 1. EVA-based hot melt adhesives were developed
for a wide variety of end-use applications. Low
ADHESIVE FORMULATION
molecular weight polyethylene resins found
their widest use in packaging applications with
The estimated distribution of polyolefin hot paper substrates, primarily paperboard cartons
melt adhesives by type is shown in Fig. 2. The and corrugated containers.
actual amount of polymer used is somewhat dif- Atactic polypropylene (APP) is tacky as pro-
ferent for the three types of adhesives because duced and is not easily formulated. It is used
the EV A adhesives are formulated with large essentially as a neat resin or extended with a
quantities of tackifiers and/or extenders, such small amount of wax or a polymer to add hot
as petroleum and synthetic waxes. Relative tack. Atactic polypropylene used to be a by-
proportions of polymer in the various types of product in the production of crystalline poly-
hot melt adhesives are estimated as shown in propylene, but with the development of new,
Fig. 3. This situation is expected to change more efficient catalysts, less atactic polypro-
during the next ten years as new polymers are pylene is produced. As a result, at least two
developed to act as adhesives for specific end- companies are now producing APP directly.
use application. This means that a greater number of precise
A typical ethylene-vinyl acetate based hot products are available; however, pricewise they
melt is composed mainly of three components: will have to bear the full cost of production. It
(1) a polymer, 30-40%; (2) a modifying or is therefore anticipated that atactic polypropyl-
tackifying resin, 30-40%, and (3) a petroleum ene resins will be developed mainly for specific
wax, 20-30%. The quantity and relative applications having higher value-added perfor-
amount of each material is governed by the per- mance.
formance requirements of the adhesive. The The properties of poly olefin polymers which
polymer forms the backbone of the adhesive, make them desirable as the base for hot melt
providing strength and toughness. The modi- adhesives are determined largely by two fac-
410 HANDBOOK OF ADHESIVES

o EVA (OLD)
o EVA (NEW)
o EVA TERPOLYMERS
b,. ETHYLENE ACID COPOLYMERS
1000
800
600 ,....,
"
~

400 ~'"'
~....,

200

100
0 08 A

80
~ I
60
0
40 "...., l~
"
0
~

L~
20 ....,
"
~
Q
P
~
10 A
....
0-
8
W
6 =~
L..J ~

4
...., p
0 '"'
...., 0
2 '"'
I
.8
'-'
.6

.4

.2

.1 , ,
o 10 20 30 50 60 70
VINYL ACHATE. %
20 30 40 50 60 70 80 90
ACID NUMBER

Fig. 1. Ethylene co- and terpolymers for hot-melt adhesives.

tors: molecular weight and the amount of co- introduced into the polymer. Considerable ex-
polymer. In the case of ethylene hompolymers pertise and experimentation are involved in se-
an increase in molecular weight provides im- lecting the proper polymer composition for a
provements in some properties; see Table 1. specific adhesive application. In fact, most ad-
Molecular weight is characterized by melt in- hesive manufacturers have now developed
dex, (a lower melt index represents an increase computerized programs which will predict an
in molecular weight). adhesive fonnulation (polymer grade, tackifier,
The potential for variations in polymer prop- and extender) to match a specific set of prop-
erties increases significantly as comonomers are erties.
 POLYOlEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 411

adhesive production are constantly being intro-

duced as will be mentioned later.

Tackifiers
Tackifiers are included in adhesive formula-
tions to increase the adhesion of the polymer to
various substrates. This is accomplished by fa-
cilitating the wetting of the substrate by reduc-
ing the viscosity of the hot melt. Besides the
Fig. 2. Polyolefin melt adhesives by polymer type. adhesive characteristics provided by the tacki-
fier, its selection is also based on several phys-
ical properties such as color, heat, UV, and
oxidation stability, and cost. The suitability of
the resin is also largely dependent on its com-
patibility with other components of the adhe-
sive blend, particularly the polymer.
Tackifiers tend to be grouped into three gen-
eral categories: hydrocarbon resins, rosin es-
ters and polytetpenes. There are numerous
commercial products in each group, with over
a hundred products available.
Fig. 3. Percent polymer distribution.
Hydrocarbon Resins. C-5 aliphatic resins
In Table 2 the property changes which can are obtained as byproducts in the steam crack-
be expected by a change in melt index for eth- ing of high naphtha or gas oils. They are largely
ylene-vinyl acetate copolymer are listed. It is composed of C-5 olefins, diolefins, and iso-
followed by Table 3 showing the effects of vi- prene monomers. Typical producers of these
nyl acetate content on polymer properties. compounds are Goodyear Tire and Rubber,
The number of polymer suppliers continues Eastman Chemical, Arizona Chemical, Her-
to increase slowly as do the types of polymers. cules, and Exxon Chemical. These resins have
A listing of some of the polymer suppliers is good color and hot strength and have good ag-
given in Table 4. New polymers for hot melt ing and heat stability properties. They are com-

Table 1. Effect of Melt Index on Ethylene Homopolymer

Adhesive Properties.
High Improves heat seal strength -+ Low
Melt .... Improves flexibility Melt
Index 500 .... Improves low temperature performance Index 2.0
Improves hot tack -+
Increases melt viscosity -+

Table 2. Effect of EVA Polymer Melt Index on Adhesive

Performance.
High melt Improves heat seal strength -+ Low melt
Index 500 Improves flexibility -+ Index 2.0
Improves hot tack -+
.... Improves low temperature performance
Improves cohesive strength -+
.... Decreases melt viscosity
Decreases open time -+
412 HANDBOOK OF ADHESIVES

Table 3. Effect of EVA Polymer-Vinyl Acetate Content on

Adhesive Properties.
Lower vinyl Increases solubility -+ Higher vinyl
acetate content Improves flexibility -+ acetate content
9% +- Higher seal strength 60%
+- Increases blocking resist
+- Increases paraffin solubility
Improves hot tack -+
Improves adhesion -+
Improves low temperature
performance -+

Table 4. Polyolefin Polymer Suppliers bility, and aging properties. Examples of these
for Hot Melt Adhesive Applications. products are Nevex 100 (Neville Chemicals)
Polyethylene Homopolymers and Piccovar L60 (Hercules).
Eastman Chemical Products Dimer-5 cycloaliphatic resins tend to be
USI Chemicals Co. somewhat unstable, but there are hydrogenated
Union Carbide Corp. grades which are sufficiently stable to have
Exxon Chemical
commercial acceptance.
Ethylene-Vinyl Acetate Copolymers Aromatic monomer resins which are highly
E.!. duPont de Nemours & Co., Inc. saturated and purified are light in color and have
USI Chemicals Co. excellent heat, light and oxygen resistance.
Union Carbide Corp. Some examples of these products are Kristalex
Exxon Chemicals
and Piccotex resins (Hercules Chemicals).
Other Olefin Copolymers and Terpolymers
Ethylene-ethyl acrylate: UCC, Dow Chemical, DuPont Rosin Esters. Rosin-based tackifiers find
Ethylene-acrylic acid: Dow Chemical continued use in hot melt adhesives because of
Ethylene-methacrylic acid: DuPont their unique property of providing compatibil-
Ethylene-vinyl acetate-methacrylic acid: DuPont
ity to a wide variety of adhesive components.
Thus, by including them among the ingredients
patible with ethylene-vinyl acetate copolymer the formulating latitude of the adhesive is
resins and with LMWPE resins, are low in cost, greatly increased. However, they have lost
and promote good adhesion to paper substrates. ground to the C-5 hydrogenated resins because
As a result, they are used extensively in pack- of their higher cost and uncertain supply.
aging hot melt adhesives. Recently Goodyear Three types of rosins are available, differ-
has introduced new grades of hydrocarbon res- entiated by the source of the material. Gum
ins, "Wingtack plus" and "Wingtack extra," rosin is derived from living pine trees, wood
which have increasingly small amounts of ar- rosins from aged pine stumps, and tall oil rosin
omaticity which increases their compatibility as a byproduct of the paper industry. Tall oil
with EVA polymers, resulting in slightly higher rosin has the largest source of supply, but it
tensile strength, elongation, and viscosity. Ag- varies with the changing fortunes of the paper
ing and color characteristics also seem to be industry.
improved. Examples are shown in Table 5. Unmodified rosins from all sources are highly
C-9 aromatic resins are produced from by- unsaturated because their main constituent is
product streams resulting from. the cracking of abietic acid, which contains a conjugated dou-
gasoline and from ethylene and propylene pro- ble bond. Thus they are subject to degradation
duction. They are primarily based on styrene, by oxygen, UV light, and heat. Therefore, the
alkyl benzene, vinyl toluene, and indene. While natural rosins must be modified to meet the sta-
these resins promote good adhesion and hot bility requirements of the hot adhesives. Im-
strength, they have poor initial color, heat sta- proved stability can be developed by several
 POL YOlEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 413

Table 5. Effect of Aromaticity on Hydrocarbon Resin.&

Ingredients Wingtack 95 Wingtack Plus Wingtack Extra
Elvax® 350 30 30 30
Paraffint H-l 20 20 20
Wingtack 50 50 50
Properties
Tensile strength, psi 605 610 660
Elongation, % 50 110 265
Brookfield Viscosity, 300°F 5400 5600 6200
Color, aged 5 hrs @ 350°F 9.5 8.0 5.5
'ASC 1985, p. 16, Leonard J. Kuma, Goodyear Tire and Rubber.

processes such as hydrogenation, dispropor- Waxes

tionation, and dimerization followed by ester-
Waxes are included in hot melt adhesive for-
ification of the rosin with glycerol or
mulations for several reasons, two of which are
pentaerythritol. The modified rosins exhibit
to lower cost and to reduce viscosity. Proper-
good adhesion, initial color, heat stability, and
ties affected by the wax content are blocking
aging characteristics.
characteristics, softening point, and open time.
Terpene-based resins are obtained from tur-
The high melting microcrystalline waxes (m.p.
pentine sulfate, a byproduct of the paper indus-
190-195°F) and synthetic waxes (m.p. 210-
try, and from limonene, a product of the citrus
245°F) are used because they contribute to high
industry. Products obtained are alpha-pinene,
temperature properties and greater cohesive
beta-pinene, and dipentene. The alpha-pinenes
strength. The higher melting paraffin waxes
are apparently the preferred product for hot melt
(m.p. 150-160°F) are used extensively in hot
adhesives as they are the most compatible with
melt coatings for their barrier, antiblocking and
EVA copolymers. Adhesives compounded with
heat seal properties as well as their lower cost.
dipentenes have excellent color and thermal
Waxes are generally included in hot melt ad-
stability, odor, oxidation resistance and hot tack
hesive formulations at the 20-30% level, but
properties. Typical of the products available in
this concentration may drop in the future.
this class are the Piccolyte series of resins
Waxes have become considerably more expen-
(Hercules). Limonene-based products are ex-
emplified by Zonatac 105 (Arizona Chemi- s.ive as refineries choose to lower their produc-
tIOn of these products. Also, synthetic waxes
cals).
produced by polyethylene producers are being
It can be anticipated that other tackifying res-
structured to provide similar properties. Fur-
ins will be introduced as new products are de-
thermore, as the polymer manufacturers mod-
veloped. For example, Lawter International
ify their products to do the complete adhesive
recently introduced a styrene/isobutylene resin
~ob, fewer and fewer additives will be required
containing a saturated polymer backbone which
m the adhesive formulation.
contributes improved heat and UV stability.
These optically clear, low molecular weight,
high styrene content polymers can be expected
HOT MELT ADHESIVES
to provide another dimension for the adhesive
APPLICATIONS
chemist to improve the versatility of hot melt
adhesives. Other examples are Amoco's alpha- The fact that hot melt adhesives are the fastest
methylstyrene and polybutenes. The latter are growing type of adhesive means they are find-
intermediate-to-Iow molecular weight homo- ing wide utility in literally thousands of indi-
polymers offering attractive properties includ- vidual applications. For convenience these
ing chemical stability, clarity, and resistance to applications have been listed in twelv~ cate-
oxidation by heat and light. gories, as shown in Table 6.
414 HANDBOOK OF ADHESIVES

Table 6. Major Hot Melt Adhesive It should also be noted that water-based
Applications. polyvinyl acetate and dextrin adhesives have
Application MM lb' been replaced by hot melt adhesives, which
now have over 50% of the market. The reasons
Case, carton, trays 116
60
for the high rate of penetration are typical of
Paper laminates
Nonwoven 50 those mentioned earlier for hot melts in gen-
Bookbinding 44 eral. But the increased speed and ease of au-
Labels 24 tomation are the primary ones.
PET bottles 18 Case sealing adhesives based on EVA resins
Bags 18
Textiles 15
are often a blend of several ingredients. A typ-
Carpet seaming 12 ical formulation is listed in Table 7.
Furniture 11 A representative hot melt adhesive formula-
Cans, tubes, drums 4 tion based on a low molecular weight polyeth-
Other 30 ylene resin would be composed of the materials
Total 400 plus
shown in Table 8. A low density polyethylene
'Estimated 1985.
based hot melt adhesive for case sealing might
contain the formulation shown in Table 9.
Packaging containers such as cases, cartons, This market is projected to grow roughly in
and trays, both manufacture and closure, are step with the growth in GNP. Changes in for-
the largest application for hot melt adhesives, mulation composition should be slightly in fa-
representing about 25 % of the total market. If
all packaging applications are included, such as
labels, bags, tubes, and cores, approximately Table 7. Hot Melt Case Sealing
60% of hot melt adhesives are used in pack- Adhesive.
aging. The other major uses of hot melt adhe- Ingredients Pans by Weight
sives are in bookbinding, product assembly and ElvaxCl 420 EVA polymer" 34
nonwoven products, and paper laminates. Al- Shellwax 300b 33
though the term hot melt adhesive is used for Zonatac 105e 33
many applications, the actual formulation of the BHT (butylated hydroxytoluene) 0.2
adhesive varies somewhat from end use to end 'DuPont Company.
'Shell Chemical.
use. The principal types of adhesive used in 'Arizona Chemical Company.
each of the categories are discussed next.

Cases. Cartons. and Trays Table 8. LMWPE Case Sealing

Adhesive.
This segment of the packaging market repre-
Ingredients Parts by Weight
sents the largest application for hot melt adhe-
sives-approximately 25% (excluding pressure Epolene C-IO" 65
sensitive adhesives). Of all the types of hot melt Atactic polypropylene" 10
Eastorez H-l00' 25
adhesives, polyolefins, as represented by EV A BHT (butylated hydroxy toluene) 0.2
copolymers and low molecular weight polyeth-
'Eastman Chemical.
ylenes, dominate this market. The EVA copoly-
mer resins probably have 65 % of the market,
with low molecular weight polyethylenes at Table 9. LOPE Hot Melt Adhesive.
30 %. The EVA hot melt adhesives hold the
Ingredients Parts by Weight
largest share because of their ease of prepara-
tion, versatility, and widespread availability. Petrothene NA593a 40
Piccotac 95 b 40
As more sources of low molecular weight poly- Microwax, 185°F MP 20
ethylene and low density polyethylene resins BHT
become available at lower prices, EVA resins 'USI Chemicals
may lose some market share. "Hercules, Inc.
 POLYOlEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 415

vor of low density polyethylene. The largest cover books may become a market opportu-
change will probably be in the polymers them- nity. A large segment of this market has resisted
selves to make them more effective on an in- hot melt penetration because of the nature of
dividual basis and thus reduce the amount of the books. The major outlet for these books is
other components. in school textbooks where continued use and
long life are important. Also, the book is ex-
pected to be opened on a desk and to remain
Bookbinding
open. This reveals one of the disadvantages of
The use of hot melt adhesives in the construc- polyolefin-based hot melt adhesives in that they
tion of books and periodicals has grown very exhibit memory. This characteristic causes the
rapidly during the past ten years. This has been book to want to close rather than remain open.
brought about by two developments. First is the Some adhesive companies have now been able
tremendous increase in the production of lower to formulate hot melt adhesives which are quite
cost paperback books. Paperbacks now consti- satisfactory in this regard. This development is
tute a major portion of all fiction and nonfiction the result of the more recent availability of the
books. Simultaneous with this phenomenon styrene-butadiene block copolymer resins. By
was the development of the "perfect binding" introducing these resins into the hot melt ad-
process. This process changed the method of hesive formulation, adhesive flexibility is in-
manufacturing books from stapling and sewing creased and memory reduced. This
to glueing of the pages at the spine or back of development has opened up the hardcover book
the book. Hot melt adhesives were ideal for this market to hot melt adhesives. A representative
process and thus took over the market. Essen- hot melt adhesive utilizing block copolymer
tially all paperback books are constructed with resins is illustrated in Table 11.
hot melt adhesives. The use of these adhesives While the potential use of hot melt adhesives
has now spread to the production of catalogs, in hardcover books offers an opportunity for
telephone books, and many trade and consumer future growth, there are some limitations. The
publications. Because of the greater adhesion public is greatly concerned about the careless
and flexibility of EVA based hot melts, EVA use of natural raw materials. Thus, the recov-
resins have been used almost exclusively in this ery and reuse of paper products is important.
application. A typical bookbinding adhesive Hot melt adhesives, as currently compounded,
might be formulated as in Table 10. are not easily redispersed as required in the re-
Since paperback books are constructed es- pulping operation. One of the major current re-
sentially 100% with hot melts, future growth search goals is the production of hot melt
of hot melt adhesive production will be related adhesives which lend themselves to the repulp-
directly to growth in paperback book sales. ing process. Limited success so far indicates
However, there is now the prospect that hard- this objective may ultimately be achieved.

Table 10. Bookbinding Hot Melt Table 11. Bookbinding Adhesive

Adhesive. Containing Styrene Block Copolymer.
Ingredients Pans by Weight Ingredients Pans by Weight
Elvax" 260 EVA' 30-40 Elvaxl!D 260" 20-35
Rosin ester tackifier, 25-45 Kraton 11 07b 15-35
R&B l00-105°C Fora! 105c 20-40
F. R. Paraffin wax m.p. 15-30 Shellftex 371 b 5-10
150-160°F Microcrystalline wax, m.p. 10-15
White microcrystallineb 5-10 170-190°F
wax, m.p. 180-190°F Antioxidant (Jrganox 101O)d 0.25
Ethyl 330 antioxidantC 0.5
'DuPont Company.
'DuPont Company. bShell Chemical Company.
"Bareco Div. Petrolite Corporation. 'Hercules. Inc.
'Ethyl Corporation. dCiOO-Geigy Corporation.
416 HANDBOOK OF ADHESIVES

Nonwovens trend is toward form-fitting leg bands, which

may be stretchable. This requires that the dia-
The nonwoven market includes such products
per adhesive both adhere to the polyolefin liner
as disposable diapers, sanitary products, incon-
and be elastic or adhere to an elastic band in-
tinent diapers, hospital sheets and pads. Other
serted in the leg area. Both systems are used.
products such as disposable caps and gowns and
An example of a general purpose EV A based
industrial throw-away garments are also in-
adhesive is given is Table 13; an elastomeric
cluded. The market for these products is ex-
adhesive formulation is given in Table 14.
panding as new uses are constantly being
The precise formulation of the adhesive is
developed, for example, in the field of filters
quite difficult, as the performance requirements
and separators in the new biotechnology indus-
are rather rigid. Tensile strength and heat re-
try.
sistance of the bond are important because the
Nonwoven products are usually constructed
diaper must not come apart and release the fluff
of polyethylene and polypropylene materials
wadding, which might harm the child. The
which are very hard to adhere to. In spite of
temperature/viscosity relationship of the adhe-
this, hot melt adhesives are used almost exclu-
sive must be controlled to permit easy appli-
sively to bond most structures. Diapers repre-
cation and surface wetting of the liner without
sent the largest product line using hot melt
puckering the liner material.
adhesives. In the future it may be that inconti-
The nonwoven market is expected to con-
nent diapers and absorbent pads will be an even
tinue to grow at a very rapid pace, at least 8 %
larger market. EVA-based hot melts are be-
annually for the next several years; thus, it is
lieved to hold about 60% of the market, with
an attractive market for hot melt adhesives.
low molecular weight polyethylene and atactic
polypropylene making up the remainder. The
Furniture
type of adhesive used is constantly under
change as the performance requirements In many of the hot melt adhesives markets the
change. The disposable diaper has penetrated hot melt accounts for a large percentage of the
approximately 80% of the total diaper market. adhesive used. This is not true of furniture.
Hot melt adhesives used in diaper construc- Furniture generally needs a rigid or structural
tion are of two general types: high viscosity adhesive, and this requirement is usually best
systems based on atactic polypropylene for the met by a liquid adhesive, for example, a poly-
end seal and lower viscosity, faster setting eth-
ylene-vinyl acetate based adhesives for the side
seam. With the evolution of the construction to Table 13. EVA Based Hot Melt
a multi-line laminating system, manufacturers Adhesive.
have adopted one or the other hot melt system Ingredient Parts by Weight
with which they feel most comfortable. The Elvax" 220· 30
composition of an atactic polypropylene based Polyterpene resin SO
hot melt adhesive is illustrated in Table 12. Microcrystalline wax, 18S 0 20
The side seam adhesive is presently undergo- Antioxidant 0.S-1.0
ing some modification as new diaper configu- 'DuPont Company.
rations are being developed. More and more the

Table 14. Elastomeric Adhesive. a

Table 12. Atactic Polypropylene Hot Ingredient Parts by Weight
Melt Adhesive.
Kraton SIS block copolymer" 20
Ingredient Parts by Weight Poly terpene tackifier" 60
Shell process oilb 10-20
APP MSOO2a 70
Antioxidant 0.S-I.0
C-S hydrocarbon resin 10
Microcrystalline wax 20 'National Starch Patent 4,526,577. I
bShell Chemical Company.
'Eastman Chemicals. 'Union Camp.
 POLYOLEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 417

vinyl acetate emulsion. As a result, hot melt Table 16. Hot Melt Product Assembly
adhesives compose only about 11 % of the ad- Adhesive.
hesive used in furniture construction. Hot melt Ingredient Parts by Weight
adhesives are used in those areas where high
Elvaxill II 5550" 35
strength is not usually required. EYA copoly- Foral AXb 64
mer adhesives are used in low temperature lam- Antioxidant 1
inations and in cabinet construction for drawer 100
comer blocks, drawer bottoms, and molding Properties
applications for decorative effects. These ad-
Brookfield Thennosel Vis- 9,500
hesives are expected to continue growing as cosity at 350°F, cP,
they replace the less stable and disappearing Lap shear adhesion, psi:
animal resin glues. pine/pine 500
Hot melt adhesives are used in limited quan- steel/steel 640
acrylic/acrylic 350
tities in the lamination of plastic sheets to wood
PVC/PVC 300
for doors and cabinets, although contact adhe- Lap shear failure, °C (OF) 82(180)
sives are generally chosen for this application.
'DuPont Company.
Edgebanding of veneered products is another "Hercules, Inc.
application for hot melt adhesives, but polyam-
ide hot melt adhesives are the pref~rred type
because of their greater heat resistance. hesive as required in the manufacture of an au-
A typical EY A hot melt furniture adhesive tomotive air filter can be prepared from the
would be formulated as given in Table 15. formula shown in Table 17.
There are indications that the manufacture of
laminated furniture will probably increase at a Labels
rate greater than GNP. Therefore, hot melt ad- The label adhesive market consists essentially
hesives should have a good future in furniture of two segments: non-pressure sensitive and
applications, assuming some improvement in pressure sensitive. Adhesives are used to ad-
product performance. The main limitation of here labels to glass, plastic and metal cans, and
the current EYA adhesives is high temperature paper and film packaging. Hot melt adhesives
performance. But this may be improved by are used in both of these categories to the ex-
using carboxylated copolymers which have tent of 40-50 % of all types. This is also true
slightly higher temperature resistance. within each category. This chapter will discuss
A higher service temperature product assem- only the non-pressure sensitive segment, leav-
bly adhesive can be formulated by using an eth- ing the other segment to be covered in Chapter
ylene acid copolymer such as Elvax® II 5550. 38.
These adhesives approach the higher service Hot melt adhesives are usually applied to the
temperature of polyamide adhesives, and thus label in advance. The adhesive is then reacti-
are a low cost alternative in many applications.
A typical formulation is shown in Table 16.
A more moderate temperature structural ad- Table 17. High Temperature
Automotive Adhesive.
Table 15. Furniture Hot Melt Adhesive. Ingredient Parts by Weight

Ingredient Parts by Weight Elvaxill II 5640 resina 40

Foral 105 rosin ester' 50
Elvaxill 420' 40 AC-8 polyethylene waxc 5
Escorez 2101 hydrocarbon resinb 30 Shellftex 451 HP processing 5
Escorez 1304 hydrocarbon resin b 10 oild
Be Square 175 microwaxc 20 Antioxidant 0.25
Antioxidant 0.5
'DuPont Company.
'DuPont Company. "Hercules, Inc.
bExxon Chemical. 'Allied Chemical Company.
'Bareco Div., Petrolite Corporation. dShell Chemical.
418 HANDBOOK OF ADHESIVES

vated by heating just before being applied to tles, several billion annually, is still expected
the substrate. Ethylene-vinyl acetate based hot to grow at about 15 % yearly over the next few
melt adhesives have been used extensively in years as they continue to replace cans and glass
this market, but are expected to lose market for many other products. The PET bottle re-
share to adhesives containing styrene-buta- quires a solid or flat base. At the present time
diene block copolymers and the general shift of this base is adhered to the plastic bottle by a
the overall market to pressure sensitive hot melt hot melt adhesive. The rapid production of bot-
adhesives. The primary reason for the greater tles requires a very rapid setting adhesive.
use of styrene block copolymers is their supe- Thus, hot melts have been the adhesive used
rior glue line flexibility, which is required in from the beginning.
plastic bottle labels. The use of plastic bottles The future of this market does have some po-
is expected to increase dramatically in the next tential deterrents. Recovery of the plastic bottle
few years. However, EVA polymer suppliers will probably be required. The current method
are working to overcome this deficiency by de- of recovery is to regrind the bottle. However,
veloping newer resins. An example of this is the base is composed of a different resin and
the DuPont Company's Elvax@ 170, which is thus must be removed. This is a costly step and
stated to have greater elastic properties, mak- suggests that in the future the bottle will be
ing it useful in the preparation of hot melt pres- redesigned to eliminate the base. If and when
sure sensitive adhesives. Perhaps the largest use this occurs, the amount and type of hot melt
of hot melt adhesives for labels has been for adhesive will be changed.
paper and plastic films used in meat packaging. The hot melt adhesives are based on ethyl-
Automatic machines for wrapping, weighing, ene-vinyl acetate or ethyl acrylate copolymers
and printing the label and then applying it to or styrene block copolymers, because of the
the package are in common use. need to adhere to polyester. The starting point
The future of hot melt adhesives in this mar- formulation for a PET bottle adhesive is given
ket will depend on the shift to pressure sensi- in Table 19. 2
tive labels. The increased use of plastic bottles
and perhaps the need to recover the plastic ma-
Carpet Seaming Tape
terial may change or dictate the adhesive com-
position. A typical hot melt label adhesive The bonding together of carpet edges is an in-
presently might have the general formulation tegral part of installing wall-to-wall carpeting.
shown in Table 18. In the past, carpet segments were sewn to-
gether by a highly time-consuming process.
Polyester Beverage Bottles Today, hot melt adhesive tapes are used by car-
pet installers to bond the carpet seams (edges)
The use of polyester (PET) plastic bottles to
together, which results in the abutted edges ap-
replace glass bottles and cans as beverage con-
pearing to be seamless. The seaming operation
tainers has resulted in significant consumption
is done at the carpet installation site.
of hot melt adhesives. The volume of PET bot-
A strip of hot melt coated tape is placed on

Table 18. Heat Activated Label Table 19. Hot Melt PET Bottle
Adhesive.- Adhesive.
Ingredient Parts by Weight Ingredient Parts by Weight
---------------------------------
Elvax~ 250 EVA b 25 Elvax~ 210 (EVA copolymer)' 10
U1traftex wax" 32 Kraton 1102 (SBS block copolymer' 25
Staybelite resin' 20 F.R. Paraffin Wax, m.p. 150°C 15
Cardipol LP 0-25 wax" 20 White mineral oil, U.S.P. 10
Armid C Amided 2.5 Sylvatac 95 b 40
---------------------------------
'Petrolite Corporation, Bareco Division. Trinonylphenyl phosphite
_______________________________ 0.15 _
tnuPont Company. 'Shell Chemical Co.
'Hercules, Inc. bArizona Chemical Co.
dAnnale IndustriaJ Chemicals. 'DuPont Company
 POL YOLEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 419

the floor, under the abutted carpet edges, with with a pressure sensitive adhesive to complete
the adhesive coated side in contact with the car- the product.
pet backing. The adhesive is activated by a spe-
cially designed hand-held heating iron. The two
carpet edges are pressed down on the activated HOT MELT APPLICATION EQUIPMENT
tape and joined directly under the iron. This
system is so successful it is almost impossible The continued rapid growth ofthe hot melt ad-
to tell the carpet is composed of more than one hesive industry has challenged the equipment
piece. manufacturers. They have met the challenge
Two types of hot melt adhesives are used in quite effectively with diverse, dependable pro-
this application, which stresses high strength duction equipment.
and shear resistance. Low molecular weight Hot melt adhesives are available as slugs (2-
polyethylene based adhesive is exemplified by 6 in.), pellets, pillows, and ropes as well as in
Eastman's Eastobond A-39. Competitive prod- drums. Slugs are used for small, intermittent
ucts are primarily based on ethylene-ethyl ac- application with hand operated or power-driven
rylate polymers. These ethylene-acrylate handguns. The adhesive rope handgun is useful
polymers are chosen because they give slightly for applying small amounts on a continuous ba-
higher shear strength performance than ethyl- sis. Automated packaging lines or other contin-
ene-vinyl acetate based products. A typical ad- uous-feed systems use pellets or other forms as
hesive formulation is illustrated in Table 20. a continuous feed to melt pots which supply the
molten adhesive to the applicator head through
heated lines. A number of available machines
Paper Laminates use drums, in which the adhesive is continu-
ously melted and drawn off as it is used. This
Paper laminating is a very large and diverse ad-
equipment is sometimes more effective than the
hesive market. Paper, film, and foil lamina-
melt pot, where the adhesive may change in
tions are a major part of the packaging market,
viscosity with long heating, or, if it is over-
and while hot melt adhesives are used in many
heated, may become charred.
of these applications, the largest outlet for hot
The major types of continuous application
melt adhesives is in the paper lamination for
equipment have been wheel coaters and glue
paper roll wrap and in the lamination for rein-
line nozzles. Simplest is a grooved wheel which
forced pressure sensitive tapes. In these appli-
turns in a melted reservoir of glue. These have
cations, a high degree of shear strength is not
been highly refined to where the amount of ad-
required, and atactic polypropylene is a major
hesive is controlled by a doctor blade for quan-
component. In most cases the atactic polypro-
titative application. A further refinement is the
pylene is used with very little additive. In the
development of the print cylinder, where an in-
case of reinforced tapes it is usually coated onto
ternally mounted doctor blade allows a precise
the substrate paper or film, a scrim or matrix of
pattern to be printed on either flexible or rigid
glass or plastic fiber is embedded in the coat-
substrates. Patterns can vary from one inch to
ing, and this is then combined with the second
a width of 72 inches, and system can operate
substrate. The laminated film is then coated
at speeds greater than 1,000 feet per minute.
The hand-held glue gun continues to receive
Table 20. Ethylene Ethylacrylate Based many modifications as to nozzle size and ver-
Hot Melt Adhesives. satility. Nozzles designed for specific applica-
tions have been produced where quantities
Ingredient Parts by Weight
warranted. These applications include elec-
EEA (18% EA)a 30 tronic assembly, furniture, automotive, and ap-
Zonester 100 rosin esterb 30-40
pliance applications.
Microcrystalline wax 40-30
Antioxidant 0.5 Equipment is now available which can sup-
'Union Carbide Corporation.
ply several application nozzles from the one
bArizona Chemical Company. melt tank. Also, the efficiency of heated supply
420 HANDBOOK OF ADHESIVES

lines has been increased to such an extent that to expand slowly because of two factors: (1)
lines 50 feet long can be used. the development of new markets and (2) the de-
Hot melt spray nozzles have been developed velopment of new polymers which will change
which permit the application of a uniform layer the compositions. Specifically, the trend is to
of adhesive, for example, in adhering textiles develop polymers which can be used as the
to foam substrates. This method is also partic- principal component of the adhesives with only
ularly useful in bonding nonwovens. minor additions of other ingredients to provide
The cost of using hot melt adhesives has been specific properties. The driving force to bring
lowered by the introduction of foamed hot melt this about is the nature of adhesive require-
applicators. This system introduces an inert gas ments in general. For example: an all purpose
into the adhesive prior to the point of dis- adhesive should be effective at temperatures of
charge. By using the adhesive foam the amount -40°F to 300°F, with adhesion of 350-1,000
of adhesive applied can be reduced as much as psi. These criteria cannot be met with the pres-
50%, thus significantly reducing the cost of the ent polymers alone.
adhesive required. The foam system can also The extent of new polymer development is
result in a thinner glue line, which is very ad- illustrated in Fig. 1. This chart shows the new
vantageous in certain end uses. polymers are extending the vinyl acetate con-
There are many excellent manufacturers of tent to higher levels, providing a wider range
equipment for application of hot melt adhesives of molecular weight (melt index) and increas-
and coating systems by many different ways in ing the number of monomers. The early poly-
different physical forms. These include high mers contained mainly 18-28% combined vinyl
and low pressure applicators, extruders, slot die acetate content. New EV A copolymers are now
coaters, roll coaters, pattern coaters, nozzles, available at up to 50 % VA content. During the
wheels, guns, spray applicators, and foam ap- 1960s and 1970s EVA resins with vinyl acetate
plicators. The following are some of the major contents of 9-33 % were available, with those
manufacturers of these types of equipment. No in the 25-28 % range having the greatest utility
intent is made to exclude any manufacturer. for hot melt adhesives. The chart can now be
However, in the interest of space the following expanded as new resins are made available. For
are offered for consideration: example, 2 Elvax® 40W and 150 (DuPont) with
higher vinyl acetate content and high MI pro-
• Nordson Corporation, Amherst, OH vide hot melt adhesives with more open time
44001 and better adhesion to plastic and film sub-
• Meltex Corporation, Peachtree City, GA strates. Other new products are U .S.1. 's Vy-
30269 nathene 2902-30/35 with a melt index of 70.
• Accumeter Laboratories, Marlborough, New resins are also being introduced which
MA 01752 have high vinyl acetate content and low melt
• Bolton-Emerson, Inc., Lawrence, MA index. Typical of these products are Elvax® 170
01842 (DuPont), with a vinyl acetate content of 35-
• Grayco/LTI, Monterey, CA 93940 37% and a melt index of 0.6-1.0; Vynathene
• Spraymation, Inc., Ft. Lauderdale, FL (USI Chemicals) EY903, 45% vinyl acetate,
33309 melt index 7.5; EY904, 51 % vinyl acetate,
A more comprehensive listing may be obtained melt index 3.5; and EY905, 51 % vinyl acetate
from the various trade and educational associ- with a melt index of 18. Resins with low melt
ations concerned with hot melt systems, which index and high vinyl acetate content find appli-
could provide information regarding manufac- cation in hot melt pressure sensitive adhesives.
turers who are associated with their organiza- Recently a new series of EV As has been intro-
tions. duced with a small amount of an acid mon-
omer. These ethylene-vinyl acetate-acid
terpolymers produced by DuPont are particu-
TRENDS IN NEW POLYMERS
larly useful in promoting improved adhesion to
The hot melt adhesive market for polyolefin polar and nonporous substrates and in in-
based polymers has matured, but will continue creased toughness, flexibility and seal strength.
 POLYOLEFIN AND ETHYLENE COPOLYMER-BASED HOT MELT ADHESIVES 421

Table 21. Ethylene/VinylacetatelAcid Terpolymers. 8

Grade Melt Index VA% Acid No. b
Elvax® 4260 5-7 28 4-8
Elvax® 4310 420-580 25 4-8
Elvax® 4320 125-175 25 4-8
Elvax® 4355 5-7 25 4-8
'DuPont Company.
bAcid number is the milligrams of potassium hydroxide required to neutralize one gram of polymer.

Examples of these products are listed in Table which provide the flexibility and tack required
21. at low temperature. Recently DuPont intro-
New ethylene copolymers have also been in- duced a segmented ethylene-vinyl acetate
troduced such as the ethylene-ethyl acrylates polymer which has more elastic properties than
promoted by Union Carbide and Dow Chemi- conventional EVA copolymers. This product,
cal. These have been followed by ethylene- Elvax® 170, gives the adhesive compounder
acrylic acid copolymers. Acceptance of these another raw material with which to compete in
polymers has been limited to specific applica- the hot melt pressure sensitive adhesive mar-
tions, probably because of their higher cost. ket.
Recently another series of ethylene copoly- Atactic polypropylene still finds use in paper
mers has emerged in the marketplace. They in- laminates and reinforced tape, but these mar-
clude a series of ethylene-methyacrylic acid kets are considered mature. Some research
copolymers introduced by DuPont under the work is currently underway to produce poly-
trade name Elvax® II. These products are de- propylene copolymers which will exhibit unu-
signed for high performance hot melt adhe- sual properties. New polyamide and polyester
sives. They are high molecular weight resins, as well as more complex polymers, as
copolymers with high acid functionality and polyamide-polyethers or polyester-polyethers,
outstanding thermal stability. Besides improv- are also under development.
ing the normal properties associated with eth-
ylene-vinyl acetate copolymers, these polymers FUTURE OF HOT MELT ADHESIVES
also promote adhesion to glass and metals, have
improved alkaline redispersibility and substrate The future of hot melt adhesives will depend to
wetting. Examples of these new polymers are a large extent on the ability of the polymer sup-
given in Table 22. pliers and adhesive compounders to create ad-
Dow Chemical has introduced a somewhat hesives which will meet the ever-changing
similar series of polymers under the Primicor requirements dictated by new manufacturing
trade name. processes and materials of construction. Hot
As mentioned earlier, new polymers are melt adhesives have provided a new method of
being introduced to provide functionality for using adhesives without organic solvents or
hot melt pressure sensitive adhesives. The first water. However, one of the main limitations of
of these were Shell Chemical's styrene-buta- hot melt adhesives is their lack of high temper-
diene and styrene-isoprene block copolymers,
Table 23. Hot Melt Electron Beam
Table 22. Elvax® 11 8 Ethylene Acid Curable Adhesive. 8
Copolymers. Ingredient Parts by Weight
Grade- Melt Index Acid No. Kraton D1320X b 50
5550 10 54 Wingtack 95 C 45
5610 500 60 Adtac IOd 5
5640 35 60 Phenolic antioxidant 1-2
5650 10 60 'J. R. Erickson. Shell Development Co., Houston, Texas, Adhe-
5720 100 66 sive Age, April 1986, p. 22.
5950 25 90 bShell Chemical.
'Goodyear Tire and Rubber Company.
'DuPont Company_ dHercules, Inc_
 422 HANDBOOK OF ADHESIVES

Table 24. Adhesive Properties.

Propenies Before EB After EB (5 mrad)
Rolling ball tack, cm 1.2 1.8
Poly ken Probe tack, kg 1.2 1.4
180· peel, pli 5.0 5.6
Holding power-kraft, min 2400A >4,000
Holding power-steel, min >4,000 3,500C,
95·C Holding power-Mylar, min 91C > 1,000
Peel temperature limit, ·C III >200

ature resistance. A method of overcoming this bond strength. 3 Both National Starch4 and
deficiency would significantly increase the util- Chemplex5 have patented ethylene copolymer
ity of hot melt adhesives. Recently J. R. combinations with polypropylene to form im-
Erickson has reported on such a method which proved hot melt adhesives.
employs a new polystyrene-polyisoprene-poly- Robots are perhaps one of the most signifi-
styrene block copolymer which can be formu- cant developments which will profoundly af-
lated into a hot melt adhesive. This adhesive fect the growth of hot melt adhesives. Robots
can then be cured by treatment with an elec- are being evaluated in many industries, and
tronic beam. Optimization of the rubber-type their utilization is essentially assured. Fortu-
polymer and formulating experience should nately, hot melt adhesives are easily adaptable
lead to an adhesive with properties unique from to application by robots. Application is reliable
the present types. and accurate and will lead to increased produc-
A typical formulation is shown in Table 23, tivity and quality. The evidence suggests that
and a list of properties before and after radia- if the partnership of robot and hot melt adhe-
tion is given in Table 24. sives is understood and wisely applied, there
The trend in new hot melt adhesives will be will be a significant place for hot melt adhe-
to develop more specific adhesives. Thus, the sives in the future.
number and range of adhesives should in- The use of robotics in the auto industry ap-
crease. An example of a specialized adhesive pears to be a natural, but other areas may also
is the development of a film heat-activated ad- exist. Penetration of the housing industry has
hesive. The adhesive film may be 5-20 mils been a goal of adhesive industry for sometime,
thick and can be cut to a variety of shapes for so far largely unattained. But the slow shift to
application. The adhesive is then activated by factory built modular homes may provide the
heat or other means such as radio frequency vi- opportunity for adhesive utilization.
bration.
Another example of the type of innovation
taking place in the hot melt adhesive industry REFERENCES
is given by Nicolmelt. They have devised a hot
melt diaper adhesive that changes from a light 1. Schmidt, R. C., Jr. and Pulleti, P. P., U.S. Patent
yellow color to a bright blue when it gets wet, 4,526,577 (to National Starch and Chemical Co.), July
thus .indicating the diaper needs replacing. 2, 1985.
2. Nelson, J., U.S. Patent 4,394,915 (to Findley Adhe-
Mothers should appreciate this and it should
sives Inc.), July 26, 1983.
also increase the sale of diapers by promoting 3. Schmidt, R. C., Jr., Decowski, S. J., and Pulleti, P.
more frequent changes. P., U.S. Patent 4,460,728 (to National Starch & Chem-
Numerous new polymer and adhesive com- ical Company), July 14, 1984.
positions are being evaluated, as indicated by 4. Schmukier, S., Machonis, J., Jr., and Shida, M., U.S.
Patent 4,472,555 (to Chemplex Co.), September 18,
the number of new patents being issued. Dow 1984.
Chemical has recently patented a composition 5. Hoenig, S. M., Flores, D. P., and Ginter, S. P., u.S.
in which 2-oxazolene was added to an ethylene Patent 4,474,928 (to Dow Chemical Company), Octo-
copolymer to produce a detectable increase in ber 2, 1984.
 24
Polyvinyl Acetal Adhesives
P. H. FARMER AND B. A. JEMMOTT
Monsanto Chemical Company
Springfield, Massachusetts

Polyvinyl acetal resins are known ,for their ex- vancing analytical techniques has changed dra-
cellent adhesion to a variety of surfaces. While matically in recent years.
the principal applications are adhesives for
glass and metal, polyvinyl acetals provide
CHEMISTRY
structural adhesion for paper, fiber and plas-
tics. They contribute flexibility and toughness Acetals are formed by well known reaction of
to coatings. Excellent pigment binding capa- one molecule of aldehyde and two molecules
bility has led to their use in printing inks, elec- of alcohol, as illustrated in Fig. 1.
trographic toners, and magnetic tape. The Polyvinyl acetals are manufactured by react-
polyvinyl acetal polyvinyl butyral is almost ex- ing aldehydes with polyvinyl alcohol in the
clusively used in the manufacture of laminated presence of an acid catalyst. Polyvinyl alcohols
safety glass where optical clarity along with are manufactured by transesterification of poly-
structural and adhesive performance is re- vinyl acetate. The catalyst is either acid or base
quired. depending on the process. Polyvinyl acetate is
Polyvinyl acetals celebrate 50 years of com- polymerized from vinyl acetate by mass sus-
mercial production. Monsanto, DuPont, and pension or batch solution or continuous solu-
Union Carbide have been the United States tion polymerization.
suppliers of polyvinyl butyral over its first half The acetals are terpolymers reflecting the
century of production. DuPont exclusively three reactions which are used in their manu-
supplies safety glass interlayer under the trade facture. The moieties are represented in Fig. 2.
name Butacite4ll • Union Carbide offers polyvi- Manufacturers offer a variety of hydroxyl lev-
nyl butyral resin as BakeliteQil. Monsanto pro- els and molecular weight. The acetate level for
duces safety glass interlayer, SaflexQII; polyvinyl commercial polyvinyl butyrals is usually low;
butyral resin, Butvar®; and polyvinyl formal offering little performance leverage for most
resin, Formvar4ll. Monsanto is the world's lead- applications. Higher acetate levels are common
ing manufacturer of polyvinyl acetals. for the polyvinyl formals to improve solubility
This chapter introduces polyvinyl acetals at the expense of strength and dimensional sta-
through their application chemistry. Physical bility.1
properties are tabulated or quantified. Various Films of polyvinyl acetals are characterized
applications are summarized. The chapter clo- by their high resistance to aliphatic hydrocar-
ses with comments on the generally perceived bons, mineral, animal, and vegetable oils; ex-
structure of the polymer which through ad- ceptions are castor and blown oils. They

423
424 HANDBOOK OF ADHESIVES

H H H

~
~
I I I
R-C + RI-OH R-C-OR + RI-OH R-C (-OR\ + H2O
11 I
0 OH

.4lcohfJl Alcohol Acetal

Aldehyde Hemiacetal

Fig. 1.

withstand strong alkalies but are subject to at- work with the manufacturer on performance
tack by acids. These properties are greatly en- optimization.
hanced when polyvinyl acetals are components As with most polymers, molecular structure
in cured adhesives and coatings. also leverages application performance. While
Many applications for polyvinyl acetal resins this is beyond the scope of this chapter, C.A.
involve curing with a thermosetting resin to ob- Finchs is an informative resource.
tain a balance of properties. Generally, any
chemical reagent or resinous material which
HEALTH, TOXICOLOGY, AND
reacts with secondary alcohols will react with
SAFETy8
acetals. Examples of probable chemistry for
crosslinking polyvinyl acetals are shown in No significant adverse health effects have been
Figs. 3-7. reported for Butvar or Formvar. In acute tox-
Hydroxyl level is the prime leverage on per- icity studies with rats and rabbits, polyvinyl
formance in most applications. The convention butyral resin is practically nontoxic by oral
herein is to express hydroxyl level as weight ingestion (LDso > 10,000 mg/kg) or dermal
percent. application (LDso > 7,940 mg/kg). Butvar had
The distribution of hydroxyl along the poly- only slight rabbit eye irritation (2.80n a scale
mer chain is considered nominally random. of 0-110) and did not irritate the skin. These
However, as discussed in the section on basic resins are not considered carcinogenic.
research, recent work shows the polymer quite Butvar and Formvar resin flash points are
nonrandom. The distribution of hydroxyl can >7oo°F. The flammable limit for Butvar dust
influence performance; particularly solution is 0.020 ounce per cubic foot in air. In appli-
properties. 2-4 Matsuda's work4 highlights the cation, Butvar and Formvar resins can be for-
influence of the acetal process on the polyvinyl mulated to meet FDA extractability
butyral heterogeneity. While commercial prod- requireme~ts. Butvar resins can be used in ac-
ucts are far less dramatically dissimilar than cordance with CFR regulations 175.105,
Matsuda's examples, it is recommended to 175.300, 176.170, and 176.180 as ingredients

H
I
CH -C
2 I
OH

A B c
PV Acetal PV Alcohol PV Acetate

Fig. 2.
 POLYVINYL ACETAL ADHESIVES 425

ACETAL ACETAL nonpolar solvents. Polyvinyl formals are solu-

T OH
To ble in mixtures of polar and nonpolar solvents.
The higher acetate polyvinyl formal products
are also soluble in glycol ethers, esters, and ke-
I
C=O
tones. Table I is a representative list of appli-
cable solvents. Examples of solubility
NCO I parameters for commercial polyvinyl acetals
I NH
R Diisocyanate I appear in Table 2.
I Tertiary Amine R The influence of the terpolymer structure on
NCO
----~·N~ solubility and compatibility can be generally
I described by Fig. 8. 7
C=O
Aqueous dispersions of polyvinyl butyral are
OH I also available. 8 The dispersion particle size is
o

~
ACETAL
~-
ACETAL
< 1 ",m. The dispersion is anionic and has a
pH of9-10.

Compatibility
Fig. 3. Reaction with isocyanates.
Polyvinyl acetal compatibility is principally
of can enamels, adhesives, and components of driven by the hydroxyl or acetate content of the
paper and paperboard in contact with aqueous acetal. A general guide for compatibility of
and fatty foods. acetals with various solids is given by the ex-
amples in Table 3. Alloying with other solids
PHYSICAL PROPERTIES is often used to alter the physical and chemical
properties of acetals to achieve the best cost/
Solubility
performance ratio.
Polyvinyl butyrals are soluble in alcohols, gly- A wide variety of compatible plasticizers
col ethers, and selected mixtures of polar and have been used. For many years, the univer-

-0--
ACETAL

I
OH

HOH'C-O---~:N~~-- C~:H
CH l CH l I

I ACETAL ~
ACETAL

o lH+
H,C-O------Or
I OH OH

CH l CHl~

ACETAL

Fig. 4. Reaction with phenolics.

426 HANDBOOK OF ADHESIVES

ACETAL

-CH-CH 2-CH-
I
OH
I
OH

o H+
II
HC
I
CH
~
o

ACETAL

Fig. 5. Reaction with dialdehydes.

sally used plasticizer for polyvinyl butyral was ible plasticizers for the butyral can be found in
triethylene glycol-bis(2-ethyl butyrate).9 Re- Ref. 17. Recommended plasticizers for the bu-
cently this has been supplanted by adipates, tet- tyral and formal can be found in Ref. 18.
raethylene glycol derivatives, butyl sebacate, Long-term compatibility of Saflex with var-
ricinoleates, and others. lO- l8 A list of compat- ious sealants can be found in Ref. 18. Sears

ACETAL
-r-
OH

N N
~'\ ~\
HOH 2C-NH - C C- NH - - - HN - C C - NH-CH OH
I II I II 2
N N N N

'-c/ MELAMINE '\C/

I RESIN I
NH2 NH2

HO
I
ACETAL ACETAL
I
o
I ~\
N N
~\
H2C-NH - C C- NH - - - HN - C C - NH-CH2
I II I II I
N N N N 0
~/
C
'\/
C
I I
NH2 NH2
ACETAL

Fig. 6. Reaction with melamines.

 POLYVINYL ACETAL ADHESIVES 427

Typical Epoxy Resin

ACETAL ACETAL
I I
OH
°I
° _~. ·rrc=o
QI\
~ C
II
°
VLc=o
I
-CH-CH.
I
OH
°I
•

/0"
-CH--CH 2

EPOXY

Fig. 7. Reaction with epoxies (anhydride cure).

PVOH 100%

PYA 0%

PVAc 100% PVOIl 0% PYA 100%

S Solubility
IS Insolubility
C CompatiblUty
IC IncompatiblUty
lfS 'Water Solubility
WR Water Resistance
SP Softening Property
Fig. 8.
428 HANDBOOK OF ADHESIVES

Table 1. Solvents for Polyvinyl Acetal Resins.

Polyvinyl Formal Polyvinyl Butyral
Low Medium Low High
Acetate Acetate Hydroxyl Hydroxyl
Acetic acid (glacial) s s S S
Acetone S I
n-Butanol S S
Butal acetate S I
Carbon tetrachloride

Cresy lie acid s s S S

Cyclohexanone s S S
Diacetone alcohol S S S
Diisobuty I ketone I I S I
Dioxane S S S S

N ,N-Dimethylacetamide s s S S
N ,N-Dimethylformamide s s S S

Ethanol,95% S S
Ethyl acetate, 99% S I
Ethyl acetate, 85% S S
Ethyl "Cellosolve" S S
Ethylene chloride s S S S
Hexane I I I

Isopropanol, 95 % S S
Methyl acetate S S
Methanol I I S
Methyl "Cellosolve" I s S S
Methyl "Cellosolve" acetate I s S I
Methylbutynol S s S S
Methylpentynol S S S S
Methylethyl ketone I I S I
Methylisobutyl ketone I I S I
N-methyl-2-pyrrolidone S S S S
Nitropropane I S I I
Toluene I S I
Toluene-ethyl alcohol s S S S
(60: 40 by weight)

Xylene I I I
Xylene-n-butanol I S S
(60:40 by weight)
S = Completely soluble.
I = Insoluble or not completely soluble.
Source: Butvar/Formvar Technical Bulletin No. 6070A, Monsanto Chemical Co.

Table 2. Solubility Parameter Ranges.

Medium
Low Hydrogen Hydrogen High Hydrogen
Bonding Solvents Bonding Solvents Bonding Solvents

Medium acetate polyvinyl formal 9.3-10.9 9.2-12.9 9.2-12.1

Low acetate polyvinyl formal 9.3-10.0 9.7-10.4 9.9-11.8
Low hydroxyl polyvinyl butyral 9.0-9.8 8.4-12.9 9.7-12.9
High hydroxyl polyvinyl butyral Insoluble 9.9-12.9 9.7-14.3
Source: Butvar/Formvar Technical Bulletin No. 6070A, Monsanto Chemical Co.
 POLYVINYL ACETAL ADHESIVES 429

Table 3. Compatibility of Acetals. *

Polyvinyl Butyral Polyvinyl Formal
Low High High Low
Hydroxyl Hydroxyl Acetate Acetate
Acrylate

Alkyd
Rezy1807-1 P P P P
Duraplex C-49 P P P P
Beckosol 1334-50EL P P P P

Alpha pinene
Newport V-40 C C C C

Cellulose
Cellulose acetate I I I
Cellulose acetate butyrate P P P P
Ethyl cellulose P P I I
Nitrocellulose, RS C C P
Nitrocellulose, SS C C I

Chlorinated rubber

Cournarone-indene P P

Epoxy
Epi-Rez 540 C C C C
Epon 1001, 1007 C C C C
Araldite 6097 C C C C

Fossil
Damar C C

Isocyanate
MondurS C C C C

Ketone formaldehyde
Advaresin KF C C P P

Melamine formaldehyde
Resimene~ 881 and 882 P P P P
Resimene 730 and 740 P P P P

Phenolic, unmodified
Amberol ST-137 C C
BKR-2620 C C P P
BV-16oo C C
BV-27l0 P P C C
GE75-108 C C C C
Resinox~ P-97 C C C C

Rosin derivatives
Pentalyn H P P
Staybelite Ester 10 C P
Vinsol C C C C

Shellac C C

( Continued on page 430)

430 HANDBOOK OF ADHESIVES

Table 3. ( Continued)
Polyvinyl Butyral Polyvinyl Formal
Low High High Low
Hydroxyl Hydroxyl Acetate Acetate
Silicone
SR82 C C P P
SR 111 C P P P
DC 840 C P P P
DCZ 6018 C P P P

Sulfonamid
Santolite~ MHP P P

Urea formaldehyde
Uformite F-240 P P P P

Vinyl chloride copolymer P

VAGH
-aegistered trademark of Monsanto Co.
C = Compatible in all proportions.
P = Partially compatible.
I = Incompatible.
*Refers to film compatibility provided mutual solvents are used.

describes the approximate solubility and com- received considerable attention in developing
patibility limits for polyvinyl butyral as quan- gel permeation measurement of molecular
tified by solubility parameter, dielectric weight. 2,3,73 For applications which require
constant, and hydrogen bonding index in ref- molecular weight to predict melt behavior,
erences. 17 ,19 This information is helpful in pre- rheological measurement above 100°C avoids
dicting the effectiveness of current the distortion of aggregates. However, even
environmentally acceptable solvents and plas- melt viscosity is not Ii true measure of molec-
ticizers. ular weight and molecular weight distribution
since branching and polymer nQnlinearity influ-
Viscosity ence high temperature rheology.
Solution viscosity continues to be the measure-
Mechanical Properties
ment of choice for screening molecular weight
of polyvinyl acetals. Where application perfor- A wide range of strength and flexibility arise
mance requires fine control of molecular from the selection of aldehyde, polymer mo-
weight, solution viscosity is impaired by the lecular length and the hydroxyl and acetate
complex solution behavior of these hydro- composition. Fig. 9 is extrapolated from the
phylic/hydrophobic polymers. Table 4 is an ex- Monsanto product bulletin and compares three
ample of the relative sensitivity of solution mechanical properties for a butyral and a for-
viscosity of polyvinyl butyral in methanol to mal of equal length, with acetates computed at
various parameters. 1.5 and 10 weight percent, respectively. The
Finchs describes the difficulties in measuring scales are in dynes/cm2 divided by 108 • Fig. 9
solution viscosity of water soluble polymers. illustrates the characteristically higher modulus
Since polyvinyl acetals have both water soluble of the formal. The circles amplify the scale.
and non-water soluble segments, solvent type The average leverage for a change of 100
plus inter- and intramolecular heterogeneity monomer units or 1 weight per cent hydroxyl
also influence viscosity . is highlighted for three mechanical properties.
Aggregation of the polymer in solution has For example, increasing the degree of poly-
 POLYVINYL ACETAL ADHESIVES 431

Table 4. Polyvinyl Butyral Solution Viscosity.

Average D. P.
1200 1700 1900 2100
.i
Variable Var. .iVisc. (cps)
D.P. 100.0 17.1 32.5 48.0
MW/MN 0.5 7.0 18.7 34.1
OH 1.0 3.5 9.4 17.1
TS 0.1 17.3
Temp. 1.0 9.5
PVB Solution = 7.5 wt % - in methanol @ 20°C. Change in viscosity corresponding to change in:
D.P. = degree of polymerization. monomer units
MW IMN = polydispersity

OH = residual hydroxyl. wt %
TS = % solids in the PVB solution

Temp. = Solution temperature. °C.

merization (DP) of a butyral or formal 100 tion of the aldehyde while hydroxyl and acetate
monomer units will increase the modulus of have significant but less influence.
elasticity 8 x 107 dynes/cm2. Polyvinyl acetals have excellent impact
Higher acetate will in general reduce modu- strength. The amount of energy absorbed by
lus. polyvinyl acetals is principally a function of the
Mechanical hardness is dominantly a func- composite in which they are employed.

Modulus of Elasticity
(dynes/cm2) x 10- 8 (ASTM D638-S8T)

60
as
60
40

20 Flexural Strength at Yield

(dynes/cm2) x 10- 8 (ASTM D790-S9T)
9
7
5
3 Tensile Strength at Break
(dynes/cm2) x 10- 8 (ASTM D38-S8T)
1

~ (dynes/cm2) x 10- 8 /100 DP

e (dynes/cm2) x 10- 8 /wt % OH

Fig. 9. Mechanical properties.

432 HANDBOOK OF ADHESIVES

Thermal Properties turer can be helpful for applications or prepro-

cessing at moderate temperature.
As with mechanical properties, a wide range of
The thennal glass transition temperature
thennal perfonnance results from the selection
(TGt) of polyvinylacetals of aliphatic aldehydes
of aldehyde, the molecular length and the hy-
can be estimated from
droxyl and acetate composition. Fig. 10 com-
pares three thennal properties for the equivalent TGt = 65 + 1.26 * (OH - 19.0)
butyral and fonnal computed in the mechanical
property example. High temperature perfor- - 0.6 * (OAC - 1.5) + 46 * Ln(4jC)
mance is dictated by the type of aldehyde and
the polymer length. Polymer length has de- OH and OAC are weight per cent hydroxyl and
creasing influence on thennal perfonnance as acetate. C is the number of carbons in the orig-
the temperature decreases. inal aldehyde. The equation is centered for a
Predicting property perfonnance of polyvi- typical polyvinyl butyral of 19 weight percent
nyl acetals at moderate temperature can be dif- hydroxyl and 1.5 weight per cent acetate. For
ficult. As is illustrated in Fig. 10, with the this typical butyral (C = 4, OH = 19.0, and
exception of acetal type, the moderate temper- OAC = 1.5) the equation reduces to a pre-
ature thennal perfonnance can be equally le- dicted thennal glass transition of 65°C. The
veraged by the polymer length, and the level of standard error of the estimate is 3 °C based on
hydroxyl and acetate. In addition, distribution data from the general references and Ref. 21.
of polymer composition and polymer length Polyvinyl acetals of any glass transition tem-
significantly influence applications. 4 ,3,2o A perature between roughly 20°C to 120°C can
close working relationship with the manufac- be obtained by fonnulating with mixed alde-

Flo" Temperature at 1000 pst

(AS'1'II D569-(9)
60
4O
30
20
Beat Seallns Temperature (1)
10
00 Beat Distortion Temperature
90 90 (AS'I'M D646-(6)
80 80
70 70
Property Respon8e
60
50
60
50 g des e/lDO DP

Bdes e/wt ~ OR

e/wt
~
del ~ OAe

Fig. 10. Thennal properties.

 POLYVINYL ACETAL ADHESIVES 433

hydes. 21 Glass temperatures for mixed alde- Thermosetting Adhesives.

hyde polymers can be estimated using the above
Polyvinyl acetals are combined with other
equations by computing C on the basis of the
components to provide toughness, flexibility,
aldehyde mole ratio used. For example: a poly-
and high adhesive strength in high performance
vinyl acetal with a respective 30/70 mole ratio
thermosetting adhesives. Their use with olefins
of butyral to hexyral would compute to have a
is described in references. 25 ,26
Cvalue of 5.4; at 19% hydroxyl the TGm equals
49°C.
Adhesion to Metal
For most applications the glass transition is
far more practically manipulated with plasticiz- The first and most extensive use of polyvinyl
ers. From Fitzhugh's data22 the mechanical formal is an insulator for electrical wire. A
glass transition temperature lowers on average 1943 General Electric patent27 describes the
1.3°C per part dibutylphthalate (DBP) added to typical 105°C formulation. Polyvinyl formal
one hundred parts polymer. The glass transi- resins have since been formulated into many
tion temperature for DBP plasticized polyvinyl different wire enamel applications. These in-
acetals, TGp' can be estimated from the fraction clude solderable enamels, high cut-through
of plasticizer P and the mechanical resin glass enamels, Freon-resistant enamels for hermeti-
transition temperature TGm' using cally sealed motors, and multicoat magnetic
wires for ISS-180°C performance. 28-30 Work
Ln( TGp/TGm ) to improve wire enamels is contained in Refs.
31-35.
= -13.8 * P1. 5 /(1 + 2.3 * P) Drum and can linings contain polyvinyl ace-
tals. In addition to adhesion, the acetals pro-
Below the glass transition temperature the poly-
vide coating uniformity, flexibility, toughness,
vinyl acetals of aldehydes with fewer carbons
and reduce cratering. They can be compounded
than butyral exhibit moduli above the 2 x 1010
and formed into baked coatings that have good
dynes/cm2 associated with fully amorphous
chemical resistance and withstand postform-
polymers. The butyral and higher aldehydic
ing. The coatings can be formulated to meet
carbon acetals are probably less oriented and
FDA requirements.
exhibit moduli in line with fully amorphous
A well known metal adhesion application is
polymers. The embrittlement temperature is
in washed primers. Application information is
precipitously lower for acetals with four or
available. 36 Additional information is provided
more carbons in the original aldehyde.
in the general references and Refs. 37 and 38.
The butyral has commercially evolved as the
The Navy has long recognized the need to pre-
dominant polyvinyl acetal; the butyral provides
treat a metal surface prior to painting to inhibit
flexible toughness over a wide range of tem-
corrosion and promote adhesion and specifies
peratures and at lower cost than the higher al-
wash primers in MIL-P-15328C and MIL-C-
dehydic carbon acetals. Where stiffer
8514B.
performance at higher temperatures is required,
the formal provides significant property ad-
Adhesion to Natural Surfaces
vancement at lowest cost.
Polyvinyl butyral is the acetal usually selected
for adhesion to natural surfaces. Application to
USES AS AN ADHESIVE wood39-42 confers good holdout, intercoat
adhesion, moisture resistance, flexibility,
Hot Melts
toughness, impact resistance, and protection
Polyvinyl butyral is an excellent base for hot- against discoloration. Application to textiles,
melt adhesives, particularly in applications with natural and synthetic, 43 improves stain and
difficult-to-bond surfaces. The butyral resin is water resistance without noticeably affecting
usually formulated with plasticizers, waxes, feel, drape, or color. Textiles with improved
and other resins. 23 ,24 fire resistance, dyeability, or leatherlike char-
434 HANDBOOK OF ADHESIVES

acteristics have been patented in the USSR and cent years architectural applications have been
Japan. 44 -47 Aqueous butyral dispersions are ad- developed in which safety, security, sound
hered to textiles where room temperature drying control, and solar energy control are mani-
is important. 8 Polyvinyl acetals are selected as fested. 62 ,63 The product permits freedom in de-
adhesives on paper in a variety of reproduction sign, and the market for architectural bent glass
technologies: reprographics, photography, xe- is growing. 64
rographic toners, and dielectric coatings.
Other Uses
Green Strength Binder
The preceding examples of applications, while
Polyvinyl butyral adheres prefired molded parts not comprehensive, illustrate the flexibility of
in a variety of applications. These range from polyvinyl acetals in application as well as func-
sand castings48 for steel forging to interim tapes tion. Not discussed are applications in inks,
for high quality ceramics for electronics. 49-53 dyes, printing plates, films, foams, filters,
In addition to adhesion to the variety of inor- membranes, and sponges. Miscellaneous ap-
ganic components in these applications, poly- plications include combustible cartridges,
vinyl butyral provides flexibility and strength wound dressing, surgical sutures, polarized
to the unfired part. In some processes these lenses, fluxes for welding and soldering, and
parts have sufficient green strength to be ma- phonograph-record cleaners. 65-72
chined.
BASIC RESEARCH
Composites Advances in analytical methods are gradually
Polyvinyl butyral finds an important role in permitting quantification of structural hetero-
strengthening high strength plastics. DuPont's geneity independent from inter- and intramo-
aromatic polyamide, Kevlar®, combined with lecular compositional heterogeneity. This
polyvinyl butyral and phenol-formaldehyde, separation has been a long standing problem in
laminates into lIght-weight bullet-resistant hel- determining accurate molecular weight data.
mets and armor plate. 54-55 Monsanto's Saflex Data by L. Mrkvickova2 and P. M. Cotts3 are
SX laminates with polycarbonate to provide a consistent with unpublished work of E. E.
transparent bullet-resistant glazing. DuPont of- Remsen. 73 NMR has also been helpful,74 and
fers an anti-Iacerative sheeting which is a lam- two-dimensional NMR measurements have
inate of polyvinyl butyral and oriented been made. 75 ,76 In spite of dramatic advances,
polyethylene terephthalate and when adhered to quantification of structure and compositional
glass provides protection against glass splinter- heterogeneity sufficient to comprehensively
ing on impact. 56 predict application performance is well in the
future.
Adhesion to Glass
ACKNOWLEDGMENT
Perhaps the accolade which best suits the nearly
half-century-old product of glass/plasticized We wish to acknowledge our co-workers within
polyvinyl butyral/glass is from John St. Clair. 57 Monsanto's Saflex and Resins business unit.
In his article on the manufacture of laminated We specifically acknowledge Drs. E. Lavin and
glass, Mr. St. Clair comments that he is not J. A. Snelgrove for their earlier labors in this
aware of any laminated glass made with poly- regard, and the preparation assistance of L. M.
vinyl butyral which could have been said to Daudelin and N. E. Franco.
have failed through old age. A history of the
product is available in Refs. 58-61. GENERAL REFERENCES
In addition to longevity the product meets
Butvar/Fonnvar Technical Bulletin No. 6070A, Monsanto
very stringent quality standards for consistent Chemical Company, 800 North Lindbergh Blvd., St.
impact performance and optical quality. The Louis, MO. 63166.
principal use is automotive windshields. In re- Lavin, E., and Snelgrove, J. A., in "Kirk-Othmer Ency-
 POLYVINYL ACETAL ADHESIVES 435

clopedia of Chemical Technology," 3rd Ed., Vol. 23, Poly(vinyl acetals) Derived from Poly(vinyl alcohol)
pp. 798-816, New York, John Wiley & Sons, 1983. and 2,6-Dichlorobenzaldehyde," Macromolecules,
16(2}, 191-296 1983.
21. Cartier, R. G., unpUblished data, Monsanto Co., 730
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436 HANDBOOK OF ADHESIVES

50. Anderson, L. C., Nufer, R. W., and Pugliese, F. G. 64. Block, V., "New Markets for Bent Glass," Glass Di-
(to I.B.M. Corp.) Gennan Patent 2,227,343 (Jan. 18, gest, Nov. 15, 1986.
1973). 65. Remaly, R. F., Shefcik, W. P., and Nelson, M. B.
51. Howatt, G. N., U.S. Patent 2,582,993 (Jan. 22, (to U.S. Dept. of the Army) U.S. Patent 3,474,702
1952). (Oct. 28, 1969).
52. Park, J. L. Jr. (to American Lava Corp.), U.S. Patent 66. Mueller, H. (to Beiersdorf A.G.) Gennan Patent
2,966,719 (Jan. 3, 1961). 1,939,916 (Feb. 4, 1971).
53. Mistler, R. E., et al. "Tape Casting of Ceramics." 67. French Patent 1,589,917 (May 15, 1970) (to Henkel
54. "A Plastic Helmet for Soldiers," Chemical Week, and Co. GmbH).
31(23), 114, 116 (Dec. 8, 1982). 68. Fritsch, S., Pharmazie, 22(1), 41 (1967).
55. Layman, P. L., "Aramids, Unlike Other Fibers, Con- 69. Marks, A. M., and Marks, M. M., U.S. Patent
tinue Strong," C & E News, 60(6), 23-24 (Feb. 8, 3,300,436 (Jan. 24, 1967).
1982). 70. Makinov, V. P., and Lezhnikov, V. P., USSR Patent
56. "Face Saving Windshields," Du Pont Magazine, SO, 360,187 (Nov. 28, 1972); Khuzman, I. A., et al.,
20 (Sept/Oct, 1986). USSR Patent 359,117 (Dec. 3, 1972).
57. St. Clair, J. R., "How High Quality Laminated Glass 71. Susuki, F. K., and Thomas, T. W. (to Liquid Crystal
Is Made" Glass Industry, Nov. 1984. Products, Inc.) U.S. Patent 4,161,557 (Mar. 28,
58. "A Century of Acheivement 1883-1983," PPG 1978).
Products Magazine. 91(2), (1983). 72. Japanese Patent 80157,698 (Dec. 10,1980) (to Shin-
59. Weidlein, E. R., "History and Development of Lam- Etsu Polymer Co., Ltd.).
inated Safety Glass," Indust. Eng. Chern., 31(5), 563- 73. Remsen, E. E., and Gillham, P. D., unpublished GPC
566 (May, 1939). work, Monsanto Chemical Company, 800 N. Lind-
60. Wise, H. G., "The Manufacture of Safety Glass," J. berg Blvd., St. Louis, MO 63166.
Record Trans. Junior Inst. Engrs., 48, 532-539 74. Schacht, E., Desmarets, G., Goethals, E., and St.
(1937-1938). Pierre, T., "Synthesis and Hydrolysis of Poly(vinyl
61. Wilson, J., "Safety Glass: Its History, Manufacture, acetals) Derived from Poly(vinyl alcohol) and 2,6-
Testing; and Development," J. Soc. Glass Technol., dichlorobenzaldehyde," Macromolecules, 16, 291-
16 (1932). 296 (1983).
62. Laminated Architectural Glass, Specification Guide, 75. Leo, Greg, unpublished analysis, Monsanto Co., St.
Monsanto Chemical Company, St. Louis., Mo. Louis, MO.
63. Architectural Saftex Interlayer for Solar Control, 76. Bruch, M. D., NMR Newsletter No. 333, Texas A&M
Technical Bulletin No. 6295D, Monsanto Chemical University, June, 1986.
Company, St. Louis, Mo.
 25
Acrylic Adhesives
DAVID R. GEHMAN
Technical Manager-Adhesives Research Dept.
Rohm and Haas Company
Spring House, Pennsylvania

In 1901, at Tuebingen, Gennany, a doctoral widely used as the basis for adhesives for pres-
candidate named Otto Rohm published a thesis sure sensitive tapes, labels, and other decora-
describing liquid condensation products ob- tive and functional pressure sensitive products.
tained from the action of sodium alkyoxides on These applications capitalize on the versatile
methyl and ethyl acrylate. He also discussed adhesion and the excellent aging characteristics
the chemical nature of the polymer materials of this class of polymer.
fonned simultaneously in these reactions. With Acrylic materials are also widely used as
this work, Dr. Rohm put in motion a chapter elastomers and thickener components in a va-
of chemical history which blossomed in the en- riety of waterborne construction adhesives,
suing half century into a significant commercial laminating adhesives, and packaging adhe-
factor in the adhesives, plastics, coatings, and sives. Sometimes, the polyacrylate portion of
other industries. During this half century, a these adhesives is minor, contributing a thick-
number of processes have reached commercial ening function to such other elastomers as sty-
utilization for the manufacture of the acrylate rene-butadiene latex and polyvinyl acetate
monomers and for the variety of polymer ma- compounds. A variety of specialty laminating
terials which are derived from those mono- adhesives, in both filled and unfilled fonn, uti-
mers. lize acrylic elastomers to bond dissimilar sur-
Polymeric products used in the design of sol- faces in operations which are perfonned via wet
vent and waterborne acrylic adhesives as well laminating, pressure sensitive laminating, con-
as 100% solids reactive adhesives all have a tact bonding, and heat sealing operations.
number of characteristics in common. The most Finally, acrylic chemistry is the basis for a
noteworthy of these features are: number of 100% solids reactive engineering
adhesives used in structural bonding applica-
• Low Temperature perfonnance
tions, generally involving metal or plastic non-
• Broad adhesion spectrum
porous surfaces.
• Water resistance
• Easily fonnulated
• Excellent optical properties
TECHNOLOGY
• Durability
• Low toxicity Chemistry
Acrylic adhesive polymers, both in aqueous Acrylic adhesive polymers are synthesized from
emulsion fonn and solvent solution fonn, are a wide selection of acrylic and methacrylic es-

437
438 HANDBOOK OF ADHESIVES

ter monomers and almost always with low lev- The acrylate polymers have an alpha hydro-
els of monomers having pendant functional gen adjacent to the carbonyl group and, there-
groups (for post crosslinking and/or special fore, have more rotational freedom than the
adhesion needs). More specifically, acrylic ad- methacrylates. The substitution of a methyl
hesives are based mainly on ethyl, butyl and 2- group for the hydrogen atom (producing a
ethyl hexyl acrylate monomers, plus small methacrylate polymer) restricts the freedom of
quantities of methyl methacrylate, and acrylic rotation of the polymer (steric hindrance) and
and/or methacrylic acids, and other specialty thus produces harder, higher tensile strength
acrylic monomers. Frequently, the acrylic and lower elongation polymers than their ac-
monomers are copolymerized with other vinyl rylate counterparts.
monomers such as vinyl acetate, vinyl chlo- The ester side chain group also affects prop-
ride, styrene, etc. The high reactivity of vinyl erties significantly. As the ester side chain be-
groups permits the synthesis of linear polymers comes larger, the tensile strength of the
of very high molecular weight. polymer is decreased and its elongation in-
Most commercial processes are free-radical- creases.
type addition reactions conducted at elevated Various monomers impart characteristic film
temperature in the presence of an initiator. properties to the acrylic polymer (see Table 1).
Acrylic adhesives are made in a variety of These monomer modifications also affect pol-
physical forms, such as organic solutions, ymer polarity and solubility, as well as the glass
aqueous emulsions, suspensions, and carrier- transition temperature of the polymer.
free solid materials that are melt applied. The characteristic properties of a polymer are
Acrylics are available as thermoplastics, which greatly influenced by the conditions of poly-
melt and flow at high temperatures, and as merization. Variations in catalyst level, reac-
semireactive or thermosetting crosslinkable tion time, temperature, and monomer con-
systems which yield solvent- and heat-resistant centration make it possible to adjust the poly-
polymers. In contrast, water soluble polymers mer's molecular weight and ultimately its
can be made through proper monomer selection physical properties.
and functional group cappings. Chemically, Solution thermoplastic acrylics form coher-
these products are long chain polymers of ent films simply by solvent evaporation without
methacrylate and acrylate esters. The physical post-filming reactions taking, place. Therefore,
properties of the acrylic polymers are influ- the properties of thermoplastic resins depend
enced by the alpha position entity of the acid primarily on the necessity of physical entangle-
(hydrogen atom or methyl group) and by the ments between long chain molecules and sec-
length of the alcohol side chain modification. 1 ondary bonding forces «5 kcal/mole). Thus,
See Fig. 1. it is possible to obtain with the same monomer

CH 2 =CH CH2 =CH

I 0 I~o_
C~OH C-OC2H5
acrylic acid ethyl acrylate

CH
CH2 =CH CH 2 =c7 3 CH 2 =CH
I .:f-O 1,,::0 I~O
C-OC4 Hg C~ OCH2 CH20H C-NH2
butyl acrylate hydroxyethyl methacrylate acrylamide
Fig. 1. Chemical structures of adhesives.
 ACRYLIC ADHESIVES 439

Table 1. Mechanical Properties. 2

Tensile
Strength (psi) Elongation (%)
Polymethacrylate
Methyl 9,000 4
N
1~~====~~----4---~--~--
Ethyl 5,000 7 E
Butyl 1,000 230 "
~ 1()3 ~-----""*-+---+---I'---
Polyacrylates m
Methyl 1,000 750
£ 102=-------~rl_--+-__I-­
'i;i
Ethyl 33 1,800
Butyl 3 2,000 ~'" 101e---------------~~~--

10° LT;;n;:;;.:;;:turi!:iiiC:re.;;r.;;;-=========~
Temperature, increasing
esters, by molecular weight variation, poly- Fig. 2.
mers with broad variation in viscoelastic me-
chanical properties.
The viscosity of solution polymers increases after increases with increasing chain length of
directly with molecular weight. Performance the alcohols, the polymers attaining a wax-like
properties begin to plateau as molecular weight consistency (Fig. 3).3
increases, but viscosity continues to increase. Numerous investigations have been made
Thermosetting solution acrylic resins are po- into the factors influencing Tg • Most of these
lymerized to lower molecular weight than ther- are related to the effect of molecular structure
moplastic acrylics, since they attain their prop- and chemical composition:
erty performance by conversion to infinite 1. Side Chain Effects. The further apart the
three-dimensional networks by chemical reac- chains in the polymer, the greater the
tion (forming primary chemical bonds). segmental mobility.
2. Chain Stiffness. The extra CH3 group in
Glass Transition Temperature (Tg) a methacrylate causes additional steric
The glass transition temperature of acrylic hindrance to movement which, in tum,
polymers is one of the most important charac- raises the glass temperature.
teristics governing many of the properties that
are important in adhesives. 100
All polymers exhibit a second order transi-
tion temperature range at which the polymer
changes from a hard, glasslike solid to a rub-
bery or liquid state, depending on the molecu-
lar weight and/or chemical bonding. This [;J
transition is a reflection of the entropy (free- ...
<:
40

dom of motion) characteristics of the polymer. '8.,. 20

At a certain temperature range, polymer mol- "E
ecules receive sufficient thermal energy to break ~
0\
out of their "frozen" configurations into a state
of rapid segmental motion. In this highly agi-
-20 •
,
tated state, the physical entanglements between -40 " n = alkyl
' ... acrylates I
the long-chain molecules have more freedom " I
of motion and thus impart the rubbery or tacky -60 '-4 ...."
semi-solid properties (see Fig. 2). As shown by 2 4 6 8 10 12 14 16
Rehberg and Fisher,4 the brittle point of the ho- Carbon atoms in the alkyl group
mopolymer drops to its lowest value with 8 and Fig. 3. Brittle points of polymeric n-alkyl acrylates and
12 carbon atoms in the alkyl group and there- methacrylates. 4
440 HANDBOOK OF ADHESIVES

3. Branching. A branched group on the side performance. If the degree of crosslinking is

chain also raises the Tg; t-butyl has a too high, brittle products are produced and,
much higher Tg than n-butyl. These trends conversely, too low a level results in poor re-
are illustrated in Table 2. sistance properties. Table 3 outlines the typical
4. Copolymers, Internal Plasticization. By catalysts and crosslinkers for the thermosetting
copolymerizing more than one type of acrylic systems. 6
acrylic monomer, polymers with inter-
mediate Tg values can be prepared. Fox5
has proposed the following equation for BONDING PROCESSES
calculating the Tg of copolymer from We can classify acrylic adhesive bond forma-
known values of the homopolymers: tion into four different processes:
• Pressure sensitive bonding
• Wet laminating
• Contact bonding
• Heat and pressure bonding
5. Crosslinking. Crosslinking prevents the
onset of rubbery flow by the formation of These approaches are dictated by coating and
chemical bonds which impede segmental drying requirements, substrate porosity, water
motion. and solvent sensitivity, open time require-
ments, and urgency of bond strength develop-
ment. Acrylic polymers are being used in all
Crosslinked Thermosets
the above bonding processes. A comprehensive
Thermosetting acrylic resins are characterized review of each follows.
as vinyl addition polymers having pendant
chemical groups capable of further reaction. Pressure Sensitive
The most important commercial materials used
Pressure sensitive adhesives form a permanent
at present contain amide, carboxyl, hydroxyl,
tacky film after the evaporation of the liquid
or epoxy functionality. As in other interpoly-
phase or after cooling of a hot melt. Bonding
mer systems, the film properties may be altered
is effected by slightly pressing the adhesive
in several ways: variation in backbone com-
surface onto the adherend. Pressure sensitives
position, use of curing catalyst, and variation
can demonstrate a wide range of adhesive prop-
in the amount of crosslinking agent.
erties, from permanent bondings to removable
Catalysts, either internal or external, have the
tapes and films.
effect of accelerating cure response at a lower
A number of polymeric raw materials are
bake temperature. Curing temperatures are nor-
used in the pressure sensitive adhesive market.
mally reduced by 50-100°F by the addition of
They include: natural rubber, polyisobutylene,
catalyst.
polyvinyl ether, various types of synthetic rub-
The level of crosslinking agent added should
ber such as styrene-butadiene and -ethylene co-
be determined for the various thermosetting
polymers, polyurethane, and acrylics.
types to determine optimization of property
The most important properties of any pres-
sure sensitive adhesive are a balanced relation-
Table 2. Glass Transition Temperature, ship of tack, cohesion, and adhesion. To these
Tg (OC). properties, acrylic pressure sensitives add the
Ester Methacrylate Acrylate valuable qualities of heat resistance and resis-
tance to aging and UV radiation. Another de-
Methyl 105 9
Ethyl 65 -22 sirable characteristic of acrylics is that, in
t-Butyl 107 41 general, tackifiers are not required because tack
s-Butyl 48 -43 can be designed into the polymer through the
n-Butyl 20 -54 proper choice of acrylic monomers. These and
2-Ethylhexyl -10 -82
other properties of acrylic pressure sensitive
 ACRYLIC ADHESIVES 441

Table 3. Catalysts and Crosslinkers for Thermosetting Acrylic Systems.

Pendant Group on Reactive Monomer
Acrylic or Methacrylic Containing Pendant Resin Co-reacted
Polymer Group to Effect Cure Catalyst
Acrylamide or methacryl- Epoxy, alkoxy arni- Acidic-AA or MAA
amide converted with noplasts, carboxyl (internal); H3P04 ,
CH20 + alcohol to an containing PTSA
ether
-COOH Acrylic or methacrylic acid Epoxy Basic-benzyl, dimeth-
ylamine, triethanol-
amine
Hydroxyethyl or hydroxyl- Alkoxy aminoplasts Acids
propyl methacrylate
-CH-CH- Glycidyl methacrylate Carboxylic polymers Acidic-MAA or AA
"o / (internal), NJ4CI,
PTSA; Basic-
DMAEMA (inter-
nal) quat-ammonium
compounds
AA: acrylic acid. MAA: methacrylic acid. PTSA: p-toluenesulfonic acid. DMAEMA: dimethylaminoethyl methacrylate.

adhesives have gained them a significant share cently aqueous emulsion acrylic polymers have
of the pressure sensitive market. been develope<;l that in many cases match the
Principal applications for pressure sensitive performance of the solvent based acrylic ad-
acrylics are a broad assortment of tapes and la- hesives. 8 The ability to coat water-based sys-
bels, decals, and other decorative films. tems on high speed film coating machines,
Acrylics also have some uses in laminating ad- along with the obvious advantages in lower
hesives, primarily for film-to-film laminates. In cost, safety, and environmental protection, has
addition, acrylics have been used in sound- led to a rapid growth in the use of water-based
deadening pads for automobiles and appli- adhesives. While the acrylic hot melts have of-
ances. fered the same advantages, there have been
To be suitable as a pressure sensitive adhe- technical difficulties in obtaining adequate co-
sive, acrylic adhesives are based on acrylic es- hesive strength without an excessively high
ters with four or more carbon atoms, the most melt viscosity which have limited their com-
common of which are n-butyl acrylate and 2- mercial use.
ethylhexyl acrylate. These acrylates are co-
polymerized with other monomers such as Formulation. Unlike the natural rubber
acrylonitrile, methyl methacrylate, other acry- pressure sensitive adhesives, acrylic adhesives
lates, styrene, vinyl acetate, and cx,{3- unsatu- are often supplied in a ready-to-use form. Nat-
rated carboxylic acids, depending on the ural rubber adhesives require time-consuming
adhesive properties required. 7 This versatility and costly mastication of the rubber followed
inherent in the acrylics has led to the design of by dissolving in solvent. 9 In addition, they must
products requiring widely different adhesive be formulated with a tackifier resin and antiox-
properties, from those of permanent labels and idants, neither of which is required with an
high performance tapes to removable labels and acrylic adhesive. The acrylic adhesives are
films. 8 known for their good UV and oxidative stabil-
Pressure sensitive acrylic adhesives are ity while the rubber-based adhesives, because
available in the form of solutions in organic of their chemical unsaturation, are poor in these
solvents, aqueous emulsions, and 100% solid properties. In general, tackifiers are not re-
(hot melt). Traditionally, acrylic adhesives quired with acrylic adhesives as tack can be de-
have been provided in organic solvents, but re- signed into the polymer by the proper choice of
442 HANDBOOK OF ADHESIVES

acrylic monomers. However, if very high tack persion against shear-induced coagulation and
is required, some of the tackifiers used with to achieve good wetting on low energy sur-
natural rubbers, e.g., rosin ester and low mo- faces, such as a silicone release liner. How-
lecular weight polyaromatics, can be added to ever, the presence of excess surfactant can lead
the acrylic adhesive. 10 to excessive foam generation during coating,
Two critical parameters of an aqueous ad- which can affect the coating properties. Excess
hesive formulation are its viscosity and rheo- foam can be controlled with a defoamer, but
logical properties. II Different types of certain defoamers can cause poor wetting of the
conventional coating equipment will require dif- surface, as evidenced by fisheyes and crater-
ferent viscosities, and the rheological proper- ing. Thus a careful balance between surfactant
ties will determine the flow and leveling and defoamer is required to get a good coat-
characteristics of the formulation. ing. 12
In solution-based adhesives, the viscosity is
controlled by the type of solvents used and the Properties and Testing. The adhesive re-
solids content of the adhesive. The rheology of quirements for a pressure sensitive adhesive
solution acrylic adhesives is generally Newton- will vary greatly with end use. While each ap-
ian. In aqueous emulsions, the viscosity of the plication will have certain specific tests, the
unformulated adhesive is low-around 100 three most common adhesive tests are peel
cps-and, if needed, a thickener is added to adhesion, shear (creep) resistance, and tack. 13
raise viscosity. Aqueous emulsion-based ad- There are standard test procedures developed
hesives generally have non-Newtonian rheol- for these tests by PSTC,14 ASTM,15 and the
ogy; that is, they experience significant Tag and Label Manufacturers Institute. 14
viscosity changes as a function of shear rate. Peel adhesion l4 ,15 is the force required to
Usually emulsions are thixotropic, i.e., shear break the adhesive bond between two sub-
thinning, but in rare cases a dilatant rheology strates. Usually this is measured by peeling
can occur, i.e., an upward viscosity progres- back the adhesive backing at 180° or some-
sion with increasing shear rate. A shear rate/ times 90° from the surface at a standard rate
viscosity profile should be obtained for all new and under carefully controlled environmental
aqueous adhesives. conditions. In some cases the bond is broken
Thickeners that are commonly used in acrylic within the adhesive layer, not at the surface.
emulsion adhesives include alkali-soluble This is called cohesive failure, and is generally
acrylic emulsions, polyvinyl alcohols, and cel- acceptable for permanent applications but not
lulosics. By proper choice of thickener the for removable applications.
rheology properties can be optimized for spe- Shear adhesion l4 is the ability of a tape to
cific coating head configurations. resist the static forces applied in the same plane
This flexibility has proven invaluable in the as the backing. It is a measure of the cohesive
design of "coater-ready" aqueous adhesives strength of an adhesive. Usually it is expressed
which are specifically designed for a wide range in the time required for a given weight to cause
of application techniques. These techniques in- a given area of adhesive to come loose from a
clude reverse roll coating, curtain coating, gra- vertical panel.
vure coating, and spray application. Key Tack is the measurement of the quick grab or
characteristics built into the aqueous adhesives stickiness of an adhesive. Tack is a surface
to permit such a wide variety of application phenomenon that is not always indicative of an
techniques include: adhesive's performance. There are several
methods of measuring tack. One test is called
• Good flow and leveling (rheology) the quick stick. 14 It is a measure of the force
• Low foam generation required to remove a tape at a 90° angle from
• Good substrate wet-out a surface to which it has been applied under no
• Mechanical stability other pressure than the weight of the tape itself.
• Uniform, efficient drying Another version of this test is called loop tack,
The aqueous-based adhesives may require the in which the pressure sensitive tape is applied
addition of a surfactant to help stabilize the dis- in a loop form using only the pressure of the
 ACRYLIC ADHESIVES 443

tape as the applied force. Another common test Aqueous acrylic contact adhesives contain no
is the tack rolling ball test. 14.15 A steel ball is solvents which could represent inhalation or
rolled down an inclined trough onto an adhe- flammability hazards. 16 In addition to eliminat-
sive. The length of adhesive required to stop ing these hazards, some aqueous acrylics pro-
the ball is measured and used to quantify the vide other benefits:
tack of an adhesive. The higher the number,
• Heat resistance
the poorer the rolling ball tack. It should be
noted that the correlation between quick stick • Clarity
• Adhesion to a broad spectrum of sub-
(loop tack) and rolling ball tack is sometimes
strates, including plastic and metals
poor. 15 Formulations containing high concen-
• Ease of formulation
trations of tackifiers can have excellent quick
• Ease of handling-can be applied by
grab properties as measured by quick stick and
brush, spray, or roller
loop tack, but high rolling ball tack. One other
• Ease of cleanup
tack measurement is the Poly ken Probe. 15 This
is an instrument that measures tackiness by While some ofthe earlier acrylics had a short
bringing the tips of a flat probe into contact with open time (bonding window), the more recent
an adhesive under known conditions and then entries permit the homeowner more flexibility
measuring the force necessary to break the in bonding time. 17 Thus, good bonding may be
bond. The force is measured in grams and re- achieved for hours after the clear point is
ported as grams of tack. reached.

Contact Bonding Heat and Pressure Bonding

Contact adhesives are used where immediate With heat-activated bonding techniques, a non-
and high bond strength is required. The adhe- blocking (tack-free) film is applied to "One sub-
sive is applied to both surfaces to be joined, strate and later reactivated by the application of
and allowed to dry completely. Then the sub- heat, which produces adhesive flow onto the
strates are bonded, generally with hand pres- second substrate during a nipping operation,
sure for consumer applications and nip rollers thereby effecting a bond on cooling. Open time
and presses for industrial bonding operations. is very short, in the several-second range. It
Open time can vary from several minutes to should be noted that, generally, acrylics may
several hours. require longer dwell time than crystalline pol-
Contact adhesives are used to manufacture ymers since, as is typical of amorphous poly-
furniture and countertops of high pressure plas- mers, they do not show the sharp melting or
tic and particle board, movable and permanent freezing points characteristic of crystalline pol-
office partitions, assemblies of cold rolled steel ymers. This bonding technique provides im-
to honeycomb cardboard, and foamed sub- mediate bond strength, as do contact adhesive
strates for both steel doors and prefabricated bonding and pressure sensitive adhesive bond-
curtain walls. Other applications for contact ing. Obviously, this method is not suitable for
adhesives include small product assembly such heat sensitive substrates. Some typical exam-
as toys, sporting goods (with substrates such as ples can be found in heat-seal food packaging
leather), aluminum foil, plastic films, rigid and a variety of vacuum forming operations
plastic and foams. such as automotive door panels.
Use of contact adhesives is a good solution Applications where acrylics see use include
for a variety of miscellaneous bonding prob- the heat sealing of cellophane to metal foil and
lems in the home where nonporous surfaces are metallized polyester film or polypropylene film.
involved and immediate high bond strength is These films are used primarily in the food
a requirement. The adhesive is applied via paint packaging area. Other applications are in the
brush or paint roller, with normal application overlay area, where clear or photoembossed vi-
recommending two coats to be applied to the nyl films are bonded to wood substrates to pro-
nonporous surface, chipboard in this case. duce a simulated expensive wood grain finish.
444 HANDBOOK OF ADHESIVES

Vacuum Bonding manufacture flexible laminates, while the stif-

fer analogs find more use in the product assem-
Vacuum bonding is practiced in the manufac-
blyareas.
ture of various automotive interior PVC trim
Typically, aqueous acrylic emulsion poly-
items such as door panels, instrument panels,
mers of 5,000-10,000 cps viscosity are coated
and van side panels. The process consists of
onto the plastic film using roll coat techniques
spraying adhesive on the rigid fiberboard or
set to yield coating weights of 15-35 pounds
plastic (usually an ABS substrate), drying the
per ream. Within a few feet after the coating
substrate, then inserting it into a vacuum form-
station the second substrate (i.e., cotton/po-
ing unit where the preheated vinyl is mated to
lyester fabric, polyurethane foam, etc.) is mar-
the rigid ABS or chipboard and maintained un-
ried to the wet plastic and then nip bonded. The
der vacuum and the residual heat for several
laminate may then pass through a series of
seconds. Immediate high bond strength is re-
heated rolls, lamp station, and finally cooling
quired, since the vinyl in some cases has been
rolls prior to being wound onto the take-up roll.
elongated several hundred percent to conform
Line speeds are relatively slow, generally being
to contoured areas.
in the 30-90 feet per minute range. Initial
The rigid substrate, usually containing con-
adhesion testing is usually a subjective hand
toured and deep-draw areas, is mounted to a
peel test, with fabric or foam failure being the
mated metal mold which has predrilled holes to ideal target. More sophisticated tests may be
allow sufficient vacuum draw on the surface of
done after the laminate has aged at least 24
the rigid fiberboard or plastic. Substrates like hours. These may include standard T -peel tests
ABS that are vacuum barriers themselves also on conventional testing machines. If water sen-
require holes to allow vacuum forming.
sitivity is a criterion, the T-peels may be per-
formed after an overnight water soak of the
Wet Laminating Adhesives
preconditioned laminate. (Preconditioning usu-
The wet laminating approach allows for im- ally consists of a 3-7 day aging at 50 % relative
mediate but relatively low strength bonding of humidity and 75°F.)
two surfaces. A short open time dictates that Typical wet bonding applications involve
the substrates be mated while the adhesive is bonding of films, paper, or plastic sheet to such
still wet. In addition, at least one of the sub- nonporous surfaces as fiberglass, fabric, thin
strates must be porous to allow water or solvent gauge open cell foams, and plywood or chip-
to escape through the laminate. Drying occurs board. The diversity in substrate surface en-
subsequent to substrate combination. Examples ergy, porosity, combining and drying
of the wet laminating technique include bond- techniques, and in-service end use performance
ing of printed vinyl film to fabric for wallpaper requirements demands careful adhesive selec-
and vinyl to foam for soft goods or furniture tion.
covering. Bonding of vinyl film, paper, or foil to fiber-
Waterborne adhesives, used almost exclu- glass for a variety of insulation products (e.g.,
sively in wet laminating operations, offer non- acoustical tile, roll insulation, fiberglass/fiber-
flammability and the low toxicity of acrylic- glass for increased thickness, rigid fiberglass
based products. These two characteristics are scrip/foil board fire retardant modified) is nor-
especially significant, since the volatile carrier mally accomplished by overcoat or spray ap-
migrates into the porous substrate and subse- plication of the adhesive to the paper, film, or
quently dissipates into the environment after foil.
bond formation has been completed. Various gauge PVC and styrene films are
Wet laminating allows for adhesive polymer bonded to a variety of fabrics and foams for
selection from permanently tacky pressure-sen- miscellaneous soft goods applications such as
sitive-type products in the Tg = -40°C range luggage, sporting equipment, lamp shades, and
to fairly stiff polymers that require some coa- wearing apparel. The bonding technique nor-
lescence for adequate film formation. Gener- mally employs roller coat application with a
ally, the lower Tg polymers are used to gravure cylinder of the adhesive to the film, and
 ACRYLIC ADHESIVES 445

at times a partial dry before nipping to the fab- mulations that still retain acrylic permanence
ric or foam. Wet tack or wet grab is an impor- properties.
tant criterion, since upon cooling there can be With their wide range of high specific adhe-
differential expansion of the two substrates. sion, acrylic emulsions may be used in a vari-
This can result in a variety of surface imper- ety of formulations for different end uses. This
fections in the final product-especially when permits the compounder to reduce inventory
thin films are used. and storage costs.
Vinyl film, saturated paper, and fabric are Filled adhesives typically are designed for the
bonded to plywood, chipboard, and steel to construction and do-it-yourself trade. Filled
produce a variety of decorative panels, from adhesives consist primarily of the base poly-
simulated wood paneling to fabric-covered mer, fillers such as calcium carbonate or clay,
modular office sections. Generally, the adhe- solvents, surfactants, dispersants, preserva-
sive is coated onto the rigid substrate via roll tives, and thickeners. Formulations are specif-
coater or spray application. Roll coater adhe- ically tailored for numerous end uses including
sive application to plywood and chipboard gen- brick mastics, carpet tile and continuous carpet
erally requires more than one pass for sufficient adhesives, floor tile adhesives, ceramic tile,
adhesive deposition, since the surfaces tend to subflooring, and panel adhesives.
absorb the adhesive. The primer or sealer coat
is generally dried completely before a second Brick Mastics. Brick mastics are the most
coat is applied. Then, this second coat is sub- highly filled adhesive formulations and are used
jected to a partial dry before nipping-some- to attach decorative brick and stone for both
times under heat-to the decorative surface interior and exterior applications. The benefits
film. When the flexible laminate is bonded to a of acrylic resins for brick mastics are specific
metal surface such as office partition sections, adhesion, water resistance, weatherability, ex-
the adhesive usually is deposited via spray ap- cellent flexibility retention, and formulating
plication onto the metal. versatility.
The wet bonding of rigid plastic sheet (high The formulation provided in Table 4 is a
pressure plastic) to chipboard requires that the starting point recommendation. Further adjust-
laminated sections be maintained in a rigid po- ments to obtain desirable color texture and han-
sition until the adhesive has completely dried dling properties can be made.
and crosslinking, if applicable, has com-
menced. The adhesive is roll coated or spray Carpet Tile Adhesive. Carpet tiles and
applied to the chipboard. continuous carpeting can be adhered to the floor

Table 4. Brick Mastic Adhesive-

Filled Adhesives Moderately Extended.
Components Parts by Weight
The broad spectrum of adhesion displayed by
acrylic adhesives make filled acrylics excellent Rhoplex AC-64 (60% solids) 100.0
candidates for bonding substrates made of cel- Triton X-405 1.4
Tamol850 0.7
lulosics, leather, fabric, ceramic, foil, plastic, Foamaster 0.4
metal, and various foams. Typical examples Biocide 0.2
include panel and subflooring adhesives, dec- Propylene glycol 5.0
orative brick mastics, ceramic tile adhesives, Varsol 2.0
carpet adhesives, floor tile adhesives, and con- Camel Carb 50.0
#60 Sand 25.0
tact adhesives. #45 Sand 25.0
Acrylics permit high pigment loading. The Sno Cal Clay 20.0
oustanding pigment-binding capability, adhe- Celluftoc 6.0
sion, and durability of acrylic polymers allow Hi Sil422 5.0
formulation at high pigment-to-binder ratios. Actysol ASE-60/Water (1/1) 1.5
Water 1.5
This permits production of cost-efficient for-
446 HANDBOOK OF ADHESIVES

with a variety of adhesives products. These Table 6. Wet Mastic Floor Tile
range from essentially nonfilled pressure sen- Adhesive - Permanently Pressure
sitive adhesives modified to allow application Sensitive.
by brush, paint roller, or notched towel, to very Components" Pans by Weight
highly filled adhesives similar to those used for
Rhoplex N-5S0 (55% solids) 100.0
applying vinyl and vinyl asbestos tile. Water 1.8
Features of aqueous acrylic resins for carpet Propylene glycol 3.0
tile adhesives are: Nopco NXZ 0.09
Triton X-405 2.5
• Water resistance StabilitelZ ester #1O/xylene (70/30) 76.7
• Durability Ammonium hydroxide (10%) 2.0
• Specific adhesion to a variety of surfaces Gold Bond R Silica (300 mesh) 80.55
• No solvent toxicity Acrysol ASE-60/water (111) 5.0
Constants
Formulations for removable and permanent
carpet tile adhesives are shown in Table 5. Pigment/binder ratio 6/1
Rosin/binder ratio 1.5/1
Percent solids 71.7
Floor Tile Adhesives. Mastic floor tile ad- Viscosity, Brookfield #4/0.3 rpm, cps 2,000,000
hesives are highly filled adhesive formulations pH 8.0
designed for use in adhering vinyl and vinyl Freeze/thaw stability, cycles 5
asbestos tile, wood parquet, carpet, and other • A suitable biocide is recommended for in-can preservation.
flooring materials. The formulations in Table 6
can be used to join two nonporous substrates,
hering tile to walls and floors. Even though
provided the substrates are joined after the ad-
these adhesives are highly filled, they still must
hesive mastic has dried. If at least one porous
exhibit a high degree of bond strength and water
substrate is involved, optimum bond strength
resistance along with desirable handling char-
can be obtained by joining the two surfaces in
acteristics like ease of trowelability, sufficient
a wet laminating operation-that is, before the
open time, and long term storage characteris-
adhesive has dried. The viscosities of the three
tics. Ceramic tile adhesives based on Emulsion
systems can, of course, be adjusted to meet
E-1997 (see Table 7) possess such desirable
specific needs. Lower RMC (raw material cost)
properties as smooth trowelability, wet adhe-
formulations can be achieved, at some compro-
mise in performance, by extending the pig-
ment/binder ratio. Table 7. Ceramic Tile Adhesive-High
Bond Strength.
Ceramic Tile. Ceramic tile adhesives are Components' Pans by Weight
highly filled adhesive mastics designed for ad-
Emulsion E-1997 (49% solids) 210.0
Propylene Glycol 10.0
Table 5. Water 70.0
Removable Permanent Tamol731 5.0
Urea 30.0
Components, parts by weight Defoamer 1.0
Rhoplex N-619 (high tack 100 Duramite Calcium Carbonate 500.0
PSA) Acramine Clear Concentrate NS2R 14.0
Emulsion E-1791 (low tack 100
PSA) Constants
Acrysol ASE-60 (thicke- 0.75 O.S Pigment/binder ratio 5/1
ner) Percent solids 76.0
Triton X-155 (surfactant) 0.3 Approximate open time 15-30 min.
Storage stability, I month @ 50°C Pass
Physical Properties Freeze/thaw stability 5+ cycles
pH 9.2 6.7 ANSI #1, wet type SO psi
Viscosity (#4/20 rpm), cps 2000 5000 Viscosity, TE/4, poise 600,000
Solids, % 55 55
•A suitable biocide is recommended for in-can preservation.
 ACRYLIC ADHESIVES 447

sion, low odor, adhesion to a variety of sub- reaction vessel for the polymerization of methyl
strates and pennanence of properties. methacrylate to a plastic with adhesion to the
The ceramic tile adhesive shown in Table 7 adherends.
is suitable for fonnulating an adhesive to meet Modified or second generation acrylic engi-
ANSI Type I and II specifications. One can sig- neering adhesives are more complicated than
nificantly reduce cost while still meeting ANSI those described above. In modified acrylic ad-
requirements by modifying the ratios of the hesives, polymerization between adherends
same ingredients to achieve a pigment/binder leads to impact resistant plastics with adhesion
ratio of 6 to 1. Likewise, repositionability and to the adherends. The following fonnulation of
open time may be extended by incorporating a Brigas and Muschiatti illustrates an early mod-
plasticizer, such as Paraplex® WP-l, at a rate ified acrylic engineering adhesive: 18
of 5 parts per 100 of polymer emulsion.
Component Parts by
ENGINEERING ADHESIVES Weight

Engineering adhesives are solventless, liquid,

Methyl methacrylate 85
Methacrylic acid 15
reactive, durable adhesives for bonding durable
substrates. There are six recognized chemical
Ethylene glycol dimethacry- 2
late
types of engineering adhesives: acrylic, anaer-
Chlorosulfonated polyethyl- 100
obic, cyanoacrylate, epoxy, silicone, and ure-
ene
thane. Strictly speaking, the first three in this
list are varieties of acrylic, but only the first
Cumene hydroperoxide 6
N ,N-Dimethyl aniline 2
will be discussed here. There is, however, con-
siderable overlap in the chemistry and proper-
The chlorosulfonated polyethylene separates
ties of acrylic and anaerobic adhesives. Since
into small rubber domains during polymeriza-
considerable progress has been made in acrylic
tion of methyl methacrylate. These domains
adhesives over the last two decades, those used
absorb fracture energy generated in the glassy
in engineering applications are now referred to
poly(methyl methacrylate) under loading.
as "modified" acrylic adhesives.
Grafting between the rubbery and the glassy
phases appears to be necessary to effect transfer
Chemistry and Technology
of energy to the rubber.
Early acrylic engineering adhesives were quite A storage-stable, no-mix version, also called a
simple in composition and thus service well to two-part surface-activated version of the above
illustrate their basic technology. An example of is described in Ref. 18 as follows:
such an adhesive is as follows:
Component Parts by
Component Parts by Weight
Weight
Methyl methacrylate 85
1. Methyl methacrylate 85.0 Methacrylic acid 15
Poly methyl methacrylate 15.0 Ethylene glycol dimethacry- 2
N ,N-Dimethyl aniline 0.5 late
2. Benzoyl peroxide 0.5 Chlorosulfonated polyethyl- 100
ene
When its components are mixed the adhesive Cumene hydroperoxide 0.4
has a pot life of about one-half hour. The mix-
ture is placed between adherends and allowed In this example the aniline activator is re-
to polymerize via a free-radical mechanism. placed by a condensate of butyraldehyde and
The free radicals are supplied from the decom- aniline which is applied to one or both adher-
position of peroxide activated by dimethyl an- ends in a thin film prior to application of the
iline. In effect, the adherends serve as the adhesive. The activator generates a free-radical
448 HANDBOOK OF ADHESIVES

flux on contact with the adhesive. This flux Radiation Curing

spreads across the adhesive layer to polymerize
The polymerization of the monomer in acrylic
it. This phenomenon is unique' to acrylic ad-
engineering adhesives can be initiated by elec-
hesives. A difficulty with this process is that
tron beam or ultraviolet (UV) radiation, pro-
the radical flux tends to die out with distance
vided that the adherends or the fillers in the
from the activator. Practical bond thickness is
adhesives are not barriers to radiation. Acrylic
thus limited.
monomers are generally more reactive to radia-
Another formulation of Toback and
tion than methacrylates. Electron beams gen-
O'Connor l9 employs hydroxypropyl methac-
erate free radicals directly in the adhesive,
rylate as the fluidizing reactive component of a
whereas UV curing requires a photosensitizer
modified acrylic engineering adhesive. A con-
or photoinitiator to provide free radicals.
densation product of three moles of hydroxy-
ethyl methacrylate, three moles of toluene
diisocyanate, and one mole of a polypropylene Application Processes
triol provides a rubber phase. Because of their reactivity, acrylic engineering
W. A. Lees20 has pointed out the difficulties adhesives are necessarily two-part adhesives.
of achieving the optimum particle size distri- No special application equipment is required for
bution of the precipitating rubbery phase. the two-part surface activated type, which is
Moser and Slowik21 have addressed this prob- also called the no-mix type. As mentioned ear-
lem by using preformed rubbery domains of the lier, it is only necessary to wipe the activator
type used in impact resistant plastics. Suitable on to the surfaces before spreading the adhe-
impact improvers are described as core/shell sive and mating the surfaces.
polymers which have a crosslinked acrylic or Two-part mixed-type acrylic adhesives are
butadiene-based elastom«r graft-linked to an applied like two-part mixed epoxy adhesives
outer rigid thermoplastic polymer. with meter or meter-and-mix equipment. The
The following two formulations illustrate the two parts may be metered into a container for
effect of the impact improver. Both were po- immediate mixing and application, or metered
lymerized between aluminum adherends which into a static mixer and immediately dispensed
have been primed with a thin film of butyral- to the adherends to be joined. A simple illus-
dehyde and butylamine condensate. tration of meter-and-mix equipment is the dou-
ble-barrel syringe, which delivers the two parts
Parts by of the adhesive to a nozzle containing static
Weight mixing elements. These elements are alternat-
Component A B ing right and left hand helices connected off
center to each other. At the other end of the
Butadiene-styrene/methyl complexity spectrum is the equipment for au-
methacrylate core/shell tomated assembly lines.
polymer 30
Hydroxypropyl methacrylate 60 77
Current Uses
Acryloxypropionic acid 10 14
Cab-O-Sil® (thickener) 9 Modified or toughened acrylic adhesives have
Cumene hydroperoxide 2 3 been used since the early 1980s to bond metal
stiffening strips to the glass fiber-reinforced
Impact-modified formulation A gave 2,200 plastic window panels of rail cars. 22 ,23 There is
psi (15 MPa) lap tensile shear strength when a similar use in truck cab construction. 24 In an-
tested by ASTM Method D-l002 and greater other transportation use, an acrylic adhesive is
than 80 in.-Ib (9 N m) of impact resistance as used to bond the components of body side doors
tested by ASTM G-17 falling weight method. of freight locomotives. 23 These components are
The comparative formulation B gave 960 psi made of steel with a zinc coating. Adhesive
(6 MPa) shear and 20 in.-Ib (2.3 N m) impact. bonding eliminates the surface blemishes of
 ACRYLIC ADHESIVES 449

spot-weld bonding. A two-part premix acrylic with an acrylic engineering adhesive. 26 Other
adhesive was the only one that met all of the uses are aircraft windshields, satellite antenna
requirements of manufacturing and use, dishes, solar energy modules, outdoor signs,
namely, minimum surface preparation, fast computer housings, and filtration screens. 27
cure, and resistance to impact, high humidity, The use of a second generation two-part
water, and oil coolant. acrylic adhesive has allowed a sports car man-
General sheet steel bonding is done with ufacturer to assemble a bumper which passes a
acrylic adhesives. 25 Wood/aluminum sails of five mile per hour impact. 28
wind-powered electric generators are bonded

APPENDIX
Suppliers of Raw Materials Mentioned in This Section

Acrarnine Clear Concentrate NS2R Mobay Chemical Company

Acrysol thickeners Rohm and Haas Company
Balab 3056A Witch Chemical
Camel Carb Campbell Company
Celluftoc Georgia-Pacific Corporation
Cellulose Flock #CP-40 International Filler Corporation
Composition T Dow Chemical Company
Cymel American Cyanamid
Dowper Dow Chemical Company
Duralmite Thompson, Weinman & Company
Ethyene glycol Eastman, Shell, Dow
Foamaster Diamond Shamrock Corporation
Formica American Cyanamid
Gold Bond R Silica Tammsco Inc.
Hi Sil422 PPG Industries, Inc.
Methocel E-4M Dow Chemical Company
Nopco NXZ Nopco Chemical Division
Pa. Limestone Pfizer
Paraplex WP-I Rohm and Haas Company
Petinos Sand Petinos Company
Propylene glycol Ashland, Dow, Olin, Union Carbide
Rhoplex acrylic emulsions Rohm and Haas Company
Robond acrylic resin Rohm and Haas Company
Stabelite Ester #10 Hercules, Inc.
Tamol dispersants Rohm and Haas Company
Texanol Eastman
Tide Proctor and Gamble
Triton surfactants Rohm and Haas Company
Varsol Exxon
Vinol540 Air Products and Chemicals, Inc.

REFERENCES 2. Rohm and Haas Company Technical Report Bulletin

MM-27 (1968).
1. Brendley, W. H., "Fundamentals of Acrylic Poly- 3. Hadley, D. J., et aI., "Acrylic Ester Polymers and
mers, Paint and Varnish Production," Rohm and Copolymers," Plastics Inst. Trans. J., 33, 237ff (Dec.
Haas, July 1973. 1965).
450 HANDBOOK OF ADHESIVES

4. Rehberg, C. E., and Fisher, C. H., Ind. Eng. Chern., 15. American Society for Testing and Materials, "Annual
40, 1429 (1948). Book of ASTM Standards, Part 22," D-903, D-2979,
5. Fox, Bull. Am. Phys. Soc., No.3 (1956). and D-3121 (1981).
6. Flory, "Principles of Polymer Chemistry," pp. 56, 16. Gehman, D. R., and Sanderson, F. T., Adhesives Age,
57, Ithaca, NY, Cornell University Press, 1953. p. 23 (December 1977).
7. Helman, S. M. (to Minnesota Mining and Manufac- 17. Baus, R. E., et al. (to Rohm and Haas), U.S. Patent
turing Company), U.S. Patent 4,175,418 (1979); Ul- 4,501,845.
rich, E. W. (to Minnesota Mining and Manufacturing 18. Brigas and Muschiatti (to E. I. duPont de Nemours
Company), U.S. Patent 2,973,286 (1961). and Co.) U.S. Patent 3,890,407 (1975).
8. Andrew, R. W., Gehman, D. R., and Sweens, B. 1. 19. Toback and O'Connor (to Loctite Corporation), U.S.
M., European Adhesives and Sealants (1985). Patent 3,591,438 (1971).
9. Mooncai, W. W., Adhesives Age, p. 28 (October, 20. Lees, W. A., J. Adhesion 12, 233-240 (1981).
1968). 21. Moser and Slowik (to Rohm and Haas Company),
10. Wood, T. G., Adhesives Age, p. 19 (July 1987). European Patent Application 87304 (1983).
II. Sanderson, F. T., and Gehman, D. R., "Acrylic 22. Lees, W. D., Adhesives Age, 24(2), 23-31 (1981).
Thickeners for Latex Adhesives," PSTC Technical 23. Seeds, A., Int. J. Adhesion Adhesive 4(1), 17-21
Seminar (June, 1983). (1984).
12. Costanzo, J. A., and Gehman, D. R., "Aqueous 24. Gordon, S., Mechanical Engineering, pp. 60-65
Acrylic Pressure Sensitive Adhesives for Labels and (Sept. 1983).
Overlays," TAPPI Conference (Fall, 1983). 25. Int. J. Adhesion Adhesives, 5(4), 201-206 (1985).
13. Satas, D., Adhesives Age, p. 38 (June, 1970); John- 26. Lees, W. A., Supplement to Polymers Paint Colour
ston, J., Adhesives Age, p. 20 (April, 1968). J., pp. 8-10 (Sept. 2, 1981).
14. Pressure Sensitive Tape Council, "Test Methods for 27. Lord Corporation PB 10-3000 (1985).
Pressure Sensitive Tape," 1985. 28. Int. J. Adhesion Adhesives, 5(1) 51 (1985).
 26
Anaerobic Adhesives
JOHN M. ROONEY
Sun Chemical Company
Carlstadt, New Jersey
and
BERNARD M. MALOFSKY
Loctite Corporation
Newington, Connecticut

INTRODUCTION ence of oxygen to prevent polymerization, but

the required amount was reduced to the point
Anaerobic adhesives are single-component liq- where air permeating through the walls of a
uids or pastes which can be stored for pro- small, half-filled polyethylene bottle was suf-
longed periods of time at room temperature in ficient to maintain liquidity for one year at room
the presence of oxygen but harden rapidly to temperature.
form strong bonds when confined between sur- Cumene hydroperoxide-based formulations,
faces that exclude air. Researchers at General being more stable than the previous oxygenated
Electric identified the first anaerobic adhesive materials, were slower to polymerize between
in the late 1940s.' They discovered that tetra- glass surfaces but exhibited rapid bond forma-
ethylene glycol dimethacrylate, oxygenated by tion between certain metal surfaces. Early re-
heating at 60-80°C in the presence of bubbled searchers had foreseen the utility of anaerobic
air, remained liquid when cooled as long as adhesives in locking threaded fittings in place
aeration was maintained. However, when the and sealing flanged metal parts, and in 1953,
air bubbling was discontinued or when the liq- the American Sealants Company (later to be-
uid was pressed as a thin film between glass come Loctite Corporation) was established to
microscope slides, rapid crosslinking occurred address those marketing opportunities. 3
forming a solid polymeric material. The first anaerobic adhesive, Loctite Sealant
"Anaerobic Permafil," as the oxygenated Grade A, was rapidly augmented by Grade C,
dimethacrylate became known, was marketed a reduced strength product, and Grade D, a
by General Electric with little success. The in- more viscous product. Surface primers were in-
herent instability of the material placed onerous troduced to accelerate bonding between less re-
restrictions on handling, packaging, and ship- active substrates. During the following 30
ping. A solution to the stability problem was years, numerous additions and improvements
provided when the cumbersome oxygenation to the product line were made. However, the
process was replaced by the addition of con- basic advantages of anaerobic adhesives were
trolled amounts of cumene hydroperoxide. 2 The evident from the outset. They offer the cus-
resulting formulation still necessitated the pres- tomer a method of assembly which simplifies

451
452 HANDBOOK OF ADHESIVES

design and reduces costs by removing the need following reaction, where T represents a tran-
for intricate mechanical locking, sealing, and sition metal:
retaining devices. Anaerobic adhesives are eas-
ily applied and form bonds rapidly at room
temperature. Bond strengths may be varied ac-
cording to the wishes of the customer. The ad- The desire to balance the reactivity and sta-
hesives contain no solvents and material outside bility of anaerobic adhesives has led to a con-
the bondline is readily removed. Extensions of tinuing search for compounds which accelerate
anaerobic adhesive chemistry have made pos- the polymerization reaction without exerting a
sible the development of porous metal sealants deleterious effect on product storability. Tri-
which improve machinability and strengthen alkyl amines were found to meet these criteria, 4
castings, preapplied dry threadlocking and gas- and were incorporated in the first generation of
keting materials for additional convenience, Loctite anaerobic products. Presumably the
and durable structural adhesives that do not re- amine acted to polarize the hydroperoxide ions.
quire elaborate curing equipment. This system remained sensitive to the nature of
the substrate, curing rapidly on copper- and
iron-rich surfaces and curing slowly or not at
CHEMISTRY OF ANAEROBIC all on cadmium- or zinc-plated metals. 5 Sub-
ADHESIVES sequent research identified a coaccelerator
combination, o-benzoic sulfimide (saccharin)
Cure Systems and Stabilizers and dialkylarylamines, which enhanced cure
The cornerstone of anaerobic adhesive chem- speeds on all surfaces. 6 Model studies suggest
istry is the set of competitive chemical reac- that gradual autoxidation of dialkylarylamines
tions occurs during prolonged storage, causing a de-
crease in cure speed and emphasizing the im-
portance of the amine in the polymerization
process. 7 The same studies indicate that the
amine reacts extensively with hydroperoxides
only at elevated temperatures, demonstrating
in which Pn denotes a free radical (an initiator that the sulfimide plays an equally vital role in
fragment, or a propagating monomeric or pol- the initiation chemistry. Preformed sulfimidel
ymeric species) and M is a vinylic monomer. amine salts have been used successfully to ini-
Under conditions where the rate of formation tiate acrylic polymerizations. g The presence of
of free radicals is low (absence of light, low low levels of water appears to improve the per-
temperature, etc.) and the concentration of ox- formance of this cure system. 9
ygen is high, the tendency to polymerize is di- Further improvements in the reactivity of an-
minished. In the Permafil system the aerobic adhesives were obtained with the intro-
oxygenated resins underwent facile decompo- duction of hydrazide accelerators. \0 However,
sition to form free radicals and large amounts incorporation of more active cure systems was
of oxygen were required to react with these made possible only by concurrent advances in
radicals and prevent polymerization. Since cu- stabilization chemistry. Early formulations em-
mene hydroperoxide decomposes much more ployed quinone polymerization inhibitors which
slowly, correspondingly fewer radicals are pro- were effective at levels of 10-1000 parts per
duced and less oxygen is required for stabili- million. II As more active formulations were
zation. The enhanced reactivity of anaerobic developed, attempts to combat premature po-
adhesives on certain types of metal surfaces can lymerization by addition of greater quantities
be explained by the presence of transition met- of inhibitor served only to reduce performance.
als on these surfaces. Transition metals undergo A significant breakthrough occurred when a
a one-electron transfer reaction with hydroper- method of removing trace amounts of contam-
oxides to generate free radicals as shown in the inant metals from anaerobic formulations was
 ANAEROBIC ADHESIVES 453

devised. 12 The method consisted of treating the chain unsaturation with the object of providing
formulations with insoluble chelating agents secondary curing sites for improved heat resis-
which would reduce the iron content to a level tance. 20 Anaerobically curable adhesives based
of 100 parts per billion or less. Enhanced sta- solely on trifunctional allylic monomers have
bilities resulting from this treatment highlight also been proposed,21 but the vast majority of
once again the sensitivity of the free-radical the commercially available products still em-
generation process to minute concentrations of ploy acrylic monomers and resins.
transition metals.
FORMULATING FOR APPLICATIONS
Monomers and Resins
Primers
One of the principal limitations of the early an-
In situations where the rate of assembly de-
aerobic adhesives was the relative brittleness of
mands extremely rapid cure times, or where the
the cured products. 13 In situations where high
surfaces to be bonded are inherently unreac-
bond strengths were unnecessary, the problem
tive, treatment of substrates with a primer is
could be alleviated by the addition of plasticiz-
often necessary. Primers consist of compounds
ers. However, a more universally applicable
which accelerate the curing reactions. Since
solution required redesign of the polymerizable
they would destabilize the adhesive if added di-
constituents of the adhesives. The structure of
rectly to the formulation, they are supplied and
short-chain polyethylene glycol dimethacry-
used as a separate component. The criteria for
lates results in rapid gelation during polymeri-
an acceptable primer include compatibility with
zation, leading to highly crosslinked networks
the adhesive, the ability to accelerate the rate
consisting of relatively polar segments. An ini-
of curing, and lack of any adverse effects on
tial response to the brittleness problem in-
bond strengths. Various thiazoles,22 butyral-
volved replacing the polyethylene glycol
dehyde-aniline adducts,23 and thioureas 24 were
segments between acrylic functions with seg-
found to meet these criteria. Since trace levels
ments derived from flexible hydrocarbons and
of transition metals accelerate anaerobic adhe-
diisocyanates. 14
sive cure, primers containing complexed cop-
In various forms, this strategy has been pur-
per have been employed successfully. 25 In
sued through numerous resin syntheses. Seg-
another system, acidic primers are used which
ments based on polytetramethylene glycol and
react with ferrocene in the adhesive to release
hydrogenated bisphenol A were capped with
the required metal ions. 26
diisocyanates and hydroxyalkylmethacry-
Primers are typically supplied as dilute so-
lates. 15 Increased flexibility was achieved by
lutions in nonflammable, nontoxic solvents and
incorporating polybutadiene segments into
applied by spraying or brushing onto the sub-
similarly capped resins. 16 Other researchers
strate.
demonstrated the utility of capping agents con-
taining both the isocyanate and acrylic func-
Microencapsulation of Curatives
tions. 17 • 18 The variations in tensile strength,
elongation, hardness, and tear strength for a An ingenious technique for separating a partic-
model anaerobic adhesive based on methyl ularly active component of a cure system from
methacrylate and an acrylate-terminated buta- the bulk of the adhesive is to enclose particles
diene/acrylonitrile elastomer are illustrated in a of the compound inside a minute, thin-walled
recent review article 19 and are ascribed to the shell, or microcapsule, which can then be rup-
formation of discrete rubbery and glassy do- tured at a desired time to release the contents.
mains within the cured polymer matrix. This technique forms the basis of preapplied dry
Attempts have been made to introduce po- threadlocking materials. 27 Such materials are
lymerizable functionalities other than acrylic cast as dry films on threaded fittings and the
into anaerobic adhesives. Monoacrylates have coated parts are storable for long periods of
been described which also contain internal time. The act of assembling with the threaded
454 HANDBOOK OF ADHESIVES

fastener causes rupturing of the microcapsules must be carefully analyzed for the presence of
and activates the threadlocking formulation. trace levels of contaminants which could im-
A recent variation of the microencapsulation pair the performance of the product.
technique involves separating the components
of the cure system by immobilizing the entire COMMERCIALLY AVAILABLE
anaerobic adhesive formulation within a low- ANAEROBIC ADHESIVES
melting-point wax. 28 The wax sluny can be ap-
Tables 1-4 list selected commercially available
plied at relatively low temperatures in the pres-
anaerobic adhesive products, illustrating the
ence of oxygen and allowed to solidify in the
variety of uncured and cured physical proper-
threaded area of a fastener. Assembly with the
ties which results when formulations are tai-
attendant exclusion of oxygen mixes the com-
lored to meet specific application needs. Many
ponents and initiates the curing process.
products are color-coded for easy recognition
and on-part identification.
Fillers
Certain applications, e.g., porous metal seal- HANDLING TECHNIQUES
ing, require an anaerobic adhesive to be a thin,
Health and Safety
free-flowing liquid. However, other applica-
tions, such as gasketing, involve filling rela- Most anaerobic adhesive formulations are based
tively large gaps. Under these conditions, an on oligomeric acrylic esters, inherently low-
adhesive which does not flow or sag is desira- toxicity materials. Various formulations con-
ble. The addition of powdered polyethylene tain additives such as adhesion promoters or
fillers renders the organic resin base thixotropic cure components, and after excessive or re-
in nature. 29 Thixotropic adhesives have also peated skin contact may cause skin irritation in
been formulated using self-structuring silica sensitive persons. Adhesives should be washed
fillers. The resulting gasketing materials can be away with water after skin contact. Nonaque-
applied from tracing lines of caulking guns, or ous hand cleaners assist in removal of adhe-
screen printed through fine mesh stencils. sive. Skin contact should be avoided by the use
of appropriate application equipment.
Plasticizers and Thickeners One indication of the relatively innocuous
nature of anaerobic adhesives is the fact that
One of the earliest and most enduring demands
products such as Loctite Pipe Sealants 567 and
voiced by users of anaerobic adhesives was for
592 have been recognized by the U.S. Depart-
a graded product series of different viscosities
ment of Agriculture as being chemically ac-
and ultimate strengths. Modification of these
ceptable for use on meat or poultry processing
physical properties is readily accomplished with
machinery. Primers normally contain volatile
the aid of thickeners or reactive diluents, which
solvents and should be used only in well ven-
raise or lower the viscosity of the organic resin
tilated environments.
base, and nonreactive plasticizers, which lower
the bond strength of the fully cured product.
Packaging
Examples of commonly used thickeners are
polyester resins, polystyrene and polyalkyl ac- Anaerobic adhesives are formulated with cure
rylates and their copolymers, and polybis- components and stabilizers balanced so as to
phenol A maleate. The principal reactive maintain storability under proper conditions for
diluents are low molecular weight monofunc- at least one year at room temperature. Storage
tional acrylates. Traditional plasticizers in- at higher temperatures leads to correspondingly
clude poly (ethylene glycol) octanoates. shorter product lifetimes by accelerating the
A key factor in selecting any additive for an free radical polymerization process. Exposure
anaerobic adhesive formulation is the effect to strong light for prolonged periods of time
which that additive exerts on the delicate bal- also has an adverse effect on storability. Con-
ance between activity and stability. Additives sequently, anaerobic adhesives are packaged in
 Table 1. Selected Commercially Available Anaerobic Adhesives: Threadlocking.
Cure Speeds at
Room Temperature
Viscosity, Torque, N-m,
Trade Name/ Gap-Filling mPa's Breakaway/ w/o Primer, w/Primer,
Application Product No. Color Ability, mm (mean) Prevailing Fixture/Full Fixture/Full
PreappJied; high
strength Dri-Loc/200 yellow 25112 10 min172 hr -1-
PreappJied; me-
dium strength Dri-Loc1202 green 23/12 10 min/72 hr -1-
PreappJied; mild
strength Dri-Loc/203 silver 19/85 10 min172 hr -I-
Smail screws;
low strength 222 purple 0.13 1000 4.5/2.5 20 min/24 hr 5 min/24 hr
General pur-
pose; medium
strength 242 blue 0.13 1000 7/4 20 min/24 hr 5 min/6 hr
Large bolts;
high strength 262 red 0.13 1500 21118 20 min/24 hr 5 min/6 hr
Gap-filling;
high strength 271 red 0.18 500 18125 20 min/24 hr 5 min/6 hr :I>
Z
High-tempera- :I>
ture resistance 272 red 0.18 7000 17.5/27 30 min/24 hr 5 min/24 hr m
:lD
10 min/2 hr 0
High viscosity 277 red 0.25 6500 12/17 60 min/24 hr III
Low viscosity 290 green 0.10 12 7/22.5 10 Ininl2 hr -I- n
:I>
Note: All products listed function satisfactorily over the temperature range -55 to 150°C (-165 to 300 0 P) except for 272, which has an upper temperature limit of 23ZOC C
(450 0 P). %
m
en
<:
m
en
~
CJI
CJI
 ~
en
CJ)
Table 2. Selected Commercially Available Anaerobic Adhesives: Sealing.
::t
Cure Speeds at :I>
Z
Room Temperature C
Viscosity, Ill!
Trade Namel Gap-Filling mPa's Temperature w/o Primer, w/Primer, 0
0
Application Product No. Color Ability, mm (Mean) Range, °C (OF) Fixture/Full Fixture/Full ~

0
General purpose Pipe Sealant White 0.50 200,000 -55 to 204 24 hr/72 hr 15 minIS hr ."
thread sealing with Tefton/592 (-65 to 400) :I>
c
Fluid power sys- Hydraulic Brown 0.13 400 -55 to 150 45 min/2 hr -1- ::t
m
tern connections Sealantl569 (-65 to 300) til

General purpose Gasket Elimina- Purple unprimed 0.25 350,000 -55 to ISO I hr/12 hr 15 min/2 hr
<:m
til
gasketing tor/515 primed 1.25 (-65 to 300)
High temperature Gasket Elimina- Red unprimed 0.25 350,000 -55 to 204 4 hr/12 hr 30 min/4 hr
gasketing tor/510 primed 0.50 (-65 to 400)
Large gaps, instant Gasket Elimina- Orange 0.75 1,500,000 -55 to ISO 30 min/12 hr -1-
seal tor/504 (-65 to 300)

Table 3. Selected Commercially Available Anaerobic Adhesives: Retaining.

Cure Speeds at
Room Temperature
Trade Name/ Gap-Filling Viscosity, Shear Strength w/o Primer, w/Primer,
Application Product No. Color Ability, mm mPa's (mean) DaN/cm2 (steel) Fixture/Full Fixture/Full
General purpose RC/OO1 green 0.13 100 210 10 min/l-6 hr 5 min/20 min
High temperature RC/620 green 0.13 7000 210 30 min/8-1O hr 5 min/8-10 hr
High strength RC/680 green 0.38 2000 280 30 min-4-6 hr 5 min/4-6 hr
Note: All products function effectively over the temperature range -55 to 150°C (-65 to 300°F) except for RC/620, which has an upper temperature limit of 232"C (450°F).
 ANAEROBIC ADHESIVES 457

pigmented containers which act as barriers to

light.
The most stringent packaging requirements
arise as a result of the need for a constant sup-
ply of oxygen. Consumption of oxygen by an-
aerobic adhesives IS a continuous process.
I I
Therefore, package design must facilitate con-
c
C)
I I tact of all parts of the adhesive with air. Stor-
:c
c
age stability is significantly higher in thin-
o walled containers than in thick-walled con-
m
II)
tainers, in low density polyethylene containers
CD rather than in high density polyethylene, and in
>
'iii o small containers rather than large.
CD II")

.c 00
-
<'I
<'I An ingenious solution to the problem of gen-
't7
<t erating a high surface area-to-volume ratio in
(J
:co thin-walled containers while maintaining the
...
CD
structural integrity of the package during han-
IU dling was devised recently. 30 This solution in-
C
<t volves constructing a rigid plastic framework
CD
j5
surrounding and supporting a soft, flexible, ac-
.!!! cordionlike package which lends itself to easy
'iij
> product dispensing.
<t
~ Dispensing Equipment and Application
iii
'u... o
II")
Techniques
CD ci
E Continuous assembly operations entail precise
E metering and application of anaerobic adhe-
o
(,) sives. Automated systems have been designed
't7
CD to cope with a wide range of end uses, from
1:) dispensing threadlockers onto small fasteners
CD
-a; to impregnating large porous metal castings
en with sealant. These systems play an essential
o:t role in augmenting the cost reductions obtained
CD
j5
through the use of anaerobic adhesive products
IU by eliminating material waste, shortening cycle
I-
times, and reducing labor.
One of the earliest and simplest applicators
was based on a peristaltic pump mechanism
which enabled amounts of adhesive varied by
a screw adjustment from 0.01 m1 to 0.04 m1 to
be dispensed. 31 Most current liquid dispens-
ing systems employ air pressure to force ad-
hesive through feed lines which are regulated
by pinch valves, diaphragm valves, or solenoid
valves. The adhesive is then dispensed onto the
substrate through handguns, spring-loaded
needle tips, or custom applicator heads de-
signed to match the contours of the substrate.
Threadlocking and sealing formulations can
also be applied simultaneously to large num-
458 HANDBOOK OF ADHESIVES

hers of threaded parts by tumbling the parts to- 30

F
gether with a small amount of the formulation. E
Gasketing products are usually viscous and '"z
often thixotropic. Intricate patterns can be laid ~
z A-Lock Wllher
down rapidly either by programmable tracing g B-Control·No Locking
C- Dlltorted Lock Nut
iii
lines or by screen printing through precut sten- Z D-Nylon Ring
o E-Se..eted Hud
cils. Anaerobic materials lend themselves to iii
z F - Loctlte 242. 282. 271. 277
screen printing since they do not cure or dry I!!
out when spread thinly on the mesh.
More elaborate equipment is necessary for
..
!:i
o

vacuum impregnation. In a typical process,

parts are suspended in a basket over liquid resin TIME. SECONDS
inside a vessel. The vessel is then evacuated to Fig. I. Effectiveness of various threadlocking methods in
remove air from the porous structure of the preventing loosening ofi"-16 bolts during transverse shock
parts. The basket of parts is then lowered into and vibration testing.
the resin and the vessel is repressurized, forc-
ing sealant into the pores and cracks in the
parts. Excess sealant is removed by centrifu- ability to establish predetermined values of
gation and the cure process is completed in a breakaway torque (the torque needed to move
warm water wash. a tightened fastener), prevailing torque (the re-
Obviously, successful application equipment sistance to further movement after the initial
design is contingent upon incorporation of ma- movement), and torque tension (the force which
terials compatible with anaerobic adhesives. clamps the mated parts together). Commer-
Components or fittings should he fabricated cially available threadlocking products are
from materials which do not contain destabil- graded according to their breakaway and pre-
izing components. vailing torques on standard nut-and-bolt assem-
blies. Figs. 2-5 illustrate the performance of a
typical anaerobic threadlocking adhesive, Loc- .
APPLICATIONS AND PERFORMANCE
tite 242, on a variety of such assemblies.
DATA
In practice, anaerobic chemical threadlock-
Threadlocking ers are used in areas as diverse as typewriter
screws, carburetor adjusting screws, railroad
The first mechanical design problem to be
solved with the aid of anaerobic adhesives was
the problem of loosening or unwinding of 10
threaded metal fasteners under periodic over-
load which makes the threads slide sideways. .. 8
This condition is commonly encountered in
fasteners which are subjected to vibration. The
..~
effectiveness of anaerobic threadlocking adhe-
~ .."
NO PRIMER

~ a
.." ....::::.
...........

. , 1-"-, . , .. "
z PRIMER T
sives is demonstrated by transverse shock and ui

vibration experiments in which nut-and-bolt as-

~
...o>-
.... ....
------- _PRIMER N

!
I'
semblies are struck repeatedly at right angles
by air hammers. Results from these experi- ~
/". I
,'I
:Ii
'v
2 '" I
ments, illustrated in Fig. 1, show that assem- I
blies treated with chemical threadlockers resist I
the unwinding forces associated with lateral 0
5 10 30 80 120 1...
movement. Most conventional mechanical CURE nME, MINUTES

locking methods fail this stringent test. 32 Fig. 2. Strength development of Loctite 242 cured with
In addition to vibration resistance, thread- different primers on "as received" steel i"-16 nuts and
locking adhesives provide the user with the bolts.
 ANAEROBIC ADHESIVES 459

•• ••

" PRIMERT

,r "

.... ;T "
" --- ,'............
__ PRIMER N
...., PAIMERT

k'OPRIMER

.... ,,:,'",;,'"
, NO PRIMER

.......... /' ""

"
-- .e-."• ---------
,.
" NO PRIMER

, "" l
I
/'
,..'
~" .. "
l /"
I I

5 •• 30 80 120 .440 5 •• 30 80 120 .440

CURE TIMES, MINUTES CURE TIME, MINUTES

Fig. 3. Strength development of Loctite 242 cured with Fig. 5. Strength development of Loctite 242 cured with
different primers on cadmium-plated i"-16 nuts and bolts. different primers on zinc-plated i" -16 nuts and bolts.

bolts on wear plates, hydraulic line fittings, and Impregnation sealants are very low viscosity
bulldozer track bolts. liquids which, when simply painted onto a sur-
face or applied under vacuum as described ear-
Sealing lier, migrate into pores, cracks, and surface
imperfections in castings, welds, or powdered
Two major application areas in whch anaerobic
metal parts. Anaerobic sealants have replaced
sealants have had a profound impact are porous
older types of sealant because of the relative
metal impregnation and liquid gasketing. Al-
ease and cleanliness of their application. Cure
though the physical properties of the products
occurs only where desired and excess resin is
directed at these areas are extremely dissimilar
easily removed. Castings sealed with the resins
in the uncured state, the cured materials share
exhibit improved mechanical properties. One
common features which render them uniquely
of the most impressive benefits of the impreg-
suitable as sealants. Both types of product cure
nation process is the improvement in machin-
to form materials which resist attack by most
ability which results from the smoothing of
industrial fluids, counterbalance the effects of
surfaces due to the filling of voids and crevices.
surface imperfections, and do not shrink or
Anaerobic gasketing products are highly vis-
crack during cure.
cous thixotropic pastes. These characteristics
minimize the tendency to sag or migrate and
•• maximize gap-filling ability. Although typical
liquid gasketing products may take several
r.... ' .
PRIMER N
__ PAIMERT
---
hours to develop fully cured properties (see Fig.
6), products such as Loctite Gasket Eliminator
"
,
"" NO PRIMER

------- --
504 are formulated to provide instant pressure

/'"
" ...
, seals even at relatively large gaps (Fig. 7). Such
, "
I
/I products find uses in transmission housings,
I l pumps, thermostats, axle covers, and compres-
,"
I

I
sors. In certain cases, liquid gaskets are used
I
I
/ to coat conventional gaskets and provide resis-
I
/
I
tance to deformation.
I

5 10 30 80 120 '440 Retaining

CURE TIME. MINUTES

Fig. 4. Strength development of Loctite 242 cured with Designers of cylindrical assemblies such as
different primers on phosphate/oil i"-16 nuts and bolts. bearings or gears have traditionally relied upon
 460 HANDBOOK OF ADHESIVES

... produces a smaller increase. Even after 2000

hours at 232°C, bonds assembled with this
400
product maintain 75 % of their initial strength.

."'5 300 Structural Bonding

z
The application areas into which anaerobic ad-
...
i
ui
:a
;:: hesives have made their most recent inroads are
those in which the adhesive is used to assemble
100
fiat, structurally bonded parts. Impetus for the
replacement of more conventional structural
.......----------------------------------
•• 'C

~- adhesives by anaerobic products can be attrib-

0
0 0.1 0.2 0.' 0.4 0.5 0.8 uted to the ease of use, lack of mixing or pot-
QAP SIZE, mm
life problems, reduced toxicity, and rapid cure
Fig. 6. Time to full cure of Loctite Gasket Eliminator
associated with the anaerobic materials. The
504 on steel flanges without primer.
incorporation of novel synthetic resins has ex-
tended the range of properties available in cured
interference fits to provide structural integrity.
anaerobic adhesives, leading to improvements
However, even carefully machined compo-
in tensile strength, impact strength, and peel
nents have a relatively low metal-to-metal con-
strength. Primers or heat can be used to accel-
tact area. Consequently, pushoff strengths are
erate cure when necessary.
reduced. Anaerobic retaining compounds fill
Table 5 contains a brief outline of results
the voids between the two surfaces, augment-
from physical property tests conducted on a
ing the mechanical action of the interference
fit. In cases where slip-fitted or worn parts are
used, retaining compounds provide structural Table 5. Physical Properties of Cured
integrity where none would otherwise exist. Loctite Speed bonder 324.
Retaining adhesives have been formulated Test Results
which exhibit improved bond strengths when
Bond Thickness, mm 0.05 0.50
subjected to high temperatures. For example, Test
Loctite Retaining Compound 620 develops a Tensile Shear Strength, DaN/cm2
50 % increase in shear strength when bonds are ASTM D-1002-65)
heated to 149°C for 2000 hours and tested at Aluminum 230 250
that temperature. Prolonged heating at 204°C Steel 225 300
2 Impact Strength, J/cm 2.1 7.3
(ASTM D-950-54)
7.0r--------------------, T-Peel Strength, kN/m
(ASTM D-1876-61)
Aluminum 5
5.6
Steel 10 8
E
j Bulk Properties
ui
r< 4.2

e
:>
Coefficient of linear thermal expan-
..
r< sion, 10- 5 cmlcml°C 12.6
.."'... Thermal conductivity, WIm- OK
~
c 0.12
2.8
Dielectric strength, V Imm 34,000
:!.
z
Volume resistivity, 10 12 ohm-em 3
!
1.4 Dielectric constant
100Hz 5.5
1 kHz 5.3
0
0 0.1 0.2 0.' 0.4 0.5 0.6
1 MHz 5.5
GAP SIZE, mm Dissipation factor
100 Hz 0.039
Fig. 7. Sealing ability of Loctite Gasket Eliminator 504
1 kHz 0.033
on nine 5-mm flanges measured immediately after assem-
1 MHz 0.045
bly.
 ANAEROBIC ADHESIVES 461

typical anaerobic structural adhesive, Loctite the edges of the component as well as a layer
Speedbonder 324. Unlike older anaerobic ad- of adhesive underneath. Exposure to ultraviolet
hesives, products based on functionally de- radiation causes the fillet to harden, immobiliz-
signed resins exhibit bonding perfonnance at ing the component and pennitting the slower
0.5 mm gaps which is at least as good as the anaerobic cure to proceed underneath.
zero-gap perfonnance. This balance of prop-
erties has qualified anaerobic adhesives for Ultraviolet Light Priming
structural bonding of dissimilar substrates in Instead of directly curing an adhesive, ultravi-
automotive glass to metal, loudspeaker mag- olet light can replace chemical primers for an-
nets, fireann components, and decorative wood aerobic fonnulations under certain conditions. 36
to cutlery applications. This technique involves applying the fonnula-
tion to a substrate and irradiating the coated
substrate for a prescribed length of time. Al-
RECENT ADVANCES
though the adhesive remains liquid, it has be-
Surfactant Resins come susceptible to anaerobic polymerization
and assembly leads to bond fonnation.
One of the benefits of anaerobic impregnation
sealants has been the comparative cleanliness
REFERENCES
of the processes in which they are used. The
original anaerobic products were soluble in 1. Burnett, R. E., and Nordlander, B. w. (to General
their uncured state in aqueous rinsing solutions Electric Co.), U.S. Patent 2,628,178 (Feb. 10, 1953).
which facilitated removal of excess material. 2. Krieble, V. K. (to American Sealants Company), U.S.
Patent 2,895,950 (July 21, 1959).
Novel fonnulations have now been developed
3. Grant, E. S., "Drop by Drop: The Loctite Story,"
which incorporate surface active agents. 33 Loctite Corporation, 1983.
These fonnulations require only a plain water 4. Krieble, V. K., U.S. Patent 3,041,322 (June 26,
wash to remove uncured material, reducing op- 1962).
erating costs and waste disposal. 5. Pearce, M. B., Appl. Polym. Symp., 19,207 (1972).
6. Krieble, V. K. (to Loctite Corporation), U.S. Patent
3,218,305 (Nov. 16, 1965).
Dual-Cure Systems 7. Humphreys, R. W. R., in "Adhesive Chemistry,"
L.-H. Lee (ed.), pp. 603-615, New York, Plenum
In certain bonding applications, it is desirable Publishing Corporation, 1984.
to combine the benefits of single-component 8. Okamoto, T., and Matsuda, H., Nippon Setchaku
Kyokaishi, 20(10), 468 (1984).
anaerobic adhesives with another cure mecha-
9. Okamoto, T., Mori, H., and Matsuda, H. (to Okura
nism which provides instant, though less du- Kogyo Kabushiki Haisha), U.S. Patents 4,433,124
rable, strength. For example, fonnulations have (Feb. 21,1984) and 4,546,125 (Oct. 8,1985).
been developed which contain conventional an- 10. Rich, R. D. (to Loctite Corporation), U.S. Patent
aerobic cure components and free-radically 4,321,349 (Mar. 23, 1982).
11. Krieble, R. H., U.S. Patent 3,043,820 (July 10, 1962).
polymerizable monomers as well as tackifying
12. Frauenglass, E., and Gorman, J. w. (to Loctite Cor-
resins which impart pressure-sensitive adhe- poration), U.S. Patent 4,262,106 (Apr. 14, 1981).
sion. 34 Materials based on this combination of 13. Murray, B., and Baccei, L., SME Paper No. AD75-
cure systems exhibit immediate adhesion but 792 (1975).
pennit repositioning before the slower anaero- 14. Gorman, J. W., and Toback, A. S. (to Loctite Cor-
poration), U.S. Patent 3,425,988 (Feb. 4, 1969).
bic cure to a high strength bond occurs.
15. Baccei, L. J. (to Loctite Corporation), U.S. Patent
Another bonding method which allows rapid 4,309,526 (Jan. 5, 1982).
assembly and gradual development of bond 16. Baccei, L. J. (to Loctite Corporation), U.S. Patent
strength hinges on a combination of anaerobic 4,295,909 (Oct. 20, 1981).
and ultraviolet light curing. 35 In the attachment 17. Hoffman, D. K. (to Dow Chemical Co.), U.S. Patent
4,320,211 (Mar. 16, 1982).
of small electronic components to printed cir-
18. Frisch, K. C., Lock, M. R., and Stuk, G. J. (to Dow
cuit boards, drops of adhesive are dispensed Chemical Co.), U.S. Patent 4,451,627 (May 29,
onto the board. Each component is then placed 1984).
on top of the drops so as to fonn a fillet around 19. Drake, R. S., and Siebert, A. R., in "Adhesive
462 HANDBOOK OF ADHESIVES

Chemistry," L.-H. Lee (ed.), pp. 393-407, New 29. Werber, G. P. (to Loctite Corporation), U.S. Patent
York, Plenum Publishing Corporation, 1984. 3,851,017 (Nov. 26, 1974).
20. Werber, G. P. (to Eschem Inc.), U.S. Patent 30. O'Donovan, M., and Lennox, A. (to Loctite Corpo-
4,569,977 (Feb. 11, 1986). ration), U.S. Patent Des. 255,870 (Iuly 15, 1980) and
21. Brenner, W., U.S. Patent 4,216,134 (Aug. 5, 1980). U.S. Patent Des. 255,871 (Iuly 15, 1980).
22. Toback, A. S., and Cass, W. E. (to Loctite Corpo- 31. Haviland, G. S., U.S. Patent 3,386,630 (Iune 4,
ration), U.S. Patent 3,625,930 (Dec. 7, 1971). 1968).
23. Toback, A. S. (to Loctite Corporation), U.S. Patent 32. Haviland, G. S., Mechanical Engineering, 105(10),
3,616,040 (Oct. 26, 1971). 17 (1983).
24. Hauser, M., and Malofsky, B. M. (to Loctite Corpo- 33. DeMarco, I. (to Loctite Corporation), U.S. Patent
ration, U.S. Patent 3,970,505 (Iuly 20, 1976). 4,069,378 (Ian. 17, 1978).
25. Bich, G. I., Burke, T. M., and Smith, I. D. B. (to 34. Douek, M., Schmidt, G. A., Malofsky, B. M., and
Westinghouse Electric Corp.), U.S. Patent 4,442,138 Hauser, M. (to Avery Products Corporation and Loc-
(Apr. 10, 1984). tite Corporation), U.S. Patent 4,118,442 (Oct. 3,
26. Malofsky, B. M. (to Loctite Corporation), U.S. Pat- 1978).
ent 3,855,040 (Dec. 17, 1974). 35. Grant, S., and Wigham, I., Hybrid Circuits, 8, 15
27. Krieble, V. K. (to Loctite Corporation), U.S. Patent (1984).
3,489,599 (Ian. 13, 1970). 36. Conway, P., Melody, D. P., Woods, I., Casey, T.
28. Cooke, B., and Wrobel, P. (to Loctite Corporation), E., Bolger, B. I., and Martin, F. R. (to Loctite (Ire-
U.S. Patent 4,497,916 (Feb. 5, 1985). land) Ltd.), U.S. Patent 4,533,446 (Aug. 6, 1985).
 27
Cyanoacrylate Adhesives
H. W. COOVER, D. W. DREIFUS, AND J. T. O'CONNOR
Loctite Corporation
Newington, Connecticut

Alkyl cyanoacrylate adhesives are unique adhesives are sold worldwide. Most are used
among the many classes of adhesives, in that for single drop applications. While numerous
they are the only single component, instant cyanoacrylate esters have been prepared, only
bonding adhesives that cure at ambient condi- a relative few are of significant commercial in-
tions without requiring an external energy terest (Table 1). Today ethyl esters account for
source. This characteristic, .coupled with an over 90 % of the commercial volume because
ability to bond a wide variety of diverse and of a combination of superior bonding proper-
dissimilar substrates, has made them the ideal ties, long shelf life, and efficient production
adhesives for numerous bonding applications. processing. The cure speed and adhesive
Though moderately high in bulk cost, they are strengths both tend to drop with increasing al-
very economical to use in practice because gen- kyl chain length. While the methyl volume
erally only one drop is required per bond and continues to decrease, the allyl ester is now
the nearly instantaneous room temperature cure being aggressively marketed as a crosslink-
makes fixtures, ovens, and expensive radiation ing, thermally resistant grade and alkoxyl-
sources unnecessary. alkyl esters are beginning to find application as
These compounds were first synthesized in low odor-low bloom variations.
1947 by Alan Ardis i ,2 ofB. F. Goodrich, who At present, there are six major producers of
reported "hard clear glasslike resins" when cyanoacrylate adhesives in the world: The Loc-
heat cured. Their adhesive properties remained tite Corporation and National Starch (Perma-
undiscovered until the early 1950s, when sci- bond) in the United States; Henkel AKG in
entists at Eastman Kodak inadvertently bonded Germany; Toa Gosei, Sumitomo, and Alpha
the prisms of an Abbe refractometer together Techno in Japan.
while characterizing a cyanoacrylate monomer. The reactivity of cyanoacrylates is directly
The first commercial result of the cyanoac- traceable to the presence of two strong electron
rylate research work was Eastman 91Q1~, a withdrawing groups (designated X and Y)
methyl ester based adhesive which was intro-
duced in 1958. First thought to be an interest- /X
ing, expensive curiosity, the new adhesive CH 2 =C,
gradually began to build a unique and substan- Y
tial niche for itself when used for bonding small where X = CN
parts that were difficult to assemble with con- Y = COOR
ventional adhesives, or by mechanical means. These groups make the double bond highly sus-
Today over 1000 tons of various cyanoacrylate ceptible to attack by weak bases. Not all elec-

463
464 HANDBOOK OF ADHESIVES

tronegative groups produce monomers that act

like adhesives. Molecules of this type that show
adhesive characteristics include: alkyl-2-cy-
anoacrylates, 3 the dialkyl methylene malon-
ates,4,5 the acyl-acrylonitriles, 6 and certain a-
substituted vinylidene alkyl sulfinates and sul-
fonates. 7

SYNTHESIS OF ALKYL-2-
CYANOACRYLATES
Two synthetic routes were employed by Alan
Ardis in 1947. I,2 The first route l involved the
II)
~
pyrolysis of an alkyl-3-acyloxy-2-cyanopro-
G)
E pionate to yield an alkyl-2-cyanoacrylate plus
o a carboxylic acid.
r:::::
o The second and today most commercially fa-
..
:E
G)
IV
-
on
00
vored method involves the Knoevenagel con-
densation reaction2 • 8 of an alkyl cyanoacetate
~ with formaldehyde in the presence of a basel
U
IV
o to yield a poly(alkyl-2-cyanoacrylate) as fol-
r:::::
IV
lows:
>
(J
o
00
CN
r:::::
o I
E n CH2
E I
o
(J
....o COOR

1 nH,O
II)

lCH,-r
G)
-f
--
l
G)
Q. +
o
~
00
0..
COORJ n
...
G)
Where B represents a basic end group. This re-
--
:is
....
IV action is usually carried out in a nonaqueous
00
organic solvent to facilitate the removal of
water from the system and to dissipate the heat
evolved during the reaction exotherm. 8
The polymerized cyanoacrylate is then heated
to a temperature of 140-260°C, forcing the de-
polymerization of the polycyanoacrylate back
to a cyanoacrylate ester:

lCH,-r 1
CN
(ARO)3PO I

l
- C H2 =C
P20S I
~
COORJn COOR

*e.g., piperidine.
 CYANOACRYLATE ADHESIVES 465

In batch-type operations, yields in excess of produce cleaner products, and the development
80% should be readily attainable. For this re- of packages with improved barrier properties,
action to occur smoothly without repolymeri- today's stabilizer systems can provide cyanoac-
zation of the monomer, the basic catalyst from rylates with shelf lives of several years.
the first reaction must have been neutralized by
the addition of a small amount of an acidic Anionic Inhibitors
compound, e.g., phosphoric anhydride, etc. 2
Since the anionic cure of cyanoacrylates pro-
In addition, a free radical inhibitor such as hy-
ceeds as a result of basic catalysis, acids should
droquinone, catechol, etc. 2 should be added to
naturally be considered as stabilizers. Acids of
the system to prevent repolymerization initi-
either the Lewis or protonic types have been
ated by the formation of free radicals at the el-
used successfully.
evated temperatures. An anionic stabilizer such
Acidic gases such as NO, S02, S03' BF3,
as S02 must also be added to the fresh mon-
and HF have the advantage of stabilizing the
omer to prevent subsequent polymerization.
monomer in both the liquid and gaseous
Continuous processes for depolymerization
phases. 3, 12, 13 This is useful in process distil-
of alkyl-cyanoacrylates have been pro-
lation as it prevents premature polymerization
posed. 9 , 10 A more recent patent, II discusses
of unstabilized monomer in distillation col-
carrying out the initial polymerization in an ex-
umns; at the same time, these acid gases also
truder in which gaseous by-products are re-
prevent the buildup of popcorn polymer in the
moved in a degassing zone. The mother
head space of partially filled user packages.
polymer produced is then mixed with hydro-
Strong protonic acids such as aliphatic and
quinone and phosphorous pentoxide in a stream
aromatic sulfonic acids 14 and mineral acids
of S02 to produce a stabilized methyl cyanoac-
have also been used in low levels as stabilizers.
rylate.
Combinations of nonvolatile sulfonic acids with
gaseous stabilizers have been reported to offer
STABILIZERS AND INHIBITORS
synergistic effects. IS Carboxylic acids and an-
Cyanoacrylate monomers are highly reactive hydrides have also been reported as stabilizers
compounds and will polymerize via anionic but generally are less effective than the stronger
and/or free radical mechanisms. The anionic acids.
reaction route is by far predominant and can be Acid strength and level are important varia-
initiated by even small amounts of a weak base bles in choosing a stabilizer. High levels of acid
such as water. Exposure to extended high tem- can overstabilize and make polymerization or
peratures, ultraviolet light, or heat in the pres- cure speed of the adhesives quite sluggish and
ence of peroxides can cause free radical can contribute quite significantly to a rapid de-
polymerization to be initiated. The extreme an- terioration in adhesive performance. Despite
ionic reactivity of these monomers was unob- the fact that water is known to be the most
served by early workers, probably due to crude common initiator of cure, it has been shown
preparatory methods which resulted in very im- that cyanoacrylates can and do contain surpris-
pure, overstabilized product. Early attempts to ingly high levels of free water (up to several
polymerize the monomers nearly always in- thousand ppm). The water, in combination with
volved thermal methods. It was not until the the strong acid stabilizer, can cause hydrolysis
early 1950s that Coover and Sheare~ of East- of the monomer, forming carboxylic acids
man Kodak, using purer material stabilized which drastically retard cure speed. Therefore,
with S02 gas, discovered the unique polymer- the lowest level of acid requisite with adequate
ization and bonding characteristics of the cy- shelf life is most desirable.
anoacrylate monomers. Other compounds have also been reported as
Inhibitors of both anionic and free radical po- effective anionic polymerization inhibitors. Or-
lymerization are essential to maintain a usable ganic sulfur compounds when added to the pre-
shelf life for cyanoacrylate adhesives. Coupled polymer slurry in the manufacturing process
with advances in manufacturing processes to before cracking or depolymerization have been
466 HANDBOOK OF ADHESIVES

reported to yield stabilized monomer. These often is, relatively high. Levels of free radical
compounds include alkyl sulfates, sulfones, stabilizers can range from 100 to several thou-
sulfoxides, sulfites, and 3-sulfolene. 16 Boric sand ppm with little or no effect on the cy-
acid chelates have been reported l7 as have tri- anoacrylate adhesives cure properties.
methyl silyl derivatives of sulfonic acids. IS Im-
idazole adducts with S02 have also been CHEMISTRY OF POLYMERIZATION
reported as latent sources of S02 in cyanoac-
rylate adhesives. 19 As previously mentioned, alkyl-2-cyanoacry-
lates polymerize rapidly by an anionic
mechanism20 in the presence of weak bases at
Free Radical Stabilizers
ambient temperatures. The reaction is highly
As a rule, free radical stabilizers have only a exothermic. The actual polymerization can be
minimal effect on the anionic polymerization depicted as follows:

CN CN
/ /
H 2C=C + Be - B-CH2-Ce Initiation
"C0 R 2 "C0 R 2

-
CN CN CN
/ / /
+ B-CH2 -Ce B-CH2-C -CH2 -Ce
" C0 H "C02R "C02R

q
2
Propagation

/ N /q - N / CN
B-CH2 -C CH2 - C ce
"C02R "C02R n
"C02R
OH CN
/ /
+ H+-+ B CH2-C CH2- C - Termination
"C02R "C02R
This reaction will continue until all available
rate, hence the selection of the type and con- monomer is consumed or until growth is inter-
centration is not as critical as with the anionic rupted by the presence of an acidic species. It
stabilizer. The most common inhibitor used is is the highly electronegative characteristics of
hydroquinone, although quinone, a methyl the nitrile (-CN) and alkoxycarbonyl
ether of hydroquinone, and methoxy hydroqui- (-COOR) groups that account for the high
none have been reported. Hindered phenols reactivity of the double bond in the monomer
such as catechol, pyrocatechol, etc., have also such that weak bases as alcohol and water ini-
been used with little or no advantage apparent tiate rapid polymerization. In general, rela-
over hydroquinone. tively low molecular weight chains are formed
Since the predominant cure mechanism of via this mechanism.
cyanoacrylates is anionic, the level of free rad- Since virtually all materials have a thin layer
ical stabilizer which may be added to stabilize of moisture adsorbed onto their surfaces, it is
against heat or UV induced gelation can be, and easy to explain the reactivity of the alkyl-2-cy-
 CYANOACRYLATE ADHESIVES 467

anoacrylates as perceived by the user. When a surfaces, as well as present possible safety haz-
thin film of cyanoacrylate adhesive is spread ards due to the adhesive's strong tissue bonding
onto a surface for bonding purposes, polymer- characteristics.
ization occurs rapidly as carbanions are gener- As a result, viscosity modification, through
ated at a very rapid rate as a result of the contact the use of various soluble polymeric thicken-
between the adhesive and adsorbed water mol- ers, represented the first attempt to modify the
ecules. The water molecules' hydroxyl groups liquid properties of cyanoacrylates. Thickeners
effectively act to initiate polymerization. Since and fillers must be compatible with the cy-
only thin films of cyanoacrylate are involved, anoacrylates and must not set off the easily trig-
complete polymerization through the bond line gered anionic cure. Polymers which have been
is extremely rapid, resulting in near instanta- used to increase the base viscosity of the mon-
neous "fixturing" of parts. omers include polymethacrylates (the most
When alkyl-2-cyanoacrylates polymerize via common), polyacrylates, polycyanoacrylates,
a free radical mechanism, the following reac- polyvinylacetates, baked polyacrylics, polylac-
tion sequence takes place: tic acid, cellulose nitrates and other esters such

CN CN
I I
R' + CH2 =C - R-CH -C,
2 I
I

1
COOR COOR

CN CN
RCH 2 -C.
I
I
COOR
+
I
nCH2 =C
I
COOR
- R{CH,-r COOR n+!

R{CH,-r l R'· - R{CH,-r lRI

COORJ[
+
COOR n

Because of the high activation energy (30 kCal1 as the acetates, propionates and butyr-
mol) associated with this reaction20 and the de- ates. 3,22.23
pendence of the reaction rate on temperature, Recently, elastomeric fillers have been in-
quantity of radicals, etc., the anionic route is corporated into cyanoacrylates to improve the
strongly favored. In general, free radical in- flexibility and toughness of the basically brittle
duced polymerization yields high molecular polymers. Copolymers of: (a) acrylonitrile, bu-
weight polymer. tadiene, and styrene; (b) methacrylates, buta-
diene, and styrene; and (c) ethylene with
methyl acrylate or vinyl acetate have been re-
FILLERS AND ADDITIVES
ported. 24 - 26 See the section on Recent Ad-
Alkyl cyanoacrylate monomers typically have vances.
viscosities in the range of 1-3 cP, which are Earlier, ester plasticizers of various types
much too low to permit convenient use in many were also reported to prevent the gradual em-
industrial applications. Water thin adhesives brittlement of the adhesive bond on aging.
will flow from the bondlines, resulting in ad- Those reported include cyanoacetates, succi-
hesive-starved joints and low bond strengths. nates, adipates, sebacates, phthalates, acyl es-
Migrating adhesive could also bond adjacent ters, phosphonates, and phosphates. Alkyl aryl
468 HANDBOOK OF ADHESIVES

ethers have also been used. 27 • 28 Plasticized for- cyanoacrylate esters are shown in Table 2, and
mulations with improved heat resistance were generally indicate that:
claimed by use of the allyl, methallyl, and cro-
• Cure speed, tensile, tensile shear, and im-
tyl esters of phthalic acid. 29 Further work to
pact strength decrease with increasing es-
alleviate the brittleness of cyanoacrylate adhe-
ter chain length.
sives and to improve their impact, heat and
• Bond hot strengths also decrease with in-
moisture resistance, teaches the use of poly-
creasing alkyl chain length. In general,
functional carboxylic acids and anhy-
cyanoacrylates are not recommended for
drides. 30 • 31 Gallic acid, gallate esters, and
long term use above 60-70°C.
tannin derivatives of gallic acid are reported to
function similarly. 32, 33 • Solvent resistance is typical of polar, lin-
ear high polymers. In nonpolar solvents,
Inorganic fillers are not widely used due to
attack is negligible, while solvents of sim-
the likely instability which would be caused by
ilar solubility parameter will weaken cured
these materials. Recently, stable thixotropic
cyanoacrylate bonds slowly. (See Table
gels (see the section on Recent Advances)
3). Moisture resistance of cyanoacrylates
which can be applied to vertical or overhead
is not considered to be a strong point of
surfaces have been prepared by Loctite. These
these adhesives, however, with proper at-
materials are prepared from silane-treated hy-
tention to adhesive and substrate compo-
drophobic silicas which are drier and consid-
sition, excellent bonds are achievable.
erably more stable than conventional silicas in
cyanoacrylate adhesives. 34 The bond properties Several special esters also deserve mention,
of these gels are identical to the flowable New- the allyl-2-cyanoacrylates and the ,B-alkoxy-
tonian cyanoacrylate adhesives. alkyl cyanoacrylates.
Cyanoacrylates may be prepared in virtually Adhesives based on the allyl ester were first
any color. Stable dyes of assorted structures areintroduced by Eastman in the 1970s as ther-
used to color cyanoacrylates for cosmetic rea- mally resistant products and have now been re-
sons or for inspectability during automated as- introduced by Permabond under the Powerbond
sembly operations. 35-38 trademark. These esters exhibit cure speeds and
Considerable work has also been done in the ultimate strengths similar to those of the ethyl
last 10 years investigating the use of various and propyl products, but are capable of
additives which accelerate the anionic poly- undergoing a second stage free radical cross-
merization of cyanoacrylates on acidic or po- linking reaction through the pendant allyl
rous substrates. These additives are covered in group. The crosslinking reaction is sluggish,
the Recent Advances section of this chapter. however, requiring significant exposures to
high temperatures (350°F) to effect. The linear
first-stage polymer will also soften consider-
PROPERTIES OF THE CURED
ably during this reaction, requiring that parts be
ADHESIVES
supported in certain applications. Nonetheless,
The lower esters of the alkyl cyanoacrylates there are applications where the added thermal
cure to clear, hard resins which exhibit good resistance of the allyl esters has proven essen-
adhesion and tensile shear strengths to a wide tial.
variety of substrate combinations. They are, The alkoxy-alkyl esters, which have methoxy
however, brittle and exhibit low peel and im- or ethoxy groups appended to the ,B-carbon of
pact strengths. Higher viscosity versions of the a standard ethyl cyanoacrylate ester, are vir-
lower esters filled with 5-10 % of tually odorless versions of cyanoacrylate ad-
poly(methylmethacrylate) resins are somewhat hesives. Though first reported by Eastman in
less brittle and can offer double the impact 1957, these are now being reemphasized by
strength of low viscosity monomeric adhe- several manufacturers with improvements in
sives, as well as significantly better peel stability and cure speed. These will be covered
strengths. more fully in the Recent Advances section.
Property relationships amongst the simple Considerable work on bis-cyanoacrylates for
 Table 2. Typical Properties of Common Cyanoacrylate Adhesives.
(3-Methoxy (3-Ethoxy
Monomer Type Methyl Ethyl Isopropyl Allyl Bbutyl Isobutyl Ethyl CA Ethyl CA
Bulk Properties
Softening point, °C (VICAT) 165 126 154 78 165 107 52
Melting point, °C 205 179 192 165 103
Refractive index, nD20 1.45 1.45 1.45 1.26 1.4 1.48
Dielectric const. @1 MH z· 3.34 3.98 3.8 3.3 5.4
Dissipation factor @1 MH z%· 2.04 0.02
Volume resistivity, Megohms-mm 3 x 10 15 9 X 10 12 7 X 10 14 5.37 X 109
Tensile strength,b steellsteel, psi 4500 4000 3000 2960 3550 4400
Elongation, % <2 <2 <2 10 <2
Flexural modulus, C psi 4.93 x 105 3.00 X 105 2.54X 105
Hardness (Rockwell) M65 M 58 R 18
All soluble in: N-methylpyrrolidone, DMF, and CH 3 N02
Bond Properties 10-15 10-15 10-15 10-15 10 20 35 5
Set Times, seconds
Steell steel
AIIAI 20 20 20 15 5
Nitrile rubber/nitrile rubber 5 5 5 5 3 0
ABS/ABS 20-30 10-15 20 5 3 -<
Tensile Shear Strength, d psi 3200 2500 3030 3120 2280 1420 2700 2400 >
z
Steel/steel 0
>
0
AIIAI 2500 2000 1530 950 1013 1420 1650 1700 ::u
Impact shear: ft-Ib/in.2 4-10 5-10 5.3 9-11 2.25 -<
r-
'ASTM 0-150. >
-I
bASTM 0-638. m
'ASTM 0-790. >
dASTM 0-1002. C
:J:
'ASTM 0950-54. m
en
<:
m
en
.,..
en
CD
470 HANDBOOK OF ADHESIVES

Table 3. Solvent Resistance of Typical times to cure. Most often a single drop,
Methyl Cyanoacrylate Adhesive Bonds. 48 activated by adsorbed atmospheric mois-
Shear ture on parts held with finger pressure re-
Strength" sults in a bonded assembly within seconds.
After I-month (See Table 3).
Immersion, • Speed of Cure. Rapid polymerization oc-
Solvent at 24°C psi
curs spontaneously within seconds to min-
None (control) 2040 utes. (See Table 4).
1,1, I-Trichloroethane 2540
Gasoline
• Strength and Versatility. High strength
2730
Acetone 26 bonds are achieved to a wide variety of
Isopropyl alcohol 3000 metallic, plastic, and elastomeric sub-
lOW-30 motor oil 2470 strates. (See Table 5).
Naphtha 1640 • Economy of Use. Because of the minimal
Toluene 1680
amount of adhesive required (1 drop/in.2)
'Steel-steel substrates.
the cost of bonding is generally less than
1 penny per bond.
improved thennal resistance has been done by On the other hand, cyanoacrylate adhesives
first preparing the anthracene Diels-Alder ad- also have several well known limitations which
ducts of monomers which were then reacted restrict their use and preclude consideration as
with glycols. The resultant intennediates were broad based general purpose adhesives. Elim-
then reacted with excess maleic anhydride to ination of these shortcomings has been the tar-
generate the bis-monomer. 39-44 Improved ther- get of significant research and development by
mal and solvent resistance were reported with most manufacturers as the need to differentiate
these products, but the procedure is difficult and product lines intensifies.
the final products very impure. The impurities
undoubtedly prevent full realization of the ben-
TYPICAL CYANOACRYLATE
efits theoretically possible with these mono-
APPLICATIONS
mers.
Some work has also been done on copoly- The unique characteristics of cyanoacrylate ad-
merizing cyanoacrylates with bis-cyanocar- hesives virtually ensure their successful use
boalkoxy butadienes which claims significant over an extremely broad and diverse range of
improvements in thennal and solvent resis- applications. The self-contained room temper-
tance. 45 ature curing properties coupled with the ability
Some interesting and significant new work on to adhere to most surfaces combine to make cy-
cyanoacrylate adhesives with improved rheo- anoacrylates the easiest way to assemble small,
logical, fast curing, and toughness properties close fitting parts. So common are the uses of
will be covered in the section on Recent Ad- cyanoacrylate adhesives that each day it is a
vances. virtual certainty that each of us comes in con-
tact with many items assembled using them.
SUMMARY OF ADVANTAGES AND In the automotive market, cyanoacrylates are
LIMITATIONS used to bond weatherstripping to automotive
bodies and to position rubber gaskets before as-
Many of the advantages of cyanoacrylate ad-
sembly. They are used to bond polycarbonate
hesives have been previously discussed, and
positioning clips to side windows of automo-
derive from their unique combination of attri-
biles, alternator hom assembly components,
butes. Still a summary of these is in order. They
and rubber gaskets to automotive thennostats.
include:
One of the most common automotive applica-
• Ease of Use. Cyanoacrylates are single- tions is the use of cyanoacrylates in the repair
component adhesives that do not require of flexible PVC side trim strips.
mixing, clamping, external energy or long Cyanoacrylates are ideal for bonding small
 CYANOACRYLATE ADHESIVES 471

Table 4. Effect of Adherend Combination on Bonding Action and

Strength. 57
Substrate Bonding Action Bond Strength
Glass-glass rapid strong initial
Aluminum-aluminum intennediate intennediate
Steel-steel intennediate strong
Glass-rubber rapid strong
Porcelain-porcelain rapid strong
Polyethylene-polyethylene intennediate intennediate
Polyester-polyester rapid intennediate
Tenite" acetate-
Tenite" acetate intennediate strong
Tenite" butyrate-
Tenite" butyrate intennediate strong
Metal-cork rapid strong
Metal-felt rapid strong
Glass-cork rapid strong
Glass-felt rapid strong
Wood-wood (maple) slow strong
Metal-leather intennediate strong
Metal-rubber rapid strong
Rubber-rubber rapid strong
Rubber-cardboard rapid strong
Glass-steel intennediate strong
Nylon-nylon rapid intennediate
Glass-Tenite" butyrate intennediate intennediate
Steel-Neoprene rapid strong

Table 5. Shear Strengths of Bonds Formed by Methyl Cyanoacrylate

Adhesives. 57
Shear Strength of Adhesive Bonds, psi
Age of Eastman 910'"
Substrates Bond Adhesive
Steel-steel 10 min 1920
48 hr 3000
Aluminum-aluminum 10 min 1480
48 hr 2700
Butyl rubber-butyl rubber 10 min 150"
SBR rubber-SBR rubber 10 min 130
Neoprene rubber-neoprene rubber 10 min 100"
SBR rubber-phenolic 10 min 110"
Phenolic plastic-phenolic plastic 10 min 750
48 hr
Phenolic plastic-aluminum 10 min 650
48 hr 920
Aluminum-nylon 10 min 500
48 hr 1440
Nylon-nylon 10 min 330
48 hr 1400
Neoprene rubber-glass filled polyester 10 min 110"
Acrylic plastic-acrylic plastic 10 min 810"
48 hr 790"
ABS-ABS 10 min 640"
48 hr 710"
Polystyrene-polystyrene 10 min 330
'Substrate failure.
472 HANDBOOK OF ADHESIVES

electronic components such as phonograph will be a key factor in the continuing growth of
needle cartridges and for tamperproofing video cyanoacrylate adhesive applications.
cassettes. Electrical coil wires are terminated
and transformer laminations unitized with cy-
REQUIREMENTS FOR SUCCESSFUL
"anoacrylate adhesives. Printed circuits are
USAGE
modified with adhesive tacked wire connec-
tions and the boards themselves often repaired In order to bond materials utilizing cyanoac-
with cyanoacrylates. Audio high fidelity speak- rylates, it is necessary to remember that poly-
ers are using increasing amounts of cyanoac- mer formation initiates at the adhesive-substrate
rylates in preference to two-component, heat interface when the adhesive comes in contact
cured epoxies. with the surface layer of moisture present on
Cosmetic items such as lipstick tubes, mir- the substrate. Polymerization then proceeds
rors in compacts and eyeshadow containers, back toward the center of the adhesive layer
brush tips and applicator swabs are also assem- rather than uniformly throughout the mass. As
bled with cyanoacrylates. a result, cyanoacrylate adhesives are not effi-
Sporting goods and toys are also important cient gap filling adhesives, since as the gap in-
application areas. Items such as athletic shoes, creases the likelihood of a growing chain being
swim masks, trophies, rubber foam recoil pads terminated by an inhibitor molecule becomes
for shotguns, as well as the feather ftetches on quite high.
an archer's arrows, all benefit from cyanoac- As with all adhesives, substrate cleanliness
rylates' unique bonding capabilities. Rubber is the key to strong, durable bonds. It is essen-
dolls and plastic doll house furniture are but tial that all mold releases, oils, residual acids,
two of the many toys that utilize cyanoacrylates etc., be removed initially. This can best be ac-
in manufacturing. complished by wiping the surface with a cloth
Many medical and dental devices are now wetted with acetone or naphtha. If the surface
being assembled with cyanoacrylates to elimi- itself is acidic, a wash in a mildly alkaline so-
nate costly molding procedures. Cyanoacry- lution or treatment with a cleaning-activator so-
lates are also being employed to eliminate the lution is recommended. For metal bonding, the
toxic solvents commonly used to bond flexibil- surface should be solvent cleaned, abraded with
ized PVC in tubing joints. sandpaper, followed again by a solvent wash.
Though not approved in the United States for Once the surfaces are properly prepared, care
surgical use, cyanoacrylates' strong tissue should be taken to ensure the use of only the
bonding capabilities have resulted in their use minimum amount of adhesive (one drop per in. 2
as chemical sutures and hemostatic agents in is recommended) needed to fill the bondline.
many foreign countries. Many lives were saved Excess adhesive can result in slow cures.
in Viet Nam through the use of Eastman Kodak For rapid fixture times, the adhesive used
developed cyanoacrylate spray kits which ena- should be as fresh as possible. Old adhesive
bled battlefield medics to stop massive blood tends to be slower, as acidic stabilizers gradu-
loss, a prime cause of combat death. ally hydrolize the monomer, forming carbox-
With the incorporation of the new surface- ylic acids. To maintain the quality of the
insensitive additives which allow rapid curing adhesive, bottles should be kept tightly closed
on acidic and porous substrates such as wood and stored in a cool, dark location. Cyanoac-
and paper, and the marketing of these versatile rylates can be safely stored in most polyethyl-
adhesives in the consumer sector, the number ene, polypropylene, and aluminum containers.
of applications where cyanoacrylates are used
is limited only by the ingenuity of the user. The
TOXICITY
new toughened adhesives with improved heat
and humidity resistance and dynamic perfor- There is currently a lack of significant data on
mance are already encroaching into areas where the toxicity characteristics of cyanoacrylate
epoxies were once the only choice. Versatility monomers-this is mainly because the mon-
 CYANOACRYLATE ADHESIVES 473

orner polymerizes so rapidly that most standard Embrittlement on heat exposure

tests (such as inhalation toxicity, etc.) are pre- Poor thermal/humidity cycle resistance
cluded. • Sensitivity of cure on porous and acidic
The work of McGee et a1. 46 shows that cy- surfaces
anoacrylate vapors can be irritating to the nose • Low gap filling ability
and throat at levels as low as 3 ppm; eye irri- • Liquid migration
tation was also experienced at levels of approx- • Lachrymatory irritating odor
imately 5 ppm and greater. Because the material • Fogging of adjacent bright or transparent
has yet to be completely evaluated, prolonged surfaces
breathing of cyanoacrylate vapors should be
Significant progress in addressing and resolv-
avoided. Only methyl cyanoacrylate has a listed
ing these performance shortfalls has been made
TLV (2 ppm) and short-term exposure limit (4
over the last several years.
ppm).47 Workers exposed to these materials
should be provided with adequate ventilation.
Toughened Adhesives
(TLV is "Threshhold Limit Value" for contin-
uous exposure, per American Conference of The ultimate quality of the cyanoacrylate ad-
Governmental Industrial Hygienists.) hesive bond falls short of what is normally con-
Studies carried out on polymerized cyanoac- sidered desirable for a true engineering
rylates revealed that oral doses of 6400 mg/kg adhesive, in terms of long term durability and
failed to kill laboratory rats. 48 While the ad- thermal, moisture, and solvent resistance. This
hesive did cause mild irritation of the skin of is due in part to the thermoplastic nature of the
guinea pigs after 24 hours exposure, there was polymer, and the relatively high shrinkage of
no evidence of skin sensitization or absorption the lightly filled adhesives. It is also generally
through the skin. accepted that the bonds have a higher than av-
Cyanoacrylates are considered combustible erage susceptibility to attack by moisture, al-
liquids. The monomer and cured adhesive will though it has been shown in early East-
both support combustion. As a result, all work man literature48 and by O'Connor and
with cyanoacrylates should be done away from Zimmermann49 that weather resistant, long
areas of open flame, sparks, and high heat. lived cyanoacrylate bonds between metals and
Obviously, contact with skin should be elastomeric materials are achieveable.
avoided; not only is the material a powerful ad- Various workers in the late 1970s began to
hesive, but when polymerization does occur, a look at different methods of reducing the brit-
rapid exotherm is evolved. tleness of cyanoacrylate bonds, through the use
of rubber toughening agents or other impact
improving additives. ABS, MBS, MABS,24,25
RECENT ADVANCES and acrylic polymers26 have been shown to be
As previously discussed, conventional cy- advantageous in improving the peel, impact,
anoacrylates perform well in numerous bond- and thermal resistance of cyanoacrylates. Sev-
ing applications, but several well known and eral other acidic impact-improving or adhe-
significant limitations preclude even wider sion-promoting additives have also been
usage. It is toward these limitations that much reported to lessen the brittleness and improve
recent research and development work has been the thermal resistance30 ,31,33 of cyanoacrylate
directed. These limitations, partially reviewed adhesive bonds. The improvements that tough-
in previous sections, include: ened adhesives exhibit are quite substantial
(Table 6), particularly after heat aging. Con-
• Lack of true engineering adhesive perfor- ventional adhesives lose a significant portion of
mance: their properties after short heat aging, while
Poor impact/peel properties toughened adhesives show much better prop-
Low thermal resistance erty retention. Similar improvements are seen
Attack by some solvents in temperature/humidity cycling tests (Table 7),
474 HANDBOOK OF ADHESIVES

Table 6. Bond Embrittlement on Heat Aging.-

Tensile Shear Strength, psi Impact Strength, ft-lblin. 2
5 Days Heat Aged, Heat Aged, Heat Aged, Heat Aged,
Adhesive RT 2 hr, 250°F 24 hr, 250°F 5 DaysRT 2 hr, 250°F 24 hr, 250°F
High Visco Ethyl 3020 2750 1410 8.5 9.6 2.0
High Impact "A" 2930 1700 360 7.8 1.4 1.0
High Impact "B" 3080 1730 1330 10.2 5.7 2.2
BLACK MAX" 3090 3770 3920 10.2 13.7 9.1
Rubber Tough-
ened
Specimens: Sandblasted steel lap sbear strips.
"A" and "B": commercially available cyanoacrylates.
'Testing carried out at room temperature.

Table 7. Cyclic Heat/Humidity Resistance on Abraded

Aluminum
5
Day 25 50
RT Cycles Cycles
Pacer TX100" 733 250 6
Pacer MR150' 1827 Fail Fail
Henkel 8400b 933 375 213
Loctite Tak PakDIC 1273 260 210
Loctite 498-TCR *c 1987 860 543
Loctite Black Max"c 2410 2130 1865
Specimens: As-received aluminum lapshear prepared with 3M Scotch-Brite pads with reagent-grade
acetone wash.
Cycle Conditions, (3 hr cycle):
30 min @ -20°F
1 hr ramp to 150°F
30 min@ 150°F, 95% RH
1 hr ramp to -20°F
*TCR-Thermal Cycle Resistant
Suppliers:
'Pacer Technology, 1600 Dell Ave., Campbell, CA 95008
"Henkel Adhesives Co., div. Henkel Corp., 4620 West 77th St., Minneapolis, MN 55435
'Loctite Corp., 70S North Mountain Rd. Newington, CT 06111

which strongly suggests that temperature cy- Thermal Resistance

cling plays a strong role in the reported low
humidity resistance of cyanoacrylate adhe- Long term thermal resistance of cyanoacrylate
sives. A plausible explanation for this behavior adhesives where constant exposure to temper-
would be that the lightly filled conventional cy- atures greater than 60-80°C is required re-
anoacrylate adhesives do not cure fully at room mains a problem. As already mentioned, an
temperature, but do postcure during heat aging, early approach was to substitute an allyl group
with resultant shrinkage. As the adhesives are in the side chain in place of the saturated alkyl
surface activated, the stress is concentrated at group.
the bond line since the monolayer at the inter- Increased thermal resistance was claimed via
face is the first to cure. The function of the rub- a two-stage cure mechanism, whereby ther-
bers and toughening additives may be to relieve mally induced crosslinking occurs after anionic
these stresses. Surprisingly, in some cases, this polymerization of the cyanoacrylate double
results in improved bond hot strengths despite bond. In practice, however, the crosslinking is
the fact that polymer thermal stability remains very slow, and assembled parts might have to
unchanged. be supported until it takes place. 50 ,51
 ,CYANOACRYLATE ADHESIVES 475

Anhydrides of polyfunctional carboxylic vators marketed by most cyanoacrylate

acids, as well as the acids themselves, have manufacturers, but in fast production environ-
been reported to improve the thermal resistance ments the use of a second component in the as-
as well as impact toughness of cyanoacrylate sembly process is often undesirable. Recent
adhesives. 30,31 Bond hot strengths are im- patents have been filed or issued teaching the
proved substantially, even though the thermal use of crown ethers,52 silacrowns,53 calixar-
decomposition temperatures of the polymer re- enes,54 and various linear polyalkylene
main unchanged. ethers55 ,56 as curing additives for use on wood
and porous surfaces (see Fig. 1). These addi-
Improved Curing Characteristics
tives are remarkably effective in accelerating
cures on such substrates and even seem to be
The sensitivity of the cure. of cyanoacrylates to effective in promoting the cure of cyanoacry-
various substrates, notably acidic surfaces late adhesives under conditions of low relative
which inhibit or slow the anionic cure, has also humidity. The slowing of cure rates during the
been a recurrent problem. This had been over- low humidity winter months can cause severe
come by the use of various basic surface acti- problems on fast automated assembly lines. The

Me Me
18-CROWN-6 \/
Si
/ \
\0 0;
o 0

CO'-IO~
1,4,7,10, 13, 16-HEXAOXA- 1,1 DIMETHYLSILA 17-CROWN-6
CYCLOOCTADECANE

5,11,17,23, TETRA-t-BUTYL
25,26,27,28 TETRA (2-ETHOXY-20XO)
ETHOXY -CALIX-4-ARENE

Fig. 1. Curing additives for lessened surface sensitivity.

476 HANDBOOK OF ADHESIVES

mechanisms of action for these additives is not groups attached to the ~-carbon of the ester side
fully understood, but since the crown com- chain:
pounds are phase transfer catalysts some inter-
action with alkali metals in the surface seems CN
likely. I
CH2 =C
I
C-O-CH
II 2 5
Thixotropic Gels
o
Highly thixotropic gel versions of cyanoacry-
lates have also become available, thickened standard ethyl cyanoacrylate
with a combination of the normal poly (methyl
methacrylate) resins and various hydrophobic CN
fumed silicas. 34 Unmodified silicas generally I
yield very unstable products due, at least in CH2 =C
part, to the large amounts of absorbed water. I
C
The new products are very easy to apply even I
on parts with three-dimensional bondline con- C-O-C
II l-I-O-CH3
2£'4
figurations and will not run off of vertical sur- o
faces. Migration from the bondline is totally
eliminated, preventing any undesirable move- methoxyethyl cyanoacrylate
ment into other critical areas. User safety with
these new gels is greatly enhanced since the CN
possibilities of splashing or running onto ex- I
posed skin are considerably reduced. Recently CH2 =C
introduced into the consumer market as a more I
C-O-C
II H -O-C2H5
2 4
user friendly instant super glue, the gel is find-
ing wide acceptance. Surface insensitive ver- o
sions with improved curing characteristics are
now being introduced which will move the cy- ethoxyethyl cyanoacrylate
anoacrylates towards a more universal adhesive
market segment. These monomers are virtually odorless and
have much lower vapor pressures so that the
blooming characteristics are greatly reduced or
Low Odor- Low Bloom Cyanoacrylates eliminated. Performance is similar but not
equivalent to that of the lower methyl and ethyl
Anyone who has used cyanoacrylates on a con-
esters. On metals or rubber the cure speeds are
tinuous basis in an area with poor ventilation is
quite fast, but the cure speeds on plastics were
familiar with the pungent, irritating, acrylic-
slower than conventional cyanoacrylates. Up-
type odor. The relatively high vapor pressure
dated, faster curing versions of these products
of the cyanoacrylate monomers which contrib-
are becoming available. As costs of production
utes to the odor can also cause evaporation from
for these adhesives are reduced, and the curing
uncured fillets; the vapors precipitate as a white
properties improved, they are expected to re-
haze on surfaces adjacent to the bondline. On
place the lower esters in many applications.
bright, decorative, or transparent parts this may
be unacceptable, often requiring the use of an
alternative adhesive. Good ventilation helps, REFERENCES
but not universally. This has led to the devel-
1. Ardis, A. E. (to B.F. Goodrich Co.), U.S. Patent
opment and marketing of alkoxyalkyl cyanoac- 2,467,926 (1949). .
rylate adhesives, which structurally are merely 2. Ardis, A. E. (to B.F. Goodrich Co.), U.S. Patent
ethyl cyanoacrylates with methoxy or ethoxy 2,467,927 (1949).
 CYANOACRYLATE ADHESIVES 477

3. Coover, H. W., Jr., and Shearer, N. H., Jr. (to East- 4,139,693 (1979).
man Kodak Co.), U.S. Patent 2,794,788 (1957). 33. Millet, G. (to 3M), U.S. Patent 4,511,686 (1985).
4. Coover, H. W., Jr., and Shearer, N. H., Jr. (to East- 34. Litke, A. E. (to Loctite), U.S. Patents 4,447,607
man Kodak Co.), U.S. Patent 2,763,585 (1956). (1984) and 4,533,422 (1985).
5. Coover, H. W., Jr., and Shearer, N, H., Jr. (to East- 35. Thomsen, W. F., and van Bramer, P. T. (to Eastman
man Kodak Co.), U.S. Patent 3,221,745 (1965). Kodak), U.S. Patent 3,699,076 (1972).
6. Toyo Rayon K. K., British Patent 1,168,000 (1969). 36. Zollman, H. T. (to Eastman Kodak), U.S. Patent
7. Shearer, N. H., and Coover, H. W., Jr. (to Eastman 4,062,827 (1977).
Kodak), U.S. Patent 2,748,050 (1956). 37. Nikata, T., Kawazoe N., and Takenaka, T. (to Sum-
8. Joyner, F., and Hawkins, G., U.S. Patent 2,721,858 itomo, Taoka), U.S. Patent 4,405,750 (1983).
(1955). 38. Kusayama, S., Nishi, E., and Stock, H. (to Pacer),
9. Imoehl, W., and Bomer, P., U.S. Patent 3,728,373 U.S. Patent 4,297,160 (1981).
(1973). 39. Buck, Carl J. (to Johnson and Johnson), U.S. Patent
10. Imoehl, W., Konigsborn, U., and Bomer, P., U.S. 3,975,422 (1976).
Patent 3,751,445 (1973). 40. Buck, Carl J. (to Johnson and Johnson), U.S. Patent
11. Wanczek, H., and Bartl, H. (to Bayer AG), DE Patent 4,033,942 (1977).
3,320,756 (1983). 41. Buck, Carl J. (to Johnson and Johnson), U.S. Patent
12. Joyner, F. B., and Shearer, N. H. (to Eastman Ko- 4,012,402 (1977).
dak), U.S. Patent 2,756,251 (1956). 42. Buck, Carl J. (to Johnson and Johnson), U.S. Patent
13. Ito K., and Kondo, K. (to Toa Gosei), U.S. Patent 4,013,703 (1977).
3,557,185 (1971). 43. Buck, Carl J. (to Johnson and Johnson), U.S. Patent
14. Kawamura, S., et al. (to Toa Gosei), U.S. Patent 4,041,062 (1977).
3,652,635 (1972). 44. Buck, Carl J. (to Johnson and Johnson), U.S. Patent
15. Lizardi, L., Malofsky, B., Liu, 1. C., Mariotti, C. (to 4,041,063 (1977).
Loctite), UK Patent GB 2,107,328B (1985). 45. Gerber, A.H. (to Lord Corp.) British Patent 1,374,464
16. Coover, H. W., Jr., and Wicker, T. (to Eastman Ko- (1974).
dak), U.S. Patent 3,355,482 (1967). 46. McGee, W.A., Oglesley, F.L., Raleigh, R.L. and
17. Schoenberg, 1. E. (to National Starch), U.S. Patent Fassett,D.W., "The Determination of a Sensory Re-
4,182,823 (1980). sponse to Alkyl 2-cyanoacrylates Vapor in Air," Am.
18. Sieger, H., and Tomaschek, H. (to Teroson), U.S. Ind. Hyg. Assoc. J. 29,558-561 (1968).
Patent 4,565,883 (1986). 47. From Threshold Limit Values for Chemical Substanc in
19. Sweeney, N. P., and Thorn, K. F. (to 3M), U.S. Pat- Wolkroom Air by the ACGrn for .l2ll. Cincinnati,
ent 3,993,678 (1976). American Conference of Government Industrial Hy-
20. Coover, H. W., and McIntire, J. M., in "Handbook gienists, 1975.
of Adhesives," 2nd Ed., I. Skeist (ed.), pp. 569-580, 48. Thomsen, William, from Schneberger, G., Adhesives in
New York, Van Nostrand Reinhold, 1977. Manufacturing, pub!. Marcel Dekker Inc., 1983, p. 305.
21. Park, J. I., in "Cyanoacrylate Resins-The Instant 48. Catalog Eastman 910 (Eastman Kodak Co.) 1971.
Adhesives," H. Lee (ed.), p. 45, Pasadena Press, 49. O'Connor, J.T. and Zimmerman, "Factors Affect Adhe-
1981. sion of Cyanoacrylate Adhesive to Bright Anodized Sur-
22. Wicker, T., and Shearer, N. A. (to Eastman Kodak), faces," paper to American Electroplaters Society, Den-
U.S. Patent 3,178,379 (1965). ver, CO (1976).
23. Wicker, T., and McIntire, 1. M. (to Eastman Kodak), 50. Halpern, B.D., Dickenstein, J., and Hoegerle, R. (to Bor-
U.S. Patent 3,527,841 (1970). den), U.S. Patent 3,142,698 (1964).
24. Gleave, E. R. (to Loctite Corp.), U.S. Patent 51. Kato, H., Tsuzi, I., Azuma, K., and Tatemishi, H. (to
4,012,945 (1978). Toa Gosei) U.S. Patent 3,825,580 (1974).
25. Millet, G. H., et al. (to 3M), U.S. Patent 4,560,723 52. Motegi, A., Isowa, E., and Kimura, K. (to Toa Gosei) U.S.
(1985). Patent 4,171,416.
26. O'Connor, J. T. (to Loctite Corp.), U.S. Patent 53. Iiu, J.C., (Loctite) European Patent Application, EP-
4,440,910 (1984). 142327 (1985).
27. Joyner, F. B., and Coover, H. W. (to Eastman Ko- 54. Harris, S.1., McKervey, M.A., Melody, D.P., Woods, J.,
dak), U.S. Patent 2,784,127 (1957). and Rooney, J.M. (to Loctite) U.S. Patent 4,556,700
28. O'Sullivan, D. J., and Bolger, B. J. (to Loctite), U.S. (1985).
Patent 3,699,127 (1972). 55. Motegi, A. and Kimura, K. (to Toa Gosei) U.S. Patent
29. Wicker, T. H. (to Eastman Kodak), U.S. Patent 4,170,585 (1979).
3,354,128 (1967). 56. Shiraishi, Y., Nakazawaki, Nakata, C., Ohasi, K. (to
30. O'Sullivan, D. J., and Melody, D. P. (to Loctite), Sumitomol Taoka) U.S. Patent 4,377,490 (1983).
U.S. Patent 3,832,334 (1974). 57. Coover, H.W. Jr. in "Handbook of Adhesives," I. Skeist,
31. Yamada, A., and Kimura, K. (to Toa Gosei), U.S. (ed), pp. 409-414, New Yolk, Van Nostrand Reinhold,
Patent 4,196,271 (1980). 1962
32. Schoenberg, J. E. (to National Starch), U.S. Patent
 28
Polyester and Polyamide
High Performance Hot Melt
Adhesives
CONRAD ROSSITTO
Emhart Fastening Systems Group
Bostik Division
Middleton, Mass.

Hot melt adhesives have been known for cen- polyesters from aromatic dibasic acids, includ-
turies. Historically, mixtures of natural waxes, ing polyethylene terephthalate (PET), now the
rosin, pitch, and other naturally occurring sub- major synthetic polymer for fibers.
stances were used alone or in mixtures to pro- Most polyamides and polyesters are conden-
duce sealing compounds for a variety of sation polymers, produced by reacting dibasic
applications. It was not, however, until the acids with diamines to produce polyamides, or
early 1950s that hot melts based on synthetic with diols to make polyesters. If derived from
polymers appeared in the marketplace. dibasic acids, the chemical structures can be
Traditionally, as now, hot melts usually have represented as follows:

J-
been made by compounding existing high mo-

~ C-R-C-NH-R'-NH
oII
lecular weight polymers with low molecular
0II Polyamide
weight resins to achieve the desired balance of

J-
properties. A great diversity of hot melts is now n

oII
~ C-R-C-O-R'-O
available from synthetic resins and polymers
0II Polyester
based on petroleum feed stock. Of all these, it
is the compounded polyamides and polyesters n

which provide hot melts with the best proper-

If produced by ring opening of caprolactam
ties.
or other lactam, the polyamide structure is:
The chemistry for these two classes of poly-
mers goes back to the pioneering work ofWal-
lace Carothers at DuPont which led to the
development of nylon 6-6, poly(hexamethylene
adipamide), the first man-made fiber. Caroth-
J~-R-NHJ- n

ers also investigated the aliphatic polyesters, In homologous series of polyesters and poly-
but found them too low in melting point to serve amides, the melt points, Tm , of polyesters are
as fibers. In England, however, J. R. Whinfield significantly lower than those of polyamides.
and J. T. Dickson of Calico Printers Associa- As the proportion of carbon atoms in the main
tion [British Patent 578,079 (1946)] developed chain is increased, the melt points of polyam-

478
 POLYESTER AND POLYAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 479

240~~~~--~------~
300
u
o ~ 20 0 1---------l~~----;::;__--___1

u
o
200
~mides
~
-
~
:J
C
~
a.
160 I-----------~

E
~
1201------------f
Linear polyethylene a.:

--
100 ~
r..
Polyesters

2 4 6 8 10
o I I I

16 18 20 22 Number of carbon atoms

Chain atoms in repeating unit Fig. 2.

Fig. 1.
commonly, on copolymers. The most common
monomers for hot melt polyamides are:
ides decrease while those of polyesters in-
crease, both approaching the melt point of • Dibasic Acids:
polyethylene as shown in Fig. 1. Dimer acid (dimerized fatty acids).
The low melt points of polyesters are asso- Dodecanedioic acid.
ciated with the flexibility of the C-O chain Sebacic acid.
bond and the low heat of fusion. The substan- Azelaic acid.
tially higher melting point of the polyamides Adipic acid.
are the result of intermolecular hydrogen bond- • Amino Acids and Lactams:
ing across amide groups of adjacent molecules. Caprolactam.
The melt point is also affected by the spacing ll-Aminoundecanoic acid.
of the polyester and amide groups since this de- Dodecalactam.
termines the crystal structure of these poly- • Diamines:
mers. The even-number carbon chains have Ethylene diamine.
higher crystallinity and therefore higher melt Hexamethlene diamine.
points. This trend is shown in Fig. 2 for poly- Diethylene triamine.
esters made from decamethylene glycol and di- Triethylene tetramine.
basic acids of varying chain lengths and for Piperazine.
polyamides made from sebacic acid and dia- Dipiperidyl propane (Dipip).
mines of varying chain length. Polyoxypropylene diamine.
From these monomers have been developed
POLVAMIDES a large variety of polyamides, which can be di-
Because the polyamides and the polyesters de- vided into four classes:
veloped for fibers are too high-melting and too 1. Polyamides made from lactams and
fast-setting to be used for adhesives, chemists amino acids.
have made copolymers to lower the melt point 2. Polyamides from condensation reactions
and increase the set time of these two classes of short chain dibasic acid and diamines.
of polymers. Today most of the polyamides and 3. Polyamides from long chain, vegetable
polyesters used in hot melt adhesives are based oil-derived dibasic acids and short chain
either on monomers not used for fibers or, more diamines.
480 HANDBOOK OF ADHESIVES

4. Polyamide copolymers and terpolymers

of short chain monomers.

The homopolymers of the first two classes

represent all the nylon fibers, as well as all the
engineering nylon plastics.
To the third class belongs most of the low
melt high melt polyamides.
The fourth class includes a very large group
of polyamides derived from a multiplicity of
monomers, resulting in very specialized hot
melt adhesives.
2A

Dimer Acid-Based Polyamides

The dimerization of C l8 unsaturated fatty acids
produces mainly dibasic acids with carbon
chain lengths of36 carbon atoms. Wheeler has
suggested several alternate C36 diacid struc-
tures that may be present, along with C I8 and
CS4 acids, in commercial dimer acid (methyl
ester):

2B

The mixture is subjected to molecular distilla-

tion to obtain dimer acids of higher purity.
The reaction of dimer acids with short chain
diamines such as ethylene diamine results in
amorphous polyamides with sharp melting
points which set rapidly. This was discovered
by scientists at the Northern Regional Labora-
tory of the United States Department of Agri-
IA
culture. 3 It was soon observed that these
diamines would react with liquid epoxy resins
in substantially stoichiometric ratios to yield
crosslinked networks. 4 By reducing the amount
of epoxy resin significantly below stoichiomet-
ric proportions, it was possible to obtain ther-
moplastic adhesives that function as hot melts. s
The first commercial dimer acid polyamides
were produced by General Mills under the trade
name "Versamid," and are now available from
Henkel. The properties of these resins are sum-
marized in Table 1.
Shortly thereafter, Emery Industries, the first
commercial producer of dimer acid, entered the
IB thermoplastic polyamide market with similar
 POLYESTER AND POLYAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 481

Table 1. Henkel Resins.

Versamid Reactive Resins
Propenies 100 115 125 140
Amine value 83-93 210-220 290-320 3S0-400
Softening point, ·C. 43-S3 viscous fluid fluid fluid
ASTM E-28, Modified
Flash point, ·C, 32S 29S 26S 18S
ASTM 0-92
.Ash, % by weight O.OS O.OS O.OS O.OS
Specific gravity, 2S·C/2S·C 0.98 0.99 0.97 0.97
Pounds/gallon,2S·C 8.2 8.3 8.1 8.1
Color, Gardner 12 max. 12 max. 12 max. 12 max.
Viscosity, cps:
2S·C 4S,000-SS,000 12,SOO-17,SOO
40·C SO,000-7S,000 8000-12,000 3000-6000
7S·C 3100-3800 700-900 200-600
IS0·C 700-1200
Versamid Thermoplastic Resins
Propenies 900 930 940 950
Amine value 3-8 3-8 3-8 3-8
Softening point, ·C, 180-190 lOS-11S lOS-liS 90-100
ASTM E-288
Penetration,2S·C, 2 3 4 IS
ASTM O-S, Modified
Flash point, ·C, 3S0 339 332 291
ASTM 0-92
Ash, % by weight O.OS O.OS O.OS O.OS
Specific gravity, 2S ·C/2S·C 0.98 0.98 0.98 0.98
Pounds/gallon,2S·C 8.2 8.2 8.2 8.2
Color, Gardner, solid 12 max. 12 max. 12 max. 12 max.
Viscosity, cps:
IS0·C 3000-4S00 IS00-3000 700-lS00
200·C 300-400
'Ring and ball method.

resins trade named "Emerez," as shown in Ta- agents for epoxies, were made by reaction of
ble 2. dimer acid with a stoichiometric excess of die-
These solid polyamides for hot melts were thylene triamine or triethylene tetramine.
made by reacting dimer acid with ethylene dia- The reaction of dimer acid with ethylene dia-
mine. Reactive resins, designed as curing mine produced resins with softening point

Table 2. Emery Industries Emerez Resins.

1530 1540 1532 1535
Amine value, mg KOH/gm,
ASTM 0-1980-61 4 4 4 4
Acid Value, mg KOH/gm,
ASTM-0-2074= 62T 4 4 4 4
Softening point, ·C,
ASTM E-28 lOS-11S lOS-liS lOS-11S 127-13S
Ash, % by weight O.OS O.OS O.OS O.OS
Specific gravity, 2S· C/2S • C 0.98 0.98 0.98 0.98
Pounds/gallon,2S·C 8.2 8.2 8.2 8.2
Color, Gardner 12 max. 12 max. 12 max. 12 max.
Viscosity, cps, 160·C 2100-2700 1200-1800 2800-3300 SOO-I000
482 HANDBOOK OF ADHESIVES

around 105-110°C. Substitutions of shorter di- (now Henkel) under the trade name "Versa-
basic acid, such as adipic, azelaic or sebacic, Ion" (Table 3).
for a portion of the dimer acid resulted in an Versalon 1140 represents a family of poly-
increase of 5-25°C in softening temperature. amides with unique adhesion characteristics. It
These resins were somewhat brittle. They was one of the first polyamides with a wide
bonded well to porous substrates but found lim- range of adhesion including fair to good adhe-
ited application unless modified by compound- sion to vinyl. The polyamides are believed to
ing in order to improve flexibility and adhesion be based on secondary heterocyclic diamines,
to nonporous surfaces. For example, blending as disclosed in U.S. Patent 3,377,305. 5
of solid thermoplastic resins with the reactive Later, another supplier of dimer acid, Union
polyamides resulted in hot melt adhesives Camp, introduced a variety of dimer acid-based
which bonded well to metals and other sub- polyamides under the trade name "Uni-Rez"
strates, and also had improved flexibility. (Table 4).
Properties would also be modified by com- In addition to the sources mentioned, special
pounding with tackifying resins, plasticizers, hot melt polyamides derived from dimer acid
etc., among them the following (asterisks de- are available from Bostik Division of Emhart
note the most popular modifiers): Corp., Terrell Industries, and Dexter Hysol.
Some of these polymers are listed in Tables 5
Tackifying Resins Plasticizers and 6.
* Paratoluene sulfon- Most polyamide adhesives are characterized
* Rosin by
* Dimerized rosin amide
* Rosin esters * N-Ethyl parato- • Sharp melt point
Rosin phenolics luene sulfon- • Excellent adhesion to a wide variety of
* Ketone resins amide substrates, including treated polyethylene
Modified phenolic N-Cyclohexyl para- and polypropylene
resins toluene sulfon- • Excellent color and low odor
Maleic resins amide • Good moisture vapor barrier properties
Triphenyl phos- • Good chemical and oil resistance
phate • Resistance to blocking
Tributyl phosphate
Phthalate esters Most polyamides, and particularly the dimer
Castor oil acid polyamides, are prone to oxidation and
must be stabilized by antioxidants, or by blan-
The first polyamides were relatively low in keting the surface of the melt with dry nitro-
molecular weight and required considerable gen. Polyamides made from hydrogenated
compounding to produce good adhesives. dimer acid are considerably more stable to ox-
However, as the purity of dimer acid im- idation, but at substantially higher cost.
proved, higher performance polyamides with The stabilizers vary with the polyamide.
higher melt points, greater strength, and better Generally, a blend of antioxidants is used; the
adhesion became available from General Mills most common of these are hindered phenolics,

Table 3. Henkel Versalon Resins.

Property 1112 1165 1175 1140
Softening point, °C, ASTM E28 112 165 172 140
Specific gravity 0.95 0.98 0.95
Viscosity, cps:
190°C 3,700 4,000 8,000
225°C 1,600 1,500 2,200 8,500
Tensile strength, psi, 23°C 2,000 850 2,100 700
Elongation, %, 23°C 300 600 450 900
 POLYESTER AND POLYAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 483

Table 4. Union Camp Uni-Rez Adhesive Grade Polyamides.

Propeny 2651 2622 2643 2641 2624 2665
Melting point, °C 100 107 124 138 162 165
Viscosity, cps, 190°C 9000 900 2000 8500 7500 8500
Color, 40% in n-butanol 5 6 5 4 6 5
Pounds/gallon at 25°C 8.0 8.2 8.1 8.2 8.1 8.1
Tensile strength, psi 550 1400 400 700 1400 2000
Elongation, % 900 50 250 700 500 500
Tensile modulus, psi 12,000 36,000 9,000 7,000 25,000 55,000
Tensile impact, 160 5 120 150 50 70
ft. -lb/in. 2
Low Tempemture 100
impact brittleness,
% passed at -20°C

phosphites, phosphates, phosphoric acid, and grid. Glue sticks are applied with a glue gun,
hindered aromatic amines. a hand held melt device.
These adhesives are available in several Hot melt applicators for melting polyamides
forms: pellets, monofilament, ground resins, are available from several suppliers, notably,
billets, and glue sticks. The pellets and ground Nordson, Meltex Corp., Bostik Fastening Sys-
resins can be applied with standard bulk hot tems Group, and Graco/LTI.
melt applicators. The monofilaments, first de-
veloped by Bostik, are applied with specialized
Adhesion vs. Composition
melting equipment. The billets are applied with
modified bulk melt equipment which melts only The various polyamides have a broad range of
the surface of the billet in contact with a heated adhesive properties. They bond well to porous

Table 5. Bostik Hot Melt Polyamide Adhesives.

Propeny 4254 4252 7279 7228
Softening Point,
ASTM E-28 112 132 163 182
Melt viscosity, cps
149°C 5,300
177°C 5,600
204°C 2,300 2,200 7,000 7,000
Tensile at break, psi 1,100 2,100 1,500 1,400
Elongation at break, % 75 200 100 60

Table 6. Terrell Terlan Polyamide Adhesives.

230 652 685 1560 1583
Softening point,
ball and ring, °C 110 174 191 139 160
Melt viscosity, cps
149°C 5,000
191°C 9,500
204°C 3,500
210°C 12,000
232°C 8,500
Tensile at break,
psi 1,200 2,200 2,000 400 2,200
Elongation at break,
psi 50 100 100 1,200 400
484 HANDBOOK OF ADHESIVES

substrates and polar surfaces. However, the polyamides. For example, high melting poly-
faster setting types do not bond well to metal amides with melt point above 160°C are used
unless the metal is preheated to allow better in bonding paper for oil filters. In this appli-
wetting. cation, polyamides capable of withstanding
Most of the general type polyamides do not 149°C are being used.
bond well to vinyl. Slower setting polyamides, Polyamides designed for bonding plastics are
synthesized by reacting dipiperidyl propane, functioning to make heat-shrinkable sleeves in
have improved adhesion to vinyl and cold electrical applications and for sealing electrical
metal. These polyamides are lower, however, connectors. Polyamides containing a secondary
in heat resistance and resistance to oil and sol- diamine, with a wide softening range, are cho-
vents. sen because of their better adhesion properties
and easy activation.
Application Systems Specially designed polyamides with high melt
points, but very low modulus, serve to encap-
Bostik Division of Emhart Corporation pi-
sulate electrical connectors. This type of poly-
oneered the use of polyamide hot melt for
amide is also being foamed with a Nordson
bonding leather in shoe manufacturing. In 1953
Foam Melter for a gasket in microwave ovens.
this company commercialized a process using
hot melt polyamides in monofilamen~ form.
Nylon-Type Polyamide Hot Melts
This composition, with a melt point 'of about
lOsoC, made by properly compounding com- When lactams are homopolymerized or short
mercially available polyamides, was passed chain dibasic acids are reacted with diamines,
through a specially designed melt body which high melt point polyamides suitable for fibers
melted a small amount of adhesive at any given or engineering plastics are obtained. Nylons
time. This patented process6 was used for fold- derived from lactam or amino acids are desig-
ing shoe upper leather prior to the stitching op- nated by the number of carbon atoms in the
eration. amino acids, while the nylons derived from the
At a later date, the same company developed7 reaction of dibasic acids and diamines are given
a process for hot printing a polyamide supplied two numbers, the number of carbon atoms in
in filament form to the toe portion of shoe up- the diamine and dibasic acid respectively:

Monomer Nylon No. Melt Point, °C

Caprolactam Nylon 6 225
Lauryllactam Nylon 12 180
1,I-Aminoundecanoic acid Nylon 11 185
Adipic acid + hexamethylene diamine Nylon 6-6 264
Azelaic acid + hexamethylene diamine Nylon 6-9 210
Sebacic acid + hexamethylene diamine Nylon 6-10 222
Dodecanedioic acid + hexamethylene diamine Nylon 6-12 212

pers. The leather, with the printed hot melt, was These polymers are too high melting and too
then softened in presence of steam and lasted high in viscosity to be suitable for hot melts,
on a shoe last. On cooling, a firm box is ob- except for a very few specialized applications.
tained. The property of this polyamide to be However, copolymers and terpolymers of the
softened by the presence of steam allowed the above monomers are suitable for hot melts,
softened upper to be lasted easily. Polyamides since the disruption of regularity in the polymer
also function in other shoe bonding operations, chain reduces the crystallinity and the forma-
such as side lasting, toe lasting, and heel seat tion of hydrogen bonds between the amide
lasting. groups, resulting in lower melting points and
Other applications of polyamides take advan- more flexible products.
tage of the good oil resistance of the higher melt Reduction of hydrogen bonding and there-
 POL VESTER AND POL V AMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 485

fore lower melt points can also be achieved by The composition of these polymers can be
condensing a secondary diamine, as the result- plotted on three-component diagrams which
ant -CO-NR- groups are incapable of hy- show the area of compositions with desirable
drogen bonding with adjacent molecules. Thus melt points for adhesives. Examples of such
the N-methylation of 50% of the amide groups compositions taken from U. S. Patent
in Nylon 6,6 results in a 120°C lowering of 3,919,033 8 are shown in Fig. 3. 6
softening point. Many of these hot melt adhesives are used in
Polymerization of three or more monomers fabric bonding. They are softened by steam, so
results in further disruption of hydrogen bond- that bonding can be achieved in the steam
ing with the consequent reduction in melt point presses extensively used in the apparel making
and chemical resistance of the polymers ob- process. Activation in presence of steam is
tained. generally achieved at temperatures below the
Many terpolymers have been synthesized and melt point of the fibers, hence low enough to
are commercially available. This class of poly- prevent damage to synthetic fabrics. Also, the
amide constitutes the basis of many of the hot steam easily penetrates the fabric, reaching the
melt, nylon type polyamides, which are used bond line quickly.
extensively in fabric bonding. The water absorption of nylons generally de-
Example of the terpolymers available are: creases as the length of the carbon chain in-
creases. Thus we see from Table 7 that the
Terpolymer Producers higher nylons absorb less water than the lower
nylons. Also, the even-numbered nylons ab-
Nylon 6,6-6,6-10 DuPont sorb less water than the odd-numbered nylons.
Nylon 6, 6-6, 12 Emser Werke, Huels, Absorption of moisture results in a slight de-
Rilsan (div. ATO crease in tensile strength, a major increase in
Chemie) ultimate elongation, and a corresponding de-
Nylon 6, 6-6, 6-12 Bostik crease in flexural modulus, as shown in Table
Nylon 6,6-9,6-12 Bostik 8.

Fig. 3.
486 HANDBOOK OF ADHESIVES

Table 7. Water Absorption Characteristics of Nylons.

Conditions 6-6 6 6-10 6-12 ]] 12
24 hrs,
100% RH, 73°F, % 1.5 1.6 0.4 0.4 0.3 0.25
Equilibrium,
50% RH, 73°F, % 2.5 2.7 1.5 1.5
Saturation,
100% RH, 73°F, % 9.0 9.5 3.5 3.0 1.9 1.4

Table 8. Effect of Moisture (Equilibrium) on Key Properties of Nylon.

Ult. Tensile Strength, Ult. Elongation, Flex. Molulus,
]& psi % ]& psi
Typeo!
Nylon Dry 50% RH a Dry 50% RH a Dry 50% RH"

6-6 12.0 11.2 60 300 410 175

6 11.8 10.0 200 300 395 140
6-10 8.5 7.1 20 220 285 160
6-12 8.8 7.6 150 340 290 180
11 8.0 7.6 120 330 170 150
12 8.0 7.6 250 270 180 165
'Equilibrium.

Since adhesives used in fabric bonding are The properties of typical polyamides are shown
subjected to washing and dry cleaning, it is ev- in Tables 9-11.
ident that a balance of steam activation and These fabric adhesives are available in sev-
wash resistance must be achieved. Resistance eral forms, most commonly as powders, pel~
to hot water washing varies with the composi- lets, films, spun-bonded webs and mono-
tion of the polyamide. The easier the hot melt filaments.
activates with steam, the poorer the resistance Powders are available in various particle size
to wash. Many dry cleanable garments have ranges, e.g., 0-74 microns, 74-210 microns,
poor wash resistance, particularly at tempera- 210-400 microns. Powders are applied to both
tures above 140°F. nonwoven and woven interface fabrics. They
On the other hand, one can synthesize poly- are sold to garment manufacturers for bonding
amides which have good wash resistance and to various parts of garments to improve ap-
dry cleaning, but do not activate as easily with pearance both before and after dry cleaning and
steam. Polyamides with the same melt point but washing. Many sewing operations are thus
with different resistance to wash and steam ac- eliminated. Also, lower weight shell fabrics can
tivation are available commercially. For ex- be used to produce garments of better quality .
ample, the following two polyamide The 0-74 micron powder is dispersed in
terpolymers with the same melt point have very water, with the addition of dispersing agents
different activating temperatures and resistance and binders, such as acrylic latex or VA-E (vi-
to hot water wash: nyl acetate-ethylene) latex. The resultant paste

Activation Temp. Max. Hot Water Dry Cleaning

Polyamide M.P. with Steam Water Resistance Resistance
Nylon 6, 6-6, 6-9 150°C 105°C 50°C excellent
Nylon 6,6-9,6-12 150°C 135°C 95°C excellent

The major suppliers of nylon terpolymers are is applied to the interface fabric through a per-
Bostik Division of Emhart Corp., Emser- forated cylinder, dried and partially fused.
Werke, and Rilsan Corp., Div. of Atochem. The 74-210 micron powder-is applied by the
 POLVESTER AND POLVAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 487

Table 9. Bostik Hot Melt Polyamides.

Property 4214 4222 4232 4930
Specific gravity 1.085 1.08 1.095 1.07
Melt point range:
Ring and ball, °C 130 130 135 152
DSC" melt point, °C 110 102 115 135
Viscosity, cps, 180 °C 425,000 190,000 300,000 325,000
Tensile at break, psi 6,000 5,000 7,500 7,500
Elongation at break, % 500 600 450 350
• Differential scanning calorimeter.

Table 10. Rilsan Platamid Resins.

Property HJ05P H165P HOO3P HOO5P HOO6P
Specific gravity 1.08 1.10 1.05 1.08 1.09
Melt point range, °C 115-125 105-115 105-115 115-125 145-150
Start of adhesion, °C 115 90 90 115 140
Moisture absorption, 68°F,
65% RH, % 3.5 2.0 2.0 3.5 2.0
Max. moisture absorption
in water, 20°C, % 10.0 6.0 6.0 10.0 6.0
Viscosity, ps, 150 °C 21,000 5,600 5,200 8,200 3,200
(1 60°C)
Characteristics High Visco Low Low Medium Low
Visco Visco Visco Visco
Plasti-
cized
High
Flexibility

Table 11. Emser Werke Griltex Polyamides.

IP 2P 4P 5P
Melting temperature range, °C 110-120 120-130 105-115 80-85
Melt viscosity, Poise, 160°C 7,000 5,000 1,000 1,300
Melt index, gllO min, 160°C 14 20 100 75
Moisture absorption, % 2.5 2.5 2.0 2.5
Glueline temperature, °C 140-160 140-160 120-140 95-120
Pressing time, sec 12-20 12-20 10-15 10-15
fusible not fusible not
with fusible with fusible
steam with steam with
steam steam
Reactivated with steam yes no yes no
Dry cleaning resistance, very good very good very good very good
perchloroethylene
Resistance to laundering, °C 60 95 40 40
Applications fusing of for hot for pressure bonding of
all front laundering and temp. leather
parts resistant sensitive hides and
bonding lace fab- fur
rics, edge
bonding
488 HANDBOOK OF ADHESIVES

lease paper. The film is used for bonding la-

~
~8pOWder Scatter Head
bels, decals, etc. onto gannents.
Spun bonded nylon fonns a nonwoven web
used for fabric bonding in clothing factories and
l:\ available in notion stores in different widths and
(0-00:::----'-:'. .'\. . .
---...,!Infrared Heaterl--! ----:::8-
0
weights for home sewing. Webs of this type are
available from Bostik and Pellon Corp.
Pellets, like powders, are printed in dot pat-
Fig. 4. Powder scatter process.
terns on fabrics by the Rotothenn hot melt pro-
cess described below. The adhesive-printed
fabrics are used in apparel manufacturing or for
continuous lamination of fabrics to other sub-
dry powder dot process (gravure roll) and fused
strates.
under infrared heaters; then the interface fabric
The manufacturers of polyamides offer them
is cooled and rolled for sale to the gannent in-
in various fonns. Rilsan Corp, supplies the
dustry. See Fig. 5
basic nylon polymers as well as powders and
The coarse 210-400 micron powder is ap-
monofilaments, Bostik Fastening Systems
plied to the interface fabric by scattering uni-
Group provides the polymers in pellet fonn, but
formly, then fused onto the fabric with infrared
also as powder, spun bonded web, and film.
heaters; then the fabric is cooled, calendered,
Emser-Werke supplies pellets and powders.
and rolled. See Fig. 4.
In all cases, a fabric containing isolated dots
POLYESTERS
of adhesive is the final product. The discontin-
uous pattern contributes to the soft hand of the Polyesters are the reaction product of dibasic
fused fabric, The closer the dots, the finner is acids with poly functional hydroxyl-bearing
the resulting hand, materials, Both the linear saturated polyesters
Film is obtained by extruding terpolymers and the unsaturated polyesters have achieved
such as nylon 6, 6-6, 12 (Rilsan, Emser- commercial significance.
Werke) or nylon 6, 6-9, 6-12 (Bostik) on re- The unsaturated polyesters are oligomers

/ EXHAUST

~
FABRIC

I R HEATERS

CLEANING BRUSH

UNUSED POWDER
RECLAIM
Fig. 5. Powder point printer.
 POLYESTER AND POLYAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 489

made from diols and unsaturated dibasic acids, urated polyesters with melt point
generally maleic anhydride. These low molec- between the Class A (fiber grade)
ular weight polymers are cured to highly cross- and the Class B polyesters.
linked networks by reacting with unsaturated
It is this last class of polyesters that finds use
monomers, usually styrene, in the presence of
in hot melt adhesives. The compositions and
peroxide catalyst. Reinforced with fiberglass,
properties of the available polyesters varies
they constitute the fiber-reinforced polyesters
widely and fall between Class A and Class B
(FRP).
polymers; typically they are derived from ali-
The linear saturated polyesters comprises a
phatic diols and aromatic diacids, notably tere-
large class of polymers with a variety of prop-
phthalic acid, and are synthesized to fairly high
erties. The main types are:
molecular weight, between tO,OOO and 30,000.
Class A: Fiber grade or engineering type The high melt points ofthe terephthalate poly-
polyesters with high melt point and esters are due to the chain stiffening effect of
molecular weight, derived wholly the p-phenylene group. This can be demon-
from aromatic diacids, diols, and strated by comparing terephthalate polyesters
hydroxy acids. with the corresponding adipate polyesters,
Class B: Low molecular weight polyesters which contain the same number of carbon at-
derived from aliphatic dibasic acid oms:

Poly(ethylene terephthalate) 265

- O(CH 2)2 - 0- OC(CH2)6CO- Poly(ethylene adipate) 45

-O(CH2)4-0-0C-o-co- Poly(buty lene terephthalate) 225

Poly(butylene adipate) 42

and excess diol. Suitable as inter- The position of the carboxyl group on the
mediates in the synthesis of poly- phenylene also has a great influence on the
urethanes, they are usually viscous melting point of the polymer. For example, for
liquids of molecular weight 1,000- polyesters derived from ethylene glycol and the
3,000. three phenylene dicarboxylic acids, the melt
Class C: High molecular weight linear sat- point is:

o
COOH

+ Ethylene glycol -+ Poly(ethylene terephthalate) 256

COOH

COOH

+ Ethylene glycol -+ Poly(ethylene isophthalate) 103

OCOOH

COOH
O~ I COOH + Ethylene glycol -+ Poly(ethylene phthalate) 78
 490 HANDBOOK OF ADHESIVES

Poly(ethylene terephthalate) (PET) is widely used in fibers and films. Sometimes a small amount
of isophthalic acid is included to modify the properties.
The polyesters for hot melts are generally polymers of more than one acid and one or more
glycols. The major monomers and their properties are listed below:

Molecular
Acids Melt Point, °C Weight

Terephthalic acid Sublimes @ 300°C 166

Isophthalic acid HOOC~ 348 166

~- CooH
Adipic acid HOOC(CH2)4COOH 149 142
Azelaic acid HOOC(CH2hCOOH 106 188
Sebacic acid HOOC(CH2}gCOOH 133 202
Dimer acid Structures shown earlier in
chapter

>
Dimethyl Esters

Dimethyl terephthalate 140.8 194

H3 COOC ( COOCH3

Dimethyl adipate H3COOC(CH2)4COOCH3 8.5 170

Dimethyl azelate H 300C(CH2hCOOCH 3 216
Dimethyl sebacate H3COOC(CH2)8COOCH3 26.4 230

Dimethyl isophthalate H3CooCO 68.0 194

- COOCH3

1,4-Cyclohexane 50 200
dimethanol

Glycols
Ethylene glycol HOCH2CH2 0H 12 62
1,4-Butanediol HOCH2CH2CH20H 20 90
1,6-Hexanediol HO(CH2)60H 42 ll8

1,4-Cyclohexane
HOCH20 CH20H 164
dimethanol

In the synthesis of polyesters, either the free acids or their methyl esters are used. The reaction
is carried in two stages:

1st Stage:

xHOOC-R'-COOH + (1 + x)HO-R"-OH ~
Cat.

2xH 0 + HO [R"-O-C-R'-C-O]xR"-OH (Polyester Prepolymer)

2
o
""
0
 POLYESTER AND POLYAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 491

2nd Stage:
!::::.
-HO[R"-O-C-R'-C]R"-OH ~ High molecular weight
II II Vac. polyester (+ excess glycol)
o 0

In the first stage the acid or acids are reacted The physical properties of the copolymers
with an excess of glycols at temperatures be- vary with melt point. The copolymers are more
tween 200°C and 240°C, generally in the pres- flexible as the composition approaches the eu-
ence of a catalyst, to produce a low molecular tectic point. Indeed, copolymers around the SOl
weight prepolymer plus water or methyl alco- 50 mole ratio of terephthalic/sebacic acid are
hol byproduct. This reaction can be carried at elastomeric in nature, and were extensively
. atmospheric pressure or under pressure. An studied by DuPont as elastic fibers. Eutectics
esterification catalyst such as zinc acetate is are also observed in ethylene terephthalate/adi-
chosen when acids are used to make the pate and butylene terephthalate/sebacate copol-
prepolymer, and a transesterification catalyst ymers. Introduction of an additional monomer,
such as tetraisopropyl titanate when dimethyl for example, sebacic acid or azelaic acid in bu-
esters are employed. tylene terephthalate/iosphthalate polymers, re-
In the second stage, the polycondensation re- sults in further modification of the properties.
action proper, the prepolymer is heated to 240- In general, introduction of the aliphatic chains
270°C under high vacuum in the presence of a results in lowering of the melting point, in-
transesterification catalyst. creased flexibility, greater adhesion properties,
The reactions are speeded by removing the and in the case of crystalline polyesters, a faster
byproducts, water or methanol in the first stage crystallization rate.
and excess glycol in the second stage. This is
accomplished by purging the reaction with in-
ert gas in the first stage and applying vacuum 300
in the second stage.

""
U
0
Many catalysts are mentioned in the litera- E 200

-
ture for making polyesters. The most com- '0
a.. ~

""
monly used are: lead acetate, sodium acetate, "iii
calcium acetate, zinc acetate, organotin com- ::::e 100
pounds, titanium esters, antimony trioxide, and
germanium salts.
~ ~
----"
The choice of catalysts depends on the o 20 40 60 80 100
TA SA
monomer and also on the application for the M,n1e % Sebacic Acid
adhesive. For example, if the adhesive is to be Fig. 6. Ethylene terephthalate/sebacate copolymers.
used in food packaging, the catalyst chosen
would be one which meets FDA approval, e.g.
the acetate of sodium, calcium or zinc. 250
Like polyamides, the polyester homopoly-

-
u
mers are seldom used in hot melts. In most ~
0

c 200
cases a better balance of properties such as melt
- ~
'0
a..
point, flexibility, rate of crystallization, etc. is
"i ~

""
achieved with copolymers. As in polyamides, ::::e 150
copolymerization can yield copolymers with a ~
~
wide range of properties. Some copolymers 100
have melt points below that of the lower melt- a 20 40 60 80 100
TA IPA
ing homopolymer. Examples of copolymers Mole % Isophthalic Acid
with eutectics are shown in Figs. 6 and 7. 9 Fig. 7. Butylene terephthalate/isophthalate copolymers.
492 HANDBOOK OF ADHESIVES

Plotting of terpolymers in three-component timum crystallization tempemture can be ob-

diagmms results in trends similar to those ob- tained by running differential thermal analysis
served in the nylon terpolymers. on samples which have been quenched in the
Polyesters for hot melts are either crystalline amorphous state. With this technique, one can
or amorphous. In the crystalline polyesters, the measure the glass tmnsition, the crystallization
mte and degree of crystallization is greatly af- tempemture and the crystalline melt point. For
fected by the composition; the more regular the example, a sample of amorphous PET would
chain structure, the faster is the crystallizationshow first the glass tmnsition at 81.8°C fol-
mte. lowed by a crystallization exotherm at 164.3°C
The crystalline polymers are derived from the and a crystalline melt point (Tm) at 251.5°C.
more symmetric acids such as terephthalic acid See Fig. 8.
and stmight chain diols. The longer the carbon Genemlly, higher crystallinity results in
chain of the diol, the lower the melt point and sharper melt points. This is important in an ad-
glass transition tempemture and the faster the hesive, as the crystalline polymers retain their
mte of crystallization. properties until the melt point is reached.
An even number of carbon atoms in the gly- Crystalline polymers generally are not as sol-
cols gives higher melt points as well as more uble as amorphous polymers and thus have bet-
crystalline and faster crystallizing polyesters: ter solvent resistance. The appeamnce of these
polymers in the crystalline state is opaque.
Tg,OC Tm,oC The amorphous polymers are derived from
Ethylene terephthalate (PET) 80 256 monomers which have side groups, such as
1,3-Propanediol terephthalate 217 neopentyl glycol, or multipolymers which have
1,4-Butanediol terephthalate 222 very little chain regularity and thus are unable
1,6-Hexanediol terephthalate 148 to crystallize.
These polymers, which are in most cases
The lower melt point and glass tmnsition re- clear, have a broader melt point range, are more
sult from the reduction in chain stiffness pro- soluble, and hence are less resistant to solvent
vided by the longer chains in the higher attack.
molecular weight diol. The shrinkage which results during crystal-
The same effect is obtained when one copo- lization sometimes has a deleterious effect on
lymerizes long chain dibasic acids with tere- the bonds. It is important, therefore, that the
phthalic acid. For example, the ethylene glycol bonds made be evaluated after the crystalliza-
copolyesters of terephthalic acid and sebacic tion has taken place. Amorphous polymers also
acid, in addition to having lower melt points, shrink on cooling, but far less.
crystallize much faster at room tempemture be-
cause of the increased mobility provided by the 2
flexible molecules. o '-C
164

The crystallization of the polymers can be

~ -2
detected by seveml changes in properties: de- £
velopment of opacity, increase in modulus, re- IL!a!S -4
duction in elongation, shrinkage, increase in 0- 6
specific gmvity. :z: -8
..
The tempemture at which the change to the -10
crystalline form takes place is dependent on the
composition of the copolymers, but is always 80 120 160 200 240 280
Temperature ('el
higher than the glass tmnsition temperature.
Some ofthe copolymers can crystallize at room Fig. S. DSC thermogram of polyethylene terephthalate
showing the three major phase transitions; glass transition
tempemture while others must be heated or (Tg) at Sl.soC, crystallization starting at 140.SoC, and
cooled to accelemte the mte of crystallization. crystalline melt point (Tmc) 251.5°C. (Courtesy the E. L.
For the faster crystallizing polymers, the op- DuPont de Nemours and Company).
 POLVESTER AND POLVAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 493

There are several manufacturers of polyes- is recommended. Preferred equipment are

ters for hot melts. The major suppliers in the screw extenders and hot grid bulk melters
United States are Bostik Fastening Systems which melt only the product in contact with the
Group, Goodyear Chemicals, Eastman Chem- . grid.
ical, and Whittaker Corp. (successor to Du- Polyesters, unlike polyamides, have little
Pont). The main products of these suppliers are tendency to char when held in the molten state
shown in Tables 12-15. for a long time. Instead, they decline in vis-
European suppliers include: Emser-Werke cosity and molecular weight. To avoid reduc-
(see Table 16), Dynamit Nobel, and Huels. tion in properties, polyesters should be exposed
Polyester hot melts are in most cases high to the lowest possible application temperatures
molecular weight products with high melt vis- and the shortest dwell time in the melt equip-
cosity. Because of this, they are applied at ment. Failure to prevent hydrolysis of the hot
higher temperatures than the olefin polymer hot melt can result in very dramatic deterioration
melts, and with equipment able to handle high in the properties of the ultimate bonds.
viscosity.
Because polyesters tend to be hydrolyzed by Uses
the presence of water at the application tem-
Polyesters are used as adhesives in two ways:
perature, it is usually recommended that the
products be dried prior to melting. To mini- 1. The polyester hot melt is applied and the
mize hydrolysis, application equipment which two substrates are immediately put to-
reduces the residence time in the molten state gether to form a bond.

Table 12. Bostik Hot Melt Polyesters.

Propeny 7102 4101 7106 4117 7199 4177 4156 7116
Color It. tan It. tan straw off-white off-white off-white off-white It. tan
Fonn granules pellets granules pellets granules pellets pellets granules
Melt Range
OF 200-248 248-271 245-260 282-288 344-350 356-360 309-314
°C 94-120 120-133 118-127 136-142 173-176 180-182 154-156
Morphology cryst. cryst. amorph. cryst. cryst. cryst. cry st. cryst.
Setting speed slow moderate moderate moderate v. fast v. fast fast moderate
Specific gravity 1.25 1.27 1.25 1.28 1.28 1.25 1.28 1.25
Acid No., 1-2 2-4 1-2
mgKOH/g
Hydroxyl no., 1-4 2-4 2-3
mgKOH/g
Glass transition, °C -5 -5 5 -6 -2 -3 -9 -6
Melt Visc., 215°C 70,000 40,000 50,000 220,000 20,000 24,000 27,000 20,000
Tensile, psi 2,500 3,400 1,500 4,700 2,000 2,500 3,500 3,500
Elongation, % 700 570 250 400 200 300 400 400

Table 13. Eastman Hot Melt Polyesters.

Propeny FA-250 FA-252 FA-300
Physical fonn pellets pellets pellets
Color white white white
Density 1.25 1.28 1.24
Melt point 212°F 230°F 266°F
Melt visc., 2\o°C 100,000 140,000 96,000
Inherent visc. 0.72 0.85 0.72
494 HANDBOOK OF ADHESIVES

Table 14. Whittaker (Formerly DuPont) Solid Polyester Adhesives.

Code 49000 4900] 4900] 49003
Apperance tough, hard, am- soft, plastic very tough, tough, flexi-
ber colored, light gray flexible, light ble, light
nontacky at color, gray color, gray color,
7]oP slightly nontacky at nontacky at
tacky at 77°P 77°P
77°C
Odor none none none none
Specific gravity 1.33 1.28 1.23 1.17
Plow melt point range, 245-275 1l0-170 260-300 190-230
OP(°C) (1l8-135)
Tensile strength, 77 °P, psi 1500-2500 1000-1500
Elongation, 77°P, % 600-1000 >2000 500-1500 >2000
Color stability excellent excellent excellent excellent
Acid number 0.5-2.5 0.5-2.5 0.5-2.5 0.5-2.5
Hydroxyl number 5.0-15.0 5.0-15.0 5.0-15.0 5.0-15.0
Dielectric strength, 2700 3200
Volts/mil
Bond strengths, 180° Peel,
77°P,lb/in.
3 mil Mylar/Mylar at 0.2- 4-6 4-6 4-6 4-6
0.3 dry mil adhesive
3 mil Mylar/copper foil at 6-8 4-6 6-8 4-6
0.4-0.5 dry mil adhesives

Table 15. Goodyear "Vituff" Hot Melt Polyesters.

Glass
Appl. Transition Dead Load
Melt Appl. Viscosity, Setting Temp. Strength
Product Typical Characteristics Point Temp. Poise Speed (tJ. °C AIiAI kg.

VPR 4302 Strong bonds to leather, vinyl, 207 240 94 Very -lOoe 250 0 P
urethane, and other porous fast
substrates. High temperature
resistance and very sharp melt
point.
VPR 4444 Less rigid than 4302. Combines 190 220 770 Past 30 0 e 250 0 P
fast set time with excellent
bonds to porous substrates.
VPR 4751 Lower viscosity version of 4444. 185 220 240 Past 30°C 250 0 P
Past setting adhesive with high
temperature service level.
VPR 5126 Strong, flexible adhesive with 174 220 670 Mod- -2°e 200 0 P
outstanding solvent and water erate
resistance. Recommended for
textile applications.
VPR 4980 Tough, flexible adhesive that 124 220 770 Slow 22°e 170 0 P
provides strong bonds to a
wide variety of substrates. Ad-
hesive can be heat reactivated
at moderate temperature.
VPR 5125 Very flexible, tough material. 115 210 130 Slow -9°e 155°P
Bonds well to metal (pre-
heated) and most thermoplas-
tics, such as vinyl,
polycarbonate (Lexan) Pheny-
lene oxide (Noryl), ABS: Ny-
lon, and polyester.
 POLVESTER AND POL VAMIDE HIGH PERFORMANCE HOT MELT ADHESIYES 495

Table 15. (Continued)

Glass
Appl. Transition Dead Load
Melt Appl. Viscosity, Setting Temp. Strength
Product Typical Characteristics Point Temp. Poise Speed (tg.!, °C AI/AI kg.
VAR 5898 Higher melting version of 5125. 123 218 185 Mod- -20°C 225°F
Outstanding bonds to wood, erate
metal (preheated) and most
thermoplastics. Excellent gen-
eral purpose high performance
adhesive.
VAR 5899 Lower melt viscosity version of 130 204 90 Mod- -8°C 225°F
5898. Longer open time for erate
difficult product assembly ap-
plications. General purpose
high performance hot melt.
VAR 5893 Combines flexibility with sharp 200 240 100 Very -lOoC 250°F
melting point. Excellent bonds fast
to most porous substrates with
a high temperature service
level.
VAR 5831 Extremely flexible adhesive with 149 218 250 Slow -lOoC 150°F
outstanding bonds to metal
(preheated) and thermoplas-
tics. Recommended for bond-
ing thermoplastic films. PET
(Mylar), (Tedlar), polyure-
thane, vinyl, moderate temper-
ature service level.
VMF 400 Rigid noncrystalline adhesive 185 240 5,000 Slow 66°C 160°F
with outstanding bonds to
metal (preheated) and plastics.
Meets most FDA requirements
for packaging adhesives.
VMF 415 Flexible, tough, noncrystalline 180 220 2,360 Slow 5°C 160°F
adhesive. Excellent bonds to
plastic films, PET (Mylar), vi-
nyl.
VAR Extremely tough, flexible adhe- 160 220 400 Fast O°c. 220°F
5825' sive. Recommended for elec-
trical and textile product
assembly applications.
VAR High temperature service level. 220 275 250 Fast 75°C 300°F
5821' Extrusion-grade recommended plus
for wire coating. More flexible
than PET.
'VAR 5825 and VAR 5821 are polyester blends. The other products are polyesters.

Table 16. Emser Griltex Hot Melt 2. The prefonned adhesive in the fonn of an
Polyesters. extruded film, web, powder, etc., is ap-
Property 6G 8G plied to substrate, then later is heat reac-
tivated and pressed to achieve a bond.
Physical form granules granules
Color off-white off-white
Density In the first category, polyesters serve in the
Melt Viscosity, 200,000 150,000 shoe industry to last different parts of the shoe.
M.P. at 200°C The adhesives are supplied either in monofila-
Melt point 130-140°C 105-115°C
ment fonn or in pellets, melted and applied to
496 HANDBOOK OF ADHESIVES

the substrate, then immediately bonded. The

adhesives for this application have high melt
point, 170-190°C, and are very fast-setting
crystalline polyesters. Toe lasting of shoes with
polyesters of this type can be accomplished !!!!!!l!!!!!!!!!!!!!!!!!l!!!l!\!\\\l\\\!\\\
with dwell time of less than two seconds.
High melting, fast crystallizing polyesters,
are also being used in continuous laminations
of fabric and plastic substrates. The adhesive is
melted via an extruder or grid-type bulk melter,
then is supplied in molten form to a gravure
coating roll. The amount of adhesive applied is
................
::::: :::::::::::::::::: :::::::::
determined by the characteristics of the gravure
)\)){)/)
)<

cell, the rheology of the adhesive, and the af- ................

finity of the adhesive to the substrate. Con- ................................
:::::::::: :::::::::::::: ::::::::
................................
trolled deposition of the adhesive is achieved ................................
by the design of the pattern and volume of ad-
hesive.
A machine for gravure printing of hot melts
has been developed by Rototherm, Anaheim, ~

California. See Figs. 9 and 10. With this pro-

cess, adhesive is applied to one of the sub-
strates, which is laminated to the second
substrate while the adhesive is still hot. Alter-
natively, in fabric bonding in the apparel in-
dustry, the adhesive is applied to one of the
substrates and later reactivated by heat to per-
mit lamination to the second substrate.
Fig. lO. Typical printing patterns with hot melts (Cour-
The other category, preformed adhesives tesy of Rototherm Company, California).

such as film, powders, webs, monofilaments,

comprises the major part of the polyester hot
melts. In this application the adhesive is posi-
tioned on the substrate, then a bond is formed
with heat and pressure. Extruded film adhe-
sives are used to bond labels, decals, embroid-
eries, etc. to garments with specially designed
heated presses.
Adhesives in powder form are applied to
woven or nonwoven fabric for the manufacture
of women's and men's garments. Powders are
also being used for in-line lamination of ure-
thane foam to upholstery fabric by heat acti-
vating the applied powder to the foam and
laminating to the fabric.
Open mesh polyester adhesive webs are ad-
vantageous in the garment industry for rein-
forcing different parts of the garments.
Fig. 9. Rotogravure printing. (Courtesy Rototherm Com- Hot-melt-type polyesters are being spun into
pany, California). fibers which are mixed with higher melting fi-
 POLYESTER AND POLYAMIDE HIGH PERFORMANCE HOT MELT ADHESIVES 497

bers, acting as the bonding agents in nonwoven Compatibility

fabrics with special properties.
Polyester hot melts are generally used uncom-
Powdered polyester hot melts also serve as
pounded. However, compounds containing
binders for nonwoven fabrics.
polyurethanes, polyethylene, hydrocarbon res-
Selection of the method of applicatioQ and
ins, etc. for specific objectives, have been re-
the correct adhesive depends on many consid-
ported in the patent literature.
erations:
1. Heat stability and properties of the hot POLVESTER AMIDES
melt.
2. Adaptability to production systems. Many polyester amides have been reported in
3. Application temperature and method. the literature, and several patents have been is-
sued.
4. Properties of the substrates, heat sensitiv-
ity, porosity, etc. One of the developments that has been widely
5. Hand desired in the finished laminate. publicized is the development of polyester
6. Performance desired of the finished amides by Monsanto. According to u.S. Patent
bonds. 3,650,999, these copolymers, trade named
Montac, are made by reacting an aromatic poly-
Polyesters have some outstanding properties: ester, such as PET or PBT, with dimer acid to
1. Adhesion to a variety of substrates. form an acid-terminated prepolymer which is
2. Outstanding adhesion to plasticized vi- then reacted with a diamine to produce blocked
nyl. polyester-amides with melt points, flexibility,
3. Excellent water resistance. and unique adhesive characteristics suitable for
4. Excellent heat resistance. structural adhesives. 10 These block copolymers
5. Low temperature flexibility. have a crystalline block derived from the
6. Very good UV resistance. polyester and an amorphous block derived from
7. Excellent electrical properties. the polyamide. Typical properties of copoly-
8. Good resistance to oil and grease. mers mentioned in the patents are shown in Ta-
ble 17.
Some limitations are: These adhesives have been promoted for
1. Specialized equipment needed for appli- bonding SMC automotive parts. Bonds equiv-
cation. alent to two-part adhesive systems such as two-
2. Limited resistance to hydrolysis at high part polyurethanes and epoxies are being
temperatures. claimed. Using Montac 5500 with a crystalline

Table 17. Poly(Ester-Amide) Block Copolymers, Examples 1-7, U.S. Patent

3,650,999
Property 1 2 3 4 5 6 7
% Crystalline polyester 30 60 60 60 30 60 60
(PET)
% Polyamide 70 40 40 40 70 40 40
Tensile strength, psi 750 3,300 3,000 3,100 1,600 2,800 3,900
Elongation, % 490 370 300 500 450 310 290
Inherent viscosity 0.75 0.68 0.61 0.59 0.89 0.67 0.79
Crystalline M.P., DC 174 185 205 ISS 168 196 185
Bond Strength, psi,
Steel/Steel 985 1,620 2,300 1,700 1,410 2,340 1,590
Aluminum! Aluminum 1,140 1,620 1,800 1,760 1,500 2,040 1,000
Creep resistance, hr >192 >192 >174 >174 >186 168 <100
Extractables (toluene/iso- <1 <1 <1 <1 <1 <1
propanol), %
Ratio, aromatic polyester 30170 60/40 60/40 60/40 30170 60/40 60/40
to aliphatic polyamide
498 HANDBOOK OF ADHESIVES

Table 18. Characteristics of Monsanto's "Montac" Resin.

Typical Montac Resin Properties
Glass Crystalline Polymer Melt
Resin Specific Transition Melting Tensile Polymer Viscosity
Type Gravity Temperature' Point" Strength b Elongationb @249°C (480°F)
Montac 5500 1.20 glcc 35°C 207°C 4,000 PSI 420% 70,000 cps
Montac 5550 1.13 glcc -15°C 168°C 2,000 PSI 600% 55,000 cps
Typical Bond Performance
25°C/77°F: Steel/Steel
Creep Resistance"
Lap Shear 5-lb. Load (J" xl"
Resin Type Tensile Strength C T-Peef Overlap)
Montac 5500 2,800 psi 1 ppiw 168 hrs. @ 150 a C
Montac 5550 1,600 psi 35 ppiw 168 hrs. @ 150°C
Adhesion to Various Substrates
Excellent Good to Excellent Fair
steel, aluminum glass reinforced polyesters some rubber
glass (e.g., SMC's, HMC's) chrome plated
ceramic systems using "Nyrim" high pressure melamine laminates
leather urethane RIM
wood polycarbonate/PBT blends,
particle board ABS
nylon polyester
PVC
Excellent environmental resistance to: moisture, humidity, most solvents, ultraviolet light, thermal shock, salt corro-
sion.
'Perldn-Elmer OSC-2
bASTM 0-63-80 Modified
'ASTM 0-1002-72
dASTM 0-1876-72
'Without bond failure

melt point of 207°C, structural bonds which 3. Cowan et ai. (to u.S. Dept. of Agriculture), U.S. Pat-
can be handled in 30 seconds are claimed. This ent 2,450,940 (Oct. 28, 1948).
4. Renfrew et ai., "Thermosetting Resinous Composi-
fast bond development reduces the need for fix- tions From Epoxy Resins and Polyamide Derivatives
turing and reduces cycle time. It is claimed, From Polymeric Fat Acids" (to General Mills, Inc.),
also, that the improved productivity makes U.S. Patent 2,705,223 (Mar. 29, 1955).
these high-priced adhesives cost competitive 5. Peerman, D. E., and Vertnick, L. R., (to General
Mills), U.S. Patent 3,377,303 (April 9, 1968).
with two-part adhesives.
6. Morris, T. C., and Chaplick, A. M., "Thermoplastic
Monsanto supplies two main polymers, Polyamide-Epoxy Adhesive" (to B.B. Chemical Co.),
whose properties are listed in Table 18. U.S. Patent 2,867,592 (Jan. 6, 1959).
7. Chaplick, A. M., and Rossitto, C. (to United Shoe
Machinery), U.S. Patent 3,316,573 (May 2, 1967).
8. Norbury, J., and Rawstron Gill, W., "Fabric Bonding
REFERENCES
Process Utilizing Powdered Interpolyamides", (to
Imperial Chemical Industries Ltd.), U.S. Patent 3,919,
1. Billmeyer, F. W., Jr., "Textbook of Polymer Sci- 033.
ence," 3rd Ed., New York, John Wiley & Sons, 1984. 9. CA 55 21656 (October 1961); Original Reference:
2. Wheeler, D. H., Milun, A., and Lima, F., "Dimer Kozlov, P.V., and E.F. Russkova Vysokomoleku-
Acid Structure-Cyclic Structures of Clay-Catalyzed lyamye Soedineniy and 1-918-24 (1959).
Dimers of Normal Linoleic Acid: 9-cis, 12-cis, octa- 10. Ashley, F., "Poly(Ester-Amide) Block Copolymer
decadienoic Acid." J. Amer. Oil Chem. Soc. 47,242 Hot Melt Adhesives" (to Monsanto Company), U.S.
(1970). Patent 3,650,999 (March 1, 1972).
 29
High Temperature Organic
Adhesives
P. M. HERGENROTHER
NASA Langley Research Center
Hampton, VA

INTRODUCTION tion to another. It is virtually impossible to have

all of the desirable characteristics in one system
High temperature organic adhesives are re-
because of the chemistry involved. For exam-
quired for joining metals, ceramics, plastics,
ple, with the present state of development of
and composites to themselves and to each other.
high temperature polymers, a high temperature
These adhesives, and other materials that are
structural adhesive system cannot offer the
required to exhibit good adhesion, are needed
combination of tack and drape in the tape as
for use in a variety of applications in the aero-
well as no volatiles. Some of the major items
space, automotive, computer, electrical,
desired in a high temperature structural adhe-
household, and oil industries. The common re-
sive are listed below:
quirement is thermal stability; but stability un-
der other environmental conditions is also • Adhesive tape with tack and drape'
needed. In some applications, the use temper- • Processability under moderate conditions
ature is not the determining factor. Stability at 'with no or little volatile evolution
high temperatures encountered during various " • Compatibility with various adherends and
processing steps (e.g., soldering) to fabricate a surface treatments
component is the important requirement. These • Mechanical performance under intended
processing temperatures can be significantly use conditions (temperature, stress, envi-
higher than the actual use temperature. In this ronment)
article, high temperature organic adhesives are • Reproducibility and reliability
defined as materials that exhibit usable stength • Repairability
after long term aging (i.e., thousands of hours) • Low cost
at 232°C or short term exposure (i.e., minutes)
at 538°C and higher. Other important parameters that demand at-
High temperature adhesives are required to tention for the successful development of a high
exhibit a unique combination of properties. temperature adhesive include the following:
This combination will vary from one applica-
• Polymer-purity, molecular weight and
molecular weight distribution, glass tran-
The use of trade names or manufacturers does not consti- sition temperature (Tg) or heat deflection
tute an official endorsement of such products or manufac-
turers, either expressed or implied, by the National temperature (HDT), and flow characteris-
Aeronautics and Space Administration. tics

499
500 HANDBOOK OF ADHESIVES

• Adhesive tape-carrier, finish, filler, sives discussed herein, discretion is advised.

drying cycle, thickness, flow, volatile Important parameters which influence the per-
content, and ambient temperature stability formance of an adhesive vary from one evalu-
• Adherend-type, surface treatment, and ation to another. These include polymer
primer properties, carrier, adherend, surface treat-
• BondIng conditions-time, temperature, ment, primer, bonding conditions, aging, and
and pressure test conditions. Thus, it is difficult to obtain a
valid comparison on the performance of poly-
Specific examples are presented to familiarize
mers as adhesives when the work was done in
the reader with some of the stringent require-
different laboratories.
ments for various applications. A favorable
combination of processability, performance and
price is obviously of utmost im~ortance. Stru~­ HISTORY
ture adhesives for use in sandWIch structures 10
The search for adhesives with mechanical
high speed aircraft should provide good fillet-
properties and temperature resistance superior
ing around the cells and high mechanical prop-
to the modified epoxy phenolics developed in
erties for the long term after thermal cycling
the 1950s actually began in earnest in the early
under stress over a temperature range of - 54
1960s. Many new polymer systems were dis-
to 232°C, and should be resistant to airplane
covered and evaluated as high temperature ad-
fluids and solvents. A thin insulating film ad-
hesives. Condensation polyimides (PIs)
hering to a ceramic substrate as used in micro-
evolved as the polymer family which offered
electronics/computers should have a low the most favorable combination of properties.
dielectric constant, low coefficient of thermal
A few commercially available condensation
expansion, and stability for several hours in an polyimide adhesive systems were developed,
inert atmosphere at processing temperature as
some of which are still currently available. Ta-
high as 400°C. Nonstick interior coating and
ble I summarizes the historical development of
decorative exterior coating on cookware should
high temperature organic adhesives. The ~~­
adhere to the aluminum substrate, exhibit ab-
proximate year of introduction refers to the 101-
rasive and scratch resistance, be stable to cook-
tial report on adhesive performance. The
ing temperatures and the effects of hot oils and
maximum use temperatures for 10 minutes and
soaps. Composite ma~rices which can be con-
100 hours at temperature are reported. In sev-
strued as adhesives for use in the internal hot
eral instances, the maximum 10 minute use
working parts of automobile engines (e.g.,
temperature was controlled by the Tg • Some of
connecting rods, wrist pins, etc.) should ex-
the polymers could undoubtedly exhibit a
hibit excellent fatigue and creep resistance, and
higher 10 minute use temperature if they have
be amenable to low cost manufacturing. These
been exposed to higher temperatures during the
are a few of the many potential applications for
fabrication process or a subsequent postcure,
high temperature organic adhesives.
hence induced crosslinking. In addition, the
The primary intent of this article is to review
adhesive strength of several of these polymers
the status of experimental and newly developed
has not been reported at temperatures higher
high temperature organic adhesives with partic-
than those listed. Although some of these ad-
ular attention to aerospace materials. Detailed
hesives have exhibited respectable strength at
information on the synthesis of various poly-
232°C in standard ASTM tensile shear speci-
mers or bonding conditions can be obtained in
mens (TSS), they may not display comparable
the references cited. Several high temperature
performance in other specimen forms (e.g.,
adhesives are commercially available, and in-
sandwich specimens) because of factors such
formation on these systems can be obtained
as low flow or volatiles evolution.
from the major adhesive suppliers. For aero-
space use, these consist primarily of modified
Benzimidazole Polymers
epoxy phenolics, toughened bismaleimides,
addition and condensation polyimides. The first aromatic heterocyclic polymer to
In comparing the performance 'of the adhe- undergo extensive evaluation as a high temper-
 HIGH TEMPERATURE ORGANIC ADHESIVES 501

Table 1. Development of High Temperature Structural Adhesives.

Maximum Use Temperature, °C
Approximate Year
of Introduction Adhesive 10 min 100 hr
1956 Modified epoxy phenolic 316 232
1964 Polybenzimidazole 538 316
1965 Polyimide 371 316
1970 Polyquinoxaline 538 316
1971 Polyphenylquinoxaline 316 316
1974 Polyarylsulfone 260 260
1975 Acety lene-tenninated imide 316 316
1975 LARC-TPI 232 232
1978 Norbornene-tenninated imide 316 260
1978 NR-150B type poly imide 316 316
1981 Acetylene-tenninated phenylquinoxaline 288 260
1983 Polyphenylquinoxalines with pendent 232 232
phenylethynyl groups
1985 Semi-interpenetrating polyimide net- 232 232
works
1986 Polyary lene ether 232 232

ature adhesive was a polybenzimidazole (PBI). exhibited good flow and accordingly good wet-
The chemistry was initially reported in 1961 ting but required high temperatures to drive the
and involved the reaction of aromatic bis(o-dia- polymerization to completion. A large amount
mines) and diphenyl esters of aromatic dicar- of volatiles (phenol and water) was evolved,
boxylic acids.) The synthesis of a PBI from the which caused processing problems and resulted
poly condensation of 3,3' ,4,4'-tetraaminobi- in porosity in the bondline, especially in large
phenyl and diphenyl isophthalate is shown be- area bonds. In spite of the processing difficul-
low: ties, good adhesive strengths were obtained

1 -2nH,o
-2nC,H,-OH
(1)

Most of the high temperature adhesive work on with PB1. 5. 6 PH 15-7 molybdenum stainless
PBIs centered on this particular polymer. In steel TSS provided strengths of 4000 psi at
high molecular weight form, this polymer has 25°C, 2500 and 1100 psi at 300°C after 100
a Tg of -435°C.2 It can be compression and 200 hours at 300°C in air, respectively,
molded at 470°C under 2000 psi to provide neat and 1100 psi at 538°C after 10 minutes at
resin specimens2 or adhesive specimens 3 with 538°C in air. Many of the aromatic hetero-
high mechanical properties. Obviously these cyclic polymers including PBI exhibit good ad-
processing conditions are unacceptable for al- hesive properties at cryogenic temperature. PBI
most all adhesive applications. Because of this, TSS provided strength of 4600 psi at -196°C.
essentially all of the eady work on PBI as a In addition, the fatigue resistance ( 106 cycles)
high temperature adhesive used a low molecu- ofPBI TSS was better at -196°C than at 25°C
lar weight prepolymer.4 The prepolymer, de- (2200 vs. 1500 psi).5
pending upon the degree of advancement, PBI is currently commerically available in the
502 HANDBOOK OF ADHESIVES

fonn of a low molecular weight prepolymer in air. 12 However, cursory evaluation as an ad-
(inherent viscosity of - 0.05-0.10 dL/ g)7 and hesive on titanium (Ti, 6AI-4V) adherends
a higher molecular weight polymer (inherent gave TSS of - 3000 psi at 25°C and poor re-
viscosity of >0.6 dL/g)8 tention of strength at 316°C. The low strength
Other types of benzimidazole polymers of 316°C was due primarily to improper pro-
where the imidazole hydrogen was substituted cess conditions and not the thennal properties
with a phenyl group9 or an arylene grouplO such of the polymer.
as in structures 1 and 2 respectively have, also Essentially no new adhesive work has been
been evaluated as adhesives. reported on benzimidazole polymers over the

These polymers are more thennooxidatively last ten years. These materials, like some other
stable than the PBI in Eq. (1) but the elimina- high temperature adhesives to be discussed, are
tion of the imidazole hydrogen resulted in less plagued by processing problems due primarily
intramolecular association and accordingly to volatile evolution and the high temperatures
more thennoplasticity and lower Tg • The ad- required to obtain adequate flow and/or ad-
hesive properties of the polymers in structures vance the prepolymer. As a class of adhesives,
1 and 2 were excellent at 25°C (>4000 psi) benzimidazole polymers currently available do
but low at temperatures > 200°C because of not exhibit promise for extensive use as high
thennoplastic failure. temperature adhesives.
A variation of a benzimidazole polymer is the
polybenzimidazoquinazoline ll of representa- Quinoxaline Polymers
tive structure 3. In small composites, this ma-
There are two types of quinoxaline polymers:
the unsubstituted with no pendent groups on the
quinoxaline ring, and the substituted, in which
phenyl groups are attached to the quinoxaline
ring. The synthesis of the unsubstituted po-
lyquinoxalines (PQ) from the reaction of aro-
matic bis(o-diamines) and aromatic
bis(glyoxals) was initially reported in 1964. 13 -
15 The synthesis of a representative PQ from
the step-growth polymerization of 3,3' ,4,4'-te-
traaminobiphenyl and 4,4'-oxy-
3
bis(phenylglyoxal hydrate) is shown in Eq. (2):
The Tgs for a series of PQs are presented in
terial has shown excellent retention of Table 2. The synthesis provides a configura-
properties at 371°C after 200 hours at 371 °C tionally unordered polymer with three isomers
 HIGH TEMPERATURE ORGANIC ADHESIVES 503

1-6nH20 (2)

-te~>©-~
distributed randomly within the polymer chain. weight form in solvents such as m-cresol. The
Because of the isomers, PQs are amorphous and solubility at solids content of 20 % (weight/vol-
soluble in the ring-closed high molecular ume) or higher permits the solvent impregna-

Table 2. Glass Transition Temperatures of

Polyquinoxalines. 16

x Ar

376

305

235

216

342

o 318
II
-c-

-0- 206
504 HANDBOOK OF ADHESIVES

tion of a carrier (e.g., 112 E-glass) and the limited development of these promlsmg
subsequent drying to low volatile content lev- polymers as high temperature adhesives.
els. The PQ in Eq. (2) filled with amorphous
boron provided the highest 371 °e strength re- Phenylquinoxaline Polymers
ported after aging at 371 °e of any organic ad-
The polyphenylquinoxalines (PPQs) are simi-
hesive. Stainless steel TSS were fabricated from
lar to the PQs but offer better solubility, pro-
boron filled PQ adhesive tape (112 E-glass) for
cessability, and thermooxidative stability.
I hour each at 344, 426, and 455°e 200 psi.
Strengths of 3350 psi at 25°e, 2280 psi at These polymers are prepared from the reaction
of aromatic bis(o-diamines) and bis(phenyl-a-
316°e after 200 hours at 316°e, 2540 psi at
diketones) as first reported in 1967. 18 Since
371°e after 50 hours at 371 °e, and 1325 psi
at 538°e after 10 minutes at 538°e were ob- their initial disclosure, extensive work has been
reported on the chemistry, mechanical, and
tained.17 Obviously the process conditions are
physical properties of PPQs. 19 A representative
too stringent for serious consideration of this
synthesis shown in Eq. (3) involves the reac-
PQ for extensive use as a high temperature ad-
tion of 3,3' ,4,4' -tetraaminobiphenyl and 4,4'-
hesive. When employing processing tempera-
oxybis(benzil) :

o 0 0 0

" "
HSC6-C-C--©.--O-----©-C-C-C6HS
" "
1-4nH 02 (3)

1Jt"~~
tures of -4oo o e, problems are encountered Table 3 presents Tgs for several representative
with bagging materials, sealants, malfunction- PPQs.
ing of autoclaves and tooling, surfaces degra- Several PPQs have been evaluated as high
dation of the adherend, residual stresses in the temperature adhesives 21 ,22 with the PPQ in Eq.
bondline, and thermal degradation of the ad- (3) receiving the most attention. As part of the
hesive. United States Supersonic Transport (SST) pro-
In spite of the high adhesive strengths at 371 gram, the PPQ in Eq. (3) was evaluated as a
and 538°e obtained for a boron filled PQ, no high temperature adhesive for joining Ti to Ti,
further work has been reported. This appears to and Ti to PI and Ti core (sandwich structure),
be an area where additional work is worth- for long term use at 232°e. Ti TSS having a
while. The PQ in Eq. (2) had a Tg of - 300 0 e phosphate fluoride surface treatment provided
but yet in adhesive form, provided high strength strengths of 4740 psi at 25°e, 3500 psi at
at temperatures significantly higher than 232°e after 10 minutes at 232°e and 3350 psi
3oo o e. Apparently, crosslinking or interaction at 232°e after 8000 hours at 232°e in air.23
with the boron filler occurred at the high pro- TSS exhibited no creep under a load of 1000
cessing temperatures to provide a material with psi at 232°e for 60 days. Sandwich specimens
temperature performance beyond that of the (14 in. X 14 in.) using Ti face sheets and PI
starting material. PQs are not commercially and Ti core gave the properties in Table 4. In
available; this undoubtedly has contributed to addition, climbing drum peel specimens from
 HIGH TEMPERATURE ORGANIC ADHESIVES 505

Table 3. Glass Transition Temperatures of

Polyphenylquinoxalines. 2o

tH,c;<:©Ly-©()::t
y Ar Tfinh' dl/g Tg,oC

-©L 2.2 370

-©- 1.3 318

-©Lo-©r 1.2 290

-0-
-©- 1.9 279

-CO-
-©- 2.3 288

- S02 -
-©- 1.4 324

Ti/Ti panels gave strength at 25°C of 70 in.- content tape «0.5%, 112 E-glass) in an au-
lb /3 in. width. The various PPQ adhesive toclave with the temperature starting at 25°C
specimens were fabricated from low volatile and increasing to 400°C under 50-100 psi dur-

Table 4. Adhesive Properties of PPQ Sandwich Specimens.

Peel Strength, Flatwise Tensile
in. -lhl3 in. width Strength, psi
Test Condition Ti Core PI Core Ti Core PI Core
25°C 28 34 800 950
232°C after 10 min 750 825
at 232°C
506 HANDBOOK OF ADHESIVES

ing -1 hour and maintaining at 400°C under than at 25°C because TSS undergo a peel mo-
50-100 psi for 0.5 hour. ment during testing and brittle materials often
More recent work with the PPQ in Eq. (3) exhibit more toughness at elevated tempera-
has involved chromic acid and phosphoric acid tures. The 710 PI matrix is brittle at 25°C due
anodized Ti surface treatments, which result in to crosslinking but becomes softer, more ther-
better moisture resistance but less thermal re- moplastic-like, and able to accommodate a
sistance than the surface from phosphate fluor- higher peel stress at elevated temperatures. This
ide treatment. Chromic acid anodized Ti TSS is in contrast to the NR150B2 matrix, which is
provided strengths of 5000 psi at 25°C (cohe- a tough, high Tg , thermoplastic PI; the
sive failure), 2,000 psi at 232°C after 5,000 NR150B2 specimens provided high strengths
hours at 232°C in air (mixed failure) and low under all test conditions. A strength of 2800 psi
strengths at 232°C after 10,000 hours at 232°C at 316°C for the NR150B2 HTS/NRI50B2
in air (100% adhesive failure).24 An anodized HTS specimens was observed, whereas pro-
Ti surface degrades when bonding tempera- nounced thermoplastic failure occurred in the
tures approaching 370°C are employed. This Ti/Ti specimens at 316°C (Tg of the ~PQ was
may have been one of the factors which caused 318°C). However when the NR150B2 HTS/
lower strengths at 232°C after aging. NR150B2 HTS specimens were placed under a
This recent work24 also showed that stressed load of 1500 psi at 316°C, thermoplastic fail-
anodized Ti wedge opening specimens of the ure in the bondline occurred in -15 minutes.
PPQ in Eq. (3) exhibited excellent resistance The effect of a 3-day water boil on the
to hydraulic fluid (Skydrol), moisture (95 % strength of adhesive specimens of the PPQ in
relative humidity at 60°C) and crack propaga- structure 4 is summarized in Table 6. The
tion at 232°C. To demonstrate the processabil- phosphate fluoride surface treatment is sensi-
ity of this PPQ, a 4 ft x 4 ft Ti bonded panel tive to moisture and this is reflected in low
(half metal-to-metal and half sandwich struc- strengths after 3-day water boil. The anodized
ture using PI core) was fabricated. The bonded surface is significantly more resistant to mois-
structure had a dense bondline as evidenced by ture than the phosphate fluoride surface, but the
ultrasonic scanning (C-scan) and high strength PPQ apparently absorbed water after the 3-day
as demonstrated by testing specimens taken water boil and became plasticized, exhibiting
from various areas of the panel. what appeared to be thermoplastic failure at
A PPQ of structure 4 with a Tg of 318°C was 288°C. This was surprising since PPQs gen-
evaluated for joining Ti to composite and com-

posite to composite for high temperature appli-

cations. 22 The molecular weight of the PPQ was erally have relatively low moisture pickup. The
controlled to obtain the best combination of composite specimens exhibit good strengths
processability and adhesive strength. The ad- after a 3-day water boil.
hesive properties of Ti/Ti, Ti/composite, and PPQs have undergone evaluation by various
composite/composite TSS are summarized in organizations and have exhibited promise for
Table 5. The strengths of the 710 HTS (PI use as high temperature structural adhesives. A
composite) specimens were higher at 288°C limiting factor in their development has been
 HIGH TEMPERATURE ORGANIC ADHESIVES 507

Table 5. PPQ Adhesive Properties. 22 . 8

Tensile Shear Strength, psi
288°C after 300 316°C after 300
Specimen 25°C 288°C hr at 288°C 316°C hr at 316°C
Ti/Tib 440 2500 2400 300· 500·
Til7lOHTSc.f 2000 3100 2800 1600 1900
7 lOHTSI7lOHTS f 3000 4200 2600 3000 2100
NRI50B2HTS/ d 6000 3700 3300 2800 2500
NR150B2HT f
PPQ with inherent viscosity of 0.61 dUg and Tg = 318°C; for Ti/Ti, 112 E-glass with A-llOO finish, tape dried to - 4 % volatile content;
other panels, unsupported PPQ film had - 4 % volatiles
'Bonding conditions: under 200 psi, 25°C to 400°C during -0.5 hr, held at 400'C for 20 min, cooled to 260'C, removed from press.
bSurface treatment: Ti(6AI-4V), phosphate fluoride.
'Unidirectional composite of Monsanto's polyimide composite matrix designated Skybond 710 and Hercules high tensile strength carbon
fiber reinforcement, composite surface treatment was mild abrasion.
dUnidirectional composite of DuPont's poly imide composite matrix designated NRI50B2 and Hercules high tensile strength carbon fiber
reinforcement.
'Thermoplastic failure.
fAll composite adherends exhibited shear-type failure in the composite.

commercial unavailability, which is associated ent types. One type consists of

with cost. Several companies have considered phenylquinoxaline oligomers terminated with
the PPQ in Eq. (2) as a potential product, but reactive groups, primarily acetylenic groups.
the problems associated primarily with the te- The other type is a linear PPQ containing pen-
traamine, a suspected carcinogen, the synthesis dent acetylenic groups. Upon heating, the ace-
of the bisbenzil, and a questionable market- tylenic groups in both types of materials
place have discouraged them. An area that undergo a complex reaction that causes branch-
merits further investigation with PPQ is the use ing and crosslinking. As a result, the Tgs for
of amorphous boron as a filler in conjunction these types of cured resins are higher than those
with high temperature curing ( e. g., > 400 0 C ). of the corresponding linear polymers.
This combination provided excellent high tem- The initial synthesis of acetylenic terminated
perature adhesive properties for a PQ but has phenylquinoxaline oligomers was reported in
not been evaluated with a PPQ. 1975. 25 An alternate synthesis26 reported in
1976 involved endcapping o-diamino-termi-
nated phenylquinoxaline oligomers with 4-(4-
Crosslinked Phenylquinoxaline Polymers ethynylphenoxy)benzil to yield acetylene-ter-
minated phenylquinoxaline oligomers (ATPQs)
Crosslinked phenylquinoxaline polymers eval- as shown in the representative scheme in Eq.
uated as adhesives are primarily of two differ- (4):

Table 6. Effect of 3-Day Water Boil on PPQ Adhesive Specimens. 22 . 8

Tensile Shear Strength, psi
Specimen" Surface Treatment 25°C 288°C Failure Mode
Ti/Ti phosphate fluoride (PF) < 1000 100% adhesive
Ti/Ti phosphoric acid anodized (A) 3530 730 25°C, 20% adhesive
288°C, thennoplastic
Til7l0HTS A/mild abrasion 2750 2620 composite
710HTSl7lOHTS mild abrasion 2650 2950 composite
'Bonding conditions, see Table 5
508 HANDBOOK OF ADHESIVES

The main advantage offered by the ATPQ over In 1981, high molecular weight linear PPQs
the linear high molecular weight PPQ was bet- containing pendent ethynyl and phenylethynyl
ter processability. Generally, small molecules groups were reported. 29 These polymers were
of the same type of material exhibit better flow soluble in a variety of chlorinated or phenolic
at lower temperatures than large molecules. In solvents, and solutions thereof could be used to
addition, the acetylenic groups react without the cast film or impregnate a carrier or reinforce-
evolution of volatiles. One of the problems en- ment. Upon heating, the ethynyl (acetylenic
countered with many acetylenic terminated het- group) and the phenylethynyl groups react to
erocyclic oligomers is that the acetylenic group provide branching and crosslinking. As a re-
begins to react prior to the formation of a com- sult, the cured polymers are insoluble and ex-
plete melt, thereby inhibiting further flow and hibit high Tgs. A few of the PPQs containing
wetting. In spite of this, Ti/Ti TSS of the pendent phenylethynyl groups have been eval-
ATPQ in Eq. (4) (where n = 2) gave strengths uated as adhesives, whereas the PPQs contain-
of 4730 psi at 25°C, 1350 psi at 260°C after ing pendent ethynyl groups did not exhibit
500 hours at 260°C and 1525 psi at 316°C.27 _adequate processability for fabrication of high
The specimens were fabricated at 316°C under strength adhesive specimens.
50 psi for 1 hour. Although the cured ATPQs The linear PPQ and the cured PPQ contain-
were less stable under thermooxidative condi- ing 10 mole % of pendent phenylethynyl
tions than a comparable linear PPQ, they ex- groups, as shown in structure 5, exhibited the
hibited improved processability. ATPQs are not tensile shear strengths in Table 7. The effect of
commercially available. crosslinking due to reaction of the pendent

Table 7. PPQ Ti/Ti Tensile Shear Strength. 3o

Avg. Tensile Shear
Processing Conditions Strength. psi
Postcure.
Final Temp .• Pressure. Time. hr at
Polymer Tg. ·C ·C psi hr Temp .• ·C 26·C 204·C 232·C
NoC=C-CJls 256 316 200 0.5 2@371 4930 2810 2370
10 mole % 281 329 200 2.0 2@371 4400 3240 3100
C=C-CJls
 HIGH TEMPERATURE ORGANIC ADHESIVES 509

phenylethynyl groups is evident in the higher Imide Polymers

strengths at 204 and 232°C. Another represen-
About the time PBI was being developed as a
tative PPQ containing pendent phenylethynyl
high temperature adhesive, PIs were also re-
groups which had undergone adhesive evalua-
ceiving attention. The early synthesis of PIs in-
tion is shown in Eq. (5):
volved the reaction of an aromatic dianhydride

x x

The Ti/Ti tensile shear strengths as a function and an aromatic diamine to form a polyamide
of cure conditions are presented in Table 8. The acid (amic acid) which was subsequently cy-
strength at 232°C of 4400 psi for the Al filled clodehydrated to the PI. 32, 33 The cyclodehy-
specimens is outstanding. PPQs containing dration is accomplished thermally when PIs are
pendent phenylethynyl groups are experimental used as adhesives. Since this early work, sev-
materials and not commercially available. eral other routes have been devised to synthe-
size PIs. A representative reaction scheme for
PI formation is in Eq. (6).

n HzN1(Y rATo NHz

~ +O.Sn
HzN NHz

+O.2n H5C6-C==C-©-~_~-©r~~_~-©rC==C-C6H5

1-4nH,o (5)

where SO% ofAr= -©-o-©r°-©-andX=H

510 HANDBOOK OF ADHESIVES

Table 8. PPQ Ti/Ti Tensile Shear Strengths. 31 •a

Tensile Shear Strength, psi
Polymer (Tg, °C) Process Conditions 25°C 232°C 316°Cb
NoC=C-C~s RT to 343°C, 100 psi, 0.5 hr hold 5600 3800 Thermoplastic
(255)
20% C=C-C6HS RT to 343°C, 300 psi, 0.5 hr hold 4430 3240 840
(262)
20% C=C-C~s RT to 343°C, 300 psi, 4 hr hold 2600 2800 1240
(278)
20% C=C-C6HS RT to 343°C, 300 psi, 0.5 hr hold; 2300 3180 1350
(283) 16 hr@ 316°C
20% C=C-C~s RT to 343°C, 300 psi, 0.5 hr hold; 4670 4400 1170
(272) 16 hr @ 316°c no glass carrier,
30 phr MD 105 Al
'Ti surface treatment, 10 V chromic acid anodized, 112 glass with A-lIOO finish, no fiUer.
"Predominantly thermoplastic failure.

where 3,3' ,4,4'-benzophenonetetracarboxylic dization (even at ambient temperature). 39 An-

dianhydride (BTDA) is reacted with 3,3'-dia- other problem with the use of the polyamide
minobenzophenone to fonn a polyamide acid acid fonn in adhesives is the evolution of water
which is converted to the PI. The Tgs for a se- during thermal conversion to the PI. This vol-
ries of PIs are presented in Table 9. Several atile evolution results in processing problems,
reviews on PIs are available. 35-38 especially in large area bonding, and in lower
Most of the early PIs were insoluble and mechanical properties primarily due to porosity
many relatively intractable. The soluble in the bondline. In spite of these problems, PI
polyamide acid was used as the processable adhesives in the fonn of polyamide acids are
precursor to PI. The polyamide acid is unstable currently commercially available.
at ambient temperature and slowly degrades due Many polyimides have been evaluated as ad-
to hydrolysis from water evolved during imi-
o 0

· <:Ml©C).. H,NVCV~
1\ 1\ IT

II
o
II
0

(6)
 HIGH TEMPERATURE ORGANIC ADHESIVES 511

Table 9. Glass Transition Temperatures of Polyimides. 34

0 0
\I \I

+<)Ql-r~>-M+
II CF II .
o 3
0
Ar 'link. dLig Tg. ·C

-©L 0.35 326

V- 0.41 297

¢ 0.64 365

-©-©r 0.40 337

--©-CH -©T 2
0.38 291

--©-o-©T 0.46 285

--©-s-©T 0.35 283

--©-so,-©T 0.31 336

-©T0-©r0--©- 0.35 229

hesives using the polyamide acid and PI fonns. minobenzene was processed into adhesive
To circumvent the volatile problem, the PI from specimens as a thennoplastic at pressures of
the polycondensation of BTDA and 1,3-dia- -200 psi and temperatures of _400°C.40 Ti
 512 HANDBOOK OF ADHESIVES

TSS gave strengths of - 3000 psi at 25°C and work,47 and this fonn may also be useful in ad-
-2000 psi at 288°C after 100 hours at 288°C hesive work, particularly sandwich structure.
in air. This fonn of LARC-TPI undergoes chain
The PI in Eq. (6) has provided excellent ad- growth with the evolution of a small amount of
hesive strengths from 25 to 232°C. This poly- volatiles to yield a relatively high molecular
mer evolved from a study on structure/property weight amorphous PI. The semicrystalline low
relationships41,42 and came to be known as molecular weight fonn of LARC-TPI is cur-
LARC-2 (Langley Research Center) and then rently under evaluation in adhesive work.
LARC-TPI. The T of the PI has been reported A series of new polyimides containing car-
as 256_275°C.41 ,:6,44 The variation in Tgs is bonyl and ether connecting groups between the
due to different methods of detennination and aromatic rings have recently been· re-
different molecular weights. Early adhesive ported. 48 ,49 Some of these PIs are semicrystal-
work43 found bis(2-methoxyethyl)ether (dig- line, with Tgs from 222 to 247°C and crystalline
lyme) to be a good solvent for the polyamide melt temperatures (Tm) from 350 to 442°C. The
acid and when these solutions were used to pre- properties of a representative PI shown in
pare adhesive tapes, Ti TSS were fabricated structure 6 are reported in Table 10.

t
o 0
II II 0 0
C"'rA 0 rArC" II II ~
<cM-~~cl-©-o-©rc-©rc-©-o--lQJ j n

II II n
o 0
6

with strengths of 6180 psi at 25°C, 2600 psi at The thin film tensile strength and modulus,
225°C and 950 psi at 250°C (thennoplastic fracture toughness (Glc , critical strain energy
failure near the Tg). More recent work has release rate), and strength of Ti TSS are excel-
shown LARC-TPI adhesive specimens to ex- lent. At 23rC the amorphous fonn of this PI
hibit excellent resistance to aircraft solvents and exhibited pronounced thennoplastic failure in
moisture while under stress. 45 This effort has Ti/Ti TSS as expected since the Tg is 222°C.
provided Ti (chromic acid anodized) TSS with However, after annealing the Ti/Ti TSS at
strengths of - 4800 psi at 25°C and - 3400 psi 300°C for 5 hours or aging at 232°C for 1000
at 232°C. Another study on LARC-TPI showed hours, crystallinity was induced to significantly
chromic acid anodized Ti TSS gave initial improve the 232°C strength. The crystalline
strength at 232°C of - 2000 psi which in- regions in the PI carry the load which allows
creased to - 3500 psi after 10,000 hours at good strength at temperature> Tg •
232 °C in air and remained constant at - 3500 An interesting PI which is not a high tem-
psi at 232°C after 32,000 hours at 232°C in perature polymer is shown in structure 7. This
air. 46 These are the highest strengths ever re- material deserved mention because it provided
ported at 232°C after aging for 32,000 hours at the highest average strength at 25°C for Ti TSS
. 232°C for any organic adhesive. of any known organic adhesive. Strengths at
Problems have been encountered in the prep- 7850 psi at 25°C, 5400 psi at 93°C and 4045
aration of high strength sandwich structure with psi at 121°C were reported. 50 The PI has a Tg
LARC-TPI due to limited flow. The final con- of 155°C, which pennitted the fabrication of
ditions generally used to fabricate LARC-TPI TSS from essentially volatile-free adhesive tape
adhesive bonds are 343°C under 200 psi. How- at 260°C under 100 psi. The polymer was fab-
ever, a new semicrystalline low molecular ricated as a thennoplastic where the time at
weight fonn of LARC-TPI with a relatively low temperature was relatively short « 15 min-
melt viscosity was recently used in composite utes).
 HIGH TEMPERATURE ORGANIC ADHESIVES 513

o 0
II II
<)~J-©:>-©-(OCH,CH,r
II
o
II
0
7

Many other high temperature PIs have also to-metal bonds and in some cases, even com-
been evaluated as adhesives but their Ti TSS posite-to-composite bonds. However, the melt
strengths were less than those reported· for viscosity is too high to permit proper filleting
LARC-TPI. The processing conditions for around the cells in sandwich structure and in
these other PIs were generally comparable to addition, the high pressure will crush the core.
or higher than those used for LARC-TPI. All Recent adhesive work with PI has been di-
high temperature PIs evaluated as adhesives rected towards improving the processability
have common problems which are volatile ev- while retaining high temperature properties.
olution from the polyamide acid and in some One representative example involves a blend of
cases the use of a mixture of monomers or high a low molecular weight acetylene terminated
melt viscosity of the PI. The use ofthe polyam- imide with a high molecular weight pI. 51 The
ide acid or monomer mixture is not recom- blend has a relatively low melt viscosity at
mended for the fabrication of high quality, large moderate temperatures. Upon heating under
area metal-to-metal or metal-to-honeycomb low pressure (50 psi), the acetylenic groups
bonded components. The volatiles are difficult react with no volatile evolution in the presence
to remove to obtain a void-free bondline and of the high molecular weight PI to provide a
high strength bond. The PI form necessitates semi-interpenetrating polymer network (SIPN).
the use of relatively high pressure, which can The reactive low molecular weight oligomer
be used for the fabrication of large area metal- improves the processability of the high molec-

Table 10. Properties of PI of Structure 6. 49

Glass transition temperature: 222°C
Crystalline melt temperature: 350°C
Solvent resistance: excellent
Thin Film Properties
Test temperature, °C 25 177 232
Tensile strength, psi 22,000 14.2 5.2
Tensile modulus, psi 630,000 540,000 245,000
Elongation, % 8.3 21.1 76.1
Fracture toughness (G[c) at 25°C: 37.8 in.-lb/in.2
Adhesive Properties'
TiiTi Tensile Shear
Test Condition Strength, psi Failure
25°C 6250 > 95% cohesive
25°C after 1000 hr @ 232°C 7120 -100% cohesive
25°C after 72 hr water boil 5140 -90% cohesive
17rC 4150 > 95% cohesive
232°C 880 -95% adhesive
232°C after 1000 hr @ 232°C 2740 - 50% cohesive
232°C after 5 hr @ 300°C 2800 - 80% cohesive
232°C after 100 hr @ 316°C 3670 > 95 % cohesive
'Pasa Jell 107 surface treatment; bonding conditions, 400°C, 1000 psi, 15 minutes.
 514 HANDBOOK OF ADHESIVES

ular weight PI while the molecular weight PI The preferred method to convert the ethynyl
enhances the toughess of the cured resin from terminated amide acid to the corresponding im-
the low molecular weight reactive oligomer. Ti ide is chemically (e.g., acetic anhydride and an
TSS gave strengths of 3300 psi at 25°C, 2800 organic base). Under chemical conversion, the
psi at 232°C and 3000 psi at 232 °C after 1000 ethynyl group remains unreacted.
hours at 232°C.51 Other combinations are being One of the major problems with ethynyl ter-
evaluated for potential use in high temperature minated oligomers with high melt or softening
adhesive and composite applications. temperatures is that the ethynyl groups begin to
A few PIs are commercially available in ad- react before the oligomer softens or melts. As
hesive form as the polyamide acid with the most the ethynyl group reacts, the temperature for
popular being FM 34B _18. 52 Another is the softening or melting of the oligomer is in-
polyamide acid form of LARC-TPI which can creased. Therefore, certain ethynyl terminated
be formulated and used to prepare adhesive oligomers such as some imides cannot provide
tape. 53 Several other polyimides, as discussed adequate wetting of the substrate, which is re-
in a review on aromatic polyimide adhesives quired to form a strong bond. Obviously, heat-
and bonding agents,54 are also available. ing rate is important with reactive oligomers.
A fast heating rate is desirable to achieve ade-
Addition Polyimides quate flow and wetting but impractical from a
manufacturing standpoint. Autoclaves and large
Two types of reactive groups, ethynyl and nor-
presses heat slowly whereas preheated matched
bomene (Nadic), have been placed on the ends
metal tooling can heat more rapidly.
of imide oligomers in an attempt to develop
The ethynyl terminated imide oligomer work
more processable high temperature PI adhe- was initially reported in 1974. 55 ,56 Neat
sives. The thermal reaction of the ethynyl resin 57 ,58 and composite57-59 properties for
groups occurs without the evolution of vola-
cured acetylene terminated imide oligomers
tiles, whereas the thermal reaction of the nor-
have been reported. These materials were ini-
bomene group may involve the release of a
tially designated HR-600 and later Thermid®-
small amount of cyclopentadiene from the re-
600 (60). The ethynyl terminated imide oligo-
verse Diels-Alder reaction (depending on con-
mer in structure 8 is representative of this class

o 0 0 0
II II II II
HC=CV<::©L~-©(:!VVV<::©L~-©(:>VC==CH
o
II II
0
I
0
II
0

ditions). Nadic end-capped amide acid of materials. Ti/Ti TSS of the cured material
oligomers can be converted predominantly to of structure 7 provides strengths of 3200 psi at
the nadic end-capped imide oligomer under 25°C, 1900 psi at 232°C after 1000 hours at
thermal conditions, generally at temperatures 232°C, and 1200 psi at 260°C after 1000 hours
< 200°C. The thermally induced reaction of at 260°C.61 Hydroquinone has been used to re-
the nadic group proceeds at a slow rate at tem- tard the thermal reaction of the ethynyl group
peratures < 200°C and at a fast rate at tem- and thereby improve the processability by in-
peratures of >275°C. However, the thermal creasing the gel time. 62 Strengths of Ti/Ti TSS
conversion of the ethynyl end-capped amide of 3800 psi at 25°C, 2100 psi at 288°C, and
acid oligomer to imide is more difficult since 2550 psi at 288°C after 500 hours at 288°C
the ethynyl group undergoes substantial reac- were reported. 62 These bonds were fabricated
tion in the temperature range of 150-200°C. in a press starting at 25°C under 50 psi, in-
 HIGH TEMPERATURE ORGANIC ADHESIVES 515

creasing the temperature to 316°C during 1.5 strengths as high as 5000 psi at 25°C and 2200
hours and holding at 316°C for 1.5 hours. The pSI. at 3160 C. 67 A beveled honeycomb panel
bonds were subsequently postcured unre- (about 2 ft X 3 ft) using PI composite skins and
strained for 4 hours at 343°C. LARC-13 as the adhesive was successfully fab-
Other work to improve the processability of ricated and performed well in static tests at 25
reactive imide-type oligomers has involved the and 260°C.67 LARC-13 is not commercially
preparation of ethynyl terminated isoimide available because of the unavailability and cost
oligomers. The ethynyl terminated amide acid of the diamine, 3,3'-diaminodiphenyl meth-
oligomer is normally treated with a chemical ane, used to prepare the oligomer. A PMR-15
cyclodehydrating agent such as triftuoroacetic type adhesive (BXRI0314-151C) is commer-
anhydride or dicyclohexylcarbodiimide to form cially available. 52
the corresponding isoimide oligomer. The
ethynyl terminated isoimide oligomer exhibits Arylene Ether Polymers
better solubility and processability than the
Several polyarylene ethers such as UDEL@
ethynyl terminated imide oligomer. 63 The
(polysulfone, Tg _190°C),68 RADEL@ (poly-
isoimide rearranges to the imide during the
phenylsulfone, Tg - 220 °C), 68 Kadel-II@
thermal curing process, generally in the tem-
(polyketone, Tg -160°C, Tm _340°C),68
perature range of about 3OO-350°C.64 The
Victrex@ PES (polyethersulfone, T
strength of Ti/Ti TSS of cured ethynyl termi-
-220°C),65 and Victrex@ PEEK (polyether~
nated isoimide oligomers is about the same as
etherketone, Tg -143°C, Tm _343 0 C)65 are
that reported for HR-6oo. Various forms of
commercially available high performance en-
ethynyl terminated amide acid, imide and
gineering thermoplastics. However, although
isoimide oligomers are commercially avail-
able. 60 the thermooxidative stability of these materials
Nadic terminated imide oligomers were first is excellent, they cannot be classified as high
temperature
. adhesives because their Tg dictates
reported in 1970,65 and led to the development thelr
ofPMR-15 (PMR means in situ polymerization use temperature. None of these polyary-
lene ethers, even in filled form, exhibit good
of monomeric reactants to yield an oligomer
retention of mechanical properties at 232°C
with number average molecular weight, Mm of
about 1500 g/mole).66 PMR-15 is used as a under stress for long term. Research is under-
matrix resin in composites for hot applications way to develop new polyarylene ethers with
higher use temperature. For example, experi-
such as components in jet engines. The first re-
port on the evaluation of Nadic terminated im- mental quantities of new versions of PEEK
ide oligomers as adhesives was in 1979,67 using (e.g., HTX, Tg = 205°C, Tm = 386°C; dif-
ferent chemical structure) with higher T sand
a material called LARC-13 (Mn = - 1300 g/
mole, structure 9). This material was processed accordingly higher Tms are being sampied to
under mild pressures (50 psi) to a final cure various organizations.
In the case of PEEK, a semicrystalline poly-
temperature of 329°C followed by an unre-
mer, Ti/Ti (chromic acid anodized) TSS gave
strained postcure at 343°C. Ti/Ti, Ti/compos-
ite and composite/composite TSS were strengths of 6370 psi at 25°C, 2590 psi at
177°C and 1770 psi at 232°C.70 The crystal-
fabricated and tested. The strengths of Ti/Ti
line regions of the polymer carry the load at
TSS were 3300 psi at 25°C and 2800 psi at
temperatures above the Tg • However, under a
260°C.67 Composite to composite TSS gave

1Vl
o

r
0 0 0
I II II II
~
lv-/1VCH'lQJT<»~¥>-trCH' 0 \:XD
r(\'yC" C"'fA 0 rArC C
II I II ~ -1.7 I
o 0 0 0
9
 516 HANDBOOK OF ADHESIVES

load of 1000 psi at 177°C, creep was observed As part of a study 74 on polyarylene ethers,
in the TSS. Perhaps a higher degree of crystal- several polymers with high Tgs as presented in
linity could have prevented or reduced the creep Table 11 were prepared. The first polymer in
behavior. These TSS were fabricated at Table 11 and an ethynyl terminated oligomer
- 380°C under 200 psi for 0.5 hour. As men- shown in structure 10 were evaluated as adhe-

o o
II II
{y-
HC==C~
c-o
o-C--©--C=CH

10

tioned previously, the high processing temper- sives. 75 The strengths of Ti/Ti TSS are pre-
atures have been considered one of the sented in Table 12. Although the specimens
detriments to the acceptance of high tempera- from the cured ethynyl terminated oligomers
ture thermoplastics as structural resins. This gave lower strengths at 25 and 93°C than the
may be a misconception, since high tempera- corresponding high molecular weight linear
tures are widely used in many manufacturing polymer, the strength at 25°C after a 72 hour
steps such as ceramic processing and metal soak in hydraulic fluid was significantly better
forming. Similar but milder conditions could be due to crosslinking. These two polymers can-
used to fabricate bonded structure from tough not be classified as high temperature adhesives
high temperature polymers. since the definition in this article is long term
An arylene ether polymer (Polymer 360 or use at 232°C. However, the results show the
Astre1360) which was commercially available7 ! advantageous effect of a small amount of cross-
in the 1970s has also undergone preliminary linking in improving the elevated temperature
evaluation as an adhesive.72 This polymer strength and resistance to hydraulic fluid.
composed of biphenyl and phenyl units con- Another arylene ether polymer in structure 11
nected by oxygen and sulfone units has a Tg of provided Ti/Ti (chromic acid anodized) TSS

11

-290°C. Because of the high Tg and high melt with strengths of 3620 psi at -54°C, 3380 psi
viscosity, a temperature of 400°C and a pres- at 25°C, 3070 and 3210 psi at 177°C initially
sure of 200 psi were required to fabricate TSS. and after 1000 hours at 177°C respectively and
On Ti substrate, strengths of 4600 psi at 25°C, 2440 and 2590 psi at 232°C initially and after
3700 psi at 232°C and 3170 psi at 260°C were 1000 hours at 232°C, respectively.76 Climbing
obtained. 73 No results on the effect of exposure drum Ti/Ti peel specimens gave 25°C values
to solvents were reported. Since this polyary- of 16.3 in.-Ib/in. width. The Ti/Ti TSS were
lene ether is amorphous, it would likely severely attacked while under stress in the pres-
undergo attack by solvents such as hydraulic ence of hydraulic fluid (Skydrol). The final
fluid or paint stripper. bonding conditions using tape (112 E-glass with
 HIGH TEMPERATURE ORGANIC ADHESIVES 517

Table 11. Properties of Polyarylene Ethers. 74

R R

H
Ar R 1Iinh' dLlg M D , glmole Tg , ·C

-©-~--©-~--©- 0.95 28,300 223

-©-~--©-M--©- CH 3 1.24 257

o ~ 0 C-©- H
0

-©-o--©-" 1.7 39,900 243

-OJ--©-<>-©-J--©- H Insoluble 231

H
0

-©-too -©- J 1.29 252

-©-~--©- H 1.00 34,000 252

-©-~--©- CH 3 0.37 294

-©-S02--©- H 0.67 26,700 280

-©-S~--©- CH 3 0.64 310

518 HANDBOOK OF ADHESIVES

Table 12. Ti/Ti Tensile Shear Strength of Polyarylene

_Ethers. 77 ••
Tensile Shear Strength, psi (Fai.lure Mode)
Linear Polyarylene Ethynyl Terminated PAE
Test Condition Ether (PAE) (M. -4000 g/mole)

25°C 5450 (coh) 4300 (mixed)

93°C 4550 (coh) 4200 (mixed)
150°C 3500 (coh) 3800 (mixed)
25°C after 72 hr soak 1500 (-50% coh) 4400 (mixed)
in hydraulic fluid
aPasa-JeU 107 surface treatment, RT to 260°C under 50 psi, held at 260°C 0.5 hr.

All00 finish) containing 0.5 % volatile content No aging and subsequent testing were per-
were 343 D C under 100 psi for 1 hour. The time formed beyond those in Table 13. Resorcinol
at temperature could be reduced to a few min- dicyanate is one of many examples where ex-
utes since this polymer is a thermoplastic (no cellent potential was demonstrated but no fur-
chemical reaction during the bonding cycle). ther results are available. Problems such as
No polyarylene ethers are currently commer- availability, toxicity, moisture and solvent re-
cially available that can be classified as high sistance, low shelf life, processability, etc.
temperature adhesives. often discourage further adhesive develop-
ment. Resorcinobdicyanate is unavailable but
Other Polymers a few other dicyanates are commercially avail-
able. 78 No adhesive properties have been re-
Although many organizations have been in-
ported on these dicyanates. The adhesive work
volved in high temperature adhesive develop-
on resorcinol dicyanate is representative of
ment for captive use and as a service to their
company funded research that is not readily
customers, most of this information is proprie-
available to the public.
tary and the remainder is seldom published. An
In addition to the high temperature polymers
example of a promising adhesive with the po-
discussed as adhesives, many other high tem-
tential for high temperature application is the
perature polymers have been reported. How-
cured resin from 1,3-dicyanatobenzene (resor-
ever, no adhesive work on these other polymers
cinol dicyanate) as shown in Eq. (7):
have been reported. Information on the chem-
istry and properties of these polymers can be
I found in various sources (e.g., Refs. 79-81).
°
.-.L
Adhesive work on some of the more promising
(7) polymers such as the polyquinolines, polyquin-
NCO--1T0CN ~ NON azolinediones and highly phenylated polyi-
~ f-~~o-f mides may not have been performed because of
the problems (e.g., high melt viscosity or vol-
Preliminary adhesive properties are presented atile evolution) which have plagued other high
in Table 13. Double lap TSS were used with temperature polymers.
stainless steel and Ti adherends whereas single
lap specimens were used with aluminum ad-
Concluding Remarks
herends. The peel moment encountered in test-
ing TSS is essentially eliminated in double lap Although several polymers have shown poten-
specimens. Therefore, brittle materials gener- tial for use as high temperature adhesives, they
ally exhibit significantly higher strength in dou- exhibit certain shortcomings such as limited
ble lap specimens than in single lap specimens. flow which necessitates the use of high tem-
As shown in Table 13, the strength of TSS at peratures and pressures, volatile evolution
232 DC after 233 hours at 232 DC was excellent. which leads to processing problems and fre-
 HIGH TEMPERATURE ORGANIC ADHESIVES 519

Table 13. Tensile Shear Strength of Resorcinol Dicyanate

Resin. 77 •a
Adherend
(Surface Treatment) Test Conditions Strength, psi
2024 TS Alb 26°C 5940
(Dichromate etch) 216°C 5490
216°C after 233 hr at 232°C 4470

17-7 PH SSe 26°C 5720

(Phosphate etch) 232°C 5680
232°C after 233 hr at 232°C 5560

8-1-1 W 26 5260
(Phosphate fluoride 177 5340
etch)
'Cured 1.5 hr at 177°C, 0.25 hr at 232°C, 1 hr at 288°C under 20 psi.
·Single lap specimens.
'Double lap specimens.

quently low strength, and high cost which dis- high speed commercial transports (fonnerly
courages their use except in specialty high called supersonic transports) may occur. These
perfonnance applications. To improve the state two areas offer the potential of a sizable market
of high temperature adhesives, research should for high temperature structural adhesives. In
be directed towards the following important addition, as improvements in processability and
items. perfonnance are made in higher temperature
adhesives, larger markets will develop which
• Better processability from volatileless sys-
will lower the cost and stimulate the use of high
tems.
temperature adhesives in other applications.
• In situ polymerization route to high Tg ,
solvent resistant, tough polymers without
volatile evolution. REFERENCES
• More durable higher temperature perfonn-
1. Vogel, H., and MaNel, C. S., 1. Polym. Sci., 50, 511
ing polymers. (1961).
• Better surface preparation of adherends, 2. Ward, B. C., Soc. Mfg. Eng., Fab. Composites Conf,
particularly Ti and composites. Baltimore, MD, Sept. 9, 1986, Paper No. EM-86-704.
• Better quality control of surface treatment 3. Powers, E., Celanese Specialty Operations, Char-
lotte, NC, personal communication.
process.
4. Levine, H. H. (to Whittaker Corporation), U.S. Pat-
• Innovative low cost process to prepare ad- ent 3,386,969 (1968).
hesive tapes and fabricate bonded struc- 5. Levine, H. H., in "Encyclopedia of Polymer Science
tures. and Technology," H. F. Mark, N. G. Gaylord, and
• Better nondestructive evaluation tests. N. W. Bikales, eds., Vol. 11, p. 188, New York, In-
tersciences Publishers Inc., 1969.
• Lower cost high temperature adhesives.
6. Levine, H. H., et aI., AFML-TR-64-365, Pt. 1, vol.
As mentioned previously in this article, a 1, Dec. 1963.
7. Technical Bulletins, Acurex Corporation/ Aerotherm
single adhesive system cannot perfonn in all
Division, Mountain View, CA 94039; PBI prepoly-
the different applications because the require- mers 2801 and 2803, PBI 1850 laminating material
ments vary significantly. As a result, high tem- and PBI 850 adhesive.
perature adhesive systems are often developed 8. Celazole® PBI Technical Bulletins, Celanese Spe-
for a particular application. High temperature cialty Operations, P.O. Box 32414, Charlotte, NC
32414.
adhesive development during the last two dec-
9. Levine, H. H., Loire, N. P., and Delano, C. B.,
ades has been sporadic primarily because of a AFML-TR-67-63, 1967.
questionable market. New markets are devel- 10. Sayigh, A. A. R., Tucker, B. W., and Ulrich, H. (to
oping in the military arena and a new thrust in Upjohn Co.) U.S. Patent 3,708,439 (1973).
520 HANDBOOK OF ADHESIVES

11. Loudas, B. L. (to 3M), U.S. Patent 3,503,929 (1970). 39. Bower, G. M., and Frost, L. W., 1. Polym. Sci.,
12. Aponyi, T. 1., and Delano, C. B., Soc. Adv. Mati. A-I, 3135 (1963).
Proc. Eng. Ser. 19, 178 (1974). 40. Burgman, H. A., Freeman, J. H., Frost, L. W.,
13. deGaudemaris, G. P., and Sillion, B. J., 1. Polym. Bower, G. M., Traynor, E. J., and Ruffing, C. R., 1.
Sci., B2, 203 (1964). Appl. Polym. Sci., 12,805 (1968).
14. deGaudennaris, G., Sillion, B., and Preve, 1., Bull. 41. Bell, V. L., Stump, B. L., and Gager, H., 1. Polym.
Soc. Chim. France, 1793 (1964). Sci., Polym. Chem. Ed., 14,2275 (1976).
15. Stille, J. K., and Williamson, 1. R., 1. Polym. Sci., 42. Bell, V. L. (to NASA), U.S. Patent 4,094,862 (1978).
B2, 209 (1964). 43. Progar, D. J., and St. Clair, T. L., Natl. SAMPE Tech.
16. Wrasidlo, W., 1. Polym. Sci., A-2, 9, 1603 (1971). Con! Series, 7, 53 (1975).
17. Hergenrother, P. M., and Levine, H. H., 1. Appl. 44. St. Clair, A. K., and St. Clair, T. L., Sci. Adv. Mati.
Polym. Sci., 14, 1037 (1970). Proc. Eng. Series, 26, 165 (1981).
18. Hergenrother, P. M., and Levine, H. H., 1. Polym. 45. Hendricks, C. L., and Hill, S. G., in "Polyimides,"
Sci. A-I, 5, 1453 (1967). K. L. Mittal, ed., Vol. 2, p. 1103, New York, Plenum
19. Hergenrother, P. M., "Polyquinoxalines," in "En- Press, 1984.
cyclopedia of Polymer Science and Engineering, H. 46. Hendricks, C. L., and Hale, J. N., in Welding, Bond-
F. Mark, N. M. Bikales, C. E. Overberger, and ing, and Fastening 1984 Symposium Proceedings,
Menges, eds., Vol. 13, p. 55, New York, John Wiley NASA Conference Publication 2387 (1985), p. 351.
& Sons, Inc., 1988. 47. Johnston, N. J., and St. Clair, T. L., IntI. SAMPE
20. Hergenrother, P. M., 1. Macromol. Sci.-Revs. Ma- Tech. Con! Series, 18,53 (1986).
cromol. Chem., C6(1), 1 (1971). 48. Hergenrother, P. M., Wakelyn, N. T., and Havens,
21. Hergenrother, P. M., Polym. Eng. Sci., 16(5), 303 S. J., 1. Polym. Sci., Pt. A, Polym. Chem. 25, 1093
(1976). (1987).
22. Hergenrother, P. M., and Progar,. D. J., Adhesives 49. Hergenrother, P. M., and Havens, S. J., SAMPE 1.,
Age, December issue, 38 (1977). 24(4), 13 (1988).
23. Hergenrother, P. M., SAMPE Quart., 3,1 (1971). 50. Harris, F. W., Beltz, M. W., and Hergenrother, P.
24. Hendricks, C. L., and Hill, S. G., SAMPE Quart., M., Inti. SAMPE Conf. Series, 18,209 (1986).
12, 32 (1981). 51. Hanky, A. 0., and St. Clair, T.L., Soc. Adv. MatI.
25. Kovar, R. F., Ehlers, G. F. L., and Arnold, F. E., Proc. Eng. Series, 30, 912 (1985).
Polym. Prepr., 16(2),247 (1975). 52. American Cyanamid Co., Bloomingdale Products,
26. Hergenrother, P. M., Div. Org. Coat. Plast. Chem. Havre de Grace, MD 21078.
Prepr., 36(2), 264 (1976). 53. Mitsui Toatsu Chemicals, Inc., New York NY 10017.
27. Hergenrother, P. M., Polym. Eng. Sci., 21(16), 1072 54. Serlin, I., Lavin, E., and Markhart, A. H., "Aro-
(1981). matic Polyimide Adhesives and Bonding Agents," in
28. Hergenrother, P. M., Macromolecules, 14, 891 "Handbook of Adhesives," I. Skeist, ed., 2nd Ed.,
(1981). p. 597. New York, Van Nostrand Reinhold Company,
29. Hergenrother, P. M., Macromolecules, 14, 898 1977.
(1981). 55. Bilow, N., Landis, A. L., and Miller, L. J. (to Hughes
30. Hergenrother, P. M., 1. Appl. Polym. Sci., 28, 355 Aircraft Co.), U.S. Patent 3,845,018 (1974).
(1983). 56. Landis, A. L., Bilow, N., Boschan, R. H., Lawrence,
31. Hergenrother, P. M., paper presented at the 1984 In- R. E., and Aponyi, T. J., Polym. Prepr., 15(2), 533
ternational Chemical Congress of Pacific Basin Soci- and 537 (1974).
eties, Honolulu, Hawaii, December, 1984. 57. Bilow, N., Landis, A. L., and Aponyi, T. J., Sci.
32. Edwards, W. M. (to DuPont), U.S. Patent 3,179,614 Adv. Mati. Proc. Eng. Series, 20, 618 (1974).
and 3,179,634 (1965). 58. Bilow, N., and Landis, A. L., Natl. SAMPE Tech.
33. Endrey, A. L. (to DuPont), U.S. Patents 3,179,631 Con! Series, 8, 94 (1976).
and 3,179,63 (1965). 59. Hergenrother, P. M., and Johnston, N. 1., Div. Org.
34. Gibbs, H. H., and Breder, C. V., Polym. Prepr., 15 Coat. Plast. Chem. Prepr., 40,460 (1979).
(1),775 (1974). 60. National Starch and Chemical Corporation, Bridge-
35. Sroog, C. E., "Polyimides," in "Encyclopedia of water, NJ 08807.
Polymer Science and Technology, H. F. Mark, N. G. 61. Bilow, N., Landis, A. L., Boschan, R. H., and
Gaylord, and N. M. Bikales, eds., Vol. 11, p. 247, Fasold, J. G., SAMPE1., 18(1),8 (1982).
New York, John Wiley and Sons, Inc., 1969. 62. Kuhbander, R. J., and Aponyi, T. J., Natl. SAMPE
36. Adrova, N. A., Bessonov, M. I., Lavis, I. A., and Tech. Con! Series, 11,295 (1979).
Rudakov, A. P., "Polyimides-A New Class of Ther- 63. Landis, A. L., and Naselow, A. B., Natl. SAMPE
mostable Polymers," Stamford, CT, Technomic Pub. Tech. Con! Series, 14,236 (1982).
Co., 1970. 64. Gay, F. P., and Berr, C. E., 1. Polym. Sci. A-I, 6,
37. Bessonov, M. I., "Polyimides-Class of Thennally 1935 (1968).
Stable Polymers," Leningrad, USSR, Nauka, 1983. 65. Lubowitz, H. R. (to TRW Systems), U.S. Patent
38. Mittal, K. L., "Polyimides," Vols. 1 and 2, New 3,528,950 (1970).
York, Plenum Press, 1984. 66. Serafini, T. T., Delvigs, P., and Lightsey, G. R., 1.
 HIGH TEMPERATURE ORGANIC ADHESIVES 521

Appl. Polym. Sci., 16, 905 (1972); (to NASA) U.S. 75. Hergenrother, P. M., Havens, S. J., and Jensen, B.
Patent 3,745,149 (1973). J., IntI. SAMPE Tech. Conf. Series, 18,454 (1986).
67. St. Clair, T. L., and Progar, D. J., Sci. Adv. MatI. 76. Terbilcox, T. F., Hill, S. E., and Hendricks, C. L.,
Proc. Eng. Series, 24(2), 1081 (1979). Final Report on NASA Contract NASI-15605, Phase
68. Amoco Performance Products, Inc., Bound Brook, NJ V, February 1987.
08805. 77. Gosnell, Rex B., Cape Composites, personal com-
69. ICI Americas, Inc., Wilmington, DE 19897. munication (work done at Whittaker Research and De-
70. Hendricks, C. L., Boeing Aerospace Co., personal velopment).
communication. 78. Interez Inc., Jeffersontown, KY 40299.
71. Minnesota, Mining and Manufacturing Co., St. Paul, 79. Reviews on particular polymers in "Encyclopedia of
MN 55144. Polymer Science and Technology, H. F. Mark, N. M.
72. Maximovich, M. G., Proceedings of 29th Annual Bikales, C. E. Overberger, and Menges, eds., 2nd
Conference, Reinforced Plastics/Composites Institute, Ed., New York, John Wiley and Sons, Inc., 1987 and
The Society of the Plastics Industry, Inc., section 1988.
18-C, p. 1 (1974). 80. Cassidy, P. E., "Thermally Stable Polymers," New
73. Maximovich, M. G., Lockheed Missile and Space York, Marcel Dekker, Inc., 1980.
Center, personal communication. 81. Critchley, J. P., Knight, G. J., and Wright, W. W.,
74. Hergenrother, P. M., Jensen, B. J., and Havens, S. "Heat-Resistant Polymers," New York, Plenum
J., Polymer, 29, 358 (1988). Press, 1983.
 30
Silicone Adhesive Sealants and
Abhesives
JOHNW. DEAN
General Electric Company
Silicone Products Division
Waterford, New York

Silicones are synthetic polymeric materials that linked elastomer from relatively low molecular
possess an extraordinarily wide range of phys- weight linear polymers by means of a chemical
ical properties. They can be low- or high-vis- reaction that forms these crosslinks and extends
cosity liquids, solid resins, or vulcanizable polymer chain length simultaneously. The re-
gums. As a class of substances, silicones are action is initiated at the time that the product is
characteristically very resistant to extremes of put into use. The principal advantage of this
temperature, to ultraviolet and infrared radia- concept is that low viscosity polymers can be
tion, and to oxidative degradation. They dis- employed in the formulation, resulting in prod-
play an unusual combination of organic and ucts that can be poured, spread, tooled, or oth-
inorganic chemical properties that are due to erwise applied very easily with little or no
their unique molecular structure of alternating molding equipment and without the need for
silicon and oxygen atoms; this polysiloxane external energy input in most cases.
chemical structure is common to all silicones. These materials are stable in storage for many
These versatile polymers can be com- months or years either as one-package or as
pounded with other chemicals and fillers into two-package systems. In general, many two-
an enormous variety of products that serve in a package systems tend to have longer shelf age
multitude of applications. This chapter will de- capabilities because the chemically reactive
scribe the product types, chemistry, and appli- components can be separated until the time of
cations of only one major class of silicone use. However, some one-component products,
products, the adhesive sealants. In addition, the such as the acetoxy sealants, also have excel-
class of silicone abhesive products will be de- lent shelf stability and remain useful for up to
scribed and discussed; these materials are em- three or four years after manufacture.
ployed where "release" characteristics are
desired, rather than adhesion.
Polymers
ROOM TEMPERATURE VULCANIZING
The fundamental component of most silicone
SYSTEMS
sealants is the polymeric siloxane referred to
The room-temperature-vulcanizing (RTV) con- earlier, most often a silanol-terminated
cept is centered on the development of a cross- poly(dimethylsiloxane):

522
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 523

phoric,9 nitric,9 selenic,1O boric, II and acti-

vated Fuller's Earth.'2.13 Most commonly,
(1)
some form of potassium hydroxide is employed
to prepare the higher-molecular-weight poly-
n mers, although other catalysts have specialized
applications. One final product of this complex
where n is about 300-1600. process is the silanol-terminated polymer de-
These polymers are made by an equilibration picted in Eq. (1).
process from other siloxanes as described be- When special properties are needed, other
low, and typically range in viscosity from about organic functional groups can be substituted for
2,000 cps to 150,000 cps. the methyl groups usually present in polysilox-
The industrial manufacture of siloxanes has anes; examples are other alkyls, phenyl, cy-
its beginnings with pure silicon, which is pul- anoethyl, and trifluoropropyl. For example, a
verized and allowed to react with methyl copolymer of dimethyl siloxane with about 5
chloride' in a pressurized fluid bed reactor in mole per cent of diphenylsiloxane affords an
the presence of a copper catalyst. Under care- elastomer that has a much lower brittle point,
fully controlled conditions, this reaction yields providing elastomeric properties down to
a mixture of methylchlorosilanes in which di- -130°F compared with the normal lower limit
methy ldichlorosilane predominates: of -65°F for all-dimethyl polymers.

CH3 CH3
Heat and .. CH3-~iCI + CI-~i-CI +
Catalyst I I
Under CH3 CH3
Pressure
Trimethylchlorosilane Dimethyldichlorosilane

CI CI
I I
+ CH -Si-CI + CI-Si-CI (2)
3 I I
CI CI
Methyltrichlorosilane Tetrachlorosilane

After separation and purification by distilla- Dimethyl silicone polymers are, because of
tion, the difunctional compound dimethyl di- their relatively low polarities, relatively com-
chlorosilane is then allowed to react with water patible with hydrocarbons and easily swollen
tQ form a hydrolyzate, which is a mixture of by fuels. Substitution for the methyl function-
cyclic and linear polydimethylsiloxanes. The ality by polar cyanoethyl and trifluoropropyl
linear components are low-molecular weight groups imparts significant polarity to these
hydroxyl (silanol) terminated polymers. elastomers and makes them resistant to swell-
This mixture can be condensed and equili- ing by nonpolar substances; these specialized
brated by a number of different catalysts, or the polymers can be compounded into very useful
cyclic siloxanes can be removed and polymer- adhesives and sealants for applications requir-
ized separately. Catalysts for these equilibra- ing fuel resistance.
tion reactions can be basic, such as the
hydroxides of lithium, 2 sodium, 2 potassium, 2
Crosslin king Systems
and cesium, 3 and potassium amide. 4 Some
acidic catalyst are sulfurics and ethylsulfuric, 6 In compounding silicone adhesive sealants, an
chlorosulfonic, 7 phosphoric, 8 pyrophos- essential ingredient is a crosslinking compo-
524 HANDBOOK OF ADHESIVES

nent that reacts with the ends of the polymer CH 3Si(OCH3h

chains to simultaneously lengthen them and Methyltrimethoxysilane
connect them laterally to form the crosslinked
network characteristic of an elastomer. A re-

ON~/CH'j
active poly functional silane is required, with
either three or four reactive groups available to
accomplish the necessary crosslinks: 23 ,24

A B
""C H 2 5 3

I I Methyl tris(methylethylketoximino) silane

R-Si-A B-Si-B
I I H
A B
CH 3Si(-N-C6H ll h
Trifunctional Silane Tetrafunctional Silane Methyl tris(cyclohexylamino )silane

Usually a catalytic agent is included, to fa- CH3

cilitate the reaction of the crosslinker with the I
polymer's silanol (hydroxyl) groups and with CH3Si( - N -COCH3h
water during the crosslinking reaction; some Methyl tris(N-methylacetamido)silane
that are commonly used are the tin soaps, alkyl
tin carboxylates,14 Si( -OC2 H5)4
Crosslinking occurs through the formation of Tetraethoxysilane
new siloxane: (Ethyl orthosilicate) (4)

In the global market, the acetoxy, methoxy,

I I and oxime curing systems are the commercially
-Si-O-Si- (3)
I I predominant curing chemistries for one-com-
ponent sealants. The tetrafunctional ethylor-
linkages that incorporate the silicon atoms of thosilicate is used in two-component
the crosslinker molecules, with the concomi- formulations.
tant release of the crosslinkers' organic func-
tional groups as simple molecules of (preferably Fillers
volatile) organic species, These low molecular
weight organic substances then evaporate from Many types of fillers have been employed for
the now-crosslinked polysiloxane which con- both one-package and two-package RTV prod-
stitutes the cured elastomeric sealant. ucts. They often serve to reinforce the polymer
Many organosilanes have been employed system to achieve significant improvements in
over the years as crosslinkers; speed of reac- strength by means of polymer-filler and filler-
tion, the nature ofthe byproducts, and cost have filler interactions. High surface area is a pre-
been major factors in the selection of systems requisite for any significant reinforcement and
for commercialization. Crosslinker silanes that the. most widely used filler is "fumed silica,"
have been employed are those that afford as by- formed in high purity by burning silanes in a
products alcohols,14-17 carboxylic acids, 18 high-temperature flame. Colorless, translucent
amines,19 ketoximes,2° aldoximes,21 and compounds are made with fumed silica or its
amides. 22 Examples of some of these organo- surface-treated versions. Carbon black (used to
silanes are shown below: reinforce organic rubbers) is another high-sur-
face area reinforcing filler effective in silicone
CH3Si(OCOCH 3h polymers, but has an obviously severe limita-
Methy ltriacetoxysilane tion of colorability. Silica-filled systems can be
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 525

easily made in any desired color with appro- ability that silicone adhesive compounds
priate pigments, and the industry standard is undergo with extremes in temperature. A typ-
consequently fumed silica. ical thixotropic silicone construction sealant can
Many other fillers are found in silicone ad- be applied with almost equal ease at room tem-
hesives, including some that provide very spe- perature or at subzero conditions, whereas or-
cific enhancements; an example is iron oxide ganic sealants typically, become extremely
for high-temperature resistance. Zinc oxide, viscous at low temperatures. The self-leveling
diatomaceous earth, some clays, and glass mi- materials are generally in the range of 10,000-
croballoons are other fillers sometimes used for 50,000 centipoises in viscosity. Thixotropic
specific purposes; there are other types of ad- paste sealants are measured in terms of their
ditives to impart special rheological properties, extrudability in grams per minute through a
such as thixotropes. Nonreactive silicone oils fixed orifice at a specified pressure; these val-
may also be included in the compound to act as ues are typically from 100 to 1000 grams per
plasticizers in the cured elastomer, and to im- minute through a ~" opening at 90 psig.
prove the extrudability of the uncured pastelike
sealant. Usually a compound will be composed ,Cure Characteristics
of several of these ingredients in varying
amounts, plus a few percent of pigments. Typ- It is possible to design a wide variation of cure
ical pigments are titanium dioxide, carbon speed into both the one-part and two-part sys-
black, and a wide variety of metal oxides, tems by choice of crosslinking chemistry and
chromates, sulfates, etc. in combinations to by varying the amount and type of catalytic
provide a range of colors to the finished prod- agent. The two-part systems normally contain
ucts. A major nonreinforcing filler often used their own water for hydrolysis of the cross-
in sealants is calcium carbonate, either with or linker and consequently are capable of deep-
without a surface treatment of stearic acid. section (over! inch) cures, gelling within a few
minutes with an active catalyst such as stan-
nous octoate, or in up to several hours with less-
PRODUCTS AND PROPERTIES active tin soaps such as dibutyl tin dilaurate.
One-part systems are packaged to remain an-
The great number of RTV silicone sealants
hydrous until dispensed, and depend upon at-
available from a growing group of manufactur-
mospheric moisture as a reactant to accomplish
ers around the world attests to the versatility of
the crosslinking reaction needed to cure them.
the technology, which is in continuous evolu-
The ultimate cure-through of a sealant bead can
tion. Silicone adhesive sealants began as exotic
take from 12 to 72 hours depending upon con-
high-priced materials in the 1960s; today the
ditions of temperature and humidity: a i II depth
pressures of competition and changing costs of
of sealant of one of the faster-curing systems
materials and processes allow silicones to com-
such as the acetoxy type will cure through at
pete in many markets formerly dominated by
25°C and 50% relative humidity in about 24
lower-cost organic sealants. The characteristics
hours. The slower curing systems may need 48-
of some typical silicone adhesive sealants will
72 hours for the same depth of cure. Exposure
be discussed in the following sections.
of the sealant surface to the atmosphere is re-
quired, and conditions of temperature and hu-
Rheology
midity are major factors affecting the rate at
Both the one-part and two-part sealants can be which the sealant will first form a rubbery skin,
made in a range of viscosities and rheologies, with subsequent progression of curing through-
from flowable and self-leveling to pastelike out the mass of sealant. Higher temperatures
thixotropic compositions that will not sag sig- and higher humidities accelerate the process.
nificantly when applied to a vertical surface. The products are also solventless, and therefore
Of particular usefulness to end-users is the have little shrinkage other than the small loss
relatively small change in viscosity or extrud- of cure byproducts.
526 HANDBOOK OF ADHESIVES

Package integrity is absolutely essential for and gasketing applications are developing, as
moisture-curing one-part sealants, in order to the advantages of this technology have become
ensure adequate shelf life. Whereas industrial apparent: relatively rapid, controlled cure rates
products tend to be used relatively promptly, in thick sections with relatively fast develop-
inventories of adhesive sealants marketed to ment of adhesion.
consumers through commercial distribution
often require that the product be usable for sev-
eral years. Aluminum squeeze tubes in small Weathering
sizes have been employed for decades success- Superior resistance to ozone and ultraviolet ra-
fully. Caulking cartridges evolved in the 1970s diation attack are inherent in the molecular
from the former spiral-wound foil laminate type structure of silicone polymers, making unnec-
to the present plastic caulker which is the in- essary the use of the additives employed to mit-
dustry standard for silicone adhesive sealants igate this weakness in many organic polymers
for both industrial and consumer packaging. used for sealants. Silicone elastomeric adhe-
For the industrial user, the sealants are also sive sealants perform without cracking and
packaged in plastic and steel pails and drums, shrinkage in long-term exposure to outdoor
with seals that are impervious to moisture. weathering in all climates, properties which en-
Two-part RTV elastomers were the earliest hance their usefulness as construction sealants
room-temperature-vulcanizing silicones and for commercial waterproofing and glazing, and
were designed to be primarily potting com- for similar purposes in the consumer market.
pounds, not adhesives. One package contained Their great durability obviates the need for fre-
a mixture of silanol-terminated polymers plus quent rehabilitative work, more than offsetting
fillers and a typical crosslinking system of ethyl their higher initial cost. See Figs. 1 and 2.
silicate and water. This mixture was stable to
storage in the absence of catalytic agents, and
was caused to crosslink (cure) when a small Strength and Elongation Properties
percentage of a tin soap (part two of the sys-
Early two-part RTV silicones were relatively
tem) was mixed in at the point of use. Within
low-strength materials with generally nonrein-
recent years, this basic system has been devel-
forcing filler systems. Most of these were used
oped into two-part adhesive sealants of greater
as potting compounds for protection of electri-
chemical complexity with considerable and
cal devices where strength and elastomeric be-
growing industrial importance.
havior were of little importance.
The second part of the two-part system may
With advent of one-part adhesive sealants and
now contain the crosslinker in some cases, plus
their development over the past quarter cen-
organofunctional silanes that serve as adhesion
tury, much progress has been made in design-
promoters and catalytic agents. The ratios of
ing products to perform over a range of property
the two components are often about ten or more
profiles to suit the requirements of specific ap-
to one, and automatic equipment enables the
plications. Three general categories may be de-
mixing and dispensing of these products to be
fined rather arbitrarily based on low, medium,
done with considerable precision. Two-part
and high strengths; see Table 1. These cate-
sealant technology is employed to make fac-
gories of sealants find use as follows:
tory-produced insulated glass windows, in
which the silicone adhesive sealant provides the • Low strength, low-modulus adhesive seal-
secondary perimeter seal for the double-glazed ants are used in building construction
window unit. This type of product is also often waterproofing applications where maxi-
used as the structural adhesive that bonds such mum extensibility is required in expansion
insulated window units to their supporting joints to accommodate movement. They
frames during the fabrication of factory-glazed maintain the seal by stretching easily
window assemblies. Other industrial adhesive without losing adhesion to the substrates.
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 527

Fig. I. Shop glazing of insulated glass units.

Fig. 2. Waterproofing high-rise building expansion joints.

528 HANDBOOK OF ADHESIVES

Table 1. Strengths of RTV Silicone Table 2. Thermal Stability of a High

Adhesive Sealants. Temperature One-Part Sealant.
Low Medium High 7 Days
Tensile strength, psi 100-200 250-600 600-1200 Exposure Original @480°F @600°F
Elongation, % 100-1200 100-700 300-1000
Tensile strength, psi 350 390 420
Hardness, Shore A 10-30 20-60 25-60
Elongation, % 400 540 300
Tear strength, lb.lin. 10-20 20-S0 SO-200
Hardness, Shore 33 2S 45
Tear strength, lb.lin. 50 43 40

• Medium-strength products tend to meet the

needs of general purpose construction, in- tance to high voltage ionization as well as ex-
dustrial and consumer applications. They tremely good corona discharge resistance.
provide a balance of strength, adhesion, Silicone elastomeric adhesives and sealants re-
and elastomeric properties for a broad tain their useful electrical properties at elevated
range of uses as both adhesives and as temperatures because of their lack of degrada-"
sealants. tion compared to many organic materials under
• High strength one-part sealants often em- similar oxidative conditions.
ploy more highly treated fumed silica for
Typical RTV silicone elastomer electrical
reinforcement, and are made with both properties are shown in Table 3.
acetoxy and alkoxy crosslinking systems.
These products frequently find applica-
tions in the aerospace industry where high- APPLICATIONS
performance adhesives and sealants are Because of their unique durability and elasto-
required; silicone adhesives are often the meric adhesive capabilities, silicone adhesive
most effective materials for bonding heat- sealants have secured increasing market share
cured silicone rubber gaskets to other sub- in a wide variety of applications in the indus-
strates. trial,25 construction,26 and consumer markets.
Over the past 25 years, they have lost catego-
Thermal Properties rization status as exotic specialty materials
Silicone elastomers are well known for their whose cost was justified only by lack of high-
superior resistance to elevated (and reduced) performing alternatives. A combination of
temperatures, with little or no loss of proper- higher organic materials costs and lower sili-
ties. Again, the siloxane polymer structure is cone manufacturing costs has, over the most
responsible for properties not seen in carbon- recent decade, made silicone adhesives and
based polymers; one reason is the inherent flex- sealants very cost-competitive for a large num-
ibility of the siloxane molecule, and another is ber of application areas, particularly when con-
its greater resistance to oxidative degradation. sidered in the light of the superior properties
When these basic properties are enhanced with that enhance their total cost-effectiveness. In-
appropriate heat-resistant fillers and additives dustrial applications in particular seem to ex-
(often iron oxide), a high temperature elasto- pand limitlessly as new demands for high-
meric adhesive can be made that will withstand performance adhesive products continue to ap-
heating in air for up to a year at 400°F without pear.
significant property losses. Resistance to even
higher temperatures can be achieved for shorter
Table 3. Typical RTV Silicone Elastomer
times, as shown in Table 2.
Electrical Properties.
Volume resistivity, ohm-em 3 X lOIS
Electrical Properties
Dielectric strength, volts/mil at 75 mil 500
The low polarity of silicone elastomers confers thickness
excellent electrical insulation properties to these Dielectric constant @60 Hz 2.S
Dissipation factor @60 Hz 0.0026
compounds, enabling them to have great resis-
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 529

Industrial Adhesives and Sealants

One-component RTV sealants can be used to

form both adherent and nonadherent gaskets
that will withstand the extremes of the auto-
motive engine environment. The automotive
industry has for many years employed RTV sil-
icones for oil-pan, valve-cover, water-pump,
and many other sealing applications directly on
engines where silicones' property advantages
are needed. The valued properties are high-
temperature durability, dimensional stability
with age, minimal shrinkage during cure, adhe-
sion to metal surfaces where required, and oil
resistance. Of very great importance is the ease
of application of these pastelike RTV s that will
conform to surface irregularities and fill gaps
that rigid, preformed, organic composition gas-
kets cannot; the need for finely machined sur-
faces is thereby reduced. The material is
applied with automated robotic dispensing
equipment, pumped from pails or drums. See
Fig. 3. Aside from engines, gasketing with
RTV silicone sealants is done on lens assem-
blies, transmission housings, rear axle covers Fig. 3. Automated application of industrial sealant as
and other mechanical assemblies where loss of automotive gasket.
grease or fluid or the prevention of intrusion of
the elements is required. tronic assemblies perfectly without shrinkage
Many other minor automotive applications when applied either as conformal coatings or
exist for RTV adhesives, such as fastening mir- as encapsulants. The usual cure system for
rors and exterior trim in place; again the shock- these products is a platinum-catalyzed addition
absorbing nature of the RTV elastomeric ad- reaction between vinyl and hydrogen groups on
hesives as well as their long-term stability and the siloxane molecules without the formation
weatherability are very desirable attributes in of any by-products; the reaction is initiated by
an environment of frequent temperature varia- heating rather than by exposure to atmospheric
tions and constant vibration. A significant af- moisture characteristic of the one-component
termarket exists for caulkers and collapsible sealant cure systems described above. Another
tubes of the same products for use as repairma~
terial for gaskets when units are disassembled
for repair, then regasketed for reassembly. An-
other automotive aftermarket application is for
windshield gasketing when broken glass is re-
placed. See Fig. 4.
Two-component RTVs also have major au-
tomotive applications that take advantage of
their superior electrical properties. All modem
automobiles make use of electronic modules
where protection is essential against shock,
heat, water and dirt. Clear silicone potting gels
serve these needs very well, and are widely Fig. 4. Aftennarket waterproofing of replacement wind-
used for this purpose; they conform to the elec- shield.
530 HANDBOOK OF ADHESIVES

unique two-component silicone product used by Specialized products are also made available
some auto manufacturers is a gel that is cured by the major manufacturers to meet both gen-
within the mechanical parts of a bumper system eral-purpose and very specific requirements.
to provide a shock-absorber for low-speed col- Por example, as mentioned earlier, the contin-
lision protection. uous service temperature of an RTV sealant can
Beside the many automotive uses, one-com- be elevated to 550-600 o P by compounding
ponent RTV products are applied in almost with iron oxide. RTV cure systems may exude
every segment of industry in which they can either mildly acidic (acetic acid), neutral
perform the functions of adhesives or as seal- (methanol), or alkaline (cyclohexylamine) by-
ants and gaskets. As with the automotive ap- products, some of which may be contraindi-
plications, some end users dispense and apply cated in certain applications such as on
RTVs from 55-gallon drums and from pails electronic assemblies. There is a general trend
using pneumatic pumps; plastic cartridges of toward neutral curing sealants whose byprod-
the product can also be employed either with ucts of cure are noncorrosive and less irritating
power equipment or manually, and there are to workers than acetic acid and amines. At least
squeeze tubes for the smallest assembly and one sealant type is compounded to have low
sealing work. flammability, for applications (typically on air-
Many household appliances, from washing craft) where this property is particularly impor-
machines and steam irons to home electronic tant. Fuel-resistant adhesive sealants are made
products employ silicone adhesive sealants as by using the fluorosilicone polymers mentioned
gaskets, to encapsulate electrical connections, earlier; the higher polarity of these materials
and as general-purpose adhesives wherever confers resistance to swelling by hydrocarbon
good adhesion, electrical properties, tempera- fuels, a property that is particularly prized in
ture resistance, and longevity are required. Vir- many aircraft applications.
tually all home aquarium manufacturers employ
silicone sealants because of the excellent long-
Construction Sealants
term bonding to glass and good clarity of the
translucent products. The outstanding resistance of silicone polymers
In other manufacturing applications, flowa- to the effects of weathering that were men-
ble one-component RTV silicones are used to tioned earlier makes silicone sealants admira-
coat circuit boards and encapsulate packaged bly suited to construction applications for
electronic assemblies to isolate them from dirt, glazing and a wide variety of other waterproof-
heat, water, and vibrational damage. These ing functions. Generally medium- and low-
types of materials can be cut out and repaired modulus products have the greatest usefulness
if needed, as can be done with the gels de- since they are better able to withstand move-
scribed above. ment (both expansion and contraction) of the
Aerospace applications have always been ex- parts of the structure that are being bridged by
tensive and are still growing, due to the out- the sealant. Silicone sealants maintain their
standing resistance of these sealants to extremes elastomeric properties for decades without
of temperature and various forms of radiation. cracking, splitting, shrinkage, chalking, or
Sealants designed to emit virtually no volatile other degradation, in all types of climates.
components in the high-vacuum environment These sealants are also much more easily
of deep space are used to fasten solar panels in gunned and tooled at low temperatures than
place and to perform other sealing functions in their organic counterparts, and they display ex-
delicate satellite assemblies where stray con- cellent adhesion to a wide spectrum of ceramic,
densable contaminants must be avoided near metal, and plastic substrates commonly em-
sensitive optical and electronjc devices. Other ployed in the construction industry, and usually
sealants are used to fasten space shuttle tiles in without priming.
place and for other applications where the Because of their great elastic extensibility,
maintenance of elastomeric properties is essen- the lower-modulus sealants are able to maintain
tial over a wide range of temperatures. waterproofing integrity in expansion joints hav-
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 531

ing relatively large movement requirements, at keting such as on water pumps, thermostats,
both high and low extremes of temperature. valve covers, etc.
The use of two-component silicone sealants Household sealant products in caulkers are
as perimeter seals for insulated glass window used for myriad sealing, caulking and reglazing
units was mentioned earlier; recent trends in the purposes inside and outside the home, most
construction of curtain wall buildings are to- often for waterproofing any kind of exterior
wards the use of both two-part and one-part sil- seam or joint. Here again the longevity of the
icone adhesive sealants to bond these sealant and avoidance of repeat caulking is a
prefabricated glass panels to the metal elements major silicone sealant advantage for the con-
of a building's structure, so that they function sumer.
as structural adhesives in addition to acting as
weatherproofing sealants to prevent the intru- ABHESIVE ELASTOMERIC SILICONES
sion of air and water.
A very successful application of the weath- Crosslinked silicone polymer systems provide
ering resistance of silicones has been made in the basis for a large class of products that are
roofing, where sprayable silicone rubber coat- abhesive, or release agents, in contrast to the
ings have been applied for nearly twenty years adhesive products discussed above. Many use-
over a number of substrates, most notably po- ful applications exist for these materials, the
lyurethane foam. The foam is itself sprayed into most widely known one being silicone release
place to serve as thermal insulation, and is then coatings for labels, and for packaging and other
spray-coated with a fast-curing, two-compo- applications where one surface must be able to
nent, self-bonding RTV elastomer to protect the release from another adhesive-coated surface
system from weathering. Large structures can when required. RTV molding products consti-
be covered with a monolithic seamless roof in tute another major class of release-type prod-
this way, providing the benefits of energy con- ucts.
servation and long-lasting weatherproofing in A low-energy surface film is required for
one system. abhesion, and dimethylpolysiloxane films have
the lowest surface energy of any polymers ex-
cept the perftuoroethylenes. For that reason,
silicone surfaces are extremely capable of re-
Consumer Sealants
leasing pressure sensitive adhesives or other
The past decade has seen substantial growth in tacky materials. The adhesives discussed ear-
the consumer market for silicone sealants, dri- lier are usually compounded with adhesion-
ven by the lower cost of do-it-yourself repairs promoting polar additives and tend to develop
on houses, cars, and appliances. adhesive links to substrates during the cross-
New products have been developed beyond linking process; their cured exposed surfaces
the familiar acetoxy bathtub caulk and trans- nevertheless also show low surface energy, and
lucent general-purpose hobby glue; these tend are not easily adhered to by organic adhesives.
to be low-odor, neutral curing products de- A film of a cured silicone release agent may be
signed to adhere without primer to an ever envisioned as if the polar oxygen atoms of the
wider variety of substrates. They are made in a siloxane chains were oriented internally toward
number of colors and are generally available in the substrate, with a layer of low-polarity
aluminum squeeze tubes and plastic caulkers; methyl groups bonded to silicon atoms pre-
good packaging and shelf stability are impor- senting at the releasing surface of the film. This
tant for sealants in this market because of structure evidently prevails regardless of how
lengthy distribution paths. the silicone film is applied or cured.
The familiar bathtub sealant containing a
mildewicide is now on the market in a low-odor
Molding Compounds
version. A number of specialty automotive
products are available also, including high- RTV molding compounds take advantage of
temperature service products for engine gas- this release capability by enabling the exact du-
532 HANDBOOK OF ADHESIVES

plication of minute detail in parts cast in sili- parts to be cast and successfully demolded, still
cone rubber molds. Typically the RTV is ofthe with excellent reproduction of fine detail.
addition-cure type in which the siloxane chains
are extended and crosslinked by the chemical Release Coatings
addition reaction of an Si - H containing cross-
Release products are fundamentally reactive
linking polymer and a dimethylpolysiloxane
RTV products sold as two or more components
polymer terminated with vinyl groups:
that are mixed to form a coating bath. The
blended mixture is then coated onto a substrate
7"- Si- H + H2C=CH-Si(CH3h-O-etc. by one of a number of techniques that will en-
able the deposition of a uniform film of the de-
Pt sired thickness. The coated stock is then passed
Catalyst (5) through an oven with a suitable combination of
residence time and temperature that will cure
the silicone by completing the crosslinking re-
action with thermal energy.
This class of materials, regardless of the type
There are no chemical byproducts of this re- of cure chemistry employed, is referred to as
action, and the soluble platinum catalyst can be thermally cured, although in fact the curing re-
effective at as little as 5ppm concentration. Al- action does begin at room temperature as soon
though it is basically a room temperature cu- as the components of the product package (re-
rable two-part system, heat is customarily used active silicone polymers, crosslinkers, cata-
to accelerate the process for economic and pro- lysts, inhibitors, and sometimes dispersants) are
ductivity reasons. The RTV is mixed, poured mixed to form the coating bath. Such factors as
over a master, and heat-cured. Organic poly- polymer molecular weight, the use of a dis-
mer parts (polyurethanes, polystyrene, etc.) can persing medium, and the coating methods re-
then be poured in the silicone rubber mold and quired for a particular product package, are all
later easily released, with highly effective re- derived from the need to maintain the product
production of fine details. This type of molding as a coatable liquid in the coating pan while
product has found many uses in the furniture still enabling rapid crosslinking to occur after
industry for the production of intricate decora- application of the coating on the substrate.
tive simulated-wood parts, and in general for Thermally cured release coatings generally
molding a myriad of decorative items. An even employ either the vinyl-hydride addition cure
more flexible type of elastomeric molding com- chemistry described above for the molding
pound has been marketed that is based on sil- compounds27 or another fast-acting chemical
anol condensation cure chemistry rather than system based on the condensation reaction be-
the vinyl-hydride addition cure just described. tween a silyl hydride crosslinking polymer (of
These lower modulus products are designed to low molecular weight) and a silanol-terminated
be softer, with good tear resistance; these prop- polymer of the same type as described in the
erties allow even more intricate and undercut earlier section on adhesive sealants, but of a
much higher molecular weight:

CH3

I
SiO Si(CH3)3
(CH 3hSiO

H
I (6)

Silanol Polymer Methyl Hydrogen

(n greater than 4000) Silicone Polymer
for solvent-based products (m = 10 to 50)
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 533

The reaction for crosslinking is:

, / Tin Soap' /
-Si-OH
/ + HSi-
, -----"--
Catalyst , + H2t
-Si-O-Si-
/
(7)

Silyl hydride (SiH) groups are very reactive heated after coating, the inhibitor decouples
and the above-described condensation reaction from the catalyst and the crosslinking reaction
occurs with such ease that a catalyzed mixture proceeds rapidly.
of the two principal reactants will gell at room A very important feature of the solventless
temperature. Solvent dispersion of the mixture systems is that no thermal energy input is re-
is commonly used to overcome this reactivity quired for the evaporation of a solvent; all the
by dilution, and also to provide a means of heat goes into the curing reaction. A second
coating what would otherwise be a very high major advantage is that no solvent-recovery
viscosity polymer mixture onto the substrate. equipment is needed, which avoids both a con-
Release systems based on this condensation siderable capital expense and a significant en-
cure chemistry are commonly sold as two-part vironmental regulatory concern.
packages. One (A) is a high-solids solution of The force required to separate an adhesive
the silanol-terminated high viscosity polymer from a silicone release coating can be modified
(commonly called a gum) plus the methylhy- over a wide range by varying the polymer sys-
drogen crosslinker. The second part (B) is a so- tern's molecular weight characteristics. Elas-
lution of the tin soap catalyst. Further dilution tomeric coatings formed from densely
of the A and B mixture is then done with more crosslinked low molecular weight polymers
solvent to achieve an approximate 5-10% sol- tend to have harder, more resinlike character-
ids content; the bath is then adequately coat- istics that allow easier release of adhesives.
able by techniques such as reverse roll, roto- Coatings derived from high molecular weight
gravure, metering rod, or doctor blade. gums with more widely spaced crosslinks tend
To raise the solids content or to render the to be more rubbery in character and to be less
system totally solventless, the molecular weight abherent, consequently requiring more force for
(and viscosity) of the silanol polymer must be separation (higher release types). A fairly re-
drastically reduced, but the working life of such cent innovation in solventless systems has been
a solventless system becomes only a few min- the separation of these systems into their com-
utes at room temperature. This becomes im- ponents, for sale as packages of tight release
practical, and since there is no known means polymer, easy release polymer with catalyst,
of inhibiting the tin soap catalyst (necessary for inhibitor, crosslinker and easy release polymer
completion of the thermal crosslinking reac- alone; the converter is thus provided with a
tion), other chemical systems are needed for greater degree of flexibility to formulate a coat-
truly solventless coatings. ing bath to meet his particular needs by tailor-
Solventless release coating systems are where ing cure rate, bath life, and release
the vinyl-hydride addition chemistry shown in characteristics for his particular application.
Eq. (5) becomes of great value because of its Since release coatings are now ubiquitous in
versatility. First, the polymer's molecular many familiar packaging and labelling appli-
weight (hence viscosity) can be reduced to the cations, the number of substrates to which they
low values required for coating without solvent are applied has also multiplied. One of the most
dilution. The noble metal catalyst (platinum- or common ones is supercalendered kraft paper,
rhodium-derived) is dissolved in it, along with upon which coatings are usually deposited at
a chemical which inhibits its activity at room the rate of about a gram per square meter to
temperature. Thus when a coating batch is give good coverage. There are now many non-
made by mixing in the methylhydrogen cross- porous films to which silicone release coatings
linker before use, the blend is stable at room are applied, including a variety of plastic films:
temperature so as to provide an acceptable pot polyethylene and polyethylene terephthalate are
life not possible without the inhibitor. When typical.
534 HANDBOOK OF ADHESIVES

The selection of a coating system can be place for release coatings that are curable with
complicated by a number of considerations. low energy expenditure, have lower space re-
The temperature and time of cure has to be con- quirements for processing, allow higher line
sidered versus the heat stability of the substrate speeds, and application to thermally sensitive
plastic or paper. The degree of dimensional substrates.
change and/or moisture loss of the substrate
during cure at a particular time and temperature
profile is a factor, also. Another consideration REFERENCES
is the tendency of the uncured coating to pen-
etrate the substrate before and during cure,
1. Rochow, E. G. (to General Electric Co.), U.S. Patent
which is also related to the attainability of a 2,380,995 (Aug. 7, 1945).
pinhole-free coating for efficient release. 2. Hyde, I. F. (to Dow Coming Co.), U.S. Patent
2,490,357 (Dec. 6, 1949).
3. Hurd, D. T., and Osthoff, R. C. (to General Electric
Co.), U.S. Patent 2,737,506 (Mar. 6, 1956).
Radiation-Curable Coatings 28 •29 4. Hurd, D. T., Osthoff, R. C., and Corrin, M. L., J.
Amer. Chern. Soc., 76,249 (1954).
Majot silicone suppliers have been developing
5. Patnode, W. I., and Wilcock, D. F., J. Amer. Chern.
radiation-curable coatings for some time now; Soc., 68, 358 (1946).
the solventless systems lend themselves to this 6. Andrianov, K. A., Dzhenchelskaya, S. I., and Pe-
approach since all the space radiant energy can trashkov, Y. K., Soviet Plastics, Plast. Massy, No.3,
be directed at the polymer system for curing, 20 (1960).
and none wasted for solvent evaporation or in 7. Marsden, I., and Roedel, G. F. (to General Electric
Co.), U.S. Patent 2,469,883 (May 10, 1949).
the substrate. The energy source referred to 8. Warrick, E. L., and McGregor, R. R. (to Dow Com-
may be either ultraviolet or electron-beam ra- ing Co.), U.S. Patent 2,435,147 (Ian. 27, 1948).
diation, and the objective is a very rapid "zero- 9. Hurd, D. T.,J. Amer. Chern. Soc., 77(2),998 (1955).
temperature" controllable cure, with much of 10. Reiso, N., and Yushi, K. K., Iapanese Patent 3,738
the control occurring through the intensity of (Jan. 19, 1955).
11. Warrick, E. L., and McGregor, R. R. (to Dow Com-
the source. ing Co.), U.S. Patent 2,431,878 (Dec. 2, 1947).
However attractive in principle, there are 12. Britton, E. C., White, H. C., and Moyle, C. L. (to
certain inherent drawbacks in this chemistry Dow Chemical Co.), U.S. Patent 2,460,805 (Feb. 8,
that might prevent radiation-curable silicones 1949).
13. Knopf, H., Beerwald, A., and Brinkmann, G. (to Far-
from making more than modest inroads into the
benfabriken Bayer Co.), West Germany Patent 957,
markets for thermal-cure products. There is a 662 (Feb. 15, 1954).
necessity for a high concentration of radiation- 14. Berridge, C. A. (to General Electric Co.), U.S. Patent
sensitive organic functionality in the radiation- 2,843,555 (July 15, 1958).
curable polymer systems, for standard silicone 15. Nitzsche, S., and Wick, M., Wacker-Chemie Co.,
U.S. Patent 3,127,363 (Mar. 31, 1964) (West German
polymers are not sensitive to UV or EB radia-
Application-Aug. 5, 1955).
tion in economically useful doses. Silicone pol- 16. Weyenberg, D. R., Dow Coming Co., US Patent
ymers modified with the necessary acrylate, 3,334,067 (Aug. 1, 1967).
epoxy, or mercaptan functional groups are more 17. Smith, S. D., and Hamilton, S. B. (to General Electric
expensive; furthermore organic photosensitiz- Co.), U.S. Patent 3,689,454 (Sept. 5, 1972).
18. Ceyzeriat, L. (to Rhone-Poulenc Co.), U.S. Patent
ers are needed in significant quantities, and
3,133,891 (May 19, 1964) (French application-Iuly
these are generally poorly soluble in silicones. 12, 1957).
Polar organic constituents tend also to raise re- 19. Nitzsche, S., and Wick, M., Wacker-Chemie Co.,
lease values and to render the cured coatings U.S. Patent 3,032,528 (May 1, 1962) (West German
more susceptible to instability in contact with Application-Feb. 20, 1959).
certain agressive adhesives. 20. Sweet, E., Dow Coming Co., U.S. Patent 3,189,576
(Iune 15, 1965).
Nevertheless, chemical and engineering work 21. Boissieras, I., Ceyzeriat, L. F., and Lefort, M. I. C.
is continuing in this area in an attempt to take (to Rhone-Poulenc Co.), French Patent 1,432,799
advantage of the opportunities in the market- (Mar. 25, 1966).
 SILICONE ADHESIVE SEALANTS AND ABHESIVES 535

22. Golitz, D., Damm, K., Muller, R., and Noll, W. (to 25. Klosowski, J. M., "Silicone Sealants as Adhesives,"
Farbenfabriken Bayer Co.), U.S. Patent 3,417,047 14th National SAMPE Technical Conference, 1982.
(Dec. 17, 1968) (West German Application-Feb. 6, 26. Wilson, R., "Silicone Glazing Gaskets," Elastomer-
1964). ics, 120 (5), 12 (1988).
23. Noll, W., "Chemistry and Technology of Silicones," 27. Eckberg, R. P., "High Solids Coatings," 8(1), 17
2nd Ed., New York, Academic Press, Inc., 1968. (1983).
24. Klosowski, J. M., and Gant, G. A. L., "The Chem- 28. Eckberg, R. P., "Radcure 84 Conference Proceed-
istry of Silicone Room Temperature Vulcanizing Seal- ings," Atlanta, GA (1984).
ants," A.C.S. Symposium Series 113, Washington, 29. Muller, U., Timpe, H. J., and Rasler, H., Plaste und
D.C., American Chemical Society. Kautschuk, 1987(5), 183.
 31
Organofunctional Silane Coupling
Agents
JAMES G. MARSDEN
Union Carbide Corporation
Specialty Chemicals Division
Tarrytown, New York

The development and increasing use of organ- have made them obvious candidates as rein-
ofunctional silanes has closely pilralleled the forcements for organic polymers; however, the
growing use of composite materials in expand- function of particulate fillers has evolved with
ing and diverse applications. From the crude time. Originally, except for the use of selected
laminates developed to meet the material short- fillers as reinforcements for elastomers, fillers
ages of World War II, composite materials have were used to control rheology and to lower the
evolved into sophisticated products that are re- cost of the composite. More recent develop-
quired to meet ever increasing performance de- ments have shown that fillers can, particularly
mands. In addition to providing a wide range with surface modification, make positive con-
of mechanical properties, many of today's tributions to composite properties while contin-
composites are asked to furnish specific elec- uing to affect rheology and costs.
trical characteristics, lend themselves to var- Common to all of the composites discussed
ious fabrication techniques, maintain their is a large interfacial area between the organic
properties after exposure to hostile environ- polymer and the fiber and/or filler. To optimize
ments, and accomplish this in an economically both the ease of fabrication and the resulting
viable manner. The challenge is indeed great. composite properties, it is necessary that as a
The composites of this discussion are com- minimum the organic polymer wet the fiber or
binations of organic polymers and glass fibers filler surface and ideally that it bond to it. This
and/or particulate fillers. Included among the chapter is concerned with the use of organo-
useful organic polymers are both thermosetting functional silicon compounds to promote the
and thermoplastic resins and elastomers. Glass wetting of the fiber/filler surface, establish
fibers are used in many forms including contin- bonds between the polymer and the fiber/filler,
uous roving, chopped strand, mat, and woven and retain these bonds under a hostile environ-
fabric, the choice indicated by fabrication ment.
method and/or property requirements. The par-
ticulate fillers encompass a wide range of ma- THEORY .
terials including refined natural minerals and
synthetic products. Prominent among these are The matrix resin of a modem mineral rein-
clays, silicates, and silicas. forced organic resin composite serves many
The high strength and modulus of glass fibers functions. It influences the method used to fab-
536
 ORGANOFUNCTIONAL SILANE COUPLING AGENTS 537

ricate the composite, it limits the environment characteristic enables groups at one end of the
in which the composite may be used (solvent molecule (usually chloro, alkoxy, or acetoxy)
resistance, ozone resistance, etc.), it limits use- to hydrolyze, and form silanols (SiOH), which
ful temperature range (oxidation, depolymer- are then able to condense with similar groups
ization), and it influences the economics ofthe on glass or other siliceous substrates. In· the
composite. However, its most critical function case of metals, or other nonsiliceous sub-
is to transfer stress applied to the composite to strates, condensation of SiOH with metal ox-
the high modulus mineral phase. In order to ef- ides or hydrolysis of ester groups with
ficiently transfer stress from the low modulus monolayers of water on the surface is possible.
matrix resin to the high modulus mineral rein- At the other end of the silane molecule are or-
forcement, it is necessary that the matrix resin ganic groups, such as vinyl, methacryloxy,
adhere to the mineral reinforcement. In addi- amino, epoxy, or mercapto, which are able to
tion, if the composite is to have practical util- coreact with the organic matrix resin.
ity, the adhesion must be retained under typical The bridging of the interface between resin
use conditions, commonly high humidity and and reinforcement by a coupling agent provides
elevated temperatures. good adhesion, and the stability ofthe covalent
The absence of direct measurements at the linkage maintains this adhesion under high hu-
interface has led to considerable speculation as midity. It is recognized that good wetting is de-
to the preferred mechanism for improved inter- sirable, both to speed the fabrication of
facial adhesion. composites and to promote contact between the
Bikerman 1 contended that an adhesive failure various components, thus making the neces-
should be considered highly unlikely; that the sary chemical reactions more efficient.
intermolecular forces at an interface are One of the first comprehensive studies on the
stronger than the cohesive strength of either mechanism of silane reaction at the interface
component. was reported by Sterman and Bradley. 3 Their
Zisman2 emphasized the requirement that the work established three significant points: (1)
resin must wet the reinforcement to achieve the greater than theoretical monolayers of silane on
desired adhesion. He described the require- fiberglass were required to achieve optimum
ments of wetting as the surface tension of the composite performance because of the accu-
matrix resin being less than the surface energy mulation of silane in the capillaries between
of the reinforcement. These conditions would glass fibers, (2) silane coupling agents are te-
appear to be met by the use of most thermoset- naciously bonded to fiberglass when applied
ting matrix resins and untreated reinforcement from aqueous solution and dried, and (3) the
(heat cleaned fiberglass), yet these combina- chemistry of the organofunctional group on the
tions produce composites with lower mechani- silane must be matched with that of the matrix
cal properties, both dry and wet, than produced resin to develop optimum composite proper-
with silane treated reinforcement. A probable ties.
explanation is that the presence of water on the Plueddemann and co-workers4 confirmed this
surface of the untreated reinforcement inter- latter point when they published the perfor-
feres with or prevents complete wetting of the mance of a wide range of organofunctional si-
reinforcement by the matrix resin. lanes in both unsaturated polyester and epoxy
A different method for bonding dissimilar composites.
materials such as organic polymer and fibrous Marsden5 described the composition and per-
glass has developed in the field of reinforced formance of a series of organofunctional si-
and filled plastics. This approach utilizes a cou- lanes that provide amine reactivity but vary in
pling agent, i.e., a bifunctional material, that compatibility with the matrix resin, provide lu-
is capable of reacting with and forming cova- bricity, and ionic types that provide antistatic
lent chemical bonds with both the organic effects. These silanes are of two types:
polymer and the substrate. Silane coupling ROOCCH2CH2NHCH2CH2CH2SiX3 and
agents are organofunctional silane monomers [R3NCH2CH2CH2SiX3] +Cl-. In each case the
(Table 1) that possess a dual reactivity. This R group was varied to change compatibility
(J'I
CAl
00

Table 1. Recommended Organofunctional Silane Coupling Agents for Various Resins.

Union
Carbide Dow Coming
Silane Chemical Name Thermosetting" Thermoplasticb ElastomersC Silane

A-I43 -y-Chloropropyltrimethoxysilane Epoxy Nylon Z-6076

A-ISO Vinyltrichlorosilane Polyester
A-lSI Vinyltriethoxysilane Polyester
A-In Vinyl-tris({3-methoxyethoxy) silane Polyester EPM, EPDM, BR
A-I74 "1- Methacry loxypropy Itrimethoxysilane Polyester, vinyl ester Polystyrene, polyethylene XLPE Z-6030
ABS, polypropylene
A-I86 (3-(3,4-Epoxychclohexyl) ethyltrimethoxy- Polyester, epoxy 11 polystyrene, ABS, SAN,
]
silane nylon, TP polyester
A-I87 -y-Glycidoxypropy ltrimethoxysilane Polyester, epoxy Z-6040
Melamine, phenolic
A-I88 Viny Itriacetoxysilane Polyester Acetal
A-I89 -y-Mercaptopropyltrimethoxysilane Epoxy, phenolic NR, IR, BR, SBR, Z-6062
A-llOO -y-Aminopropyltriethoxysilane }---iEpoXY, melamine Nylon, polycarbonate EPM, EPDM, CR,
A-1l20 N-{3(aminoethyl)--y-aminopropyltrimethox- Phenolic PVC, PP, PE, PMMA, NBR Z-6020
ysilane TP polyester, PPO
A-1lOO -y-Ureidopropyltriethoxysilane Epoxy, melamine
1 Nylon, PVC
]
Phenolic
A-llll bis({3-hydroxyethy l)--y-aminopropy ltrie- Epoxy Acetal, polycarbonate
thoxysilane polysulfone, nylon
A-ll06 Aqueous solution of -y-aminopropyl sili- Epoxy, melamine Nylon
cone
A-lI28 Proprietary amino Epoxy
Vinylbenzylamine functional silane Epoxy, polyester Nylon, polyolefins Z-6032
'Thennosetting resins make use of the Silanes listed on the same line. In addition, A-I 100 and A-1120 are suitable for either epoxy, melamine or phenolic.
~he thennoplastic resins polystyrene, polyethylene, ABS and polypropylene use either A-174 or A-186 while polystyrene, ABS, SAN, nylon and TP Polyester are served by A-186 or A-187. Nylon ... PPO make
use of either A-lloo or A-1I20.
'The four elastomers headed by EPM ... are coupled with the aid of A-151, A-In or A-174. The eight elastomers headed by NR ... require A-189, A-lloo or A-1I20.
 ORGANOFUNCTIONAL SILANE COUPLING AGENTS 539

with the matrix resin and lubricity of treated properties of these systems offers a challenge
fiberglass and in the case of the ionic silanes to to workers in several disciplines.
provide anti-static effects. While these mate-
rials have not as yet found commercial accep- APPLICATIONS
tance in fiberglass sizes, they do offer another
Perhaps the most meaningful confirmation of
way to affect some of the important properties
the efficacy of organofunctional silanes in im-
of fiberglass reinforcement.
proving and maintaining the properties of rein-
During this period there were several at-
forced composites is the use of these materials
tempts to interpret the effect of chemical cou-
in commercial applications. A listing of end
pling between resin and reinforcement on the
uses of composite materials is almost endless
mechanics of the interface. Kumins and
and is growing daily. The purpose of this sec-
Roteman 6 proposed a boundary layer, includ-
tion is to discuss some of the uses in general
ing the silane coupling agent, of intermediate
and to indicate the magnitude of property im-
modulus between the resin and the reinforce-
provements that can be obtained by the use of
ment. Erickson7 suggested that the reinforce-
silane coupling agents.
ment and/or silane coupling agent could
selectively adsorb components of the resin and
Thermosetting Resins
modify the properties of the resin at the inter-
face relative to the bulk resin. Fiberglass-reinforced thermosetting resins were
A stress-relaxation mechanism was proposed for many years the entire composites industry.
by Plueddemann8 that postulated the formation The development of organofunctional silanes
and hydrolysis of stressed bonds between cou- as interface modifiers was carried out using
pling agent and reinforcement in the presence thermosetting resins, and this application area
of water. He also requires that the resin at the justified the original commercialization of si-
interface be rigid, not rubbery. The require- lane coupling agents. The range of properties
ment of a rigid interface may be true for rein- that can be produced by composite materials is
forced resins; however, the excellent aptly demonstrated in the reinforced thermo-
reinforcement obtained by the use of silane sets. High performance is achieved by the use
coupling agents in mineral filled rubber raises of fiberglass filament wound composites, while
some interesting questions. Do the reinforced the low end of the performance scale is served
resin and the reinforced rubber function by the by particulate filled resins. In the area of fiber-
same mechanism? Does the interaction of si- glass reinforced composites, required strength
lane/rubber/filler result in a rigid interface in an can be designed into the composite by the
overall elastic system? These questions remain choice of the amount and orientation of the fi-
to be resolved. berglass used. Table 2 indicates the range of
In summary, organofunctional silanes have flexural strengths that can be obtained using a
been extremely effective in improving and general purpose polyester resin and various
maintaining the properties of reinforced com- forms of readily available fiberglass reinforce-
posites by providing adhesion between the ma- ment.
trix resin and the reinforcement. A variety of
silane coupling agents are commercially avail- Table 2. Flexural Strength of Various
able that appear to meet current requirements, Glass Reinforced Polyester Resin
particularly for the thermosetting resins. The Composites. a
newer technologies, the use of silane coupling Glass Content Flexural Strength
agents in reinforced thermoplastics and elasto- (wt%) (psi x 10- 3 )
mers, are just developing. Their requirements Chopped strand mat 35-45 30-40
in terms of interface modification are in the Woven roving 55 40-50
process of being defined. Products are being Satin weave cloth 62 65-90
made and used with today's silane coupling Unidirectional roving 70 150-180
agent technology; optimizing the potential 'General-purpose polyester resin; commercial reinforcements.
540 HANDBOOK OF ADHESIVES

The choice of a particular thennosetting resin The same type of strength improvement is
for a specific composite application is governed found in foundry cores or shell molds when si-
by a number of factors. Among these are cost, lane coupling agents are used. Foundry shell
cure conditions, use temperature, electrical molds are thin-walled, fragile composites of
properties, etc. All of the thennosetting resins sand and resin which permit the casting of var-
can be reinforced with fiberglass; for optimum ious precise units especially for the automotive
performance, each will require a silane cou- industry. Aminosilane addition to a phenolic or
pling agent on the glass selected to match the furan/sand mixture results in stronger molds
chemistry of the resin. Table 3 shows the effect and cores that resist handling damage and deg-
a properly selected silane can have on the ini- radation in adverse environments. Tables 5 and
tial and retained properties of composites pro- 6 illustrate the options that are available with
duced from four different thennosetting resins. silane addition. One can achieve increased per-
In addition to the use of fiberglass to rein- fonnance at the same resin concentration or
force thennosetting resins, large amounts of equivalent perfonnance at reduced resin con-
particulate fillers are used with thennosetting centration.
resins to produce composites. The reasons for Table 7 illustrates that a much stronger alu-
adding a filler to a resin are many: to reduce minum oxide filled grinding-wheel composite
costs, control rheology, reduce shrinkage, etc. results with aminosilane coupling agent than
In many cases, however, the addition of a filler without. A greater safety margin for wheels is
produces a significant loss in both mechanical achieved during frictional heat buildup and un-
and electrical properties, particularly after ex- der wet grinding conditions.
posure to water. The use of an organofunc- The concept of a metal filled resin is useful
tional silane, either integrally blended into the in the tool and die industry, where in certain
resin-filler mix or pretreated onto the filler sur- applications the costly, time-consuming fabri-
face, can prevent or greatly minimize the cation of solid metal molds is being replaced
losses. Typical of the results that can be by relatively inexpensive, easily fabricated
achieved are shown in Table 4. This table de- metal filled resin systems. Table 8 shows how
scribes the effects produced by several silane silane coupling agents can offer strength im-
coupling agents on the mechanical and electri- provement in this composite system. 9
cal properties of an epoxy resin filled with three Sand filled epoxy resins find utility as simu-
different mineral fillers. The retention of elec- lated terrazzo flooring, concrete highway and
trical properties after water exposure is partic- bridge abutment repair kits, and in various other
ularly impressive. applications where a concrete substitute is re-
quired that is convenient to use and cures rap-
idly. Table 9 indicates the strength
Table 3. Effect of Silanes on Glass improvements that can be produced in these
Reinforced b Thermoset Resins. systems by the use of silane coupling agents,
Flexural Strength both initially and after environmental aging.
Resin System Silane Dry Wet
Polyester control 60,000 35,000 Thermoplastic Resins
A-174 87,000 79,000
The coreactivity of organofunctional silanes
Epoxy control 78,000 29,000 with highly reactive thennosetting resins dur-
A-186 101,000 66,000
ing cure is not unexpected and offers a ready
Melamine control 42,000 17,000
explanation for the specificity shown by a given
A-18? 91,000 86,000
resin for an optimum perfonning silane. How-
high
ever, thennoplastic resins are nonnally consid-
dry temperature"
ered rather completely reacted and quite inert
Phenolic control 69,000 14,000
A-llOO 85,000 50,000 under nonnal process and molding conditions.
"Aged 100 hr at Sooop and tested at Sooop.
It is, therefore, surprising that a similar speci-
bl81 style woven glass cloth. ficity between resin and organofunctional si-
 ORGANOFUNCTIONAL SILANE COUPLING AGENTS 541

Table 4. Effect on Flexural and Electrical Properties of Silane Additives to Filled Epoxy Resin
Composites. a
Flexural
Strength Dielectric Dissipation Dielectric
(psi X 10- 3 ) Constanf Factor Volume Resistivity (ohm/cm) Strength (V/mil)
Filler/Silane b Dry Wete Dry Wef Dry Wef Dry Wef Dry Wef
Clear resin 18.1 16.0 3.44 3.43 0.007 0.005 >8.2 X 10 16 >8.1 X 10 16 >414 >413
50% Wollastonited
Nyco
Control (no silane) 15.8 9.8 3.48 22.10 0.009 0.238 4.9 X 1016 3.3 X 10 12 >391 n.t,
A-186 18.1 13.3 3.42 3.57 0.014 0.023 1.9 x 1016 2.4 X lOIS >400 388
A-187 18.7 15.2 3.30 3.42 0.014 0.016 1.8 x 1016 1.2 X lOIS >356 372
A-llOO 16.7 12.6 3.48 3.55 0.017 0.028 1.2 x 10 16 2.0 X lOIS >408 >410
50 % Minusil 1OJ.! f
Control (no silane) 22.4 10.3 3.39 14.60 0.017 0.305 >8.4 x 1016 5.1 X lO" >381 103
A-186 22.0 14.5 3.48 3.52 0.016 0.023 >8.0 x 10 16 1.4 X lOIS >367 >360
A-187 23.2 21.4 3.40 3.44 0.016 0.024 >8.2 x 10 16 1.7 X lOIS >357 >391
A-llOO 20.0 12.0 3.46 3.47 0.013 0.023 >8.1 x 1016 1.8 X lOIS >355 >355
50% ASP-4W
Control (no silane) 14.1 10.0 4.35 8.07 0.018 0.163 3.5 x 10 16 4.2 X 1013 >344 280
A-186 12.4 10.7 3.43 6.54 0.012 0.059 2.4 x 1016 2.5 X lOIS >375 >407
A-187 14.6 ILl 3.17 3.26 0.012 0.093 1.8 x 1016 1.4 X 10 14 >382 >356
'Composites contain 50 wt% filler in 100 parts ERL-2774 Resin (Union Carbide Plastics Division), 80 parts MNA & 0.5 parts BDMA.
bSilane loading base on filler is equal to a monomolecular layer.
'Tested after 72 hr immersion in boiling water.
dlnterpace Corporation.
'Measured at 1000 cycles according to ASTM D-150.
f Crystalline silica, Pennsylvania Glass Sand Corp.
"Kaolin Clay Minerals and Chemicals Division, Phillip Corp.

Table 5. Effect of A-1100 on Shell Molds Using Phenolic

Resin and Foundry Sand. a
Phenolic Resin A-ll00 (0.025 Percentage
Solids Content Control wt% based on sand) Improvement
3.5% 587 777 32
2.5 too resin-poor to
mold
'Tensile strength of molded "dog bone" specimens.

Table 6. Effect of Amino Silane Coupling Agent A-11 00 in Furan Resina Binder for
Foundry Sand Composites.
Tensile Strength, psi Scratch Hardness
% % A-ll00 (based Work Life,
Binder on binder) 65% R.H. 93% R.H. 68% R.H. 93% R.H. min
2.0 0 153 84 94 93 14
2.0 0.4 318 248 95 93 15
1.2 0 120 68 89 80 25
1.2 0.4 212 115 93 85 28
'Data obtained by Quaker Oats, Ltd. Chemical Research Division on a "no bake" composite containing filfan binder, lake sand, and
catalyzed with 35% phosphoric acid (85%).
542 HANDBOOK OF ADHESIVES

Table 7. Effect of Amino Silane Coupling Agent A-11 00 on

Flexural Strength of Phenolic Resin Bonded AI 2 0 3
Composites. a
% Flexural
Dry Flexural Strength, psi
Al2 0 3 Grit Strength
Size No Silane With Silane Improvement
12 2070 3060 +48
20 2988 4086 +37
36 4176 5328 +28
60 5544 6408 +16
'These test composites were fonnulated to contain 92 wt % Ai 20, and 8 wt % of an 80/20 mixture of
powdered and liquid phenolic resin. A-lIOO is applied at 0.1 wt% based on grit weight.

Table 8. Effect on Flexural and Compressive Strength of Silane Addition to an

Epoxy-Aluminum Composite. a
Flexural Strength, psi Compressive Strength, psi
72 hr 72 hr
Silane Additive Initial H2 0 Boil Initial H2 0 Boil
None 620 470 2,110 2,100
1 wt% A-1100 1,240 1,310 2,970 3,220
1 wt% A-186 1,240 1,200 3,700 3,990
1 wt% A-187 1,110 1,030 3,230 3,430
Flexural and compressive strength specimens were cut from these castings after a cure of 16 hr at room temperature followed by 2 hr at
350 o P.
'61.5 wt % aluminum needles.

lane treated reinforcements exists in thermo- proposed that the reactive polymers chemically
plastic composites. react with the silane coupling agent, while the
Both Plueddemann lO and Sterman and nonreactive polymers exhibit compatibility with
Marsden II published on the use of organofunc- the silane treated surface as indicated by solu-
tional silanes in glass reinforced thermoplastic. bility parameters. Sterman and Marsden, while
Plueddemann divided thermoplastic resins into recognizing that wetting of the silane treated
"reactive" and "nonreactive" categories. He surface by the matrix resin is desirable, pro-

Table 9. The Effect of Addition of Various Silanes to Sand Filled Epoxy Resin
Composites.
Tensile Strength, psi

Specimen Control
Resin Content, % Conditioning (no silane) A-I87a A-llooa A-I86 a

15.0 dry 925 1,225 1,030 1,040

freeze-thaw b 500 800 835 790
8 hr H20 boil 215 440 355 500
12.5 dry 850 1,150 1,120 900
freeze-thaw b 435 740 510
8 hr H20 boil 110 260 285 300
10.0 dry 705 730 750 570
freeze-thaw b 155 190 120
8 hr H20 boil 110 140 200 145
'Silane concentration was 0.1 wt% based on sand.
"Freeze-thaw cycle: 24 hr immersion in R.T. Water; 8 hr at -30°C; 16 hr at R.T.
 ORGANOFUNCTIONAL SILANE COUPLING AGENTS 543

pose chemical bonding between matrix resin achieved with a complete size that lubricates
and silane as the most likely mechanism for the and protects the glass as well as allowing the
reinforcement of thermoplastic resins by silane contained silane coupling agent to develop
treated fiberglass. In a subsequent publication 12 adhesion between the glass and matrix resin.
they showed that the reaction between an ole- The use of conventional organofunctional
finic silane and a nonreactive resin such as silanes, as described in the section on filled
polypropylene could be promoted by the addi- thermosetting resins, has been tried in filled
tion of a free radical source. Table 10 indicates thermoplastic resins with mixed results. Oren-
the magnitude of strength improvement that can ski and co-workers 13 reported good results with
be produced by the use of a silane coupling the use of Union Carbide A-IS7 and A-lIOO in
agent in a glass fabric reinforced composite uti- wollastonite filled engineering resins at high
lizing a variety of thermoplastic resins. filler loading. Attempts to extend this approach
If the promise of glass reinforced thermo- to less reactive thermoplastic resins, such as
plastics is to be realized, the composites must polyolefins, were less successful.
be fabricated by high speed, low unit cost in- A different approach has been proposed to
jection molding of chopped glass reinforced enhance the properties of filled thermoplastics,
resins rather than the slower techniques for pro- utilizing a family of organosilicon chemicals.
ducing the prototype laminates shown in Table This new approach proposes that coupling the
10. The injection molding method places strin- matrix resin to the inorganic filler is necessary
gent requirements on the glass fiber size. In ad- but not sufficient to optimize the overall prop-
dition to coupling the matrix resin to the glass, erties of the composite. The organosilicon
the silane must protect the glass during the high chemicals provide multifunctional reinforce-
shear mixing and allow good dispersion of the ment promotion effects at the filler-matrix
fibers in the matrix resin. boundary, including (1) coupling the filler to
The fiberglass producers have done an out- the matrix resin and (2) modifying the matrix
standing job in this regard. Tables 1I-13b show resin in the region near the filler particle. These
some of the properties of injection molded inter-phase modifications result in improved
composites of 30% glass/70% resin using ny- composite mechanical properties, increased
lon, poly(butylene terephthalate) and polypro- impact strength, improved filler dispersion, and
pylene, respectively. In all cases, the use of higher extrusion throughput rates. In selected
unsized virgin roving produces strengths greater resins, these matrix modifications also result in
than that of the neat resin; and as predicted by higher heat distortion temperatures and the
Table 10 the use of a silane coupling agent pro- coupling chemistry employed provides im-
duces a significant gain over virgin glass. How- proved long term heat aging.
ever, in each case, the highest values are The first products resulting from this ap-

Table 10. Effect of Silane Finishes on Mechanical Properties of Glass Cloth

Reinforced Thermoplastic Resins. a
Flexural Strength % Improvement Over Controf'
Elevated
Temp.
Resin Silane Dry Wef (OF)
Polystyrene A-174 100 95 70 (200)
Polyvinyl chloride A-llll 83 100
Nylon A-Illi 110 160 150 (400)
Poly carbonate A-lloo 30 60 20 (250)
Polymethyl methacrylate A-lloo 45 90 25 (200)
Acrylonitrile-butadiene-styrene A-187 145 228 145 (150)
'Laminates contain 11 plies of 18 I-type glass cloth, 40-45% resin.
'Control is heat-cleaned glass cloth reinforcement.
'Immersion for 16 hr in water at 120°F.
544 HANDBOOK OF ADHESIVES

Table 11. Physical Properties of Glass Reinforced Nylon 6,6 (0% Glass-70% Nylon
6.6).
Tensile
Flexural Heat
Modulus, psi x
Flexural Modulus Distonion
Tensile Strength, psi 105
Strength psi x Temp. of
Size psi 10 5 Dry Wet Dry Wet (0C)

Commercial 39,100 11.1 25,800 21,600 17.4 14.4 487(253)

No.1
Commercial 30,800 9.3 21,400 18,800 16.8 13.2 492(255)
No.2
A-l100 24,900 7.7 14,800 14,600 15.8 11.4 498(259)
A-ll60 29,200 7.4 18,700 16,400 14.4 12.2 472(244)
A-186 30,100 9.3 22,400 19,000 16.0 13.2 473(245)
A-187 31,300 10.0 20,500 15,800 15.2 14.4 481(249)
Virgin roving 17,100 8.1 10,000 8,600 15.4 10.4 459(237)
No glass 12,600 2.4 8,900 8,300 3.1 2.7 165(74)

proach were introduced by Godlewski 14 for work 15 has shown they appear to be equally
polyolefin/mica composites. The use of this useful in glass fiber reinforced polyolefins. The
two-component additive package, Union results shown in Table 16 indicate that the use
Carbide PC-IA and PC-IB (proprietary com- of PC-IA and PC-IB produces significant
positions), produce significant property property improvements in a glass fiber rein-
enhancement in mica filled polypropylene and forced polypropylene composite that contains a
mica filled high density polyethylene, as shown polypropylene compatible reinforcement.
in Tables 14 and 15. These materials may be The continuing interest in changing the com-
used to pretreat the mica or they may be inte- bustion characteristics of composites has fo-
grally blended during compounding. In addi- cused attention on ATH (alumina trihydrate)
tion to property enhancement, the use of these filled high density polyethylene. Attempts to
products are claimed to increase extrusion rate. incorporate high loadings of ATH into HDPE
While these products were originally intro- normally leads to processing difficulties and
duced for use in filled polypropylene, recent degradation of composite properties.

Table 12a. Dry Physicals of Glass-Reinforced PBT. a

Flexural Tensile Heat-Distonion
Flexural Modulus, Tensile Modulus, Temperature, d
Izod Impact Strength
Strength, psi X Strength, psi X °F(°C)
Size psi 10 5 psi 10 5 Notch b Unnotch C
No glass 13,800 3.5 7,600 3.5 0.7 8.4 158(70)
Virgin rov- 16,000 9.6 9,300 11.2 0.7 5.2 394(201)
ing
Commercial 30,700 11.3 19,100 12.2 2.1 13.8 428(220)
No. 1
Commercial 30,300 10.3 18,500 11.7 2.1 12.7 426(219)
No.2
Commercial 28,900 9.5 18,700 12.5 2.4 12.8 430(221)
No.3
A-1100 23,600 10.5 14,200 11.9 0.9 7.5 405(207)
A-186 22,200 10.6 24,300 12.0 1.3 8.9 412(211)
A-187 24,700 10.2 14,400 11.7 1.4 9.6 415(213)
'Celanese J-105 thennoplastic polyester, poly(butylene terephthalate) with 30% glass.
"Ft x lb/inch of notch.
'Ft x lb/inch of width.
'At 264 psi.
 Table 12b. Wet Strength Retention of Glass-Reinforced PBT.
Tensile Strength, psi Tensile Modulus, psi x lOs
16hr % One-Week % 16hr One-Week
Size Dry Wet" Ret. Boif' Ret. Dry Wet" Boif'

No glass 7,600 7,500 99 1,700 23 3.5 2.8 3.0

Virgin rov- 9,300 8,400 90 3,000 33 11.2 8.3 7.0
ing
Commercial 19,100 18,500 97 9,500 50 12.2 11.6 10.4
No. 1
Commercial 18,500 18,000 97 12,200 66 11.7 1l.8 10.5
No.2
Commercial 18,700 17,700 95 10,300 55 12.5 12.1 10.0
No.3
A-llOO 14,200 13,100 92 6,600 47 11.9 10.3 8.5
A-186 14,300 12,900 90 5,200 36 12.0 11.3 8.5
A-187 14,400 13,800 96 6,000 42 11.7 11.6 8.7
'16 hr in 50 0 e water.
bOne week in loooe water.

Table 13a. Dry Physicals of Reinforced Polypropylene. a

Flexural Tensile Heat-Distonion
Flexural Modulus, Tensile Modulus, Temperature,d
Izod Impact Strength
Strength psi X Strength, psi X °F(Oe)
Size psi lOS psi lOS Notch" Unnotch C
No glass 6,600 1.5 4,500 2.2 0.5 14.5 142(61)
Virgin rov- 8,100 5.3 4,900 9.5 0.9 5.0 246(119)
ing
Commercial 13,800 4.8 8,300 8.5 3.3 7.7 306(152)
No. 1
Commercial 10,500 5.2 6,600 8.1 2.6 6.1 298(148)
No.2
Commercial 12,100 4.9 7,600 7.9 3.7 8.0 280(138)
No.3
A-llOO 9,900 4.8 5,600 8.8 1.9 5.3 280(138)
A-174 10,900 5.3 6,000 8.8 2.5 6.7 295(146)
'Hercules Pro-Fax 6523 premix with 30 wt% chopped glass strand.
"In ft x lb/inch of notch.
'In ft x Ib/inch of width.
dAt 264 psi.

Table 13b. Wet Physicals of Reinforced Polypropylene. a

Tensile Strength, Tensile Modulus,
psi psi X lOS
%
Size Dry Wet" Ret. Dry Wet"
No glass 4,500 4,300 96 2.2 1.9
Virgin roving 4,900 4,300 88 9.5 5.5
Commercial No. 1 8,300 7,200 87 8.5 6.6
Commercial No.2 6,600 6,100 92 8.1 6.6
Commercial No.3 7,600 7,200 95 7.9 7.0
A-llOO 5,600 5,000 89 8.8 5.8
A-174 6,000 5,400 90 8.8 7.4
'Hercules Pro-Fax 6523 premix with 30 wt% chopped glass strand.
bAfter boiling for 24 hr.

545
546 HANDBOOK OF ADHESIVES

Table 14. 50% Mica 8 Filled Polypropylene b Composites.

Without Additives With UCARSIL PC-1AIPC-1B"
Tensile strength, psi 4,300 7,070
Tan. flexural modulus, psi x 103 1,430 1,210
Flexural strength, psi 7,400 10,600
Notched lzod impact strength, ft-Ib/in. 0.13 0.20
'Grade 200 HK, Marietta Resources, Ltd.
bPro-Fax 6523 PM Powder, Hercules, Inc.
'Total 1.25% based on total composite, 4/1 ratio.

Table 15. 50% Mica 8 Filled High Density Polyethylene b Composites.

Without Additives With UCARSIL PC-IAIPC-IB"
Tensile strength, psi 3,510 5,530
Tan. flexural modulus, psi x 103 510 590
Flexural strength, psi 5,080 7,260
Notched Izod impact strength, ft-Ib/in. 0.23 0.27
'Grade 200 HK, Marietta Resources, Ltd.
bG-7006, Union Carbide Corp.
'Total 1.5% based on total composite, 2/1 ratio.

Table 16. 30% Fiberglass 8 Reinforced Homopolymer pp.b

Composite Properties
Without osce With 2% UCARSIL PC-IAIPC-IBd (3/1 ratio)
Tensile strength, psi 6,140 8,850
Flexural modulus, tan., psi x 103 750 750
Flexural strength, psi 9,100 12,600
Notched Izod impact strength, ft-Ib/in. 1.5 1.4
Unnotched lzod impact strength, ft-Ib/in. 3.2 4.3
'OCF-885BD (3116 in.).
bpRO-FAX 6523.
'Organosilicon chemicals.
dlntegrally blended.

Godlewski 16 has reported that the use of two Elastomers

new materials, Union Carbide FR-IA and FR-
1B (proprietary compositions) permit easier in- Mineral filled elastomers are not usually con-
corporation of high levels of ATH into HDPE sidered to be composite materials, although
and to significantly enhance composite prop- they have many of the characteristics common
erties as shown in Table 17. to composites. Chief among these is the exis-

Table 17. Property Enhancement in a 65% ATH 8 /HDPE b Composite.

65% ATH Composites
Unfilled Without UCARSIL With UCARSIL
HDPE FR-1AIFR-IB FR-IAIFR-IB"
Tensile strength, psi 3,080 2,750 4,750
Flexural strength, psi 3,250 3,850 6,050
Tan. flexural modulus, psi x 103 150 320 350
Gardner Impact strength, in.-Ib/in. 10 200
Unnotched Izod impact strength, ft-Ib/in. 2 14
'Alcoa Hydral 710.
bG-7030 From UCC.
'UCARSIL FR-IA/FR-IB (III rato) 2% based on ATH amount.
 ORGANOFUNCTIONAL SILANE COUPLING AGENTS 547

tence of a large interfacial area between the tions, is relatively effective in improving the
continuous organic polymer phase and the dis- modulus and tensile properties. The 'Y-amino-
continuous dispersed mineral phase. It is well propyltriethoxysilane (A-l1oo) also provides a
known that poor wetting of a filler by a poly- high level of filler-elastomer interfacial bond-
mer is manifested by vacuole formation in a ing, as evidenced by the physical property data.
stressed system at a low level of stored energy. In addition to the low physical properties
These vacuoles often act as stress concentrators shown by the mineral filled elastomer without
and catastrophic failure occurs at much lower silane in Table 18, two other factors have lim-
levels of stored energy than would be the case ited the use of mineral fillers. These are heat
for a well wetted or bonded system. As has buildup in flexing (likely related to poor wet-
been discussed for the case of thermosetting and ting of the filler by the elastomer) and poor
thermoplastic resins, this interface can be ef- abrasion resistance, particularly as it relates to
fectively bridged by the use of a silane cou- road wear. Wagner!8 has studied the effect of a
pling agent selected to participate in the cure mercapto-functional silane (A-189) on these
chemistry of the specific elastomer. Ranney and properties and compared the results to those
Pagano!7 studied the relationship between si- obtained using a carbon (HAF) black filler. Ta-
lane functionality and resultant elastomer prop- ble 19 summarizes his results.
erties in a mineral filled EPDM system. Table As would be expected, the mercaptosilane
18 summarizes their results. increases the modulus and tensile to values
Clearly, the use of saturated aliphatic silanes comparable to those of the carbon black com-
such as the amyl (A-16, amyltriethoxysilane) pound. In the Goodrich flexometer test, the heat
and methyl (A-162, methyltriethoxysilane), buildup, which is known to be a rather severe
substituted products is largely ineffective due problem, is 27°C, which is well below the
to lack of reactivity in this free radical system. value obtained with carbon black. The mercap-
The rather small increase in tensile properties tosilane also improves the compression set and
observed may be ascribed to improved filler- the Pico Abrasion Index. Significantly, the
elastomer wetting. Road Wear Index was improved to give equiv-
The organofunctional coupling agents all give alency to the carbon black compound.
very significant improvements in modulus and At present, a large area of interest in silane
tensile, but to different degrees, depending on coupling agents in elastomers is in wire and ca-
their relative reactivity in this peroxide cured ble applications.!9 The electrical properties of
system. The methacryloxypropyltrimethoxysi- white filled EPM and EPDM cables deteriorate
lane (A-174) is considerably more effective rapidly under conditions of high humidity, due
than vinylsilane (A-I72), as could be predicted to adsorption of water at the filler/rubber inter-
from the relative reactivity of the double bond face. The use of silanes prevents water ingress
moiety. The 'Y-mercaptopropyltrimethoxysi- and maintains the electrical properties. Table
lane (A-189), capable of chain transfer reac- 20 shows the effect of various silanes on the

Table 18. Effect of Organofunctionality Table 19. Effect of Mercaptosilane

of Silane Coupling Agent on Physical Coupling Agent on a Silica-Filled SBR
Properties of Peroxide-Cured EPDM. Compound.
Properties SBR 1502 100 100 100
Hi-Sil233 60 60
300% Tensile
N-285 Black 60
Modulus Strength,
Mercaptosilane A-189 1.5
Silane Monomer psi psi
300% modulus, psi 725 1980 2220
Control, no silane 420 895 Tensile, psi 2680 3760 3520
Amyl (A-16) 410 995 Elongation, % 580 460 460
Methyl (A-162) 500 1,050 Hardness 71 67 74
Vinyl (A-I72) 1,110 1,380 Goodrich ftexometer t:.T, ·C 47 27 41
Mercapto (A-189) 1,200 1,540 Compression set, % (B) 25 12 20
Amino (A-ll00) 1,440 1,640 Pico abrasion index, % 81 131 170
Methacryloxy (A-174) 1,660 1,660 Road wear index 79 114 110
548 HANDBOOK OF ADHESIVES

Table 20. Electrical Properties of Hard Clay Filled EPDM

Compounds Containing a Silane Coupling Agent.
Silane
None A-l72 A-174 A-l89 A-llOO
S.I.C. (specific inductive capacitance), kC/sec
Unaged 2.91 3.00 2.91 2.93 2.94
7 days 6.08 3.35 3.30 3.53 5.04
14 days 6.84 3.58 3.31 3.69 5.57
Dissipation Factor, sec/cycle-ohm-farad
Unaged 0.009 0.008 0.005 0.007 0.007
7 days 0.182 0.025 0.017 0.024 0.101
14 days 0.188 0.024 0.018 0.024 0.100

electrical properties of a clay filled EPM com- terface; Studies and Theories," presented at 25th An-
pound. nual Meeting, SPI, Feb. 1970.
8. Plueddemann, E. P., •• Adhesion Through Silane Cou-
Silane coupling agents are now used with pling Agents," presented at 25th Annual Meeting SPI,
mineral fillers in passenger tires (tread stock, Feb. 170.
carcass, and sidewall), off-the-road tires, en- 9. Ziemianski, L. P., "A Survey of the Effect of Silane
gine mounts, and in many specialty applica- Coupling Agents in Various Non-glass Filled Ther-
mosetting Resin Systems," presented at 22nd Annual
tions such as conveyor belts, gaskets, ignition
SPE Conference, Montreal, Canada, Mar. 1966.
wire, hose compounds and solid golf balls. 10. Plueddemann, E. P., "Silane Coupling Agents for
While the automotive segment employing SBR, Thermoplastic Resins," presented at Annual Meeting
natural, and butyl rubber represents the largest SPI, Feb., 1965.
market segment, the combination of the mer- 11. Sterman, S., and Marsden, I. G., "The Effect of Si-
capto- or aminosilane with a mineral filler in lane Coupling Agents in Improving the Properties of
Filled or Reinforced Thermoplastics," presented at
nitrile, neoprene, EPDM, and other specialty Annual Meeting SPE, Mar. 1965: The Effect of Silane
elastomers has provided a new and exciting Coupling Agents in Improving the Properties of Filled
formulation technique for obtaining high per- or Reinforced Thermoplastics," Polymer Eng. Sci.,
formance elastomeric products. 6(2) (Apr. 1966).
12. Sterman, S., and Marsden, I. G., "The Effect of Si-
REFERENCES lane Coupling Agents in Improving the Properties of
Filled or Reinforced Thermoplastics II," presented at
1. Bikerman, I. I., "The Science of Adhesive Ioints," Annual Meeting SPI, Feb., 1966.
New York and London, The Academic Press, 1961. 13. Orenski, P. I., Berger, S. E., and Ranney, M. W.,
2. Zisman, W. A., "Surface Chemistry of Glass Fiber "Silane Coupling Agents-Performance in Engineer-
Reinforced Plastics, " presented at 19th Annual Meet- ing Plastics," presented at Annual Meeting SPI, Feb.
ing SPI, Feb., 1964. 1973.
3. Sterman, S., and Bradley, H. B., "A New Interpre- 14. Godlewski, R. E., "Organosilicon Chemicals in Mica
tation of the Glass-Coupling Agent Surface Through Filled Polyolefins, " presented at Annual Meeting SPI,
Use of Electron Microscopy," presented at 16th An- Feb. 1983.
nual Meeting SPI, Feb., 1961; "A New Interpretation 15. Godlewski, R. E., "Performance of Organosilicon
of the Glass-Coupling Agent," Surface Through Use Chemicals in Fiberglass Reinforced Homopolymer and
of Electron Microscopy, SPE Transactions (Oct. Copolymer Polypropylene," presented at Annual
1961). Meeting SPI, Ian. 1986.
4. Plueddemann, E. P., et aI., "Evaluation of New Sil- 16. Godlewski, R. E., Proc. 42nd Ann. Tech. Conf. SPE,
ane Coupling Agents for Glass Fiber Reinforced Plas- 229-233 (1984).
tics," presented at 17th Annual Meeting SPI, Feb., 17. Ranney, M. W., and Pagano, C. A., "Silane Cou-
1962. pling Agent Effects in Ethylene Propylene Diene Ter-
5. Marsden, I. G., A-l100: "Evolution of a Family of polymers," The American Chern. Soc., Rubber
N-Functional Silanes," presented at 27th Annual Division Meeting, Miami, Florida, Apr. 1971.
Meeting SPI, Feb., 1972. 18. Wagner, M. P., "Non-black Reinforcers and Fillers
6. Kumins, C. A., and Roteman, I., "Effect of Solid for Rubber," Rubber World, 46 (Aug., 1971).
Polymer Interaction on Transition Temperature and 19. Ranney, M. W., Sollman, K. I., and Pickwell, R. I.,
Diffusion Coefficients," J. Polymer Sci., AI, 527 "Silane Coupling Agents in Sulfur-Cured EPDM
(1963). Elastomers," Paper No. T-71, A.C.S. Rubber Divi-
7. Erickson, P. W., "Historical Background of the In- sion meeting, Cleveland, Ohio, Oct. 15, 1971.
 32
Non-Silane Coupling Agents
HARRY S. KATZ
Utility Development Corporation
Livingston, New Jersey

Surface treatment of substrates has been an im- pling agent by weight of the material to be
portant factor in obtaining well bonded struc- treated. The performance of this method will
tures. Modifying or treating the substrate depend upon the extent to which the coupling
surface is usually essential for achieving a bond agent will migrate to the interface during later
that will survive long term stress and exposure processing of the composite.
to environmental conditions. In composites Coupling agents can provide benefits as pro-
technology, the term coupling agents has been cessing aids for polymer matrix composites.
used to designate chemicals that are used to Dramatic reductions in viscosity can occur in
treat the surface of fillers and reinforcements in some highly filled liquid polymers when a rel-
order to obtain optimum physical properties and atively small quantity of an appropriate cou-
for long-term retention of physical properties. pling agent is added to the formulation.
Coupling agents are chemical molecules with Silanes are currently the predominant cou-
dual functionality, wherein one part of the mol- pling agents, and these materials have been
ecule will adhere to one surface, e.g., filler or presented in another chapter of this Handbook.
reinforcement, while another part of the mole- The following sections will review non-silane
cule provides a bond to the other material, e.g., materials that are being used as coupling agents
the polymer matrix. Thus, a bonded bridge is to improve the processing and properties of
formed between two different materials. polymer matrix composites.
Coupling agents have usually been applied
by two different methods. The first and pre-
TITANATES/ZIRCONATES
dominant method has been the application of
the coupling agent to the surface of the filler or Titanates and zirconates produced by Kenrich
reinforcement. Typically, this has been accom- Petrochemicals, Inc. have received much atten-
plished by treating the filler or reinforcement tion in recent years, and show promise of af-
with a dilute solution of the coupling agent, fording some remarkable improvements in
then evaporating the solvent. The objective is processing characteristics and final properties
to obtain a controlled and uniform thin coating of many composite systems.!
or monomolecular film of the coupling agent Typical generalized structures of titanate and
onto the treated surface. Application levels zirconate coupling agents are shown in Fig. 1.
have usually ranged between 0.1 % and 1 % by One of the proposed mechanisms for the effec-
weight of the treated material. The second tiveness of the titanates in some composite sys-
method, the integral blend procedure, involves tems is shown in Fig. 2. The water of hydration
the addition to the resin of about 1-2 % of cou- at the inorganic filler or fiber surface is re-

549
550 HANDBOOK. OF ADHESIVES

Properties of Titanate/Zirconate Coupling Agents

Stearic Acid CH. 0 0

Fundicmality; I U U
Aida Dlapenion Clio-Of -O-TI(O- P-O- P(OCoH,,>z).
01 MIneral FUlen
in Polyoleflna
I
OH
Greater Stability
In Wet EnYiJonmenta

Quat TItanate Water Soluble

u n II
C-O-TI(O-j-O-P(OCaH,,>Z).
I I'
CHo-O H Oe ~

'It/'
R-N-R

Phoepbite Functicmality;
Recl_ Epoxy ViKoeity
WiD AccelentinlCure

NeoalkDxy TItanate Eliminatee I'I'etreat- o 0

ment AIIociatec1 with U II
HiSh Te~penture Thermo- RO-O-TI(O-P-O-P(OCaH,,>Z>Z
plutic:nnd Polyurethane. I
OH

NeoalkDxy ZIrconate Accelentee Peroxide-

andAir-bMed Curet;
e.I., PolJftlerSMC/BMC

~tomntanate Ultra-bilh Thermal

Propertie. for Spe-
ctalty ApplicatioN

Fig. 1. Typical generalized structures of titanate/zirconate coupling agents. (Courtesy Kenrich Petrochemicals, Inc.)

placed with a monomolecular layer of organo- riety of polymer disciplines is well documented
functional titanate. This improved wetting at in the literature 14 and in a Reference Manual
the inorganic/organic interface increases the published by Kenrich.
degree of displacement of interstitial air by the Improved bonding of fiberglass, Kevlar, and
organic matrix. Dispersion tests by Kenrich carbon fiber to a variety of elastomeric, epoxy,
showed that 0.5% titanate coupling agent by and peroxide cured unsaturated thermoset sub-
weight on calcium carbonate reduced the vis- strates has been achieved by including minor
cosity of a 50% calcium carbonate filled dioc- proportions of organotitanate or organozircon-
tyl phthalate from 177 ,000 cps to 2,600 cps. ate coupling agents in various polymer mat-
Fig. 3 shows that 1 % by weight addition of ti- rices. 2 The addition of 0.2% LZ 97, which is
tanate to Ti02 changed a 40% diocytl phthalate a Kenrich zirconium (IV) neoalkenolato-tris(3-
system from a nonflowing viscosity to a very amino)phenylato compound, to an anhydride-
fluid state. cured epoxy/fiberglass pipe results in a dra-
Use of organometallic coupling agents (ad- matic increase in interfacial adhesion. Fig. 4
ditives) as process aids, adhesion promoters, shows that a control without the LZ 97 has the
and physical property enhancers in a wide va- fiberglass strands evident within the composite,
 NON-SILANE COUPLING AGENTS 551

NO TITANATE TITANATE
....... "
---o_~
\

Fig. 2. The proposed mechanism for deposition of a monolayer of triorganotunctional titanate to effect the elimination
of inorganic water of hydration and air voids resulting in deagglomeration. (Courtesy Kenrich Petrochemicals, Inc.)

whereas the addition of the titanate provides an be system dependent. For example, the en-
improvement in interface adhesion that elimi- hancement of processability effected by the
nates the appearance of separate glass fibers. coupling agent appears to be the primary basis
The enhancement of adhesion provided by for the upgrade in properties observed in
asymmetric organotitanates and zirconates in CaC03 filled polyolefins, whereas the im-
reinforced composites appears to be a conse- proved mechanical properties by use of ami-
quence of the interaction of multiple mecha- nozirconates in glass filled nylon appears to be
nisms, induding ligand-specific interfacial primarily a result of the bonding of the cou-
wetting enhancement, primary chemical bond pling agent to the glass surface and the resin
formation between the substrate particulate and matrix. 3
resin matrix, and, in many instances, matrix re- Monte and Sugerman3 have shown specific
polymerization and reinforcement surface organotitanium/organozirconium derived cou-
modification. The particular mechanism which pling agents as being effective especially in im-
is dominant in a specific application appears to proving the impact strength in composites as
widely disparate as CaC03 filled polypropyl-
ene and polyvinyl chloride, glass filled polyu-
rethane, and Kevlar reinforced epoxy.
The organotitanate and organozirconate cou-
pling agents and their analogs have been effec-
tive in promoting adhesion between various
components of polymer laminates and lami-
nates/coatings to metallic and inorganic sur-
faces.
Kenrich is the outstanding company that has
conducted research on titanate and zirconate
coupling agents and produced these materials
Fig. 3. The addition of 1 wt% of titanate in a 40% Ti02 !
DOP dispersion creates a remarkable change in viscosity. for adhesives and composites. This effort has
The material at left has no titanate. (Courtesy Kenrich led to many patents related to their products.
Petrochemicals, Inc.) U.S. Patent, 4,600,789 (July 15, 1986) and
552 HANDBOOK OF ADHESIVES

Fig. 4 . Fiberglass wound epoxy pipe. The control on the left shows the fiberglass windings projecting through the
anhydride-cured epoxy pipe wall . The sample on the right, containing 0.2 % LZ 97 has the same degree of fiberglass
reinforcement, but shows no apparent fiberglass because of almost complete interfacial adhesion of epoxy to reinforce-
ment.

4,623,738 (November 18, 1986) were granted fibrous and particulate inorganic substances and
to G. Sugerman and S. J. Monte of Kenrich for certain organic particulates, thereby resulting
a new generation of neopositioned quaternary in hydrophobic, organophilic fibers and parti-
carbon type (neoalkoxy) coupling agents which cles having improved rheological properties
exhibit novel thermal stability-even when in- which facilitate higher filler or fiber loading
troduced into unfilled polymers at 400°C. levels," e.g., in fiberglass-reinforced polyester
Dupont has a line of organic titanates, TY- laminates. Laminate performance was equiva-
ZOR TPT, TBT, and TOT, that can be used to lent to that obtained with a methacrylato silane
modify surfaces so that they are oleophilic or coupling agent and superior to methacrylato
hydrophilic . These products are dispersion aids chromic chloride. According to Cohen's U.S.
and promote dispersion of pigments in resins Patent 4,764,632 (August 16, 1988), multi-
and paints. They modify surfaces to make them functional amino zircoaluminates are effective
more compatible with adhesives and thereby as high temperature adhesion promoters.
promote adhesion. Zircoaluminate coupling agents are analo-
gous to the silanes. Each of their product line
has organic functionality and an inorganic
ZIRCOALUMINATES
backbone, so that one end can interact with the
Zircoaluminates or aluminum zirconium me- matrix resin and the inorganic component will
tallo-organic complexes have proven useful as have an affinity for the filler or reinforcement
coupling agents and adhesion promoters. surface.
On September 3, 1985, two patents were A representative structure of this type of ma-
granted to L. B. Cohen, assigned to Cavedon terial is shown in Fig. 5. Cavedon line (Table
Chemical Co., Inc., Woonsocket, R.I.: U.S. 1) includes amino, carboxy, oleophilic, meth-
Patent 4,539,048 and 4,539,049, describing acryloxy, and mercapto functionality .
aluminum zirconium metalloorganic com- The potential of this line of coupling agents
plexes "useful as coupling agents." These has been described in a number of publica-
complexes "chemically modify the surface of tions. 5 -9
 NON-SILANE COUPLING AGENTS 553

RX Ian line marketed by DuPont. These materials

I
c
are coordination complexes of carboxylic acids
with trivalent chromium chlorides. Volan is
0""'" ' 0 usually applied to glass fabric by a specific
I
AI
I
Zz
treating and washing step, known in the indus-
try as the "A" finish. This finish was qualified
Fig. 5. Representative structure of zircoaluminate cou- under military specification MIL-F-9118A,
pling agents. RX is an organofunctional group. October 11, 1954, and was the standard finish
for glass filament reinforcements for many
years. However, its use tapered off when the
Cavco Mod Adhesive Applications silanes proved to offer better performance, es-
Cavco Mod CPM has been used in a blue pecially with regard to water resistance. A test
polyamide ink to enhance adhesion to untreated that was frequently used for accelerated deter-
polyethylene. This is a first report indicating mination of long-term resistance to water was
that the conventional process of corona dis- to expose the fiberglass laminate for 2 hours in
charge of PE, PP and polyester film may be boiling water. In this simple test, a laminate
obviated by use of Cavco Mod. containing glass filaments without a coupling
Cavco Mod APG has been used to improve agent will exhibit great loss of flexural strength,
the bond of epoxy adhesives for both metallic in the order of about 40%. The Volan A treat-
and nonmetallic substrates. It has been used in ment will provide good retention of flexural
CaC03/Epoxy to reduce viscosity and promote strength in this test; however, properly selected
adhesion to a variety of substrates. It has also silanes will provide excellent retention of the
been used in an adhesive, which was described flexural strength.
in U.S. Patent 4,690,966 (L. B. Cohen, 1986), The Chemical Abstracts Index name for the
to enhance bonding between rubber and metal prime component of Volan is methacrylato
substrates. chromic chloride hydroxide. The CAS Registry
Cavco Mod C has been used in a phenolic Number is 15096-41-0. The structure is shown
primer to promote adhesion of a rubber-based in Fig. 6.
coating to steel.
Polymer Additives
There are polymer additives that can serve the
MISCELLANEOUS COUPLING AGENTS function of coupling agents. 1O Acrylic acid-
modified polypropylene has been used to im-
Chrome Complexes
prove the properties of filled and reinforced
Among the first commercial products used as polypropylene compounds. Fig. 7 shows the
coupling agents for glass filaments was the V0- improvement in tensile strength that is obtained

Table 1. Cavedon Zircoaluminates.

Functionality Cavco Mod Products Recommended Resins
Amino A Epoxy, nylon, phenolic,
APG urethane, furan, melamine,
PVC
Carboxy C, C-l Polybutylene terephalate,
CPM, CPG, C-IPM Acrylics, SBR
Oleophilic F PE, PP, polybutadiene
FPM
Methacryloxy M Unsaturated polyesters,
Methacryloxy loleophilic M-l PE, PP, polybutadiene,
MPM, MPG, M-IPM ABS
Mercapto S NBR, SBR, EPDM,
SPM neoprene
 554 HANDBOOK OF ADHESIVES Mica types

D200HK

~200NP

Fig. 6. Methacrylato chromic chloride. % Acrylic acid modified PP

Fig. 7. Acid-modified polypropylene/mica composite.

Acid-modified PP raises tensile strength of PP filled with
when acrylic acid-modified polypropylene is untreated mica (200 HK) to a higher level than with more
added to a mica-filled polypropylene. expensive surface-treated mica (200 NP) and no added
BP Perfonnance Polymers, Inc., Hacketts- coupling agent.
town, N.1. has several grades of polypropylene
that have been grafted with acrylic acid. This 3 : 1 respectively. They have been shown to
modified polypropylene has provided improved provide improved adhesion, better dispersion,
bonding to mica, talc, and glass fiber in poly- reduced viscosity, and improved mechanical
propylene composites. properties in filled and reinforced thennoplastic
Copolymers of styrene and maleic anhydride composites. Fig. 8 shows the structure of the
are produced by Sartomer Company under the SMA resins. Table 2 shows the improvement
trade name SMA resins. Grades 1000, 2000, in tensile strength and tensile modulus that re-
and 3000 are unmodified copolymers with sty- sults from the addition of SMA resin to a poly-
rene-maleic anhydride ratios of 1 : 1, 2: 1, and propylene/clay composite.

styrene Malcic SMA 1000 m=1-3

Anhydride 11=6-8
Fig. 8. SMA resins.

Table 2. Effect of SMA Resin on Polypropylene/Clay Composites.

Flex Ult.
Tensile Strength, psi
Composite" PP/ Modulus, Elongation,
Clal/SMA Resin Yield Break psi %
_c 374,000
70/30/0 3340 4.6
70/30/1.3 SMA 4280 4020 423,000 4.4
1000
70/30/1.3 SMA 4060 3600 426,000 5.3
2000
70/30/1.3 SMA 4270 4160 451,000 4.1
3000
'Composites prepared by dilution with virgin PP of 70/30 Clay/PP concentrates containing 3.0 parts SMA resin.
"Hydride 10 (Georgia Kaolin Co.).
'No yield.
 NON-SILANE COUPLING AGENTS 555

Table 3. T-Peel Strength of SMA Resin Modified Polyethylene.

SMA
T-Peel, lblin.
Resin, wt
Substrate % Aluminum Steel
LOPE" 0.1 0.3
LOPE" 1000 (1 0) 0.2 0.6-1.6
LOPE" 3000 (10) 0.1-2.3 0.5-2.8
LOPEb 0.3 0.2
LOPEb 1000 (10) 4.1-5.3 3.7
LOPEb 3000 (10) 0.2 0.4
'Dylan 2020F (ARCa Polymer.;, Inc.).
'Super Dylan SOP 640 (ARCa Polymer.;, Inc.).

SMA resin modified polyethylenes were Composites Interface Symposium, Case Western Re-
compared to unmodified resins in adhesion to serve University, Cleveland, Ohio, June 1988.
4. Monte, S. J., and Sugerman, Gerald, "New Titanates
aluminum and steel. Table 3 indicates that and Zirconates For Tire Cord Adhesion," Presented
adhesion is significantly improved by the ad- at the 7th Annual Meeting and Conference of the Tire
dition of about 10% of the appropriate SMA Society on Tire Science and Technology, The Urliver-
resin. sity of Akron, Akron, Ohio, March, 1988.
5. Cohen, L. B., "Zircoaluminate Surface Modifiers
Fluorosurfactants Present New Opportunities In Pigmented Plastics,"
SPE RETEC, Coloring of Plastics, Philadelphia, dct.
DuPont produces a line of fluorosurfactants, 2,3, 1984.
tradenamed Zonyl, that have been recom- 6. Cohen, L. B., "Mineral Filled Resins: In Situ Surface
mended for use as a resin additive for improved Modification With Zircoaluminate Metallo Organic
Coupling Agents," SPE ANTEC, Paper 636, New
wetting and bonding with fillers. Orleans, Apr. 1984.
7. Cohen, L. B., "Irreversible Surface Modification with
References Zircoaluminate Coupling Agentsa: High Performance
in Composite Materials," Society of the Plastics In-
1. Katz, H. S., and Milewski, John V., "Handbook of dustry, 39th RP/C Conf., Houston, Jan. 16-19, 1984.
Fillers for Plastics, " New York, Van Nostrand Rein- 8. Cohen, L. B., "Zircoaluminates Strengthen Premium
hold Co., 1987. Range Of Chemical Coupling Agents," Plastics Eng.,
2. Sugerman, G., Monte, S. J., Gabayson, S. M., and 39(11), pp. 29-32 (1983).
Chitwood, W. E., "Enhanced Bonding Of Fiber Re- 9. Cohen, L. B., "The Chemistry and Reactivity of Zir-
inforcements to Thermoset Resins," SAMPE Tech- coaluminate Coupling Agents for Filled and Rein-
nical Conference, Minneapolis, MN, Sept. 1988. forced Plastics," Society of the Plastics Industry, 41st
3. Sugerman, Gerald, and Monte, Salvatore J., "The RP/C Conference, Jan. 1986.
Usage of Organometallic Reagents As Catalysts And 10. "Polymers as Modifier Additives," Plastics Tech-
Adhesion Promoters In Reinforced Composites," nol., 15-19 (July 1988).
 33
Resins for Elastomer-Based
Adhesives
JOHN S. AUTENRIETH
Hercules Incorporated
Retired
and
KENDALL F. FOLEY
Hercules Incorporated
Wilmington, Delaware

Elastomer-based adhesives are widely used in solutions of rubber were used for laminating
industrial and household applications. Pressure and waterproofing textile products. Later, such
sensitive tapes and labels, hot melt packaging adhesives were vulcanized after application.
adhesives, disposable products, construction Adhesives made with natural rubber latex were
adhesives, and hot melt bookbinding adhesives first prepared in the middle of the 19th Cen-
are just a few of the adhesive systems which tury. The early solvent cements were seldom
have shown rapid market growth in recent formulated with resins, although the inclusion
years. Other types of elastomer-based adhe- of rosin was found to be beneficial. Strength
sives have been developed for high-strength requirements in these early adhesives were, for
structural applications required by the aircraft, the most part, low.
automotive, and construction industries. The With the development of synthetic elasto-
wide range of properties available in these ad- mers during World War II, new types of ad-
hesive systems is due in part to: (a) the variety hesives appeared for application to a broader
of properties obtainable in natural and synthetic range of substrates and for use at higher tem-
elastomers and (b) the many modifying mate- peratures. Styrene-butadiene and butadiene-
rials such as tackifying resins, reinforcing res- acrylonitrile copolymers found application in
ins, fillers, plasticizers, and curing agents new adhesives. There were also significant
which may be incorporated into the adhesive concurrent developments in adhesives based on
formulation. chlorinated rubber, polychloroprene (neo-
prene), and poly sulfide rubber. Development
of carboxylic elastomers, silicone rubbers, and
HISTORICAL BACKGROUND
polyurethanes followed.
The earliest rubber adhesives were merely sim- The introduction of a number of elastomer-
ple solutions of unmodified natural rubber. The thermosetting resin blends extended the appli-
adhesive properties of raw natural rubber were cation of elastomer-based adhesives to struc-
recognized as long ago as 1791, when naphtha tural applications. These blends typically
556
 RESINS FOR ELASTOMER-BASED ADHESIVES 557

consisted of reactive phenolic resins with neo- from the derivatization of wood, gum, and tall
prene or nitrile rubber. The key properties of oil rosin. These are low molecular weight res-
these adhesives were high strength and low ins, with the Mw seldom exceeding 2000 and
creep. often below 1000. In addition, thermoplastic
The commercial introduction of the thermo- and thermosetting phenolic resins are often in-
plastic block copolymers in 1965 gave impetus corporated into high performance adhesives.
to the development of high performance pres- Tackifying resins comprise the subject matter
sure sensitive and hot melt adhesives. These for most of this chapter and will be discussed
unique materials, based on styrene endblocks in detail later.
and either isoprene, butadiene, or ethylene-bu- Plasticizers and softeners include the phthal-
tylene midblocks, have become established as ates such as dioctyl phthalate and diisobutyl
the elastomer of choice in some of the fastest phthalate, natural oils such as lanolin, and par-
growing segments of the adhesive and sealant affin, naphthenic and aromatic oils obtained
industry. from petroleum refining. Liquid resins from
rosin or petroleum feedstocks can serve the dual
purpose of tackification and plasticization.
ADHESIVE COMPONENTS
Fillers are materials such as carbon black,
Elastomer-based adhesives typically contain an zinc oxide, clays, chalk, whitings, calcium sil-
elastomer and a tackifying or modifying resin icate, and barium sulfate. These materials are
as key components. A number of other ingre- used to reduce cost, increase hardness, im-
dients may be included: prove abrasion resistance, and to modify the
cohesive strength of the formulation.
1. Elastomer.
Curing agents are incorporated into the ad-
2. Tackifying (modifying) resin.
hesive formulation to increase the cohesive
3. Plasticizer or softener.
strength of the elastomer. Sulfur was the most
4. Fillers.
commonly used curing agent in early natural
5. Pigments.
rubber adhesive systems, but it has been largely
6. Curing agents.
replaced by organic peroxides and isocyanate
7. Antioxidants.
crosslinking systems.
An elastomer is a natural or synthetic poly- The antioxidants used in adhesive formula-
mer with rubberlike properties. These materials tions are similar to those used in rubber com-
exhibit high extensibility and quick, forceful pounding and include materials such as the
recovery. Examples of elastomers used in ad- aromatic amines, substituted phenols, and hy-
hesive applications are: droquinoes. Elastomer and resin manufacturers
typically incorporate antioxidants (0.1-0.3 wt
• Natural rubber. %) in their products for protection during stor-
• Acrylic copolymers. age and shipment. Adhesive formulators will
• Styrenic block copolymers. usually add additional antioxidant to protect the
• Butyl rubber. adhesive during processing and use. It is not
• Chlorinated rubber. unusual for an adhesive formulation to contain
• Polyisobutylene.
as many as three or four different types of an-
• Styrene-butadiene rubber (SBT).
tioxidants.
• Polychloroprene (neoprene).
In addition to the components cited above,
• Silicone rubber.
aqueous adhesives based on rubber latexes and
• Ethylene-propylene copolymer rubber.
resin emulsions also employ a wide variety of
• Polyurethanes.
materials, such as protective colloids, emulsi-
• EPDM. fiers, thickeners, and emulsion stabilizers. The
The tackifying (or modifying) resins which primary function of these additives is to pro-
are used in formulating elastomer-based adhe- vide stability to the aqueous adhesive. They do
sives are obtained by the polymerization of pe- not necessarily enhance the adhesive properties
troleum and terpene feedstreams, as well as of the finished composition. In fact, a careful
 558 HANDBOOK OF ADHESIVES

compromise must be reached between the dis- operation itself is one of skill and art. Temper-
persion properties and the perfonnance char- ature, speed of rolls, surrounding atmosphere,
acteristics of the adhesive. Migration of time of milling, and clearance between the rolls
stabilizers can reduce the tack of pressure sen- are all variables which are difficult to duplicate,
sitive adhesives upon aging or can cause stain- not only from machine to machine, but for each
ing of backing substrates. Improper use of batch operation on the same machine. The abil-
stabilizers in latex adhesives can also result in ity to mill to the same level of degradation is
poor resistance to moisture in the final appli- essential to obtaining a consistent cohesive
cation. strength in the adhesive fonnulation. Differ-
ences in milling levels become especially ap-
TYPES OF ELASTOMER-BASED parent in the shear resistance of natural rubber
ADHESIVES pressure sensitive adhesive unless the cohesive
strength is regenerated by curing of the adhe-
Pressure sensitive adhesives based on a variety
sive.
of elastomers and applied from either latex,
The measurement of the effects of mastica-
solvent, or hot melt systems have shown rapid
tion on the molecular weight of the rubber can
growth in recent years. In addition, the devel-
be time-consuming even with sophisticated
opment of hot melt assembly adhesives based
techniques such as size exclusion chromatog-
on the styrenic thennoplastic elastomers is a
raphy. The viscosity of natural rubber is usu-
key factor in the production of disposable dia-
ally measured by means of a Mooney rotating
pers and other sanitary products. Even though
disk viscometer,l an established method for
the current emphasis of elastomer-based adhe-
following the effect of mill time and condi-
sive development is on pressure sensitive ad-
tions. Adhesive fonnulators have successfully
hesives, large volumes of solvent cements,
used this instrument to correlate Mooney vis-
latex cements, and mastics are still produced.
cosity to rubber end-use properties.
Solvent cements are generally produced by
Solvent Cements
removing the milled elastomer from the mill
The preparation of many solvent cements, mas- and dissolving it in solvent. This "cutting" of
tics, and pressure sensitive adhesives involves the rubber into a solvent is accomplished in
milling or mastication of natural rubber. The low-speed mixing equipment known as churns
elastomer, obtained by the coagulation of nat- or in a variety of high-speed, heavy-duty mix-
ural rubber latex, is usually kneaded by passing ers. For natural rubber and SBR, solvents such
repeatedly between two steel rolls moving at as toluene, hexane, or naphtha are commonly
different speeds or in a Banbury-type mixer, used. For nitrile, neoprene, and other polar
usually at an elevated temperature. The poly- polymers, polar solvents such as methyl ethyl
mer is subjected to compression followed by ketone (MEK) , methyl isobutyl ketone
strong shearing forces. The very high shearing (MIBK), or chlorinated solvents may be used,
force mechanically ruptures the elastomer alone or in blends with the nonpolar solvents.
chains, thus reducing the molecular weight of The blend of solvents finally used by the ad-
the rubber. Whereas the starting material was hesive producer will depend not only on sol-
essentially elastic and capable of undergoing vent power, but on the relative rates of
pennanent defonnation only under extreme evaporation which control drying time. The
loads, after milling, it becomes softer, readily dissolved rubber can then be blended with
defonnable, and soluble in both aliphatic and whatever additives are needed to obtain the de-
aromatic solvents. sired adhesive perfonnance.
In practice, it is difficult to define and control The process of masticating and dissolving
rubber milling conditions. The concentration natural rubber is important for pressure sensi-
and type of natural products in raw natural rub- tive fonnulation as well as for solvent cement
ber vary, as do the amount and type of mate- production. Pressure sensitive tapes and labels
rials in the synthetic rubbers. These variables based on natural rubber are a significant part of
influence the result of mastication. The milling the rapidly growing pressure sensitive adhesive
 RESINS FOR ELASTOMER-BASED ADHESIVES 559

industry and will be discussed in more detail sible, and pressure sensitive adhesives based on
later. natural rubber, SBR, and acrylic latexes have
Solvent cements are usually supplied at con- become a significant part of the adhesive in-
centrations of 10-25 % solids, with viscosities dustry. The production of tackifying resin dis-
in the range of 1,000-30,000 cPs. They may persions will be discussed in more detail later
be applied by brush, spray, doctor blade, re- in this chapter.
verse-roll coater, hand roller, trowel, and many Latex adhesives offer several advantages over
other application methods. The proper coating solvent systems. In addition to being more en-
of the adhesive is obtained by establishing the vironmentally acceptable, latex systems offer
correct viscosity for the particular application minimum fire hazards, easy cleanup of equip-
method. After application, the solvent is re- ment, and higher solids content. A rubber latex
moved by ambient drying or by forced drying is considerably less viscous at much higher sol-
in heated ovens or tunnels. ids content than a corresponding solvent sys-
Solvent cements encompass a wide range of tem.
performance properties, from the simple natu- Natural rubber latex at 40% solids is much
ral rubber based cements which are widely used lower in viscosity than a 15 % solids solution
for low performance applications in homes and of milled rubber in toluene. In addition, the
schools to the structural applications of contact natural rubber in latex form is of much higher
adhesives based on polychloroprene and reac- molecular weight than the milled rubber. This
tive phenolic resins. higher molecular weight yields much higher
shear resistance when formulated into pressure
sensitive adhesives.
Latex Adhesives
A key aspect of formulating latex adhesives
A rubber latex is a two-phase system consisting with rubber and resins is the compatibility of
of particles of rubber dispersed in water. Pro- the individual latexes. Dispersing agents may
tective colloids and other stabilizing agents will be cationic, nonionic, or anionic. Knowledge
be present in a latex to keep the rubber well of the chemical nature of the systems is critical
dispersed and to prevent agglomeration or co- to preventing coagulation of the solids when
agulation of the rubber particles. Natural rub- blending a rubber and a resin latex.
ber is collected as a latex from certain species While solvent cements may provide greater
oftropical trees, in particular, Hevea brasilien- ultimate strength than latex systems, the latter
sis. The rubber particles exist as globules of 1- types find wide use and are often necessary for
3 microns diameter at a solids level of 35-40 %. certain bonding requirements. Solvent systems
A number of synthetic rubbers are produced penetrate into a porous substrate, with the re-
by emulsion polymerization and are, therefore, sult that multiple applications are often neces-
available in latex form. Those of greatest com- sary to put enough adhesive on the surface to
mercial interest are SBR, acrylic, neoprene, and form a satisfactory bond. Since latex systems
vinyl acetate-ethylene. Rubber latexes, partic- exhibite better "hold-out" on porous surfaces,
ularly natural and SBR, have been used for one coat of such an adhesive is often sufficient
many years in carpet and upholstery backsiz- for good bonding.
ings, bag, shoe, and bookbinding adhesives,
tile mastics, tire cord dips, and wookworking
Mastics
adhesives.
Environmental concerns, which have re- Mastics constitute a special type of adhesive
sulted in restrictions on the use of organic sol- which may be either latex or solvent-based. The
vents, have been the impetus for a strong unique characteristic of mastics is their ex-
interest in the use of rubber latexes in the for- tremely high viscosity. Most mastics contain
mulation of pressure sensitive tapes and labels, natural rubber, SBR, or a blend. Some asphalt
can sealants, and contact adhesives. The avail- or bitumen may be added to lower raw material
ability of suitable rubber latexes and tackifying cost. Tackifiers and fillers are widely used.
resin dispersions have made this change pos- Mastics are used in large volume, chiefly in
560 HANDBOOK OF ADHESIVES

industrial applications and in the construction sensitive tape were in surgical tape and in fric-
industry, where low bond strengths are ade- tion tape for electrical, plumbing; and similar
quate. They are used to install vinyl, rubber, or fastening applications. These were typically
wood floor tiles, ceiling and ceramic wall tiles, cloth-backed tapes which did not necessarily
vinyl and linoleum sheets, indoor-outdoor car- strip cleanly from the contacted surface. Later
peting, and in the automotive industry for fas- developments yielded general purpose masking
tening insulation, silencer, and lining pads. tapes for household use and high-temperature
A simple latex mastic for applying ceramic resistant masking tapes for automotive painting
tiles and wood flooring can be made by adding applications. Polypropylene film-backed pack-
a high solids solution ( > 80 % solids) of an ap- aging tapes constitute a significant portion of
propriate tackifying resin to an SBR latex with the pressure sensitive tape industry today.
sufficient agitation to disperse the resin in the Pressure sensitive tapes and labels are of-
latex. Fillers may also be used in such a for- fered with a variety of backing materials such
mulation. Such a mastic would then be applied as crepe paper, aluminum foil, fabric, cello-
to the floor or wall by trowel. The tile to be phane, kraft paper, cellulose acetate, polyester
bonded is applied immediately with pressure film, polyethylene, polypropylene, plasticized
before a skin forms on the mastic. poly(vinyl chloride), woven glass fiber cloth,
or other flexible materials. Pressure sensitive
adhesives may be applied from solvent, latex,
Pressure Sensitive Adhesives
hot melt, or radiation cured 100% solids sys-
Pressure sensitive adhesives constitute the fast- tems. A wide variety of coating methods are
est growing segment of the rubber-based ad- utilized such as roll coating, calendering, slot
hesive industry. A variety of pressure sensitive die, and transfer coating.
tapes and labels are available, such as: A key factor in the growth of pressure sen-
sitive adhesives has been the development of
• Tapes: elastomers specially designed for pressure sen-
Packaging.
sitive applications. Natural rubber is an impor-
Medical.
tant elastomer in these applications, as are
Masking.
carboxylated SBR latexes and solvent and latex
Office/consumer.
acrylic. The thermoplastic block copolymers
• Labels:
based on styrene endblocks and a rubbery mid-
Permanent.
block of isoprene, butadiene, or ethylene-bu-
Removable.
tylene, and the styrene-butadiene multiblock
Low temperature/freezer grade.
copolymers have become established as the
Film and foil.
elastomers of choice in some of the fastest
Pressure sensitive adhesives, unlike cements growing segments of the pressure sensitive ad-
or hot melt packaging adhesives, are formu- hesive industry. These highly stable and ver-
lated to remain permanently tacky at the appli- satile materials offer a combination of
cation use temperature. The challenge to properties which permit the formulation of
formulate such products has been met by the high-performance adhesive systems. The
development of specially designed tackifying unique molecular block structure of these co-
resins and polymers. Such adhesives are char- polymers offers special challenges to the ad-
acterized by rapid adhesion to the bonding sur- hesive formulator, and these will be discussed
face. By the proper choice of polymer and in more detail in the section on tackifying res-
resins, the adhesion characteristics can be var- ins.
ied to give permanent or removable adhesives
as well as adhesives which show either adhe-
Hot Melt Adhesives
sive or cohesive failure upon peeling. These
formulating principles will be discussed in more The class of adhesives applied in hot melt form
detail in the section on tackifying resins. has become a significant part of the adhesive
The first commercial applications of pressure industry in recent years. The environmental
 RESINS FOR ELASTOMER-BASED ADHESIVES 561

pressures on solvent based adhesives which has FUNCTION OF RESINS IN

given impetus to latex adhesives have also ELASTOMER-BASED ADHESIVES
given increased impetus to developing suitable
Resin Types
hot melt systems. A key reason for the growth
of hot melt adhesives has been the development In the formulation of early elastomer-based ad-
of more thermally and oxidatively stable mod- hesives, it was soon learned that a simple sys-
ifying resins and elastomers. tem consisting of natural rubber alone gave only
These thermoplastic hot melt adhesives are marginal performance as a finished adhesive.
composed of 100% solids nonvolatile mate- Most commercially available synthetic elasto-
rials, i. e., containing no water, sol vents, etc. mers have little tack, either to themselves or to
They are solid at room temperature, but melt other surfaces. Modifiers were found to con-
and flow readily at application temperature, tribute improvement in the adhesive perfor-
275-350°F. After application, bonding and mance characteristics.
cooling, hot melt adhesives return to a solid Tackifying and modifying resins are repre-
state and develop their ultimate strength. sented by a variety of products of many differ-
The early hot melt adhesives were not strictly ent chemical types and physical properties. To
definable as rubber-based adhesives. Most a new adhesive formulator, the array of resins
"rubber" polymers such as natural rubber and offered must seem bewildering and the choice
random SBR are of such molecular weight and of an appropriate resin must seem to be nothing
structure that they do not melt readily to a more than mix and test. There is, however, a
workable coating consistency at a temperature body of knowledge concerning elastomers and
below which thermal degradation and decom- resins which allows for a systematic approach
position take place. Certain synthetic poly- to the selection of the best modifying resin for
mers, however, lend themselves to the a particular system. This systematic approach
formulation of a wide range of hot melt adhe- will be discussed in more detail shortly.
sive compositions. Polyamide and polyester The first point of confusion concerns the ter-
resins, ethylene-vinyl acetate (EVA) copoly- minology of tackifying vs. modifying resins.
mers, ethylene-ethyl acrylate (EEA) copoly- Strictly speaking, all resins added to an adhe-
mers, low molecular weight polyethylene and sive formulation modify the properties of that
amorphous polypropylene, and certain vinyl system and thus would be considered modify-
ethers have found application in hot melt ad- ing resins. The majority of resins are added to
hesives. These adhesives have found wide use an elastomer to generate increased tack or
in packaging, industrial, and construction ap- adhesion properties and are, thus, correctly
plications. called tackifying resins. Resins used in EVA,
The commercialization of the styrenic tri- polyethylene, or other non-pressure sensitive
block copolymers in 1965 and the introduction hot melt adhesives are incorporated primarily
of the styrene butadiene multiblock copolymers to modify the viscosity and control open time.
in the early 1980s have caused an increased in- Thus, they are more correctly called modifying
terest in the application of hot melt adhesives. resins. With the development of block copoly-
Not only have these materials greatly expanded mer-based pressure sensitive adhesives, an-
the applications of hot melts into product as- other class of resin, the endblock reinforcing
sembly such as disposable diapers and other resin, has come into widespread use. These
sanitary products, but the ability to formulate resins associate only with the styreneic blocks
hot melt pressure sensitive adhesives from these of the copolymers and increase the shear resis-
copolymers has been a boon to the pressure tance of the adhesive formulation.
sensitive adhesive industry. Hot melt pressure Modifying resins have the following char-
sensitive adhesives are ideally suited where fast acteristics:
production speeds, relatively low raw material 1. Low molecular weight, thermoplastic
cost, and the elimination of the need to remove polymers (Mw 200-2000);
or recover solvent are essential to the favorable 2. Viscous liquids to hard, brittle glasses at
economics of the manufacturing process. room temperature;
562 HANDBOOK OF ADHESIVES

3. Obtained from the derivatization of rosin

-~~
or by the polymerization of petroleum
distillates, turpentine fractions, coal tar,
and pure monomers;
4. Range from water-clear to dark brown or
black in color; and
5. Are soluble in aliphatic and aromatic hy-
W
CH3 'COOH
Fig. 2. Abietic acid.
drocarbons as well as in many other com-
mon organic liquids.
twelve resin acids have been identified . .Abietic
The general classes of resins, based on their acid, Fig. 2, is a common resin acid.
chemical nature, are: The derivatization of rosin focuses on the
carboxyl group and the double bonds. Double
1. Rosin, modified rosin, and rosin deriva- bond reactions such as isomerization, hydro-
tives; genation, dehydrogenation, polymerization,
2. Hydrocarbon resins; and and Diels-Alder adduction are typically carried
3. Terpene resins. out. Reactions of the carboxyl group include
salt formation, esterification, hydrogenolysis,
Rosin resins are produced from the three
ammonolysis, and decarboxylation. Fig. 3 is a
types of rosin-gum, tall oil, and wood. Fig. 1
schematic or rosin derivatization carried out by
shows the sources and processing steps used to
one manufacturer, Hercules Inc.
obtain rosin from pinewood.
Hydrocarbon resins are typically classified by
Although unmodified rosin has some appli-
the chemical nature of the feedstreams used,
cation in low quality mastics and construction
i.e., aliphatic, aromatic, cycloaliphatic, or
adhesives, rosin is typically modified to en-
mixed aliphatic-aromatic feedstreams. The
hance its oxidative and thermal stability and to
main classes of resins commercially available
obtain a range of physical properties such as
are:
softening point and melt viscosity. Rosin is a
complex mixture of tricyclic unsaturated resin 1. Aliphatic resins (C-5);
acids with some nonacidic components. At least 2. Aromatic resins (C-9);

WOOD ROSIN GUM ROSIN TALL OIL ROSIN

CRUDE TALL OIL

(APPROX. 4S%
RESIN ACIDS)

fRACTIONATION.
EXTRACTION. OR
CHEMICAL TREATMENT

Fig. 1. Sources of rosin from pine wood.

 RESINS FOR ELASTOMER-BASED ADHESIVES 563

HYDROGENATE

ESTERS .-----ESTERS-----, ESTERS

/'\...PE*I /'\... PE

*-
GLYCEROL TRIETHYLENE GLYCEROL PE GLYCEROL
GLYCOL

~
METHYL ESTER
6

rESTERS,
GLYCEROL PE

REDUCE WITH CAT. HJ 4

PENTALYN
C

VACCUM DIST.

_-----Il'------;.~ REMAINS

*1 HYDROABIETYL ALCOHOL

DROPS.P*( ,ESTERS - - - , ,ESTERS - - - ,

RESIN NAME I GLYCEROL PE GLYCEROL PE
*J PENTA ERYTHRITOL *4 L = LIQUID 167

Fig. 3. Hercules, Inc., rosin derivatization.

3. Aromatic/aliphatic resins (C-5/C-9); and adhesion is necessary. To produce a suit-

4. Pure monomer resins based on styrene, able adhesive, three key criteria are required:
alphamethylstyrene (AMS), and vinyltol-
1. Tack or wetting properties;
uene; and
2. Adhesive strength; and
5. Hydrogenated resins.
3. Cohesive strength.
Polyterpene resins, aromatic-modified ter-
Tack is a term that is difficult to define in
pene resins, and phenolic-modified terpenes are
specific terms. Tack frequently represents a
produced from alpha-pinene , beta-pinene, d-lim-
combination of many physical properties. Mea-
onene, and dipentene. Examples of the various
surement of tack by application of finger pres-
resins listed by chemical type, trade name,
sure, a common technique, is obviously not
physical properties, and manufacturer are found
quantitative. In adhesives technology, tack may
in Table 1.
be defined as the property of a material which
enables it to form a bond of measurable strength
Tack
immediately upon contact with another sur-
Before discussing the function and selection of face, usually with low applied pressure. Tack
resins for adhesives, some discussion of tack is thus "instantaneous" adhesion and differs
 Table 1. Modifying Resins- Types and Properties.
Softening Point,
°C
Acid
Resin Type Trade Name No. Drop' R&Bb Manufacturer
Rosins:
Gum rosin 165 78 China, Brazil
Tall oil rosin 163 80 5,6
Wood rosin Pexite® 160 80 73 1
Modified Rosins:
Polymerized rosin Poly-pale resin 144 102 95
Hydrogenated rosin Staybelite 160 76 68
Disproportionated rosin Dymerex resin 140 148
Rosin Esters:
Pentaerythritol-wood rosin Pentalyn A 12 111
Glycerine-hydrogenated wood rosin Staybelite Ester 10 8 83
Pentaerythritol-hydrogenated wood
rosin Pentalyn H 12 104
Glycerine-highly hydrogenated wood
rosin Foral85 9 82
Pentaerythritol-stabilized rosin Pentalyn 344 10 104
Hydrocarbon Resins:
Aliphatic petroleum Piccotac® series 0 70-115 1
Escorez® series 0 90-115 2
Wingtack® series 0 86-115 3
Aromatic petroleum Piccovar4' series 0 10-60
Picco® 5000 series 0 70-140 1
Nevchem® series 0 70-150 4
Dicyclopentadiene Piccodiene® 2215 0 115
Heat reactive Neville® LX series 0 90-155 4
Aromatic modified aliphatic Hercotac® 1149 0 96
Super Sta-Tac® 0 80-100 7
Polymerized Terpenes:
Alpha-pinene Piccolyte® A series 0 115-135
d-Limonene Piccolyte C series 0 10-135
Beta-pinene Piccolyte S series 0 10-135 1
Aromatic modified Zonatac® 105 0 105 5
Terpene phenolic Nirez® 2000 series 0 122-148 7
Polyterpene Nirez 1000 series 0 10-135 7
Pure Monomer Resins:
StyrenelAMS Kristalex® series 0 25-140
AMS/vinyl toluene Piccotex® series 0 75-120
Styrene Piccolastic® series 0 5-75
Hydrogenated Hydrocarbon:
Cycloaliphatic Regalrez® series 0 18-138 1
Escorez 5000 series 0 80-120 2
Super Nirez series 0 100-120 7
Regalite® series 0 70-120
Reinforcing Resins
Endex® series 0 155-160
Kristalex 5140 0 140 1
Cumar4' Lx-509 0 155 4
'Hercules drop softening point
bASTM Method E28-67 Ring & Ball method
Manufacturers :
I. Hercules Inc. 3. Goodyear Chemicals. 5. Arizona Chemical Co. 7. Reichhold Chemicals, Inc.
2. Exxon Chemical Co. 4. Neville Chemical Co. 6. Union Camp Corp.

564
 RESINS FOR ELASTOMER-BASED ADHESIVES 565

from final strength. The time required for de- ined the relationship between viscoelasticity
velopment of strength by means of tack is very and peel adhesion of rubber-resin blends.
short compared to the time allowed for devel- More recently, Class and Chu4 extended the
opment of maximum strength. The measure- use of dynamic mechanical measurements to a
ment of tack of a pressure sensitive tape or label systematic study of resin-elastomer blends
when the adhesive is applied to a surface with- which revealed the relationship between the
out applied pressure and then immediately re- structure, concentration and molecular weight
moved is known as quick stick. of resins and their effect on the viscoelastic
Tack is a function of the rheological prop- properties of elastomers. Dynamic mechanical
erties of the adhesive as well as the surface en- data typical of that obtained from an elastomer
ergy characteristics of the adhesive and the or elastomer-resin blend is shown in Fig. 4. G'
bonded surface. Resins modify both the rheo- is the elastic or storage modulus, G" is the vis-
logical properties and surface energy of the ad- cous or loss modulus, and the ratio of G" / G'
hesive formulation to give the proper flow and gives the tan 0 curve. The temperature at which
wetting characteristics. Tack is sensitive to the tan 0 curve shows a maximum corresponds
variations in temperature, pressure, rate of ap- to a dynamic glass transition temperature. Class
plication and removal of pressure, and contact and Chu showed that with these types of mea-
time. surements, the effect of modifying resins on the
Adhesive strength refers to the strength of the viscoelastic properties of elastomers can be
bond produced by contact of an adhesive to a readily determined. Resins which are compat-
surface. Again, this ultimate strength will de- ible with an elastomer will cause a decrease in
pend on temperature, pressure of application, the elastic modulus G' at room temperature and
and time of contact. Adhesion of pressure sen- an increase in the tan delta peak or glass tran-
sitive adhesives is usually measure by a peel sition temperature. Resins which are incompat-
test. ible with an elastomer will cause an increase in
Cohesive strength refers to the internal the elastic modulus G' at room temperature and
strength of an adhesive or the ability of the ad- will show two distinct maxima in the tan delta
hesive to resist splitting. The clean peel of an curve.
adhesive from a surface requires that the co- Chu has also characterized numerous com-
hesive strength of the adhesive be greater than mercial pressure sensitive adhesives and shown
the adhesive strength to the bonded surface. that elastic modulus and glass transition tem-
Unlike tack and adhesion, which are dependent perature are key viscoelastic properties in char-
on the surface being bonded, cohesive strength acterizing pressure senSItIve adhesive
is not influenced by the substrate. performance. An excellent review outlining the
characterization of pressure sensitive adhesive
by dynamic mechanical measurements and dis-
Tackifier Function cussing how these data can aid in the formu-
lating of adhesives has been recently published
Tackifying resins enhance the adhesion of non- by Chu. 5
polar elastomers by improving wettability, in-
creasing polarity, and altering the viscoelastic
I. .. STlIIA&E ___us
properties of the adhesive mass. The under-
/
standing of how resins modify the viscoelastic /'
properties of elastomers has developed signifi- llOOUWs. lff
-w, /
/

cantly since the later 1960s. In 1966, C. Iff

Dahlquist2 defined the performance of pressure Iff

TAN 6

sensitive adhesives on the basis of creep com-

pliance. Sherriff, Aubrey, and co-workers3 later
demonstrated the effect of adding low molecu- TE..... ·C

lar weight resins to natural rubber and exam- Fig. 4. Viscoelastic properties of polymers.
566 HANDBOOK OF ADHESIVES

T ackifier Selection the resin-elastomer blend will thus increase as

the level of resin is increased. The decrease in
The major factors which determine the utility
the elastic modulus will be determined by the
of a resin as a tackifier are:
compatibility of the resin with the elastomer.
1. Chemical structure; Thus, a formulator may be working with a
2. Molecular weight; and compatible resin-elastomer blends but only cer-
3. Molecular weight distribution. tain combinations will allow him to obtain the
desired level of elastic modulus and glass tran-
Other factors of importance are: sition temperature.
1. Softening point; An adhesive formulator has limitations on the
2. Initial color; amount of resin which can be incorporated into
3. Color stability when heated; and an elastomer in an attempt to obtain the desired
4. Oxidative and UV stability. combination of rheological properties. All
resin-elastomer blends show a variation in ad-
The modification of an elastomer by a low hesive properties vs. the concentration of resin.
molecular weight resin is determined by the Fig. 5 shows probe tack as a function of resin
compatibility (or solubility) of the resin in the concentration for a natural rubber-resin ester
elastomer. Compatibility is necessary for gen- blend. This type of resin response curve is typ-
erating tack, but compatibility does not insure ical of all adhesive systems. In Fig. 5, little
that the desired adhesive properties will be ob- enhancement of tack is seen up to 40 % resin
tained. Rheology studies have shown that ad- concentration. Between 40 and 65 % resin, there
hesive performance is related to the elastic is a rapid increase in tack, followed by an
modulus at application temperature and to the equally rapid drop off in tack above 65 % resin.
glass transition temperature of the resin-elas- Above, 65 %, the system becomes overloaded
tomer blend. A tackifying resin has a glass in resin, incompatibility develops, and tack
transition temperature higher than that of an drops. The maximum in a resin response curve
elastomer. The glass transition temperature of will be determined by the general compatibility

PARTS RESIN PER HUNDHII PARTS RUDER

10 30 50 70 100 150 200 300 «Xl 600 900

~...
1200
l\o
~ 1~
Q

~ 800

;:
~
~
w
________--o---o--o
J
... 200

PERCENT TACKlfYING RESIN IN NATURAL RUIIER

Fig. 5. Probe tack vs. resin concentration for natural rubber-rosin ester blend.
 RESINS FOR ELASTOMER-BASED ADHESIVES 567

of the resin with the elastomer. Typically, the Table 2. Resin Cloud Points.
lower softening point versions of chemically DACP, DC OMSCP, DC
similar resins will develop maxima at higher (Polar MMAP, DC (aliphatic
resin loadings than the higher softening point Resin solvent) (aromatic) solvent)
resins. Staybelite 10 <0 <0 <-10
A simple test of compatibility is the clarity ester <0 2 <-10
of a resin-elastomer blend. A 1 : 1 blend can be Foral85 <0 15 <-10
prepared in solution and cast onto a glass plate. Foral105
The solvent is allowed to evaporate and the cast Piccotex 120 <0 10 60
film observed for clarity. A clear film indicates Piccotex 75 <0 0 -22
good compatibility while a cloudy or opaque Piccolyte S-1l5 56 87 <-10
film indicates some degree of incompatibility. Piccolyte S-135 61 95 <-10
A more quantitative indication of compati- Piccopale" 100 70 97 10
bility can be obtained with solvent or hot melt Piccotac B 55 90 <-10
cloud point tests. The solvent cloud point tests
are based on the idea that resins will be com-
patible with elastomers of similar chemical na- ters would have wide compatibility with most
ture. Thus aliphatic resins will be effective elastomers-a fact that is well known. The
tackifiers for aliphatic elastomers such as nat- other resins show more selectivity. The high
ural rubber, while aromatic resins are needed cloud points in the polar and aromatic solvent
for aromatic elastomers such as SBR. Some blends in conjunction with a low OMS cloud
resins, e.g., rosin esters, will be compatible point explains why C-5 aliphatic resins are
with many different types of elastomers. Sol- compatible only with aliphatic elastomers such
vent cloud point tests are carried out in three as natural rubber and the isoprene midblock of
solvent systems which represent aliphatic, ar- the styrene-isoprene-styrene block copolymer.
omatic, and polar systems. The solvent blends Hot melt cloud point test can also be carried
used by Hercules are: out with resin/polymer blends.
The choice of resin tackifier influences not
1. Odorless mineral spirits (OMS), an ali- only the initial adhesive performance, but also
phatic solvent; the retention of adhesive properties upon ag-
2. Diacetone alcohol/xylene (DACP), a po- ing. Color retention and resistance to oxidation
lar blend; and and UV degradation are key considerations in
3. Methylcyclohexane/aniline (MMAP), an choosing a tackifying resin. Glycerine or pen-
aromatic blend. taerythritol esters of unmodified wood rosin ex-
The resin is dissolved in the test solvent either hibit fair tack properties initially, but have poor
at room temperature or at elevated temperature. aging characteristics primarily because of resin
The solution is then cooled and the tempera- oxidation. Esters of rosins which have been
tures at which an initial and full cloud appears stabilized by hydrogenation or polymerization,
are recorded. Low cloud points indicate good e.g., Foral 85 or Foral 105, possess the best
solubility in that solvent type and predict good combination of properties for adhesive use.
solubility of that resin in elastomers of the same The stability of hydrocarbon resins varies
chemical nature. As a rule of thumb, cloud greatly depending on chemical structure. Re-
points greater than 70°C indicate poor compat- sidual unsaturation in the resin molecule is the
ibility while cloud points less than O°C indicate point for oxidative attack. Aliphatic C-5 resins
excellent compatibility. Table 2 shows cloud and terpene resins can be protected with an-
points for four types of resins-rosin esters tioxidants to give good aging characteristics.
(Staybelite 10 Ester and Foral 85, 105), pure Aromatic resins vary considerably in structure,
monomer aromatics (Piccotex), poly terpene but generally show good oxidative resistance.
resin (Piccolyte), and C-5 aliphatic resins (Pic- The most stable modifying resins available are
copale, Piccotac). The low cloud points of the those classified as hydrogenated resins. These
rosin esters in all blends predicts that rosin es- resins are the result of hydrogenating aromatic,
568 HANDBOOK OF ADHESIVES

aliphatic, or cycloaliphatic resins to remove as Table 3. Modifying Resins for Block

much unsaturation as possible. The water-clear Copolymers.
initial color and color stability under oxidative,
A. Midblock Tackifiers:
UV, and elevated temperature conditions make Rosin esters
these the resins of choice for high-performance Aliphatic C-5 hydrocarbon resins
applications. Terpene resins
The development of the styrenic block co- Aromatic-modified aliphatic resin&
Hydrogenated resins
polymers has created special challenges for B. Endblock Compatible Resins:
resin manufacturers. These block copolymers Rosin esters
are oftwo basic types. The first are the triblock Aromatic resins
copolymers, consisting of an elastomeric mid- Low molecular weight resins
block and thermoplastic polystyrene end- C. Endblock Reinforcing Resins:
High softening point aromatic resins
blocks. These can be either the linear triblock
copolymers, such as the Kraton polymers from
Shell Chemical Company or the Europrene poly-
Table 4. Adhesive Performance- Effect
mers from Enichem, or radial block copoly-
of Mw and MWD.
mers, initially produced by Phillips Petroleum
and now available from Petrofine SA under the SIS 100 100 100
Piccotacill> 95 100
tradename Finaprene. The linear triblock co- Piccotacill> B 100
polymers are the most widely used in the ad- Piccopaleill> 100 100
hesive industry. Quick Stick, oz/in. 66 38 1
The second type of polymer is the multiblock 180 0 Peel, oz/in. 105 80 35
copolymer based on styrene and butadiene, Shear resistance, (min) 10,000+ 10,000+
SAFT,oC 105 105
available from Firestone Synthetic Rubber and
Latex Company under the tradename Stereon.
This material has a much higher level of sty-
structure, all three of these resins should be
rene than do the triblock copolymers (43 % vs.
compatible with the isoprene midblock of a sty-
30% max.), but the formulation techniques
rene-isoprene-styrene block copolymer. Pic-
used with this material would be similar to
copale 100, with the highest molecular weight
those used to compound a styrene-butadiene
and broadest molecular weight distribution,
triblock copolymer.
generates poor adhesive properties. Piccotac B,
Block copolymers, like most elastomers, re-
intermediate in molecular weight and molecu-
quire modifying resins to develop the desired
lar weight distribution, generates reasonable
adhesive properties. Tack is built into the for-
properties, while Piccotac 95, with the lowest
mulation by the use of midblock associating
molecular weight and narrowest molecular
resins, while enhanced thermal resistance and
weight distribution, generates maximum adhe-
strength properties can be obtained by the use
sive properties. These data thus show that in a
of endblock associating resins. The challenge
homologous series of resins, the lowest molec-
to resins suppliers has been to design resins that
ular weight resin with the narrowest molecular
will associate exclusively with the desired
weight distribution generates optimum tack
phase. Resins that associate with both phases
properties. There may be, however, other con-
are desired in some cases, and they can be ef-
siderations such as optimizing shear resistance
fective tackifiers, but they typically cause a se-
in a pressure sensitive adhesive that would
vere loss in the cohesive strength of the
cause a formulator to choose a resin that does
formulation. Table 3 lists modifying resins for
not give optimum tack.
block copolymers.
Table 4 shows the effect of molecular weight
LATEX-BASED PRESSURE SENSITIVE
and molecular weight distribution on the tack-
ADHESIVES
ifying effectiveness of three C-5 aliphatic res-
ins. These three resins have softening points in It has been previously mentioned that govern-
the range of 92-100°C. Based on chemical ment restrictions on the use of organic solvents
 RESINS FOR ELASTOMER-BASED ADHESIVES 569

enacted in the 1970s gave impetus to the de- emulsions can be as high as 10-12. If such a
velopment oflatex-based pressure sensitive ad- resin emulsion is blended with a low pH elas-
hesives. Although a number of synthetic tomer latex, latex shock will often result and
elastomer latexes were commercially available the elastomer and resin will coagulate. Latex
along with the natural rubber latex, most of shock can be minimized by the use of additives
these latexes were not ideally suited for pres- to the resin emulsion, but even similarity of pH
sure sensitive adhesive formulation. Latex does not always insure latex compatibility.
manufacturers and resin suppliers thus began Many anionic emulsifier systems are suscep-
development programs which have resulted in tible to coagulation by strong acids or multi-
SBR, acrylic, and vinyl acetate-ethylene la- valent cations. Again, additives can enhance
texes well suited for pressure sensitive adhe- the ion tolerance of resin emulsions, but careful
sive applications and resin emulsions that are testing is necessary.
effective tackifiers for these elastomers. Stability to shearing forces is critical to latex
Resin dispersions can be prepared in two adhesives. Pumping and coating operations put
general ways. In the direct method, a liquid high shear forces on the latex which will result
material is added directly to an emulsifier so- in coagulation and grit formation if sufficient
lution and dispersed with good agitation. If the mechanical stability is not present.
resin is solid at room temperature, it must be Once the proper compatibilities and stabili-
either dissolved in a organic solvent or melted ties are obtained, the elastomer-resin blend can
and added molten to the aqueous phase. Any be prepared. At this point, another difference
organic solvent is usually undesirable and must between solvent or hot melt and latex adhesives
be removed after emulsification. arises. In solvent or hot melt systems, at the
In the inversion method, a water in oil emul- time of application, the resin and elastomer are
sion is first formed by slowly adding water to intimately mixed. Removal of solvent or cool-
the resin phase in the presence of an emulsifier. ing results in the desired adhesive properties.
As more water is added, an inversion point is In a latex system, the degree of mixing of the
reached at which water becomes the continuous components is not as extensive. Merely remov-
phase and the dispersion becomes an oil in ing the water at room temperature usually does
water emulsion. Fine particle sizes are devel- not result in the desired level of tack. Some
oped by shearing the viscous mass at the in- heating of the system is required to mix the
version point. After inversion, water is added components on a molecular scale and achieve
to reach the desired solids level which is typi- the desired adhesive properties. The softening
cally 55-60% solids. 6 point of the tackifier resin is usually the deter-
The key emulsion properties that a resin sup- mining factor in how much heating must be ap-
plier attempts to control are: plied. Low softening point resins will diffuse
more readily into the elastomer and require less
1. Total solids; heating. Fig. 6 is a schematic of this process.
2. pH; Even when the adhesive properties are ob-
3. Particle size; tained, emulsifier aging characteristics remain
4. Viscosity; a concern. Migration of the emulsifier to the
5. Mechanical stability; surface of the adhesive can cause loss of adhe-
6. Surface tension; sion. In addition, the moisture resistance of the
7. Freeze-thaw stability; and dried film must be determined. Some emulsi-
8. Ion tolerance. fiers show a strong tendency to absorb moisture
from the atmosphere and to re-emulsify the top
A number of factors must be considered in layer of adhesive, resulting in the loss of adhe-
blending elastomer latexes and resin disper- sion.
sions. A formulator must determine that the Resin manufacturers, elastomer producers,
emulsifier systems are compatible. Many resin and adhesive formulators have combined their
dispersions are prepared with anionic emulsi- knowledge to control the many factors in latex
fiers based on rosin acids. The pH of these adhesive formulation. The result is a growing
570 HANDBOOK OF ADHESIVES

SOlUT'ON OF I!VAP
BLENO Of LA"1'E'k SOL"SM"1'
E'LAS"1'Ot\tct ~ Rt4&IN
RESIN D'SPERSIO"
Fig. 6.

application for latex adhesives, particularly inthe resistance to shear of a tape under constant
pressure sensitive tapes and labels. load. It is the force required to pull a pressure
sensitive tape from a standard test panel in a
PRESSURE SENSITIVE ADHESIVE direction parallel to that surface. It is usually
TEST METHODS measured in tenns of the time required for the
tape to slip a certain distance. This test mea-
The Pressure Sensitive Tape Council6 has de- sures the cohesive strength of the adhesive
veloped a series of test procedures for the de- bond.
tennination of tack, adhesion, and shear Probe tack is a test in which a 0.5 cm di-
properties of pressure sensitive adhesives. The ameter probe is contacted with an adhesive film
most commonly used tests are: at a specified application pressure and dwell
1. 90 quick stick;
0 time. The force required to remove the probe
2. 180 peel adhesion;
0 from the adhesive is a measure of tack. 6
3. Rolling ball tack; and
4. Shear adhesion-room temperature and ACKNOWLEDGMENT
elevated temperature. The authors wish to acknowledge the contri-
Quick stick is a measure of how readily a butions of their many Hercules colleagues who
pressure sensitive adhesive adheres to a test over the years have contributed to an under-
surface with no applied pressure other than the standing of resin chemistry and adhesives ap-
weight of the adhesive backing. The test strip plications. The infonnation in this chapter is
is peeled immediately after application. compiled from their achievements.
Peel adhesion is the force required to remove
a pressure sensitive tape or label from a test REFERENCES
surface at a specified angle and rate of peel. 1. Mooney, M., Ind. Eng. Chem., Anal. Ed., 6, 147
This gives a measure of the ultimate strength (1934).
obtained by the adhesive and the dwell time be- 2. Dahlquist, C. A., Proc. Nottingham Conf. on Adhe-
fore peeling must be specified. In this test, the sion (1966). In "Adhesion: Fundamentals and Prac-
adhesive tape or label is applied to the test sur- tice," London, MacLaren and Sons, Ltd.
3. Aubrey, D. W., and Sherriff, M., J. Polym. Sci.,
face with a specified force. Polym. Chem. Ed., 16,2631 (1978); 18,2597 (1980).
Rolling ball tack is a unique test method in 4. Class, J. B., and Chu, S. G., J. Appl. Polym. Sci., 30,
which a small ball of specified weight and di- 805-825 (1985).
ameter is rolled down an incline plane onto an 5. Chu, S. G., "Handbook of Pressure Sensitive Adhe-
sive Technology," 2nd Ed., D. Satas, ed., New York,
inverted test adhesive strip. The distance the
Van Nostrand Reinhold Co., 1988.
ball rolls before stopping is an measure of the 6. Wherry, R. W., "Resin Dispersions for Water Based
tack properties of the adhesive. Pressure Sensitive Adhesives," Pressure Sensitive Tape
Shear adhesion is a method of detennining Council Seminar, May, 1979.
 Section C
Adherends and
Bonding Technology
 34
Bonding Plastics
RICHARD T. THOMPSON
Loctite Corporation
Newington, Connecticut

Modern products exploit many of the inherent bly. Mechanical fasteners concentrate the
design and manufacturing advantages of plas- stresses into a few areas in the joint.
tics. Although designing with molded plastic While a rigid metal component may accom-
often allows a reduction in the number of parts modate these stresses easily, a more flexible
needed, usually some assembly operations re- plastic part of the same cross section may re-
main. Sometimes the product is too complex to quire extra stiffening in the form of ribs, in-
mold in one piece, or it may require properties serts, or bosses. Much of the design simplicity
available only in metal, ceramic, elastomers, of molded parts can be lost in making provision
or other materials. for mechanical assembly. By contrast, a bonded
Selection of an assembly method is a critical joint requires no extra design provision other
step in the overall design process. It should be than a check to ensure that enough joint area is
analyzed at the same time as other factors so available and that the adhesive meets service
that all elements contribute effectively to the requirements.
product. Failure to do so raises the risk of dis-
covering errors after the material has been se- Fluid Tight Joints
lected and the mold fabricated. It is not safe to If fluid-tight joints are required, this require-
assume that a suitable bonding process exists ment can readily be achieved with a bonded de-
for every combination of design, materials, and sign. Mechanical joints usually require an extra
product operating environment. sealing component such as an 0 ring. Extra
sealing devices can add to the size, cost and
BONDING DESIGN ADVANTAGES overall complexity of the design.

Material Versatility Simplified Molding

Bonding allows selection of nearly any plastic The shape of a product may make it impossible
used by itself or in combination with elasto- to mold without complex tooling. In many
mers, metals, glass, ceramics, wood or other cases it is possible to lower costs by using sev-
plastics. No other assembly method is this ver- eral simpler moldings and bonding them to-
satile. gether.

Even Stress Distribution SURFACE INTERACTIONS IN BONDING

The ability to spread load evenly over the joint In the most fundamental sense, successful join-
area is especially important in plastic assem- ing of plastics always involves significant in-

573
574 HANDBOOK OF ADHESIVES

teractions between the surfaces being joined complicated by the fact that wetting of the plas-
and the bonding agents used in the process. The tic surfaces does not occur as readily as metal
interactions involved can be as simple as pen- surfaces. Special attention may be required in
etration of an adhesive into a porous surface, preparing the surfaces for joining.
or more complicated, as in the wetting of poly-
mer surfaces. Whatever the mechanism, there
Molecular Diffusion and Interpenetration
can be no joint without some form of interac-
tion. In adhesive bonding of metals, ceramics and
Plastics are distinguished from metals and other inorganic materials, it is assumed that no
other traditional materials in that there are a mixing of the adhesive and the substrates occur
wider variety of potential interactions that can and that the interface is a well defined bound-
contribute to the joint strength. In analyzing the ary between the two materials.
situation, the following classification of inter- In the case of polymer joining, the assump-
actions has been used by D. W. Aubrey. I tion of no physical mixing is not reasonable.
Welding of plastics, using heat or solvents, is
Mechanical Interlocking a clear example of interpenetration occurring at
the joint surface.
Most materials have some surface roughness or
Other examples are less obvious and may go
porosity which will allow an adhesive to pen-
unrecognized. For example, cyanoacrylate ad-
etrate before hardening. If significant porosity
hesive is a solvent for some polymer surfaces,
is present, as in a polymer foam, mechanical
and may actually dissolve and mix with some
interlock can be the most significant single in-
of the surface before it hardens. As a result, the
teraction contributing to strength and durabil-
bonds exhibit excellent durability toward mois-
ity.
ture and other environmental stresses, seem-
Joints based on mechanical interlock have
ingly in contradiction to the adhesive's poor
predictable strength and durability since these
reputation for service under these conditions.
properties are related to the bulk properties of
The interpenetration provides durability which
the substrate materials and the adhesive layer.
is absent when the same adhesive is used on an
If the substrate materials and the adhesive se-
inorganic substrate.
lected are suitable for the environment, no
When hot melt adhesives are used on plas-
trouble is expected with joint durability.
tics, a certain amount of interpenetration may
Even if the surface is not porous, the micro-
occur if the hot melt causes surface melting of
scopic roughness present on most surfaces adds
the substrate. In effect, such a joint may as-
a mechanical contribution to the strength of the
sume some of the characteristics of a weld.
joint and increases the total interfacial area
available for other bonding.
JOINING PROCESSES
Physical Adsorption/Wetting
Metal joining operations, such as welding,
Provided a liquid adhesive wets the surface of brazing, or bonding, are easily understood as
the plastic, attractive forces occur between the distinct processes. However, the technologies
liquid and the two solids. The magnitude of tend to become blurred in the field of plastic
these forces is directly related to the surface joining owing to the variety of bonding inter-
tension of the liquid and inversely to the gap actions that are possible. The person joining
between the components. plastics with a fluid may not be aware of
For closely fitted components, significant whether a weld or an adhesive bond is being
strength is achieved even with nonhardening created, although the difference may be critical
liquids. If an adhesive is used, the hardening to the success of the joint. In describing the
process strengthens the joint by adding resis- processes, efforts will be made to discuss the
tance to shear and cleavage forces. significance of the interactions that are occur-
As will be discussed later, plastic bonding is ring as well as the actual process.
 BONDING PLASTICS 575

Solvent Welding and Cementing The methods differ in the manner in which
the heat is generated. Heat welding uses con-
Many thennoplastics can be welded together
tact with hot gasses or hot plates, while ultra-
using organic solvents or combinations of sol-
sonic welding generates heat by rubbing the
vents. In solvent welding, the solvent pene-
surfaces together at ultrasonic frequencies.
trates between closely fitted parts, dissolves the
Electromagnetic bonding utilizes induction
surface, and causes them to fuse together.
heating of a ferromagnetic powder fonnulated
When the solvent dries, strong, durable bonds
into an adhesive or previously applied to the
are fonned based on the interpenetration of the
surface of the components.
polymer chains.
The process is simple and low in cost, but
Adhesive Bonding
requires close fitting parts and the availability
of suitable solvents. While different plastics can Adhesive bonding is the most versatile of these
be joined if both are soluble, joints involving joining processes, since all classes of plastics
inorganic materials or thennoset plastics are and other materials can be joined. Adhesive
impractical. bonding of plastic involves several of the join-
Solvent cements contain dissolved polymer ing interactions previously described, depend-
and can be used if gaps are present. These ma- ing upon the characteristics of the adhesive and
terials create a welding action if the substrate the substrates being joined.
polymer is soluble, and at the same time will 1. In all cases mechanical interlock is pres-
leave a gap filling film between the compo- ent, since almost all surfaces have some
nents. If porous substrates are used, mechani- degree of surface roughness or porosity.
cal interlock can take place. If surfaces are not However, the degree of mechanical inter-
soluble or porous, joint strength can still be lock can be extremely low in the case of
generated if the cement wets the surface. Ce- plastic parts produced from highly pol-
ments are capable of joining more types of ma- ished molds.
terials than solvents alone, and will tolerate 2. The degree of physical absorption de-
larger bondline gaps. pends on whether or not the adhesive wets
Solvent based joints require a carefully con- the surface. If good wetting occurs, this
trolled process to achieve good results. The process can lend substantial strength to
time between application and assembly is crit- the joint. Without good wetting, it is dif-
ical. If the time is too short, excess solvent is ficult to achieve practical adhesive bond
trapped in the joint. If the wait is too long, the strengths.
film may dry too much and there may be in- 3. It is sometimes easy to overlook the fact
sufficient flow to properly join the surfaces. that molecular diffusion and interpenetra-
A trend toward greater regulation in handling tion can occur during the fonnation of
solvents and cements is restricting the choices "adhesive bonds." Adhesives, by them-
available. Safety issues should be addressed selves or in combination with carrier sol-
early in the selection process. vents, can have a solvating effect on the
surface of plastic parts. This in tum al-
lows interpenetration of polymer mole-
Heat Welding, Ultrasonic Welding, and
cules and may lead to bonds of
Electromagnetic Welding
exceptional durability.
These techniques share the common feature of
heating the polymer surfaces above the melting BONDING TECHNOLOGY
point, joining them, and allowing them to cool
Surface Wetting Criteria
under pressure. Since significant mixing and
interpenetration of the polymers occurs, dura- As a first approximation, wetting of a surface
ble joints are created which often approach the occurs when the surface tension of the liquid
strength of the plastic itself. adhesive is lower than the critical wetting ten-
576 HANDBOOK OF ADHESIVES

sion of the solid surface. (See also Chapters 3 avoided, since it often contains lubricants to as-
and 4.) If this condition is not met, the liquid sist in finishing wood. Wipers used in the pro-
does not spread and forms a round droplet on cess should be free of sizing agents or other
the surface-as when water beads up on a soluble contaminants. 2
freshly waxed automobile. While cleaning and abrasion cannot always
In metal bonding the issue of wetting is eas- make large differences in bonding characteris-
ily settled. Clean metal surfaces have ex- tics, using this procedure first insures that prob-
tremely high critical wetting tensions, in the lems are not caused by surface contamination.
order of several hundred dynes/cm. As a con- Another potential benefit is that removal of the
sequence, adhesives with a typical surface ten- surface layer may expose polymer with better
sion of 35 dynes/cm have little trouble wetting wetting and bonding characteristics.
metal surfaces. If wetting problems occur, it is
almost always the result of contamination on Flame Treatment Flame treatment can be
the substrate surface, a condition that can be used as an effective means of changing the sur-
quickly checked with the water break test. If face characteristics of plastics. Flame treating
water with a surface tension of 73 dynes/cm is accomplished by passing the surface of the
wets the surface, it is a safe assumption that no plastic through the oxidizing portion of a nat-
problem will be encountered with lower sur- ural gas flame. The surface is rapidly melted
face tension adhesives. and quenched by the process and some oxida-
Unfortunately, wetting problems on plastics tion of the surface may occur at the same time.
are not as easily resolved. Since adhesives and Exposure time to the flame is a few seconds.
plastics are both polymers, they may have sim- While specially designed gas burners are avail-
ilar surface tensions and critical wetting ten- able for this process, preliminary laboratory
sions. Under the most favorable of conditions, trails can be conducted using the outer (oxidiz-
adhesives will still wet the surface. However, ing) portion of an ordinary gas burner.
plastics such as polytetrafluoroethylene, poly- Flame treating is widely used for polyethyl-
ethylene, or polypropylene have such low crit- ene and polypropylene, but also has been ef-
ical wetting tension that bonding is not practical fective with thermoplastic polyester,
without surface treatments designed to raise its polyacetal, and polyphenylene sulfide.
value.
Chemical Surface Treatments. Chemical
Surface Preparation surface treatments are often used to improve
Conditions may require the use of surface prep- plastic bonding. The most common involve
aration on plastics. Previously mentioned were strong oxidizing agents such as chromic acid to
cases in which the surface is too smooth for etch the surface. Polytetrafluoroethylene
mechanical interlock or has too low a critical (PTFE) and other fluoropolymers are treated
surface tension for wetting. In addition, other with etching solutions based on dispersions of
conditions may be critical. This includes the metallic sodium in organic solvents. Surfaces
presence of mold releases, plasticizers, or other treated in this way undergo dramatic improve-
contaminants on the surface of the part. Meth- ment in wetting characteristics and can be read-
ods of surface preparation are discussed below. ily bonded using a wide range of adhesives. In
some cases it is possible to purchase PTFE
Cleaning and Abrading. One of the sim- treated in this fashion.
plest methods of surface treatment is cleaning
and abrading. The most common procedure is Plasma Treatment. Plasma surface treat-
a solvent wipe, followed by abrasion and a fi- ment is a relatively new technology which is
nal solvent wipe. proving useful for improving wetting. In this
Grit blasting is often the most effective abra- process, parts are exposed to ionized gases
sion method. Aluminum oxide cloth is also ef- generated by radio frequency energy in a sealed
fective. Commercial sandpaper should be chamber under extremely low pressures. By se-
 BONDING PLASTICS 577

Table 1. Solubility Parameters of

Plastics.
0, hildebrands
Polytetrafluoroethylene 6.2
Polychlorotrifluoroethylene 7.2
Polydimethyl siloxane 7.3-7.6
Ethylene-propylene rubber 7.9
Polyethylene 7.9-8 .1
Polystyrene 8.6-9.1
Poly(methyl methacrylate) 9.3
Poly(vinyl chloride) 9.5-9.7
Amino resins 9.6-10.1
Epoxy 9.7-10.9
Polyurethane 10.0
Ethyl cellulose 10.3
Fig. I. Liquid beads on surface of polypropylene prior to Poly(vinylchloride-acetate) 10.4
plasma treatment (top). After treatment, liquid spreads (be- Poly(ethylene terephthalate) 10.7
low). Surface tension of liquid is 35 dynes/centimeter. Cellulose acetate (secondary) 10.4-11.3
Cellulose nitrate 9.7-11.5
Phenol-formaldehyde 11.5
lecting appropriate gases and exposure condi- Poly(vinylidene chloride) 12.2
tions it is possible to clean, etch, or chemically Nylon 6,6 13.6
activate the surface . Significant differences in
surface wetting can result (see Fig. 1). Bond
strength is often increased by a factor of two to
three . Because a closed chamber must be evac- Table 2. Solubility Parameter of
uated to employ plasma treatment, the process Solvents.
lends itself to large numbers of small, high-
Solvent Fractional
value parts. For larger parts it can be harder to Parameter Polarity
justify economically, since fewer parts can be (6 . hildebrands) (P)
treated in one cycle. 3
n-Perfluorohexane 5.6 0
n-Hexane 7.3 0
Landrock has compiled a comprehensive list
Cyc10hexane 8.2 0
of specific surface treatments for various types Amyl acetate 8.45 0.067
of plastics. 4 1,I,I-Trichloroethane 8.3 0.069
Carbon tetrachloride 8.6 0
Solubility Parameter Toluene 8.9 0.0001
Ethyl acetate 9.1 0.182
In the second edition of this Handbook, Mi- Trichloroethylene 9.2 0.005
ron and Skeist stressed the importance of the Methyl ethyl ketone 9.3 0.510
solubility parameter in formulating adhesives Chloroform 9.3 0.017
Methyl acetate 9.6 0.182
for plastics. The concept of solubility parame- Cyc1ohexanone 9.9 0.380
ter has been discussed in Chapter 1. Table 1 Tetrahydrofurane 9.9
gives the solubility parameter for many plas- Dioxane 10.0 0.006
tics. Table 2 gives the solubility parameters of Acetone 10.0 0.695
many solvents for plastics, along with their Carbon disulfide 10.0 0
Nitrobenzene 10.0 0.625
fractional polarities. Dimethyl formam ide 12.1 0.772
In comparing the data, Miron and Skeist Nitromethane 12.6 0.780
found confirmation of many known facts about Ethanol 12.7 0.268
the solubility of plastics. "Polystyrene (8.6- Dimethyl sulfoxide 13.4 0.813
9.1) is soluble in toluene (8.9), but not in hex- Ethylene carbonate 14.5 0.924
Phenol 14.5 0.057
ane (7.3) or acetone (10.0) . Tetrahydrofurane
Methanol 14.5 0.388
(9.9) and cyclohexanone (9.9), or mixtures of Water 23.2 0.819
the two, are preferred solvents in dope cements
578 HAND800K OF ADHESIVES

for bonding PVC pipe (9.5-9.7 for the unplas-

ticized homopolymer). Cellulose acetate (10.4-
11.3) is dissolved in blends of acetone (l0.0)
with a minor proportion of ethanol (12.7). " In
general the closer the values, the higher the
probability that the solvent will be a good
welding agent for the plastic. Such a solvent
may also be a good pretreatment for the plastic
to allow more interpretation between the sub-
strate and adhesive.
If the adhesive application method requires a
solvent, the solubility parameter of the sub- Fig. 2. Crack in polyetherimide tensile bar caused by ex-
strate is a significant criterion for solvent selec- posure to incompatible solvent.
tion. In practical cases it is not uncommon to
change the solvent blend to get a better "bite"
In most cases the possibility of stress crack-
into the surface. In more precise terms, the sol-
ubility parameter of the adhesive solution is ing can be eliminated by following these guide-
being adjusted to achieve a higher degree of lines:
interaction between the adhesive and the sub- • Work with parts that are in a low stress
strate. condition. If excessive stresses are molded
in, they can be reduced by changing the
Adhesive-Plastic Compatibility molding conditions or by annealing the
parts after molding.
When bonding metals and other inorganic ma- • Use the minimum quantity of adhesive
terials the issue of adhesive-to-substrate com- necessary and cure it as quickly as possi-
patibility seldom arises. Cases of damage to ble.
these materials are few and are typically the re- • Remove excess adhesive from parts as
sult of unusual circumstances. However, in soon as possible.
bonding plastics, care must be taken to avoid • Use only cleaning solvents and primers
crazing or stress cracking. This occurs when which are compatible with the plastic.
incompatible adhesives or solvents are applied • When in doubt, check with the suppliers
to the surface of a stressed plastic part. Soft- of the plastic or the adhesive.
ening and weakening of the surface leads to the
formation of cracks. Liquid adhesive may pen- ADHESIVE JOINT DESIGN FOR
etrate into the crack, causing further damage. PLASTICS
Eventually, the crack may propagate through
the entire part leading to failure (see Fig. 2).5.6 Compared to metals and many other engineer-
Conditions necessary for stress cracking in- ing materials, plastics have lower tensile
clude: strength, lower elastic modulus, and a higher
coefficient of thermal expansion. These differ-
• Stresses in the part, either from an exter- ences strongly influence the way joints are de-
nal source or as the result of "frozen-in" signed and adhesives are selected. In the
molding pressures . paragraphs that follow the significance of these
• Presence of liquid adhesive, as cured ad- differences will be briefly analyzed.
hesive is not known to cause cracking. The lower tensile strength of plastics makes
• Time for both stresses and adhesive to in- it common to design lap joints that are stronger
teract. The length of the time interval is than the plastic itself. Consider the example of
typically minutes, but may be as long as Fig. 3. The load capacity of the adhesive, act-
ten days depending upon the severity of ing over a shear area of 0.875 in. 2 , is greater
the conditions. than the tensile capacity of the plastic operating
 BONDING PLASTICS 579

Plastic Break Load

.125 in2 X 7,000 Ibs/in2 = 875 Ibs
~
_ _-J=-.125

Bonded Joint Break Load

.875 in2 X 1,500 Ibs/in2 = 1,312.5 Ibs

• Plastic breaks at 875 Ibs.

• Same overall assembly strength
achieved with overlap of only .58 inch.
Fig. 3. Plastic fails before bond when large overlaps are used.

1111111"111111111
..t!.~..~.IIIJllrIl::::II::!I:!::II
~_.1.~ Undeformed state

~II"""~
~ III II lilt---- Uniform shear deformation of
the adhesive
--HIIIII.
t 1'1 I I II Ir-- Differential straining of the
adherends

~11111f-- Adherend bending

Fig. 4. Schematic drawings of bonded tensile lap-shear specimens, greatly

exaggerated to illustrate effect.

Table 3. Suitability of Joining Methods for Plastic Assembly.

Solvent Heat Ultrasonic
Plastic Adhesive Welding Welding Welding
ABS y Y Y Y
Acetal Y N Y Y
Cellulosic Y Y Y Y
Nylon Y Y Y Y
Polycarbonate Y Y Y Y
Polyetherirnide Y Y Y Y
Polyethylene N N Y Y
Polymethyl methacrylate Y Y Y Y
Polyphenylene oxide Y Y Y Y
Polyphenylene sulfide Y N N N
Polypropylene N N Y Y
Polystyrene Y Y Y Y
Polyurethane Y N N N
Polyvinyl chloride Y Y Y Y
Polytetrafluoroethylene Y N N N
Diallyl phthalate Y N N N
Epoxy Y N N N
Melamine Y N N N
Phenolic Y N N N
Thermoplastic polyester Y N Y Y
Thermoset polyester Y N N N
Urea Y N N N
580 HANDBOOK OF ADHESIVES

on a cross-sectional area of only 0.125 in. 2 • As capacity of the plastic remains in balance with
a result, the plastic breaks outside of the bonded the bond strength. The use of thicker laps or a
joint area. If it is desired to increase the strength stronger plastic is also an option.
of the overall assembly, the best option is to With an elastic modulus of approximately
increase the width of the bonded joint rather 300,000 psi, a typical unreinforced thermo-
than the overlap. In this way, the load carrying plastic is over one hundred times more flexible

Table 4. Selection Chart for Bonding Plastics to Themselves or Other Materials. a, b

1 2 3 4 5 6 1011 12 13 14 21 22 23 24 25 26 27 41 42
Thennoplastics
ABS y Y Y Y Y Y Y Y Y Y Y Y
Acetal Y Y Y Y Y Y Y Y
Cellulosic Y Y Y Y Y Y Y Y
Nylon Y Y Y Y Y Y Y
Polycarbonate Y Y Y Y Y Y Y Y Y
Polyetherimide Y Y Y Y Y Y Y
Polyethersulfone Y Y Y Y Y Y Y Y Y Y Y Y Y
Polyethylene Y Y Y Y Y Y Y Y Y
Polyethylene terephthalate Y Y Y Y Y Y Y Y
Polymethyl methacrylate Y Y Y Y Y Y Y Y Y Y Y Y Y
Polyphenylene oxide, Y Y Y Y Y Y Y Y Y Y Y Y
modified
Polyphenylene sulfide Y Y Y Y Y Y Y Y Y Y Y Y Y
Polypropylene Y Y Y Y Y Y Y Y Y Y
Polystyrene Y Y Y Y Y Y Y Y Y Y Y Y
Polyurethane Y Y Y Y Y
Polyvinyl chloride Y Y Y Y Y Y Y Y Y Y Y
Polytetrafiuoroethylene Y Y Y Y
Thennosets
Epoxy Y Y Y Y Y Y Y Y Y Y
Melamine Y Y Y Y Y Y Y Y Y Y Y
Phenolic Y Y Y Y Y Y Y Y Y Y Y Y Y
Polyester Y Y Y Y Y Y Y Y Y Y Y Y Y
Urea Y Y Y Y Y Y Y Y Y Y Y Y
Other Materials
Ceramic Y Y Y Y Y Y Y Y Y Y Y Y Y Y
Fabric Y Y Y Y Y Y Y Y Y Y
Leather Y Y Y Y Y Y Y Y Y Y Y Y Y
Metal Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
Paper Y Y Y Y Y Y Y Y Y Y Y
Rubber Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
Wood Y Y Y Y Y Y Y Y Y Y Y
'Directions: (1) FOR PLASTICS TO THEMSELVES, CONSIDER ADHESIVES MARKED "Y". (2) FOR MIXED SUBSTRATE
JOINTS, CONSIDER ADHESIVES MARKED "Y" ON BOTH SUBSTRATE UNES.
bAdhesive code numbers:

Elastomeric
1. Natural rubber Thermosetting Resin
2. Reclaim 21. Resorcinol phenolic
3. Neoprene 22. Epoxy
4. Nitrile 23. Reactive acrylic
5. Urethane (also thermosetting) 24. Butyral phenolic
6. Styrene·butadiene 25. Polyester
26. Anaerobic
Thermoplastic Resin 27. Silicone
10. Acrylic
11. Cellulos nitrate Miscellaneous
12. Polyamide 41. Rubber latices
13. Hot·melt copolymer blends 42. Resin emulsions
14. Cyanoacrylate
 BONDING PLASTICS 581

than a steel component of identical shape. In parts, the environment in which they function,
the design of bonded joints this means that and the manufacturing process by which they
elastic defonnations, that could be safely ig- are to be assembled.
nored in metal joints, become critical. Instead Tables 3 and 4 are a good starting point to
of the unifonn stress distribution nonnally as- detennine which assembly method or type of
sumed for lap joints, bending and differential adhesive offers promise for the plastics you
straining of adherends can create extreme stress wish to join. The choice of assembly method
concentrations at the ends of the joint overlap can be further narrowed by considering the
(see Fig. 4). economic factors which would be involved to
These excess stress concentrations in lap integrate the material into the manufacturing
joints can be effectively reduced by using more process. 9
flexible adhesives, thicker or more rigid sub-
strates, shorter overlaps, or thicker bond lines. 7 TEST METHODS FOR ADHESIVES
When materials with different coefficients of
Table 5 gives a list of useful test methods for
thennal expansion are joined, shear stresses re-
evaluating the perfonnance of joining methods
sult when the assembly is heated or cooled. In
on plastics. Most of the infonnation was ob-
the case of inorganic materials, problems have
tained from a list compiled by Rice. 10 See Vol-
been noted in assemblies involving steel to alu-
ume 15.06 of the Annual Book of ASTM
minum or aluminum to glass even though the
Standards" for details of the test methods; see
difference in expansion rates of these materials
also Rice's Chapter 5 in this Handbook.
is relatively small.
In the case of plastics, the problem is aggra- Table 5. Test Methods for Plastic
vated by the fact that the potential differences Bonding.'o
in expansion rate can be up to an order of mag-
Test Method Description
nitude higher. This can best be prevented in the
design stage by careful selection of materials. 1. Tensile Tests
ASTM 0897 Test method for tensile
In cases where a mismatch is unavoidable, use
properties of adhesive
of more flexible adhesives or thicker bondlines bonds
is helpful. Schneberger has suggested the use ASTM 01344 Cross lap tensile test
of flexible primers to help absorb some of the ASTM 02095 Tensile properties using bar
differential strain, 8 In extreme cases a rubber and rod specimens
buffer can be bonded between the substrates to 2. Shear Tests
absorb the strain. ASTM 04501 Block shear test method
ASTM 03163 Lap shear test for plastics
ASTM 03983 Thick adhered test method
SELECTION OF A BONDING METHOD
3. Peel Tests
Bonding process selection can best be under- ASTM 0903 180 0 peel test
stood if it is thought of as an assembly method ASTM 01781 Climbing drum peel
rather than a complex chemical technology. 4. Cleavage Tests
Bonding processes are functionally equivalent ASTM 03807 Cleavage/peel test for engi-
to other assembly methods such as screws or neering plastics
staples, but differ in that the chemical technol- 5. Adhesion
ogy is less visible and understandable to the av- ASTM 03808 Spot adhesion test
erage user. The mechanical ingenuity behind a 6. Adhesive-Plastic
special mechanical fastener is easy to see, while Compatibility
the chemical ingenuity of a high technology ad- ASTM 03929 Bent beam method for
evaluating compatibility
hesive may be lost in the complex jargon of the
specialist. 7. Wetting Characteristics
In selecting a bonding method for plastics the ASTM 02578 Wetting tension of plastic
films
key factors to consider are the function of the
582 HANDBOOK OF ADHESIVES

REFERENCES 6. "Standard Practice for Evaluating the Stress Cracking

of Plastics by Adhesives Using the Bent Beam
1. Aubry, D. W., "Bonding in Flexible Joints," Joint Method," ASTM D3929.
Symposium on Adhesive Bonding of Flexible Mate- 7. Thompson, R., "Five Design Considerations for Ad-
rials, The City University, London, September 25, hesive Bonded Plastic Joints," SME Paper AD85-776,
1985. Atlanta, Georgia, 1985.
2. "Standard Practice for Preparation of Plastics Prior to 8. Schneberger, G., "Polymer Structure and Adhesive
Adhesive Bonding," ASTM D 2093, Annual Book of Behavior," in "Adhesives in Manufacturing," pp. 51-
ASTM Standards, Vol. 15.06, 1986. 56, New York, Marcel Dekker, 1983.
3. Coopes, I., and Gifkins, K., "Gas Plasma Treatment 9. Thompson, R., "Adhesive Bonding," in "Modern
of Polymer Surfaces," J. Macromol. Sci. -Chem., Plastics Encyclopedia," pp. 350-352, New York,
A17(2), 217-226 (1982). McGraw-Hill, 1985.
4. Landrock, A. H., in "Adhesive Technology Hand- 10. Rice, J. T., "A Classification Outline for the Ameri-
book," pp. 84-106, Park Ridge, NJ, Noyes Publica- can Society for Testing and Material (ASTM) Com-
tions, 1985. mittee D-14's Adhesive Standards," SME Adhesives
5. Thompson, R., "Guidelines for Plastic Bonding with '85, Atlanta, Georgia, 1985. See also Chapter 5 in this
Anaerobic and Cyanoacrylate Adhesives," SPE 37th Handbook.
Annual Technical Conference, pp. 996-999, 1979.
 35
Bonding Textiles to Rubber
THOMAS S. SOLOMON
Brecksville, Ohio

When J. B. Dunlop made his first pneumatic

006
I

tire in 1888, Irish flax was used as the rein-

forcing material. Cotton, however, quickly re-

ooQ ~ ..:Oc
placed flax because of material cost savings,
and cotton was used in tires until World War
...... CH~CH.~CH,........ CH,/

II. It was used with no adhesive treatment since

the mechanical interlocking brought about by I I
protruding filament ends was enough to adhere I I

~ »"D ,
cotton cord to the rubber. However, as tire per-

¢C'"' '¢c
I I

formance requirements became more demand-

ing it was necessary to use man-made fibers as
reinforcing materials.
/CH
'

O
~ ~
In the 1940s rayon was used almost exclu- OH OH
CH

sively in tires. It was difficult to adhere rayon ---lndlCII... I:tOndinI ....

....il..... tor
to rubber mechanically because of the smooth OH furtMr clo......d. .

I
surface of the rayon filaments. Fortunately, two I

Dupont Co. chemists, W. H. Charch and D. Fig. 1. Resorcinol-fonnaldehyde structures.

B. Maney I found that incorporating a resorci-
nol-formaldehyde thermosetting resin into a
rubber latex made a cord adhesive which gave tno and two para pOSItIons. Resorcinol acts
excellent adhesion of rayon to rubber carcass much more rapidly than phenol under similar
compounds. The same "RFL" cord adhesive conditions. The reaction product of resorcinol
was also used when nylon was introduced as a and formaldehyde can be represented as in Fig.
tire reinforcing material in 1947 and when glass 1. 2
fiber was introduced as belt material in belted Depending on the molar ratio of the two
bias and radial tires. reactants we can obtain products which range
from syrupy liquids at low formaldehyde levels
to completely crosslinked thermosetting resins
RESORCINOL FORMALDEHYDE (RF)
at high levels of formaldehyde. Novolaks used
The resorcinol molecule, like phenol, under- in tire cord adhesive are RF resins of low for-
goes substitution at ring hydrogen positions. maldehyde content (mol ratio of resorcinol to
The two hydroxyl groups act as electron donors formaldehyde 1.00/.40 to 1.00/.75) and are
to the aromatic ring. This electron donating ef- prepared under acidic conditions. These resins
fect directs incoming substituents to the one or- are manufactured and sold commercially as

583
 584 HANDBOOK OF ADHESIVES

Table 1. Novolak RFL Dip Recipe. H H

Resin Solution % Solids Parts Dry Parts Wet H2C === C - C === CH2 70 Parts
Penacolite R-2200 70 19.02 27.17 Butadiene
NaOH Solution 50 1.40 2.80
Fonnaldehyde 37 2.88 7.78
Water 267.29
Total Solids 23.30 305.04
Latex and Resin Solution 15
Resin Solution (above) 7.64 23.30 305.04
Vinyl pyridine latex 41.00 100.00 244.00
123.30 549.04
Styrene
Total solids: 22.46 %
FIR (dry): 15.14/100 parts
Resinllatex (dry): 19.02/100 parts
15

Table 2. "In Situ" Resin Fabric Dip.

Resin Solution % Solids Parts Dry Parts Wet Vinyl Pyridine

Resorcinol 16.10 16.10 Fig. 2. Latex composition for FRL adhesive dips.
Fonnaldehyde 37 5.24 14.16
NaOH 50 1.26 2.52
Water 251.12 hlltes the superior adhesion to a direct dipole-
22.60 283.90 dipole intemction between the more polar vinyl
Total solids: 7.96% pyridine terpolymer and the textile fiber. A
Resin aged 6 hours at 23°C third view is that the pyridine nuclei facilitate
Latex and Resin Solution: the intemction of the resin and the rubber phase.
Resin solution 7.96 22.60 283.90 A typical Cord Processing Unit is shown in
VP latex 41. 10 100.00 243.31 Fig. 3, where the fiber is dipped in RFL, dried
Water 17.68 at 150°C, and heat set at tempemtures of 175-
122.60 544.89 240°C.
Total solids: 22.5%
Age 18 hours at room temperature EVALUATION OF ADHESION
Static Adhesion
both liquids (70-75 % solids) and dehydmted
Adhesion is represented by the force required
brittle solids. See Table 1.
to pull an embedded cord through and out of a
Resoles are prepared in situ and then added
rubber block in the H-Test, T-Test, and U-
to a rubber latex to be used as a cord adhesive.
Test. 3,4 In these methods, the force is affected
See Table 2.
by the embedded length of the cord, the mte of
loading, and the tempemture of the test sample.
LA TEX TYPE (L)
Measurements are frequently made at 1()()-
Natural and SBR latexes were first used in RFL 130°C, since tempemture in a running tire may
adhesive systems. However it was found that be this high. Fig. 4 illustmtes these pull-out
latexes containing vinyl pyridine terpolymer (BI tests.
S/vP) gave high levels of adhesion of fibers to Adhesion of textile fabric to rubber is some-
rubber. Fig. 2 illustmtes the chemical compo- times evaluated by stripping a two-ply speci-
sition of this latex. men. The specimen, Fig. 5, consists of rubber-
The reason for this good adhesion has been test fabric-inner rubber-test fabric-rubber.
a subject of speculation for some time. One ex- Again the sample may be tests at room tem-
planation is the exceptionally high strength of pemture as well as any desired elevated tem-
the vulcanized terpolymer itself. Another attri- perature.
 BONDING TEXTILES TO RUBBER 5B5

Hot
Dryer stretch Normalizing
zone zone zone

Accumulator

Tension Wind
rolls up

Fig. 3. Tire cord processing machine. 47

Cord FACTORS WHICH AFFECT ADHESION

~Old In order to obtain maximum adhesion of dipped
rayon or nylon to rubber compounds several
Rubber factors must be considered.

Effect of Formaldehyde-to-Resorcinol
Jig Ratio of RFL Adhesive
To obtain a high level of adhesion it is rec-
Jaw ommended that the formaldehyde-to-resorcinol

! mol ratio of the adhesive dip be in the range of

2: 1 (Fig. 6).

H test T test U test Effect of RF Resin-to-Latex Ratio on

Fig. 4. Test specimens and testing features of pull-through Adhesion
type tests. 47
Adhesion can be affected by the resin-to-Iatex
ratio in the adhesive dip. Too much resin in the
adhesive can result in stiff cords with poor fa-
1.7MM

8
~
~

2CM
;:;6
RUbber'E:::~~~~;;~~
layers
8..,.. 4
c:
o
"ij
=g 2
Strip test specimen I
J:
O~----2~/1----~~~1----~----~~
O.7MM
-II-- } Th ickness of
rubber layers
Formaldehyde/resorcinol ratio
1.7 MM
Fig. 6. Formaldehyde-to-resorcinol ratio of the adhesive
Fig. 5. Peel sample for testing fabric to rubber adhesion. dip-effect on adhesion.
586 HANDBOOK OF ADHESIVES

'iii
8
~ 10.4
~ 8.8
• •
0
0
";'
c:
0
.,
'in
..c: 5.6
"0
IV
I
:J:
8.9 9.3 9.7 10.1 11.5
pH
Fig. 9. Effect of RFL pH on tire cord adhesion to rubber.

ammonium hydroxide is used to catalyze the

o 5 10 15 20 25
RF reaction (Fig. 9).
Parts resin solid per 100 parts latex solid
Fig. 7. RF-to-rubber solids in tire cord adhesives-effect
on cord adhesion. 47
THEORY OF RFL ADHESION
The nature of the fiber plays the most important
tigue resistance, while too much latex can give role in RFL treatment of tire cords. We know
unsatisfactory film strength and low bonding that rayon and nylon cords are easy to bond to
strength. A ratio of 1 : 4.5 to 1 : 6.0 RF to rub- rubber by RFL treatment, but polyester cord is
ber solids as shown in Fig. 7 is considered op- extremely difficult. This can be attributed to the
timum for most tire cords. nature and structure of the fiber.
There a number of opinions on how RFL
Effect of RFL Dip Pickup functions with rayon and nylon. Rayon con-
Generally bond strength increases with pickup tains active OH groups on its polymer chain
of cord. About 4-6%, as shown in Fig. 8, is while nylon contains amide groups (CONH).
considered optimum for satisfactory adhesion MoultS suggests the formula in Fig. 10 for ad-
of cord to rubber. hering of RFL to rayon. A similar possibility
could exist with nylon. He suggests a chemical
Effect of RFL pH on Adhesion reaction between the methylol groups on the RF
molecule and the active hydrogens on both
Optimum cord adhesion is obtained at dip pH rayon and nylon.
of about 9.5 when only sodium hydroxide is M.W. Wilson favors a dipole-dipole inter-
used in the dip recipe, while adhesion is not action between the RF resin and active groups
significantly affected at any pH over 8.0 when on rayon and nylon. In his paper Wilson6 dwells
in depth on the potential of hydrogen bonds be-
tween RF and fiber surface. He pictures this
8 occurring according to the structure in Fig. 11.
'iii
a.. The question arises as to whether the adhe-
~
U
sion mechanism between RF resin and rubber
o
8 is one of mere physical entanglement or
whether specific chemical interaction is in-
volved as well. Dlugosz7 has shown, by elec-
tron microscope examination of adhesive films,
that the two phases of the adhesive remain dis-
crete, and that the resin takes the form of a net
o 2 4 6 8 10 which encloses the latex particle. He concluded
Adhesive pick·up (%) that the adhesive functions principally by pro-
Fig. 8. Effect of RFL pickup on cord to rubber adhesion. viding two mechanically interlocked phases,
 BONDING TEXTILES TO RUBBER 587

OH

OH

CH2
I
o OH OH OH
I I I I
--O--CH /" CH--CH
/CH--CH
CH--O--CH '\CH--O--
'CH-c/ 'CH-c/
I
C~OH
I
CH20H
Fig. 10. Moult's theory of adhesion of RFL to rayon tire cord.

each with separate affinities for the substrates sorcinol, which reacts with an active hydrogen
which are being united. atom, such as the allylic hydrogen of the iso-
On the other hand, it is well known that prene unit of natural rubber. The product after
phenol-fonnaldehyde resins are able to vulcan- rearrangement is a benzenoid resorcinol nu-
ize diene rubber. Two basic types of mecha- cleus having, in this instance, the rubber mol-
nisms have been postulated for this interaction. ecule attached to it (Fig. 12).
The first, associated with van der Meer, 8 in- The second type of mechanism, associated
volves the fonnation of a methylene quinone with Greth,9 suggests the fonnation of chroman
intennediate, fonned from the methylolated re- structure between the benzene ring of the re-
 ~C) g:
co
I :J:
o ~
Z
C
I co
C " J, J - J ROBBER COAT o
o
;0::
./ 'C-OH
o I "':J~...... " ......;>_;> ;> o."
I C-OH F --= :>=:> \ / ~
C'C./ _+.,./ C
:J:
(0 J=J m
H C"'- C-...C ~ / C::::::C\ <:m
OH o UI
I ~.... C...... C C_
CH2 C LtTsxROBBER (L)
!I ~OOI
~
c"~O l ~ '\
I I c...c cHz ;>
~ /c C I
C', .::~""
" OH \
I H i..." ;>
, C- ""
~lJ}J~
""";>_;>__ ; > "
f.:\
oI
~ ":,.,~C\ -+ o rn, ". 0 c-.c 0!J \ Q)>""
I Ii H '-<'llt--C",,:::-C
I ~ /O~p
~ ;>~_;>'-
if cI+
00 \ "
C-OHCH2 C
~lJ}J~~~~
C'C./ "c
I I
OOH\(RF)
~
o1 0 C

(I H 1
F =dipole-dipole or H bond attraction. V =vulcanization bond.

Fig. 11. Rayon-RFL adhesion scheme accordin2 to Wilson.

 BONDING TEXTILES TO RUBBER 589

o
HOC~CH2

U
Fig. 12. Van der Meer's scheme for adhering RFL to
rubber. 47

6_C_:_2~:t1CH20H
OH

...
OH

I CH2

CH - C
I
2 "
CH
I
CH2
I
Fig. 13. Greth's theory for adhering RFL to rubber.47

sorcinol and the double bonds of butadiene adhesion may be due to reduced ability to form
units in the diene synthetic rubber. Fig. 13 il- hydrogen bonds, lack of reactive hydrogen in
lustrates this type of mechanism. the polyester molecule and its hydrophobic na-
ture. One of the most important methods for
adhering polyester to rubber requires a first
ADHESION OF POL VESTER TIRE
treatment of the fiber with an isocyanate or a
CORD
blocked isocyanate. The isocyanate, -NCO,
There is practically no adhesion between has a specific action for both polyester and rub-
polyester tire cord and RFL adhesive dip. Poor ber. Polyester was first treated with dilute or-
590 HANDBOOK OF ADHESIVES

OCN-G-rn,-G-NCO -G-OH +

METHYLENE BIS(4-PHENYL ISOCYANATE) PHENOL

HEAT AT 24<f'C

Fig. 14. Typical blocking-unblocking reaction.

ganic solutions of an isocyanate, and after dip was a polyurethane resin. The primary
drying given a second treatment of a standard source of the hydroxyl for polyurethane for-
RFL. However, the isocyanate-in-solvent mation is the epoxide resin.
treatment of polyester cord was never commer- The probability of a major role of the poly-
cialized, except for V-belt cords, because of the ester group in reaction with dip chemicals
need for solvent recovery, ventilation, and tox- during cure is quite low. The polyurethane-
icity. polyester bond is pictured primarily as a phys-
Isocyanates form addition products revers- ical interaction rather than a chemical one.
ibly with compounds which contain moderately Iyengar11 reported that the polyurethane from
reactive hydrogen, such as phenol, oximes, methylene-bis(4-phenyl isocyanate) and the
lactams and malonates. Fig. 14 is an example epoxide have a cohesive energy density of to.5.
of a typical blocking-unblocking reaction. Polyethylene terephthalate has a cohesive en-
These addition compounds, called "blocked ergy density of to.3. The compatibility be-
isocyanates," are stable to water. They have tween these two networks would be quite high
been used in place of free isocyanate. The and the probability exists for adhesion by the
phenol-blocked isocyanates are the most com- diffusion theory of Voyutskii. 12
mon. In 1957 the DuPont Co. \0 developed an Figure 15 shows the effect of subcoat pickup
aqueous dip based on blocked isocyanate. This on adhesion after a topcoat of RFL. Optimum
process, called 0-417, used phenol-blocked subcoat pickup for both adhesion and economy
methylene bis(4-phenyl isocyanate) and a water is about 1.0%.
soluble epoxide, the reaction product of glyc- Heat set conditions for polyester tire cord are
erine and epichlorohydrin. RFL is used as the
topcoat or second step dip:
17.0
Hylene MP" 3.56 parts <V 15.6
Nagase 010A epoxideb 1.34 c..
~
AerosolOT 0.10 ;- 14.2
:::l
Water 95.00 0.
± 12.8
100.00 parts -0
"0
u 11.4
"DuPont Co., no longer available. Blocked isocyanates are avail-
able from other companies. 9.9
bNagase Co., Ltd., Japan.
0.0 0.4 0.8 1.2
The reaction of isocyanate and epoxide showed % Subcoat pick-up

that the major product during cure of the 0-417 Fig. 15. Cold H-pull adhesion vs. subcoat pickup.
 BONDING TEXTILES TO RUBBER 591

g 0-417 subcoat cured at: Table 3. Pexul Polyester Single-Step

-X;
.<: Adhesive Dip .
] 5
"0 Parts
-0
u Component by Weight
> 4
Q. 3.4
N Koppers Penacolite R-2200 resin

-5'"
(70%)
3 0.17
~
Sodium hydroxide
Q)
Water 18.8
g 2 30.0
~ Pexul (20%)
'"c.
Q)
2040C
Vinyl pyridine latex (38 %) 31.8
~1L...J..-='::"':"'~""""'"---=-~----:~~=- Water 12.6
120 150
Formaldehyde (37 %) 1.0
"RFL" topcoat adhesive curing temperature (OC)
Water -.LQ...
Fig. 16. Effect of curing temperature on polyester adhe- 98.8
sion.

very critical in order to obtain maximum adhe- chlorophenol with formaldehyde. The reaction
sion to rubber. A heat set temperature of at least mechanism for resin formation is shown in Fig.
230-240°C is necessary to develop good adhe- 17 while the actually dip recipe is illustrated in
sion of polyester to rubber compounds. Some- Table 3.
what lower temperatures of 21O-220°C are Many other one-step adhesive dips for poly-
required for RFL topcoat heat set. Fig. 16 ester fibers have been patented over the last 15
shows the effect of curing or heat set conditions years. The adhesion activating agents in the
on polyester adhesion using the D-417 two-step RFL dip are usually based on isocyanates or
adhesive system. Heat set temperatures for the cyanurates such as triallyl cyanurate, triphenyl
D-417 subcoat are shown within the graph cyanurate, etc. Other agents are also used based
structure, while heat set temperatures for the on condensation polymers similar to that used
RFL topcoat are shown along the abscissa of in Pexul. A more detailed discussion on this
the graph. Adhesion rating of 1 indicates poor subject is given in Rubber Chemistry and Tech-
adhesion while 5 shows excellent adhesion with nology, Vol. 58, No.3 (1985).
100% rubber coverage on the pulled polyester
cord sample. This figure shows that high heat Chemical Activation of the Polyester
set conditions are necessary for both subcoat Surface During Fiber Spinning
and topcoat adhesives in order to obtain opti-
An important development in polyester tech-
mum adhesion of polyester to rubber.
nology occurred when Fiber Industries Inc. 14
activated the surface of polyester filaments dur-
Pexul or H-7 Single-Step Adhesive Dip
ing the actual melt spinning of the fibers. It was
for Polyester
then only necessary to apply a single topcoat of
One of the first single-step adhesive dips for standard RFL for optimum adhesion of fiber to
polyester was developed by ICI. I3 This adhe- rubber. The undrawn filaments as formed in the
sive was based on a co-resin of resorcinol and spinning process were dipped in a finish solu-

-DC
OH OH OH OH

CH20HOI
OH

+3
~
I c~
~I
~
OH HO OH
Cl Cl
. Fig. 17. Reaction mechanism for active ingredient in t>exul cord dip.47
592 HANDBOOK OF ADHESIVES

Table 4. Composition of Finish Solution ber reinforcement materials. Aramid fibers have
Used to Activate Polyester Fiber Surface been engineered for the reinforcement of radial
During Spinning. tires and mechanical goods, including hoses,
0.1 % sodium carbonate conveyor belts and power transmission belts.
5.0% glycidyl ether made from epichlorohydrin and glyc- These high strength fibers are prepared ac-
erine (epoxide equivalent 140-160) cording to the methods described in the 1971
5.0% spin finish containing approximately 60% dime- U.S. Patent issued to S. L. Kwolek.16 Solu-
thy lsiloxane
5.0% spin finish containing 75% ethoxylated sorbitan
tions of polybenzamide and poly(p-phenylene
monooleate (20 moles polyoxyethylene) and 25% terephthalamide) exhibit liquid crystal proper-
ethoxylated octylphenol (12 moles polyoxyethy- ties. When these polyamide solutions emerge
lene) from a spinneret they have almost perfect mo-
84.9% water lecular orientation, and the emerging fibers,
therefore, have a very high orientation of
polymer molecules. The resulting fibers are
tion which had the composition given Table 4.
very strong in comparison to other fibers.
The dipped filaments were then drawn at high
Iyengarl7 discusses in detail the mechanism for
temperatures in order to heat set the adhesive
adhesion development of aramid fibers to rub-
onto the cord.
ber. Thermodynamic compatibility of the sub-
Subsequently numerous other attempts were
stra.te and adhesive was shown to be a key
made to activate the surface of polyester fibers
requirement for promoting bonding to the ar-
during the melt spinning operation and thus
amid surface. Such compatibility is attained
eliminate the necessity for double dipping the
when the solubility parameters (0) of the sub-
cord. Most of these cord finishes were based
strate and adhesive are matched. Iyengar17 also
on epoxides and silanes. Again blocked iso-
proposes a two-step adhesive for aramid fiber
cyanates and cyanurates were popular additions
adhesion to rubber. The first step or subcoat
to the fiber finishes during melt spinning.
would consist of the composition shown in Ta-
ble 5. An RFL topcoat based on preformed RF
ADHESION OF GLASS TIRE CORDS resin is then used as the second-step dip Table
TO RUBBER
6). . . 'all
Most of the aramid adhesive systems Imti y
Some glass tire cord is still being used in the
used were based on a first-step dip of either an
belts of belted-bias and radial passenger tires.
epoxide or a blocked polyisocyanate and then
However, the use of glass in belts has been lim- ~ 18·
a second or top coat of RFL. Wenghoeler 10
ited because of the preference of steel wire in
his patent disclosed a somewhat different first
radial tires. Still, there has been some research
step dip which consisted ofbis({3-azido-formyl
work done in order to improve the dynamic
oxyethyl)isophthalate. After ~rying, the. cord
performance of glass belts in tires.
thus treated, was then dipped 10 a phenohc ad-
A significant development was disclosed by
hesive and cured at 230°C for 60 seconds. A
Lin. ls He replaced part of the vinyl pyridine
patent issued to Van Gils 19 uses a one-step d'Ip
terpolymer latex in the adhesive recipe with
based on vinyl pyridine latex, trimethylol-
polybutadiene latex. Glass cords dipped in this
phenol, resorcinol-formaldehyde resin, and
polybutadiene latex adhesive were more resist-
ant to fracture under cold weather conditions.
Table 5. Composition of First Step for a
This was attributed to the lower tg of polybu-
Two-Step Adhesive for Aramid Fiber
tadiene compared to vinylpyridine-styrene-bu-
Adhesion to Rubber.
tadiene rubber.
Nagase NER 010A (epoxide)" 2.22 parts
10% Sodium Hydroxide 0.28
ARAMID ADHESION 5% Aerosol OTb (75% solids) 0.56
Water 96.94
One of the most significant developments in fi- Total 103.06 parts
ber technology over the last fifteen years was aNagase Co., Ltd., Japan
the introduction of aromatic polyamides as rub- bAmerican Cyanamid Co.
 BONDING TEXTILES TO RUBBER 593

Table 6. Composition of Second-Step Dip for a Two-Step

Adhesive System for Aramid Fiber Adhesion to Rubber.
Parts
Wet Dry
Water 141.0
1. Ammonium Hydroxide (28%) 6.1
Preformed RF resin (75%) 22.0 16.5
II. Vinyl pyridine latex (41 %) 244.0 100.0
Water 58.0
III. Formaldehyde (37%) 11.0 4.1
Water 58.0
IV. HAF black dispersion (25 %) 60.3 -.lll
Total 600.4 135.7

water. Elmer,2o in a patent issued to General ter tire cords22 in Fig. 18. At the same ozone
Tire & Rubber Co., uses an aqueous adhesive level, adhesion of exposed cords to rubber de-
composition of phenol-aldehyde resin and a vi- creases as the humidity level increased during
nyl pyridine latex. Treatment is preferably re- exposure. Several methods have been proposed
peated three times. Other adhesive treatments in order to reduce the adverse effects of atmo-
for aramid fibers will undoubtedly be devel- spheric exposure. Encapsulation of the rubber
oped in the future as its use expands as a rubber latex particles helps prevent the reaction of
reinforcement element. ozone with diene rubbers. 23 Polymers of methyl
methacrylate, acrylic acid, and N-methylol ac-
EFFECTS OF ATMOSPHERIC rylamide are added to RFL for use as cord dips
POLLUTANTS ON ADHESION OF RFL for rayon, nylon, and polyester tire cords.
COAT TIRE CORDS TO RUBBER Adams24 added N, N' -ethylene-bis-stearamide
to tire cord adhesives in order to reduce the ad-
The adhesion of RFL-coated tire cords to rub-
verse effects of atmospheric pollutants. Micro-
ber can be adversely affected if the dipped cords
crystalline waxes25 and/or Fischer-Tropsch
are exposed to ozone, UV light, nitrogen ox-
waxes can be added to adhesive dip formula-
ides, sulfur dioxide, or air before vulcanization
tions in order to minimize the loss of adhesion
into rubber. Iyengar 21 proposed that ozone ex-
to rubber when the cords are processed in fuel
posure of RFL reduces adhesion because ozone
oil or kerosene-heated dryers. A most impor-
attacks the double bonds of the butadiene com-
tant factor in preventing adhesion losses of
ponent of the rubber latex and impairs its co-
dipped RFL fabrics is to wrap the dipped fabric
curing with the solid rubber compound. In-
rolls immediately with layers of heavy kraft pa-
frared studies by Solomon22 reinforced this ar-
per and cardboard. This prevents direct expo-
gument. When typical RFL films were exposed
sure of the fabric surface to atmospheric
to ozone, the IR spectrum showed an increase
degradants and in most cases will prevent ex-
in IR absorption at 1720 cm -I, corresponding
cessive adhesion losses.
to an increase in the carbonyl content in the
exposed film. An RFL film with no ozone ex-
RUBBER ADHESION TO BRASS-
posure did not show this absorption at 1720
COATED STEEL WIRE
cm -I. The increased carbonyl content is due to
the reaction of some double bonds in the rubber The performance of steel belted tires, as with
with ozone and therefore, would leave fewer tires reinforced with other fibers, is dependent
unsaturation sites for rubber crosslinking and to a large extent on the adhesive bond between
adhesion. the tire cord and the rubber in the skim stock
The synergistic effect of humidity and ozone surrounding the cord. The use of a thin brass
is demonstrated with nylon, rayon, and polyes- layer on steel tire cord is the major adhesive
594 HANDBOOK OF ADHESIVES

MPa

10.0

9.0

8.0

7.0

c:
0
Ox;
6.0

..
~
'C
I
:I:
5.0

4.0

3.0

2.0
--Opphm03
1.0 - - - 20pphm 0 3

o 4 5 6
Hours exposure

Fig. 18. H-adhesion losses-1680/2 nylon at different levels of humidity and ozone at 30·C.

for bonding steel cords to rubber. The mecha- of steel cord surfaces and rubber-brass inter-
nism of rubber-brass adhesion has been the faces. He observed that an interface film of re-
topic of much speculation and fundamental re- active products is always fonned. By means of
search for years, and sophisticated instruments the chemical shift principle he identified the
have been used for the analysis of steel cord species CuxS, ZnS, and ZnO as the constituents
surfaces and the rubber-brass interface. of this film, with CuxS always on top. He pos-
tulated that CuxS, a nonstoichiometric type of
Nature of the Rubber-Brass Bond copper sulfide, acts as the adhesive which
bonds the metal to rubber through a catalytic
Sanderson26 discovered the adhesion of brass to
effect on the vulcanization reaction.
sulfur-vulcanizable rubber over 100 years ago.
However, van Ooij32 claims that there is now
Interest in the mechanism of this bond fonna-
direct evidence that chemical bonds do not ex-
tion has been spurred on by the advent of the
ist between the Cu and rubber. This was shown
steel-belted radial tire. Buchan and Rae27 ,28
in an experiment where milling of CuxS into
postulated that chemical bonds are fonned be-
rubber showed no reinforcement effect and
tween copper atoms on the brass surface and
therefore no adhesion to the polymer. Van Ooij
sulfur atoms of crosslinked polymer molecules:
says that the important criteria for good bond-
I ing are whether CuxS is fonned or not, its co-
-c- hesive strength, its adhesion to the substrate,
I which consists of brass still covered with ZnO.
Cu-S-C- Also important is the ZnO which has been
I partly converted to ZnS as well as the rate of
-C- secondary corrosion reactions which proceed
I underneath the CuxS film once it has been
Van Ooif9-31 was the first to apply XPS (X- fonned. The schematic of oxide film on brass
ray photoelectron spectroscopy) to the analysis coated steel is depicted in Fig. 19.
 BONDING TEXTILES TO RUBBER 595

Cu Zn thickness leading to different brass grain size, plating

- CU20 sA
0 0 0 0 0 0 0
0
weight, mechanical deformation of the electro-
0 0 0 ZnO
50 50 0
0
0
0 0
0
00
0
0
0 0 Wllh 10M deposit, thermal treatments, and compound
0
0 0 0 Cu composition. The optimum copper content of
CuZn the brass coating at constant plating weight was
with 500.4.
ZnO reported to go through a maximum which could
be 60%, 67-70%, or 75% copper depending
on the rubber compound used in adhesion test-
ing. They reported that adhesion was optimum
for most rubber compounds when the brass
coating thickness was in the 0.2 ~m range and
65 35 CuZn the copper content in the brass was 68 %. To-
day most of the wire used in the rubber industry
for reinforcement in tires has a brass coating
thickness of about 0.2 ~m and a composition
Fig. 19. Schematic of oxide film on brass-coated steel
cord. 48
of approximately 70% copper and 30% zinc.

Other Factors Affecting Adhesion of

In van Ooij's model, brass develops a high Rubber to Brass Coated Steel Wire
bond strength to rubber because the sulfide not
Rubber Compound Effects. Buchan34 re-
only has good adhesive and cohesive proper-
viewed natural as well as synthetic rubber com-
ties, but is also very porous so that the rubber
pounds and their adhesion to brass. However,
molecules become entangled in this film during
compound studies are to some extent largely
vulcanization. This .phenomena is depicted in
empirical because of the complexity of the dif-
Fig. 20.
ferent compound systems used in the rubber in-
dustry today. One can, however, draw several
Effect of Brass Composition and
conclusions from the many adhesion studies
Plating Weight on Brass Reactivity and
made to date.
Adhesion
1. Sulfur is very important in the bonding re-
The first in-depth study on the effect of coating action. The minimum sulfur loading for good
properties was done by Maeselle and De- bonding is about 2 phr. Generally sulfur-to-ac-
bruyne. 33 They studied the effects of brass-cop- celerator ratios of over 4 to 1 give high adhe-
per content, variations of plating conditions sion values.
2. Sulfenamide-type accelerators are com-
monly used in the rubber industry for rubber-
brass bonding. Bertrand's35 study showed that
Rubber N-cyclohexyl-2-benzothiazole sulfenamide
(CBS), N-t-butyl-2-benzothiazole sulfenamide
thickness
(TBBS) and N ,N-dicyclohexyl-2-benzothia-
zole sulfenamide (DCBS) all gave high bond
strengths. The ultra-accelerators such as tetra-
methyl thiuram disulfide (TMTD) and tetra-
ZnO l00A
methyl thiurum monosulfide (TMTM) in small
.. .. .. .' : .:. '.
'
. .. : . ' amounts or in combination with sulfenamides
CuZn
gave very low bond strengths.
3. Hicks, Lyon, Chirico, and Ulme?6,37
made a comprehensive study of carbon black
'-- - - loadings and properties on adhesion. Pullout
Fig. 20. Schematic of interfacial sulfide film in rubber- force increases with black loading, and reached
brass bonding showing mechanical interlocking. 48 an optimum at 50-60 phr. It appears from this
 596 HANDBOOK OF ADHESIVES

and other studies that the effect of carbon black formed resins such as resotropin (a precon-
properties and loading can be interpreted as densed resorcinol-formaldehyde resin), as
being a mechanical one. proposed by Cunningham and Hart,43,44 or
4. Zno and stearic acid are important ingre- Penacolite Resin B:18 from Koppers CO.,45
dients in all rubber compounds. Carpenter's which react with hexa can also be used for
made a statistical study on the effect of ZnO. bonding rubber to wire.
ZnO loadings of 2, 5, and 8 phr were com- Results obtained by Van Ooij in his ESCA
pared. It was reported that average particle size studies on the composition of interfaces be-
was most important for optimum adhesion. tween rubber and brass46 confirm that cobalt
Hicks39 reported an optimum content of 15 phr salts and HRH form essentially the same inter-
ZnO. Conflicting results such as these have also facial products with a standard brass surface.
been reported by others and most probably in- Therefore, the mechanism of brass-rubber
dicate that the effect of ZnO is dependent on bonding must be the same for both bonding
the other ingredients in the rubber compound. systems and differences in adhesion values must
It is known40 that stearic acid is converted into be explained by a modification of rub~er prop-
zinc stearate during the initial stages of the erties (crosslink density, cure rate, modulus,
cure. However, there are so many factors af- etc.) or the rate of brass attack. Clearly, adhe-
fecting zinc stearate formation that it is difficult sion of brass to HRH-NR compounds cannot be
to access its affect on rubber adhesion. explained on the basis of hydrogen bonds with
5. Antioxidants used in the rubber industry the substrate, as in rubber-to-textile bonding.
do not exert any great effects on rubber-brass
adhesion. REFERENCES

1. Charch, W.H., and Maney, D.B. (to E.!. du Pont

Adhesion Promoters for Rubber-Brass
Co.), U.S. Patent 2,128,229 (August 30, 1938).
Adhesion 2. Noe, J.P., et aI., Rubber Plastics News, 14 (May 29,
1978).
Most of the tire companies used cobalt salts
3. Kenyon, D., Trans. Inst. Rubber Ind., 38, 165 (1962).
and/or a variation of the HRH system in their 4. Wood, J .0., Rubber Chem. Technol., 40, 1014
steel cord skim compounds. (1967).
5. Moult, H., in "Handbook of Adhesives," 2nd Ed., !.
Cobalt Salts. Barker41 studied the effects of Skeist (ed.), p. 495, New York, Rheinhold Publ.
Corp., 1962.
cobalt stearate, cobalt naphthenate, and a pro-
6. Wilson, M.W., TAPPI, 43(2), 129 (1960).
prietary boron-containing metal-organic com- 7. Dlugosz, 5th Intematl. Conf. Electromicroscopy, S.S.
plex on adhesion to brass. He concluded that, Breese (ed.), Vol. I, 1962.
with properly optimized compounds, little or 8. van der Meer, S., Rubber Chem. Technol., 18, 853
no benefit is obtained from the use of cobalt (1945).
9. Greth, A., Angew. Chem., 51,719 (1938).
insofar as initial adhesion is concerned. All
10. Shoaf, C.J. (to E.!. duPont Co.), U.S. Patent
salts, however, improved steam-aged adhesion 3,307,966 (March 7, 1967).
to some extent. Other studies tend to support 11. Iyengar, Y., J. Appl. Polym. Sci., 15,267 (1971).
these claims. 12. Voyutskii, S.S., Adhesives Age,S, 30 (1962).
13. ICI, Belgian Patent 688,424 (1967); French Patent
1,496,951 (1967).
HRH Systems. A review of currently avail-
14. Fiber Ind. Inc., B.P. 1,328,804 (July 25, 1973).
able bonding agents such as HRH and modifi- 15. Lin, K.C., et aI. (to Owens-Coming Fiberglas Corp.),
cations thereof, is given by Weaver. 42 HRH U.S. Patent 4,060,658 (November 17,1977).
designates the use of hexamethylenetetramine 16. Kwolek, S.L. (to E.I. du Pont Co.), U.S. Patent
(hexa) , resorcinol, and a hydrated silica as 3,600,350 (August 17, 1971).
17. Iyengar, Y., J. Appl. Polym. Sci., 22, 801 (1978).
additives to rubber in order to improve adhe-
18. Wenghoefer, H.M. (to E.I. du Pont Co.), U.S. Patent
sion to brass coated wire. Normally about 1.5 4,102,904 (April 5, 1984).
phr hexa, 2.5 phr resorcinol, and 15 parts of 19. Van Gils, G.E., et aI. (to General Tire and Rubber
silica are added to a wire skim stock. Pre- Co.), U.S. Patent 3,888,805 (July 19, 1975).
 BONDING TEXTILES TO RUBBER 597

20. Elmer, O.C. (to General Tire and Rubber Co.), U.S. 34. Buchan, S., "Rubber to Metal Bonding," London,
Patent 4,404,055 (October II, 1983). Crosby Lockwood and Sons, 1959.
21. Iyengar, Y., J. Appl. Polyrn. Sci., 19, 855 (1975). 35. Bertrand, G., Adh. Elastorn. Con! Int. Caout. Sess.,
22. Solomon, T.S., "Adhesion Retention of Tire Cords 34, 109 (1970).
Using Carboset Resins in Cord Adhesives," presented 36. Hicks, A.E., and Lyon, F., Adhesives Age, 21 (1969).
at the Rubber Division ACS Meeting, Atlanta, GA, 37. Hicks, A.E., Chirico, V.E., and Ulmer, J.D., Rubber
March 27, 1979. Chern. Technol., 45,26 (1972).
23. Solomon, T.S., (to BFGoodrich Co.), U.S. Patent 38. Carpenter, G.T., Rubber Chern. Technol., 51, 788
3,968,295 (July 6, 1975). (1978).
24. Adams, H.T. (to Uniroyal, Inc.), U.S. Patent 39. Hicks, A.E., presented to the Eighth Annual Lecture
3,816,457 (April 8, 1975). Series, Akron Rubber Group, Akron, OH, March 3,
25. Hartz, R.E., and Adams, H.T., J. Appl. Polyrn. Sci., 1971.
21,525 (1977). 40. Porter, M., in "Organic Chemistry of Sulfur," A. Oae
26. Sanderson, E., British Patent 3288 (1862). (ed.), Ch. 3, p. 71, New York, London, Plenum Press,
27. Buchan, S., andRae, W.D., Trans. Inst. RubberInd., 1977.
20, 205 (1945). 41. Barker, L.R., NR Technol., 12,77(1981).
28. Buchan, S., and Rae, W.D., Trans. Inst. Rubber Ind., 42. Weaver, E.J., Rubber Plastics News, July 1978.
21, 323 (1946). 43. Cunningham, W.K., and Hart, D.R., abstract in Rub-
29. van Ooij, W.J., Surface Sci., 68, 1 (1977). ber Chern. Technol., 48, 346 (1975).
30. van Ooij, W.J., presented at an International Confer- 44. Cunningham, W.K., and Hart, D.R., abstract in Rub-
ence on Surface Physics and Chemistry, Grenoble, ber Chern. Technol., 48, 1103 (1975).
France, June 1-3, 1977; les Couches Minces, 308 45. Koppers Product Application Guide, Compounding
(1977). No.1, 1975.
31. van Ooij, W.J., Kautsch. Gurnrni Kunstoffe, 30, 739 46. van Ooij, W.J., Rubber Chern. Technol., 52, 605
(1977); ibid., 30, 833 (1977). (1979).
32. van Ooij, W.J., Rubber Chern. Technol., 57, 442-445 47. Takeyama, T., and Matsui, J., Rubber Chern. Tech-
(1984). nol., 42, 159 (1969).
33. Maeselle, A., and Debruyne, E., Rubber Chern. Tech- 48. van Ooij, W.J., Rubber Chern. Technol., 57, 421
nol., 42, 613 (1969). (1984).
 36
Wood Adhesion
LAWRENCE GOLLOB*
Group Leader, Research and Development
Georgia-Pacific Resins
Decatur, Georgia
and
J. D. WELLONS
Manager, Thermosetting Resins
Georgia-Pacific Resins
Atlanta, Georgia

INTRODUCTION bonding are derived by the nature of the inter-

action of the substrate with the resin. Because
The bonding of wood dates back to the ancient
wood is a dimensionally anisotropic and chem-
Egyptian Pharoahs, for whom artistic inlaid
ically heterogeneous substrate, its properties are
wood veneers, bonded with animal glues, were
strongly influenced by climatic conditions such
created by skilled artisans for the purpose of
as temperature and humidity. The properties of
adornment. Today bonded wood products serve
composites made from wood components are
as a major structural component of shelter and
also influenced by wood particle size and ge-
furnishings, which continue to be cherished for
ometry, and by manufacturing process varia-
aesthetic in addition to practical purposes.
bles. The unique ability to manipulate the resin
Wood bonding technology has evolved into a
system's chemistry allows for the desired mar-
complex interdisciplinary science involving
riage of wood and adhesive, resulting in a suc-
fields of chemistry, engineering, and materials
cessful bond and a useful wood/adhesive
science as well as wood science and wood tech-
composite. The following sections will outline
nology. The size and shapes of wood to be
the nature of the challenges and opportunities
bonded are limited only by man's imagination,
apparent in a variety of products encountered
ranging from microscopic fibrous material in
in modem wood bonding applications.
hardboard to huge structural laminated mem-
bers. The adhesives are no longer primarily an-
imal glues but rather synthetic polymeric resins
ADHESION TO WOOD
formulated and characterized with the assist-
ance of state-of-the-art chemical instrumenta-
Mechanisms for Adhesion in Wood
tion.
Composites
The challenges and opportunities for wood
Several common thermodynamic and kinetic
parameters are involved in the process of bond
*Author to whom correspondence should be addressed. formation. The adhesive may be applied either
598
 WOOD ADHESION 599

as a liquid or dried powder. If applied as a Mechanical Interlocking. Adhesive poly-

powder, the adhesive will become liquid upon mer and porous wood fibers invariably inter-
the application of heat during processing. Dur- twine both microscopically and molecularly to
ing the initial stages of bonding the liquid resin form mechanical interlocks when an adhesive
must be of controllable viscosity so it can flow spreads, penetrates and wets a wood surface.
across the microscopically rough surface typi- The contribution of these interlocks to adhesive
cal of wood, penetrate and fill voids within the bond strength is not easily isolated and mea-
surface, and fill gaps between the substrates to sured. Adhesive must penetrate beyond dam-
be bonded. The adhesive mobility is insured aged fibers at the wood surface. Penetration two
either by heating, solvation, or both. to six fibers deep into the wood and penetration
The mobile adhesive wets and then pene- of fiber walls on a molecular scale are generally
trates and absorbs into the wood fibers. Strong thought to be necessary for durable structural
attractive forces are necessary for the adhesive bonds. This penetration may be necessary to
to displace contaminants and adhere to wood provide added surface across which other
fibers. The solvent, if present, will typically bonding mechanisms can act, to mend submi-
wet and absorb into the fibers at a greater rate croscopic fractures, or to provide a transition
than the adhesive polymer, leaving most of the zone having mechanical properties intermedi-
adhesive resin concentrated at the wood inter- ate to those of adhesive and those of the wood.
face and first few cellular layers. Bonding
problems can occur if too little or too much ad- Physical Attraction. Physical attraction be-
hesive flows into the wood. tween wood and adhesive polymers can occur
Pressure and heat are applied in the process from van der Waals forces and hydrogen bonds.
of curing a thermosetting adhesive resin. The This physical adsorption (specific adhesion) can
resin viscosity typically decreases initially in a be quite strong, especially the hydrogen bonds
thermoplastic response to the heat. The viscos- between polar hydroxy groups on fiber-wall
ity then increases in response to crosslinking of carbohydrates and adhesive polymer. Many ad-
the polymer molecules in the resin, the kinetics hesive chemists consider physical attraction to
of which are influenced by heat. The resin be- be the primary bonding mechanism. It is cer-
comes solid and the heat and pressure are re- tainly exceedingly important as a first step in
moved as the process is completed. The the formation of wood-adhesive interfaces, ac-
duration of the thermoplastic phase controls the counting for solvent wetting and adhesive poly-
amount of flow into the wood and must be care- mer absorption into cellular wall fibers.
fully manipulated for each process. In the case
of bonding at ambient temperatures, such as in Chemical Bonding. Covalent chemical
lumber laminating, the resin is typically cata- bonds between wood fiber and adhesive through
lyzed chemically and cured under pressure. the sharing of electrons is probable in cross-
Solvent loss influences adhesive cure in ad- linking adhesive systems. However, the pres-
dition to chemical crosslinking. The presence ence of such bonds may not be essential to
of excessive solvent can result in too much flow waterproof adhesive bonds. Intermolecular
and resin overpenetration or strike-in. Too lit- physical attractions are sufficient for water-
tle solvent can result in too little flow and glue- proof adhesive bonds.
line dryout. The rates of solvent loss and
crosslinking increase with heat, however each
Factors Influencing Bond Formation
rate increases differently with temperature.
The actual bonding between the adhesive The bonding of an adhesive to wood fibers is a
polymers and the wood polymers is attributed balance of several common thermodynamic and
to a combination of three mechanisms: me- kinetic parameters and their interaction. A de-
chanical interlocking, physical attraction, and ficiency in these or any other aspect of the bond
covalent chemical bonding. The relative im- formation can result in a composite with unsat-
portance of these three mechanisms is still the isfactory qUality. Wettability is a necessary
subject of debate among adhesive chemists. condition for adhesion and is preliminary to ad-
600 HANDBOOK OF ADHESIVES

hesive penetration and diffusion, but good wet- evaporated or diffused away from the glueline,
ting does not assure good bonding. Adhesive penetration is completed during the thermo-
distribution and adhesive properties strongly plastic phase of cure rheology. Wetting and dif-
influence the final bonded product. Wood bulk fusion must also take place during the
properties and surface properties also influence thermoplastic interval when pressure and heat
the interaction of adhesive and substrate. cause the adhesive to become fluid. Gelation of
thermosetting adhesives immobilizes the ad-
Wettability. Good wetting is synonymous hesive polymer. The amount of diffusion and
with intimate molecular contact between ad- penetration prior to gelation determines if there
hesive . and wood substrate, which must be is enough gap filling, enough or too much cel-
compatible for good adhesion. Thermody- lular penetration, and enough residual polymer
namic estimates of the surface free energy of at the site of the interface for good bond for-
wood are difficult because these are primarily mation.
nonequilibrium values due to the wood's swell- Because wood is hygroscopic, its moisture
ing and change in wettability with time, partic- content is strongly subject to ambient temper-
ularly when water is the solvent. Contact angle ature and relative humidity. The ability of the
measurements are rarely performed at the tem- wood substrate to pick up or lose moisture after
peratures used in actual bonding and then with drying will in tum influence the rate and mag-
great difficulty. Wood properties such as ex- nitude of solvent diffusion, particularly in wa-
tractives, density, porosity, and related differ- terborne adhesive systems. Water will also
ences in roughness influence measured values. extend the thermoplastic phase of cure rheol-
The presence of nonpolar extractives, aging of ogy. Manipulation of the resin's hygroscopic-
the surface, and heating and drying of the wood ity and cure characteristics provide the basis for
fibers all tend to decrease surface energy and matching the seasonal diffusion/penetration
wetting. needs with a resin's performance in a wood
Lignin is likely somewhat less wettable than composite manufacturing facility.
carbohydrates when exposed to polar solvents,
due to differences in their ability to interact with Adhesive Distribution. The adhesive is
hydrogen bonding solvents. Wetting between frequently applied as a continuous film in ply-
solidly attached fibers and adhesive must occur wood and laminated lumber using roller
for good adhesion. Because of the ability of spreaders and curtain coaters. Spray applica-
aqueous caustic and aqueous phenol to swell tions rapidly are becoming the standard for
.and dissolve components on the wood surface, construction plywood. Particle, flake, and fi-
poor wetting is rarely a limitation with these berboards are spot welded by small amounts of
adhesive systems. adhesive, relative to surface area, applied as
liquid droplets with spray nozzles or applied as
Diffusion and Penetration. Thermosetting powder particles with a molten slack wax or
condensation polymers such as phenol-formal- wax emulsion to temporarily bind the powder
dehyde and urea-formaldehyde resin systems particles to the wood surface.
generate water as a byproduct of cure. If water The ideal resin distribution for a particle-
also is the solvent, it is a requirement that the board manufacturer is usually defined by the
solvent water diffuse into the wood to lower the maximum board properties obtainable when
concentration of water at the interface which using a given minimal amount of adhesive. The
might otherwise inhibit cure. Water, or other cost of a continuous film of adhesive becomes
solvent(s) if present, will carry mobile lower prohibitive as wood particle size decreases in a
molecular weight polymer fractions into the cell composite because of the enormous wood sur-
interstices and cell walls. This "chromato- face area involved. How to obtain and measure
graphic" effect is the initiation of penetration. the ideal resin distribution is subject to debate.
If spray dried or other non-solvent-borne ad- Wood particle geometry, amount of adhesive
hesives are involved, or after the solvent has applied, adhesive application method, spray
 WOOD ADHESION 601

nozzle configuration, adhesive droplet or par- characterize cure rheology. Fracture mechanics
ticle size, and adhesive surface tension all in- may be used to characterize physical strength
fluence distribution. properties of either the cured resin or the com-
Although an ideal adhesive distribution is dif- posite.
ficult to define, bonding problems often can be The techniques mentioned above are but a
traced to nonideal adhesive distribution. Bond- few of the tools useful in characterizing a res-
ing problems occur when excessive adhesive is in's properties, so that its properties may be
captured by either coarse or fine particles. If more closely matched to the requirements of
some particles capture no adhesive resin at all, the final product.
bonding problems can be more dramatic. Inef-
ficient blending can reduce the strength of com-
Wood as a Substrate
posites because individual flakes or particles
receive little or no adhesive. Increased resin Surface Structure and Texture. Wood
application rates can frequently compensate for surfaces are rough at the microscopic level. The
inefficient blending, but at an additional raw roughness is caused by the inherent anatomy of
material cost to the composite manufacturer. the wood and the method of surface prepara-
Screen fractionation and determination of ad- tion.
hesive distribution from one particle size to an- Wood is structurally composed of fiber
other has assisted in identifying distribution shaped cells. The surface texture varies from
problems, and in the design of adhesive/wood species to species, hardwoods to softwoods. In
blending systems. addition to grain orientation that results from
the fibrous nature of wood, different types of
Adhesive Properties. Adhesive perfor- wood occur within a tree. Juvenile wood is
mance depends on its ability to flow, wet, and formed during the first years of a tree's life and
penetrate the fiber walls, and to cure within is composed of relatively short fibers. The
prescribed temperature and time limits. The heartwood of a tree differs chemically from the
cured adhesive must have enough cohesive sapwood. Annual growth consists of alternat-
strength to impart the desired physical strength ing rings of springwood and summerwood,
properties to the composite. Insights into the each differing in density and porosity. All these
effects of formulation variables on resin cure factors account for differences in texture as well
rheology are gained with the aid of state-of-the- as permeability, density, and compressibility.
art as well as simple instrumental and obser- The preparation of the wood for composite
vational methods. manufacture involves some combination of
The chemical composition of adhesive resins sawing, planing, milling, thermomechanical
may be characterized spectroscopically by nu- pulping or other machining which increases
clear magnetic resonance in either the liquid or surface roughness. The result is torn fibers, ex-
cured state. Infrared and ultraviolet methods are posed cell lumina, and, in general, gross irreg-
also applicable. High pressure liquid chroma- ularities which can hinder good adhesive
tography (HPLC) will characterize the low mo- bonding.
lecular weight fractions of resins while gel Adhesive penetration to undamaged fibers is
permeation chromatography (GPC) will char- necessary for anchoring. Pressure is needed
acterize the high molecular weight fractions. during processing to assure good wood-to-wood
GPC may be coupled with a laser light scatter- contact, and also to contain the steam formed
ing photometer for absolute molecular weight by the water that is the byproduct of conden-
measurements. sation in the case of phenolic and amino resins.
Cure rate may be characterized by gel times The wood-to-wood contact must be nearly in-
and stroke cures, and more quantitatively with timate and the gluelines must be thinner than
a differential scanning calorimeter (DSC). Dy- the diameter of a fiber for durable adhesive
namic mechanical analysis (DMA) and tor- bonds. Because of the variety of wood shapes
sional braid analysis (TBA) may be used to used in bonding, from small fibers in fiber-
602 HANDBOOK OF ADHESIVES

board to lumber in laminated lumber, the range

of machining and milling techniques is great.
Bu~ all have at least one common need: proper
mamtenance of wood reduction and surface
preparation equipment will help to minimize
problems further down the production line.

Chemical Composition of the Surface.

Wood surfaces are as heterogeneous chemi-
cally as they are texturally. Three bulk surfaces
are exposed when a fiber is cut open. These are
the cell cavity, the severed cell wall and the
middle lamella or the bonding area between in-
dividual fibers. The cell wall accounts for the
greatest volume of material, but the chemistry Fig. 1. Lignocellulose structure.
of each of the layers can become critically im-
portant in a given bonding situation.
In addition to the major cell wall polymers
The fibers of wood are analogous to rein-
already mentioned, extractives Oow molecular
forced concrete. Oriented cellu.ose polymer
. weight organic molecules) may be present in
molecules compose microfibrillar strands.
differing amounts. While usually minor com-
These are encased in a sheath of other carbo-
ponents (i.e., less than 5%), extractives may
hydrate polymers. A continuous network of
be present in quantities as high as 10-30% by
amorphous phenolic lignin polymer interpene-
weight in some species in the heartwood or in
trates the carbohydrate frame and bonds it to-
unhealthy wood. As cells die in the sapwood,
gether. Numerous hydroxy groups are available
extractives are deposited in those fibers, con-
for hydrogen bonding in the carbohydrates
verting them to heartwood. The chemical com-
making them highly polar. Because lignin is an
position ofthe extractives is variable, as is their
alkylated phenolic, it is less polar but still may
influence on bonding. Water soluble sugars and
provide additional reactive sites on the pheno-
tannins may migrate to the wood's surface dur-
lic ring. The lignocellulosic matrix is present
ing drying. Acidic extractives, frequently found
in significant quantities wherever a fiber is cut.
in hardwood species, may interfere with proper
In addition, an assortment of metabolic by-
wetting, act as a barrier to penetration of the
products and protoplast residue may be pres-
adhesive, or interfere with resin cure resulting
ent.
in bonding problems. Nonpolar extractives such
The exposed cell cavity may be warty in ap-
as terpenes and fatty acids may also interfere
pearance microscopically. This layer consists
with adhesive bonding. Although the cellular
primarily of metabolic byproducts and residue
major and minor chemical constituents present
from the protoplast.
a heterogenous array of polarities and molecu-
The lignocellulosic cell wall may be further
lar sizes, wood-fiber surfaces are nonetheless
subdivided in four sublayers: S3, S2, S1, and
readily bonded by many polar and nonpolar ad-
P. (See Fig. 1.) The S layers are secondary wall
hesives.
layers differing primarily in orientation of cel-
lulose microfibrils. The S3 is adjacent to the
The Influence of the Substrate's Physical
cell cavity. The S2 layer occupies the greatest
and Chemical Structure on Bond
volume of the secondary wall. The S 1 layer is
Formation
adjacent to the primary wall layer P, which
lacks the fibrillar orientation of the secondary Ph~sical characteristics of the substrate having
wall. The middle lamella consists primarily of an mftuence on bond formation include wood
lignin which bonds the individual fibers in an~tomical features and wood physical prop-
wood. erties. Chemical characteristics of the substrate
 WOOD ADHESION 603

having an influence on bond fonnation are the to absorb less water from the adhesive. Possi-
wood's major components and minor compo- ble causes are migration of extractives to the
nents or extractives. surface, pyrolysis, oxidation of hydroxyl
The cellular heterogeneity of wood results in groups or other chemical reactions of the sur-
surface roughness and variability in texture, face.
porosity, density, and hardness or compressi-
bility. Because of the rough surfaces, pressure ADHESIVE SYSTEMS
is required to assure good wood-to-wood con-
A great variety of adhesives have been used as
tact needed for bond formation. High density
assembly glues with wood for home projects,
wood having a high hardness will be difficult
furniture, and other nonstructural applications.
to compress. Such woods are less confonnable
Polyvinyl acetate (PV A) in aqueous emulsion
under pressure and difficult to bond. Adhesive
is a common wood glue for such applications,
penetrates more slowly in dense woods. The
but lacks water resistance and tends to creep
broad range of densities found in a single com-
under sustained load. Epoxy and urethane ad-
posite may create bonds of differing quality
hesives are costly, but are used in limited ap-
from region to region.
plications.
Wood is hygroscopic and may gain or lose
The greatest volume of wood adhesives for
water to the environment. When water is re-
structural applications are thermosetting
moved, the fiber wall collapses or shrinks.
phenol-formaldehyde (PF) or urea-formalde-
When the fiber wall absorbs water, it swells.
hyde (UF) polymers or their derivatives. PFs
Wood will equilibrate at constant temperature
are the commodity for exterior applications,
and humidity. But the environmental condi-
while UFs are the commodity for interior ap-
tions of most composite manufacturing facili-
plications. Because each composite product and
ties are not constant. Wood is gaining or losing
the associated process may require a somewhat
water and shrinking or swelling prior to, during
different resin, many variations of PF and UF
the process of, and after bond formation. These
resins are available. Isocyanate crosslinking
dimensional changes influence the bonding
resins are used to a lesser extent than PFs or
process. Glueline stresses can develop during
UFs in manufactured board. Although these
the curing process prior to the development of
resins impart a durable, water resistant bond
adequate cohesive strength. The shrinking and
suitable for exterior application, the cost per
swelling of wood can also stress the glueline
pound of adhesive is greater than for PFs or
after the composite has been manufactured. Be-
UFs.
cause of these possible stresses, wood is gen-
erally dried to a moisture content approximating
Phenolic Resins
that to be encountered during use.
Chemically, wood extractives may have the General Properties. Phenolic resins gener-
greatest influence on bond formation difficul- ally are aqueous solutions of alkaline-catalyzed
ties. They may reduce wettability. They may phenol-formaldehyde polymers. A typical resin
form a barrier at the interface causing mechan- would be about 40% solids, containing phenol,
ical weakness. Extractives can interfere with formaldehyde, and sodium hydroxide in molar
desired curing of the adhesive at the interface. ratios of about 1: 2 : 0.75, and might average
This is of great concern if extractives alter the 10-50 phenol units linked together. These can
pH and buffer characteristics of the wood and be spray dried for application as a dried pow-
the adhesive is sensitive to pH and buffer. Ex- der. Phenol-formaldehyde resins are cured with
ternal catalyst systems may be useful to over- heat under pressure. The resultant bond is
come wood buffer problems. highly water resistant and heat resistant. The
The surface of the substrate can change durability and weatherability of phenolic-
chemically during heating and drying, resulting bonded wood composites enables them to be
in thermal inactivation. Thermally inactivated rated for exterior use.
wood surfaces may be less wettable and tend Resorcinol is a derivative of phenol, having
604 HANDBOOK OF ADHESIVES

an additional hydroxy group on the benzene is a methylolated phenolic. Mono-, di- and tri-
ring. The hydroxy group is positioned such that methylol derivatives are possible.
it activates the molecule toward reaction with The second step, shown in Fig. 2, is a con-
formaldehyde because the activity of the ortho- densation step. Water is generated as a conden-
para positions is heightened. Partial substitu- sation byproduct and is formed with a methylol
tion of phenol with resorcinol accelerates cure hydroxy and neighboring active proton. The
of these phenol-resorcinol-formaldehyde (PRF) combination of addition-condensation steps
resins. PRF resins or resorcinol-formaldehyde yields a polymer network which is the back-
(RF) resins, in which all phenol had been re- bone of the adhesive resin. The reaction steps
placed with resorcinol, may be used in appli- leading to resin formation are generally per-
cations such as lumber laminating where formed at elevated temperature in a chemical
ambient-temperature curing is needed. These reactor capable of heating, cooling, good agi-
will cure without additional heat input. The tation, vacuum distillation and atmospheric re-
bond is also waterproof and heat resistant and flux.
is rated for exterior applications. Phenol and The properties of the resin may be modified
resorcinol are the main phenolics used in phe- by varying any of the synthesis parameters.
nolic resins, but a variety of other phenolic de- These variables include the molar ratio of for-
rivatives may be co-reacted in minor amounts maldehyde to phenol, catalyst, their rate of ad-
to impart desired characteristics. dition, the concentration of raw materials
during the cook, the type of catalyst used, the
General Chemistry. Phenolic polymers are temperature profile during the cook, the pres-
formed with a phenolic or phenol derivative ence of a dehydration step, the presence of a
monomer and formaldehyde crosslinking agent neutralization filtering step, the target nonvol-
in two discrete steps. The first step, shown in atiles content, the degree of molecular ad-
Fig. 2, is an addition or methylolation step. vancement, and the presence of additives to
Formaldehyde reacts with an active ortho or impart special characteristics. The effect of
para proton to form the addition product which varying the synthesis parameters is to vary the

3. METHYLOlATION:

Gr
OH OH

CH:PH HOH2C~CH20H
I"
/'
+ +
+~
CH20H

b. CONDENSATION'

OH OH
,Ie

"e
Fig. 2. Reactions in the fonnation of PF resins.
 WOOD ADHESION 605

molecular and/or colligative properties of the in place of the urea (MF), yielding a durable
polymer network. Properties monitored may adhesive.
include molecular weight, molecular weight
distribution, functional groups, cure rheology, General Chemistry. UFs, MFs, and MUFs
viscosity, and cure speed. By evaluating the polymerize in discrete addition (methylolation)
molecular and colligative properties of the ad- steps and condensation steps (Fig. 3) similar to
hesive resin, its consistency may be monitored the chemistry previously described for PFs.
and its mill performance may be controlled. There are four reactive sites on a urea molecule
but only three sites may methy10late due to
crowding.
Applications. PRFs and RFs are used pri-
Synthesis parameters are modified, as with
marily in lumber laminating and ambient tem-
the PFs, to alter resin properties. Molar ratio,
perature bonding a,pplications. PFs are used
catalyst system, raw material concentration and
primarily in hardboard, plywood, oriented
their rate of addition, target nonvolatiles, a de-
strand board (OSB), and waferboard. It is used
hydration step and additives may all be varied
to a small extent in particleboard. Because PFs
to modify and impart special properties to a
generally do not develop the tack of UFs, they
resin. Properties monitored may include mo-
are not easily used on caulless particleboard
lecular weight, molecular weight distribution,
lines.
functional groups, cure rheology, viscosity, and
The resin may be applied as a neat liquid but
cure speed.
more frequently is used in conjunction with ex-
tenders and fillers to improve gap filling, mois-
Applications. UFs are the primary com-
ture retention, and cure characteristics and to
modity binder in caul and caulless particle-
control pot life. The resin may be spray dried
board processes and medium density fiberboard
and applied with molten wax or wax emulsion
(MDP). They can be formulated to develop tack
as a carrier. Products manufactured with phe-
and generally are used as a neat liquid. Acid
nolics are generally rated for exterior use.
catalysts are frequently used unless the wood
species is acidic such as southern pine or oak.
Products manufactured with UFs are rated for
Amino Resins interior application. Use of MUFs or MFs in-
creases bond durability and imparts water re-
General Properties. Amino resins are gen- sistance to the bond, speeds cure rate, and
erally aqueous solutions of acid-catalyzed urea- reduces potential formaldehyde release.
formaldehyde (UF) polymers. A typical resin
would be about 60% solids containing urea and
Diisocyanates
formaldehyde in molar ratios of about 1: 1.2.
UFs are cured with heat under pressure and General Properties. Diisocyanate resins are
usually with an acid catalyst if the wood spe- generally liquid, consisting of a mixture of
cies is not acidic. The resultant bond is not lower molecular weight monomers and oligo-
water resistant, especially at elevated temper- mers. The resin can be 100% nonvolatiles the-
ature. Formaldehyde is slowly released from oretically because no solvent is generated as a
UFs as they decompose. Even at low concen- byproduct of the chemical reactions associated
trations, the released formaldehyde may be a with cure. Isocyanates are very reactive and are
nuisance in poorly ventilated living quarters. cured with heat and pressure. The resultant
Melamine consists of a resonance-stabilized bond is highly water resistant and heat resist-
carbon-nitrogen six-membered heterocyclic ant. The durability and weatherability of diiso-
ring with three functional amine groups. Mel- cyanate bonded wood composites enables them
amine may be copolymerized with the urea in to be rated for exterior use. Diisocyanates can
melamine-urea-formaldehyde (MUF) resin to co-react with PF or UF resins, but are gener-
increase the durability of the UF, but at an in- ally more expensive on a solids basis than either
creased cost. Melamine may be used entirely of the former.
606 HANDBOOK OF ADHESIVES

a. METHYLOLATION:

o
HOH 2C...... N/ C'N/CH20H
+ +
+ H/ 'CH 20H

h. CONDENSATION:

Fig. 3. Reactions in the fonnation of UF resins.

A typical diisocyanate resin is based on iso- droxyls, and amines. Because too much water
mers of methylene-diphenyl-diisocyanate can deactivate the diisocyanates, wood mois-
(MOl) as the monomer units. Other types of ture content must be carefully controlled. There
isocyanates can be used. Toluene-diisocyanate
(TOI) is very reactive, but also very volatile. REACTION WITH HYDROXYL GROUPS:
Because TD! is so volatile and reactive, it can o
crosslink in human lungs and it is therefore not -N=C=O + HO-R ---+
II
-N-C-OR
practical for hot press applications in the wood ~
industry. Because polymeric MOl (PMDI) has
CHAIN GROWTH WITH WATER:
advantages of low vapor pressure, high reactiv-
ity, and acceptable viscosity, wood resins fre-
quently consist of a significant percentage of o
PMOI (Fig. 4). O=C=N-R-N-~-OH
I
H
~ decomposition
General Chemistry. The reactive portion of
the isocyanate is the - N=C=O functional O=C=N-R-f-H + CO 2
group. A stepwise addition reaction occurs H

across the double bond (Fig. 5). The t O=C=N-R-N=C=O

-N=C=O group can react with active hydro-
gens under either alkaline or acidic conditions.
A variety of self-reactions readily occur as well
as reactions with water, alcohols, polyols, hy-

POSSIBLE REACTION WITH WOOD HYDROXYLS:

WOOD} OH O=C=Nf or R}N=C=O

!
n WOOD] 01h1R or R}r8-0-{ WOOD

Fig. 4. Typical structure of polymeric methylene-di-

phenyl-diisocyanate (PMDI). Fig. 5. Reactions in the fonnation of diisocyanate resins.
 WOOD ADHESION 607

is a strong likelihood of covalent linkages be- resin chemistry likely will remain for many
tween isocyanate resin and wood substrate. Be- years as a mixture of thennodynamic and ki-
cause the -N=C=O group is also highly netic knowledge, semiempirical theory, and
reactive with metals, release agents are fre- fonnulation art.
quently necessary to prevent pennanent bond-
ing to metal caul plates or press platens. VENEER AND SOLID WOOD
Properties of the isocyanate resin may be mod- COMPOSITE PRODUCTS
ified by changing the monomers used in the
Veneer and solid wood composite products are
resin or by reacting them with additives, such
manufactured for building and construction
as polyols.
commodity markets and for specialty markets
such as marine applications and aesthetic de-
Applications. Isocyanates are used com-
cor. Bonding systems vary based upon the ser-
mercially to a minor extent in manufactured
vice demands placed upon the final product,
board as a specialty adhesive. They are used in
interior versus exterior. Construction and dec-
particleboard, OSB, and waferboard for special
orative plywood are veneered panel products.
products where color as well as exterior dura-
Laminated veneer lumber (LVL) is a veneer
bility are important.
product which competes with lumber. Lumber
laminates fonn majestic beams often for dual
General Concepts of Adhesive
structural and aesthetic applications.
Structure-Property Relationships
Construction plywood is primarily phenolic
Resin chemistry is a mixture of thennodynamic bonded for an exterior rating. Decorative ply-
and kinetic knowledge, semiempirical theory, wood is primarily bonded with UF resins for
and fonnulation art. Chemists have sought and interior applications such as wall panels and
continue to seek instrumental and other meth- hardwood flooring tiles. Both types of plywood
ods to predict perfonnance prior to plant trials. are composed of layers of veneer or wood with
Methods of chemical analysis, rheological alternating grain orientations that are bonded
characterization, mechanical analysis, pilot with heat and pressure.
plant evaluation, fracture mechanics, and mul- As the thickness of the wood members to be
tivariate statistical analysis all are useful tools. bonded increases, heat transfer from the hot
Lab studies are generally designed to bracket press becomes limiting, and a more reactive
the conditions which are likely to be encoun- resin system is required. Radio frequency (RF)
tered in field trials. When trends are identified, curing processes may also be used. Laminated
theoretical explanations are fonnulated. veneer lumber may be heat cured if the com-
The perfonnance properties of a resin may posite thickness allows heat transfer. Alter-
then be predicted based on structural data which nately, PRF resin systems are used which will
chemically or otherwise characterizes the resin. cure at ambient temperature. PRF resin sys-
Because data frequently are generated in a lab tems are used in lumber laminating applica-
or pilot experiment, field trials are necessary to tions and are cured at ambient temperature
confinn the theory generated by the trend anal- under pressure, generally with a catalyst to pro-
ysis. Generally, the same trend will be identi- mote cure.
fied in the field trial if the lab experiments were Adhesive systems for construction plywood,
properly designed. The magnitude ofthe trend, decorative plywood, LVL (laminated veneer
however, is likely to differ between controlled lumber), and lumber laminates are a heteroge-
lab or pilot experiments and daily mill opera- neous mixture consisting primarily of resin with
tion. Fonnulation changes are then needed to extenders, fillers, and catalysts. The adhesive
accommodate mill operating and environmen- mixture allows for a better matching of adhe-
tal peculiarities. The observational skills of the sive with mill operating parameters than would
fonnulation chemist are the art in these manip- easily be obtained solely with the use of neat
ulations of the resin fonnulation. Because of resin.
mill operating and environmental peculiarities, The blending of a resin with other ingredi-
608 HANDBOOK OF ADHESIVES

ents frequently results in reduced overall glue particleboard, to long thin particles or strands
costs. But cost is only one of several benefits in oriented strand board, to thin wafers in wa-
gained by using an adhesive mix. Extenders, ferboard. PF resins are primarily used in hard-
such as wheat flours, are used to manipulate the board, oriented strand board, and waferboard.
hygroscopicity of the adhesive mix. Manipu- UF resins are primarily used in fiberboard and
lation of the adhesive's hygroscopicity allows particleboard, although some PF and isocyan-
control of the glueline's tendency to dry out at ate resins are used to a limited extent in some
one extreme or overpenetrate due to excessive particleboard applications.
moisture at the other extreme. These tenden- Hardboard is manufactured either by a wet
cies must be controlled by mill operators to re- process or a dry process. Either thermome-
spond to changing mill conditions, such as chanical or mechanical milling may be used to
wood species mix and ambient temperature and reduce the wood chips to fibers or pulp. A water
relative humidity, which influence the wood's suspension of fibers is formed on a moving
equilibrium moisture content. screen which is hot pressed to a high density
Fillers, such as nutshell flours, remain par- board in the wet process. Resin (usually 1-2%
tially undigested in an adhesive mix. These tend PF solids on a wood solids basis), wax, reten-
to reinforce the physical strength of the glue- tion aids, and wet strength additives may be
line when properly cured. When glueline added to the slurry. Exterior home siding is one
stresses such as expansio,n and contraction ini- of many markets for this product. Alterna-
tiate a fracture in the glueline, the fracture tends tively, the mat may be formed with dried fiber
to propagate. The fracture propagates because that has already been blended with resin, then
the stresses become concentrated at the crack pressed for dry process hardboard. Low density
tip and because thermosetting crosslinked res- insulation board also may be manufactured
ins tend to be brittle when cured. When a prop- from fibers with wax and little or no additional
agating crack tip contacts a filler particle, the binder. Board properties may be modified by
stresses are then redistributed over a greater adjustment of pulp additives in the wet process,
volume of material, which effectively stops the bond forming parameters, press closing rate,
propagation of the crack and disperses the press temperature, press time, and post-press
stresses in the vicinity of the crack tip. coatings.
The glueline in a veneer product is generally Fibers used in the manufacture of medium
thought of as a continuous film. The surface of density fiberboard (MDF) do not go into a
the veneer is frequently rough and imperfect, slurry mix. The wood chips are generally fed
containing lathe checks. The core layers of ve- into a pressurized steam injected digester which
neer products may contain additional voids due thermally softens the chips. Upon release from
to knots and gaps between edge-butted veneer. the digester the chips pass from high pressure
An additional benefit of incorporating the resin to low pressure and are passed through a rotat-
into an adhesive mix is the ability of the mix to ing disk refiner. The combination of depressur-
aid in gap-filling and bulking of the adhesive ization and refining forms a thermomechanical
between veneers. Catalysts may also be added pulp. The fibers go directly to dryers after re-
to the mix to regulate cure speed. The pot life fining. UF resin and wax may be applied at the
of the adhesive must be monitored in all gluing point between refiner and dryer in blow line
applications. blending. The resin does not advance appreci-
ably in the dryer. Alternatively, the resin may
be applied by a conventional blender after the
MANUFACTURED BOARD
fibers are dried. The blended fibers are formed
In contrast to veneer composites, in which the into a mat and hot-pressed. An RF unit may be
glueline is present as a continuous film, in used to assist in resin cure. Because of the gen-
manufactured board products the bonding sites erally tight edges and smooth surface ofMDF,
are present as spot welds. The wood particles great quantities are consumed by the furniture
range in size from fibers in hardboard and fi- industry. The tight edges are good for cutting
berboard, to a mixture of fibers and particles in edge profiles while the smooth surfaces provide
 WOOD ADHESION 609

a good substrate for vinyl print or paper over- uid PF resin or a spray dried, powder PF resin
lays. which is distributed onto the individual flakes
Particleboard is manufactured from wood with the assistance of molten wax or wax emul-
chips or shavings from lumber planing mills sion which also acts as a sizing agent. Wafer-
which are mechanically reduced to particle size board is used for sheathing and siding.
(0.5-3 mm wide by 1-30 mm long). Manage-
ment of wood shavings inventory, the milling FUTURE CHALLENGES
and the drying of shavings control the quality
of particles used in board manufacture. Bulk Some future challenges can be predicted al-
density and particle geometry influence the mat ready based on current trends, driven either by
handling characteristics on the production line the marketplace or by government regulators,
and the final obtainable board physical prop- which may be extrapolated into the future.
erties. Finer particles are segregated either me- Market driven challenges are generally moti-
chanically or air classified by blowing air and vated by a desire to increase profitability or to
deposited in surface layers during mat forma- improve quality (which results in improved
tion, while coarser particles go into the core or profitability). The changing availability of ad-
center of the board. In the blending and form- hesive raw materials can alter the relative price
ing operation, the surface and core furnish may structure of resin systems. Government regu-
be handled separately and may even use differ- lations can alter the availability of resin sys-
ent resin systems. In addition to all of the pre- tems or the potential liability of working with
vious operations, moisture content, wood a given adhesive system.
species mix, press closing and decompression Dryer capacity is a limiting factor in many
rates, and press cycles all influence the board's plywood manufacturing plants and a source of
final physical properties obtained. For floor un- high energy costs in most board-making oper-
, derlayment applications, modulus of rupture is ations. The ability to bond veneers and parti-
an important physical property. The market cles at a higher moisture content represents a
pays a premium for industrial particleboard that potential cost savings and increased productiv-
can be used as furniture components. Particle- ity in plywood and board manufacture. A cur-
board is becoming more competitive with MDF rent and future market driven trend is to develop
by producing smoother surfaces and tighter adhesive systems which will cure when used to
cores. Because particleboard and MDF are bond wood at a higher moisture content.
generally used for interior applications, they are The upgrading of particleboard for industrial
bonded with UF resins. MUF, PF, and iso- applications is a challenge directed at improv-
cyanate resins are used where additional dura- ing product quality. The majority of opportu-
bility or reduced formaldehyde emissions are nities for improving board quality are in mill
critical. operating parameters. Opportunities for modi-
The wood chips for oriented strand board fication of the resin system for improved sur-
(OSB) are milled so that they are dimensionally faces lie in going from single resin systems to
larger in the longitudinal direction (i.e., 2-10 surface and core resin systems. The incorpo-
cm) and narrow in the radial direction (i.e., ration of melamine into the resin system may
0.1-2 cm). Because wood is anisotropic, the further enhance board surfaces, but at higher
strands are layered with the core strands per- resin cost.
pendicular to the surface strands, similar to the The supply of raw materials for adhesives is
layers of veneers in plywood. The resulting closely tied to the availability of petroleum.
board has good dimensional stability. OSB Toluene and other raw materials for the syn-
competes with plywood for sheathing and sid- thesis of phenol are also used as octane boost-
ing applications and is bonded with PFs or iso- ers for unleaded gasoline . Availability and price
cyanates for exterior durability. are often volatile. Adhesive manufacturers are
The wood chips for waferboard are milled challenged by opportunities to use alternate raw
into flakes or wafers (i.e., 1-4 cm wide by 3- materials. Board manufacturers are challenged
8 cm long). They are bonded with either a liq- by variable adhesive costs. Naturally occurring
610 HANDBOOK OF ADHESIVES

phenolics derived as byproducts of wood utili- Ten years into the future may see new board
zation have found a use in resin systems in products, new bonding applications, and new
many parts of the world, but have not yet been innovative adhesive systems. Some future
economical in the U.S. However, those eco- challenges can be predicted based on current
nomics are subject to change based on the trends and will be met by those who currently
availability of petroleum. see opportunities to meet those challenges.
Government regulations have historically fo- Some future challenges cannot be predicted. By
cused on formaldehyde emissions from manu- extrapolating the individual and collective in-
factured board products. These emissions are dustrial ability to formulate opportunities to
primarily associated with UF resin systems. meet past challenges, the unpredictable future
Modern UF resin formulations have drastically challenges will also be met with creative, ef-
reduced emissions. Board surface porosity can fective and profitable solutions which will ben-
also be decreased to reduce emissions. Even efit our society.
with improvements in board surfaces and UF
resin systems, the specter of additional regu-
lation cannot be overlooked. BIBLIOGRAPHY
Isocyanate resins, although expensive, were
once viewed as a possible alternative to UF res- Bryant, B. S., "Wood Adhesion," in "Handbook of Ad-
ins. Isocyanates are highly reactive and pose hesives," 2nd Ed. I. Skeist (ed.), pp. 669-678, Van
Nostrand Reinhold, New York, 1977.
certain health hazards during board manufac-
Pizzi, A. (ed.), "Wood Adhesives: Chemistry and Tech-
ture, particularly fumes near the hotpress. The nology," Vol. I, Vol. 2 New York, Marcel Dekker,
mill workers' health may be a future concern 1983, 1989.
to regulatory agencies. Wellons, J. D., "Adhesives for Wood," "Encyclopedia
Opportunities to meet future challenges are of Materials Science and Engineering" in M. B. Bever,
(ed.), pp. 73-78, New York, Pergamon Press, 1986.
limited only by the creativity of the industry.
Wellons, J. D., "Bonding in Wood Composites," in
Products exist in the marketplace now which "Adhesion in Cellulosic and Wood-Based Compos-
were merely concepts five years ago, and were ites," J. F. Oliver (ed.), pp. 127-146, New York,
unrecognized as opportunities ten years ago. Plenum Press, 1981.
 37
Sealants and Caulks
JOSEPH W. PRANE MICHAEL ELIAS
Industrial Consultant Chemark Consulting
Elkins Park, Pennsylvania Group Inc.
Cincinnati, Ohio
and
RUSSELL REDMAN
Ineon Division
Tremeo, Inc.
Cleveland, Ohio

Sealants and caulks are used to fill joints, gaps from noncuring tapes to extruded preformed
and cavities between two or more similar or tapes; types of materials vary from bituminous
dissimilar substrates. Sealants and caulks seal to high modulus silicone polymers. For pur-
these discontinuities in structures for economy, poses of this discussion, sealants and caulks
convenience, and functional necessity. Their will be classified as low, medium, and high
purpose is to isolate and control conditions, movement products. 98
such as water and weather, to optimize the Over the last 40 years, a wider variety of
functioning of the structure being sealed. To- sealants and caulks, especially high perfor-
day the number of applications for sealants and mance sealants, have been developed to satisfy
caulks in construction, industrial and consumer the new high technology needs of transporta-
markets is growing. These materials are re- tion, aerospace, and construction applications
quired to seal and adhere to the appropriate (see Fig. 1). An example of the increased seal-
mating surfaces over a wide range of tempera- ant performance requirements was the intro-
tures, environmental stress and joint movement duction of curtainwall construction in the early
conditions. These surfaces to be sealed include 1950s as a new architectural design. It created
a wide variety of glass, concrete, masonry, the need for sealants that compensate for foun-
wood, steel, aluminum, and plastic sub- dation settling, temperature changes and wind-
strates. l - ll ,87,98,102 created stresses on the curtainwall panels. The
Caulks are materials used for sealing sub- cured sealant must demonstrate adhesion and
strates where only minor or no elastomeric movement capability while resisting the dele-
properties are required. Sealants are elasto- terious effects of temperature extremes, water,
meric materials with adhesive qualities used for sunlight, and environmental pollutants. 80
sealing substrates. Sealant/adhesives are elas- The sealant must absorb stresses when the
tomeric materials with adhesive qualities which curtainwall panels shift relative to each other
provide structural strength when joining sub- because of the settling of these high-rise build-
strates. These materials range from noncuring ing with live and dead building loads. These
mastics to curable elastomeric sealants, and stresses on the sealant are shear, compression,

611
612 HANDBOOK OF ADHESIVES

TYPICAL USES

Precast Roofs

Perimeter Joints

n
Gravel Stops

Corrugated Sheet Lap Joints

Curlaln Wall

Precast Panel

Coping and Reglet Joints Typical Glazing Details

Fig. 1. Construction applications for sealants.

and extension. The sealant must compensate for wall panels' wind-created bending and flexing.
thermal expansion and construction of a wide For example, an 8' x 10' x i" thick lite of
variety of curtainwall materials. Table 1 lists plate glass will deflect 1-i inches at its center
the coefficient of thermal expansion of a variety under a 120 mph windload. With all these
of substrates. The sealant must seal common stresses, the sealant must maintain ·a watertight
curtainwall materials such as aluminum and and airtight structure in these curtainwall de-
glass, with aluminum having a thermal coeffi- signs over time in a wide range of environmen-
cient of expansion 2.5 times that of glass. The tal conditions. Furthermore, these sealants must
sealant must compensate for the stresses caused maintain their movement capability and adhe-
by wind loading, which will place both positive sion with acceptable aesthetics. 102
and negative loads on the curtainwall system. This chapter will overview the types of caulks
The sealant will have to accept a skewed and sealants available today. Typical formula-
squeezing and pulling effect due to the curtain- tions and properties will be presented for the
 SEALANTS AND CAULKS 613

Table 1. Coefficients of Linear FORM, TYPE, AND PERFORMANCE

Expansion of Common Building Materials
(in.fin.-oF x 10- 6 ). Forms
Clay, masonry (Brick, clay or shale)
Tubes or Cartridges. These are filled
Brick, fire clay 3.6
Tile, clay or shale 3.3 caulking cartridges, typically 10.7 ounces to
Tile, fire clay 2.5 one quart, applied by hand or power-activated
Concrete
caulking guns.
Gravel aggregate 6.0
Lightweight structural 4.5 Bulk Materials. These are single or muIti-
Concrete, masonry component sealants and caulks sold in units
Cinder aggregate 3.1 from 1.5 to 50 gallons, to be applied by knife
Dense aggregate 5.2 or filled into caulking cartridges (see Fig. 2) or
Expanded-shale aggregate 4 .3 mechanical pumping equipment. Multicompo-
Expanded-slag aggregate 4.6
nent materials (two or more components) are
Volcanic pumice & aggregate 4.1
typically mixed by powered drill mixer (see
Metals Fig. 3) or meter mix equipment.
Aluminum 13.0
Brass, red 230 10.4
Bronze, arch. 385 1l.6 Extruded Tapes. These are preformed rib-
Copper, 110 9.8 bons or profiles of butyl rubber, neoprene, or
Iron polyvinyl chloride, and may be either solid or
Cast gray 5.9 expanded. They may be supplied as composite
Wrought 7.4
Lead, common 16.3
structures with rubber cores, rubber rod spacer,
Monel 7.8 or aluminum shims surrounded or embedded in
Stainless steel an adhesive or sealant.
Type 302 9.6
Type 304 9.6 Types
Structural steel 6.7
Zinc 19.3 As supplied in a cartridge, in bulk or as ex-
Glass, plate 5.1 truded tapes, sealants and caulks are of nine
Plaster
types, described below.
Gypsum aggregate 7.6
Perlite 5.2 Hot Pour Sealants. These must be melted
Vermiculite aggregate 5.9 to the recommended temperature for proper
Plastics handling and performance (especially adhe-
Acrylics 40-50
Lexan® 37.5
Phenolics 25-66
Plexiglas® 39
Polyesters, glass reinforced 10-14
PVC 33
Vinyls 24-40
Stone
Granite 6.2
Limestone 3.5
Marble 7.3

various polymer types, as well as information

on how to select, test, and properly install seal-
ants and caulks. Fig. 2. Sealant application from caulking cartridge.
614 HANDBOOK OF ADHESIVES

Nonsag, One-Part, Chemically Cured

Sealants. These materials cure by chemical
reactions, usually involving the crosslinking of
polymers. They are applied by knife, caulking
cartridge, or bulk dispensing equipment into the
joint, being sure to wet out the sides of the sub-
strates. Manufacturer's recommendations
should be followed for types of bulk loading
guns, nozzles, and bulk dispensing equipment.

Nonsag, Multicomponent, Chemically

Cured Sealants. These sealants also cure by
chemical reactions, usually involving the for-
mation of crosslinked polymers. The sealant
base, curing agent, and color pack (if required)
are mixed together according to the sealant
manufacturer's recommendations. After mix-
ing, the sealant is filled into cartridges, dis-
pensed from automatic mixing equipment, or
applied with a knife.

Heat-Softened, Nonsag Sealants. These

sealants and caulks require heating to be prop-
erly dispensed and applied. They may be heated
Fig. 3. Power mixing. in ovens, heat chests, or boiling water to the
manufacturer's recommended temperatures.
sion). Application should be in one operation, For proper application and perfonnance, care
and remelting is not advised unless pennitted must be taken not to overheat them prior to ap-
by the manufacturer. plication, nor to apply below the manufactur-
er's minimum temperature recommendations.
Cold Pour, Multicomponent, Chemically
Cured Sealants. These materials cure by Strip Sealants - Cold-Applied Mastic
chemical reactions, usually involving the Strips. These sealants are supplied with
crosslinking of polymers. The sealant base, backing paper for proper handling and appli-
curing agent, and color pack (if required) must cation. A suitable length of the strip sealant is
be thoroughly and uniformly blended. It is es- applied (adhered) to one of the joining surfaces
sential that the full contents of the curing agent with backing still in place. The paper is then
be transferred to the base prior to mixing ac- removed and the other joining surface is placed
cording to the sealant manufacturer' s specifi- in position for sealing. Exact storage, han-
cations. These materials can be poured directly dling, and application instructions must be fol-
from the mixing vessel into the joints to be lowed.
sealed.
Strip Sealants - Hot-Applied Preformed
Nonsag, Noncured Sealants. These non- Strips. These sealants are also supplied with
curing materials are sufficiently thixotropic to backing paper. The backing paper is removed
be applied in vertical joints without appreciable from a suitable length of strip sealant and fit
sag or weep. They are applied with a knife or into the slot to be sealed. The strip is then
caulking cartridge into the joint and forced heated to the manufacturer's recommended
against the sides of the substrates. They may temperature. Caution must be taken that the
require wanning to be applied properly. heat-softened material achieves continuous
 SEALANTS AND CAULKS 615

contact with the sides of the joining surfaces to The key perfonnance properties most often
be sealed. used to select a sealant or caulk are movement
capability, adhesion, life expectancy, and ma-
Compression Seals. These are prefonned terial cost. With the proper design and assem-
cellular elastomeric products available in either bly of the structure to be sealed, a critical
precompressed or uncompressed fonns. The property is the amount of movement a sealant
sealant may utilize external and/or internal ad- or caulk will accept prior to failure, expressed
hesive elements. The seal is obtained by plac- in percent extension ( +) and percent compres-
ing the prefonned material in compression sion ( - ). Adhesion is the tendency of a sealant
between the joining surfaces. Exact storage, or caulk to bond to a surface or material when
handling, and application instructions must be under a separating stress. Sealants can fail in
followed. adhesion by cleanly separating from the surface
(adhesive failure) or tear internally in the seal-
Performance ant, not affecting the bond line between the
Sealants and caulks fall into three categories: sealant and surface (cohesive failure). Sealants
low, medium, and high movement materials. and caulks will vary in their perfonnance lon-
They vary widely in the test properties shown gevity with regard to weathering, temperature
in Table 2.98 and chemical environment of the application.
Always a consideration is overall cost, which
Table 2. Sealant and Caulk Properties. embraces material cost, installation cost, and
Propeny Typical Units
life cycle cost (perfonnance and life expect-
ancy). Table 3 outlines a range of caulks and
Uncured sealants and their characteristics. 6, 10,98
1. Skin-over time minutes
2. Tack-free time hours
3. Sag, weep inches POLYMERS FOR SEALANTS, CAULKS,
4. Extrusion rate grams/minute AND GLAZING COMPOUNDS
5. Flow seconds
Cured
Sealants, caulks, and glazing compounds are
1. Durometer hardness Shore A points nonnally highly pigmented (40-80%) compo-
2. Tensile at maximum pounds/inch2 sitions based on a wide variety of polymeric
elongation percent vehicles. Some 15 families of polymers are uti-
3. Elongation at maximum pounds/inch2 lized singly or in polyblends to achieve the
tensile pounds/linear inch
4. Modulus pounds/linear inch
storage characteristics, application properties,
5. Tear physical perfonnance, and durability required
6. Peel for each application at minimum cost. They are
Application discussed here in order of increasing cost.
1. UV resistance
2. Ozone resistance Asphaltic and Other Bituminous
3. Staining/ dirt pickup Materials
4. Color change
5. Application temperature Asphaltic materials are supplied in solvent-di-
range luted, emulsion, or hot-poUred fonns. Rubber
6. Service temperature range
is used for reinforcement in high solids for-
7. Adhesion
8. Durability mulations. The latter are more important be-
9. Compatibility cause of better adhesion and lower shrinkage.
10. Compression set Typically, the sealant contains 50-60% asphalt
11. Solvent resistance blend (needle penetration 10-110), 20-30%
12. Life expectancy
ground rubber (from tire scrap) and 20% cyclic
Cost hydrocarbon. The sealant is applied at 250-
1. Material
400 o P. Durability can be as high as 5 years if
2. Installation
properly applied.
616 HANDBOOK OF ADHESIVES

Table 3. Sealant Characteristics.

Movement
Capacity Advantages Disadvantages
Lower Movement Caulks
Oil/resin-based ±5% Lowest cost; easily applied and No recovery; slow cur-
tooled; primeriess preparation; ing; can stain sub-
good color stability; fast skin- strate; moderate
ning shrinkage; for static
joints
Polybutene/polyisobutylene ±5% Good adhesion; low shrinkage; Dirt pickup; low cohe-
excellent UV lozone res is- sive strength; poor
tance; low cost; good water solvent resistance;
resistance can stain substrate;
for static joints
Medium Movement Caulks
and Sealants
Latex ±7.5% Fast skinning and cure; immedi- High shrinkage; poor
ate paint-over; good adhesionl water resistance; can
UV resistance; easy applica- freeze below OaF;
tion/cleaning mostly indoor use
Butyl ±7.5% Good adhesion; good water re- Slow curing; high
sistance; good color stability; shrinkage; low re-
little surface preparation; caps covery; relatively
neoprene gaskets soft
Hypalon ±12% Excellent UV lozone resistance; Slow curing; high cost;
impervious to water; fair re- high shrinkage;
covery; remains flexible tough gunnability;
not for interior use
Neoprene ±12% Bitumen/asphalt compatible; High shrinkage; only
good water resistance; good dark color; very slow
adhesion to metals; low cost curing; stains wood/
stone
Solvent Acrylic -7.5% to No primer required; excellent a" maximum width;
+12% adhesion; excellent UV resis- poor recovery;
tance; good chemical res is- strong curing odor;
tance; nonstaining; tough poor water resis-
curing tance; slow curing
Higher Movement Sealants
Polysulfides ±25% Good UV Iwater resistance; Slight curing odor; less
won't stain masonry; fast UV resistance/recov-
through cure; good adhesionl ery than the follow-
durability; broad color range ing; primer required
for porous surfaces
Urethanes ±25% Excellent UV lozone/tear/chemi- Light colors can dis-
cal resistance; excellent recov- color; poor water
ery; little shrinkage; joints up immersion resis-
to 6" wide; 20-30 year life tance; surface prim-
ing required
Silicones ±25% to Excellent UV lozone/heat resis- Surface preparation
±50% tance; no shrinkage; 20-30 critical; slight curing
year life; excellent recovery; odor; dirt pickUp;
nonstaining concrete/aluminum
adhesion difficult
 SEALANTS AND CAULKS 617

Oleoresinous Table 5. Elastic Glazing Compound

(Professional Glaze).
Vegetable oils are used as the binder for put-
ties, elastic glazing compounds, and architec- % weight
tural caulking compounds. Clarified raw soybean oil 7.0
Aged linseed oil (blown) 2.0
Soya fatty acids 0.2
Putties. Used in the glazing of wood sash,
Mineral spirits 1.8
putties are generally based on linseed oil, filled Calcium carbonate, fine 30.0
with calcium carbonate or blends of calcium Calcium carbonate, coarse 55.5
carbonate and titanium dioxide. Formulations Fibrous talc -..l1
are shown in Table 4. Containing 11-12% oil, Total 100.0
they dry by oxidation to hard, inflexible joints lb/gal 18.6
with little movement possible. Putties are sup- Nonvolatile, % 98
plied as bulk compounds for knife application
to wood ot metal sash. Most putties are used in caulks are lower in viscosity than glazing com-
industrial, commercial, and maintenance glaz- pounds, consequently can be applied from
ing; however, significant quantities continue to caulking cartridges rather than by knife. 100
be used by homeowners in residential glaz-
ing. 1oo Polybutene

Elastic Glazing Compounds. Based on The C4 olefins go into three types of sealants:
blown soya or linseed oils, these materials are polybutenes, butyl rubber, and polyisobutyl-
formulated with selected calcium carbonates ene. Polybutenes are largely linear, low molec-
and fibrous fillers plus small amounts of fatty ular weight homopolymers of butene-I, used in
acids for easy working properties (knifing) on sealants either as prime vehicles or as modify-
large glazing installations. Most of these ma- ing polymers. They are relatively low cost,
terials are used in industrial and commercial nondrying, tacky polymers. They are used in
construction and maintenance. the formulation of three types of compounds:
1. Nondrying mastic sealers for concealed
Architectural Caulking Compounds. metal-to-metal joints where elasticity and
These materials, also called oil-based caulking resistance to staining are not essential,
compounds, contain 15-20% blown or heat- e.g., hidden joints in curtainwall con-
bodied vegetable oil, usually soya, plus 5-8 % struction, acoustical sealants, hidden au-
fatty acids and polybutenes. Since these latter tomotive panel sealants, and gap fillers.
polymers do not harden on aging, they prevent 2. Rope caulks and extruded tapes for non-
embrittlement of the compound. Pigmentation critical glazing and weatherstripping ap-
is usually high in calcium carbonate, with fi-
brous talc or other fibrous filler to provide non- Table 6. Architectural Caulking
slump characteristics. Solvents up to 3-4% are Compound (Drying Oil Caulk,
often added to improve working. Oil-based Gun Grade, Neutral Shade).
lb gal
Table 4. Linseed Oil Putties·
Blown soybean oil 245 30.0
Type [, Type ll, Polybutene (920-950 MW) 110 15.0
% weight % weight Soya fatty acids 16 2.0
Calcium carbonate (max.) 88 79 Calcium carbonate, fine 800 35.6
Ti02 10 Fibrous talc 200 8.4
Linseed oil (min.) ..ll ...!l 6 % Cobalt naphthenate 4 0.5
Total. 100 100 Mineral spirits ~ ~
Total 1,430 100.0
lb/gal 18.3 19.6
Nonvolatile, % 99+ 99+ lb/gal 14.3
Nonvolatile, % 96
'Federal Spec. IT-P-79Ia, modified: white lead replaced by TiO,.
618 HANDBOOK OF ADHESIVES

Table 7. Polybutene-Based Sealant of about 75-85% NV. They shrink signifi-

(Rope Caulk). cantly; nevertheless, they can be formulated
% weight with fillers and plasticizers to increase their sol-
ids level. A low percentage of a drying oil,
Polybutene (1300-1500 MW) 27.4
3.2
e.g., 3% dehydrated castor oil, encourages
Petrolatum
Tall oil fatty acid 0.6 skinning and resistance to dirt pickup. These
Fibrous talc 34.4 caulks are applied by gun. A typical composi-
Calcium carbonate 32.6 tion is shown in Table 8.
Titanium dioxide (rutile) ~
Total 100.0 Two-Component Sealants. 14-17 Two-
Ib/gal 13.8 component butyl sealants are room temperature
Nonvolatile, % 99 + vulcanized materials. Low in moisture vapor
transmission and easy working because of low
molecular weight and semi-liquid form, these
plications or for bedding compounds in
sealants are filled with calcium carbonate and
small window frames. (Table 7 illustrates
titanium dioxide, plasticized with polybutene,
a typical rope caulk.) A knife-applied
and may be modified with epoxy and silane
mastic sealer would have about the same
adhesion promoters. The cure system is p-qui-
percentage of a lower molecular weight
none dioxime activated with a peroxide.
polybutene. Rope caulks and polybutene
tapes are sold in rolls of up to 100 feet. Preformed Tapes. 18- 2o Preformed tapes of
3. Plasticizing modifiers for oleoresinous butyl, usually vulcanized, are extruded semi-
caulks, butyl caulks and tapes, and for
solid sections with pressure-sensitive adhesion.
certain elastomeric sealants. Since they are 100% solid, there are no prob-
lems of shrinkage or solvent evaporation. Sold
Butyl Rubber and Polyisobutylene
in rolls interlined with release paper, they are
Polyisobutylene, pm, is a homopolymer of often used together with liquid sealants or solid
high molecular weight. The butyl elastomers spacers, shims, etc. They vary from low cost,
are copolymers of isobutylene with sufficient highly polybutene-extended tapes for trailers
isoprene (0.5-2.5 %) to permit crosslinking. and mobile homes, to partially or fully vulcan-
Most butyl compositions are one-component, ized butyl rubbers with little polybutene con-
e.g., tapes or liquid gun-grade caulks. They tent for high-rise glazing and automotive
may be modified with plasticizers such as poly- windshield sealants.
butene, or tackifiers and fillers such as calcium
carbonate and fibrous talc. Two-component, Table 8. Butyl Caulking Compound
curing butyl sealants are also available. 12, 13, 19 (Gun Grade, Aluminum Shade).
Premasticated butyl cutbacks for the sealant lb gal
industry are also available, as are a series of Butyl rubber (035 grade, 50% NV 388 55.0
depolymerized butyls, to improve compound- in mineral spirits)
ing and processing ease. Chlorobutyl rubbers Petroleum resin (60% NV in 74 10.0
are also produced; these have found limited use mineral spirits)
Hydrogenated rosin, methyl ester 8.5 1.0
in sealant formulations, mostly in tapes.
Denatured ethyl alcohol 1.3 0.2
Amine-modified bentonite 25 1.7
One-Component Butyl Caulks. 12.13 Calcium carbonate, fine 400 17.8
These are superior to oleoresinous caulks in Fibrous talc 100 4.2
weather resistance, ozone resistance, and im- Aluminum paste (73.5 % NV in 34 2.5
permeability to gases and vapors. Although not mineral spirits)
Mineral spirits ~ ~
truly elastomeric, they can be used safely in
Total 1,080.8 100.0
joints with movement of up to 10-15%. They
are solvent solutions of uncured butyl elasto- Ib/gal 11
Nonvolatile, % 74
mers with 17-20% polymer and solids content
 SEALANTS AND CAULKS 619

Table 9. Butyl Rubber Architectural

Sealing Tape (Light Gray).
Ib % weight
Butyl rubber (268 grade) 100 21.2
Calcium carbonate, surface coated 200 42.4
Silica, hydrated, precipitated 50 10.6
Zinc oxide, surface treated 10 2.1
Antioxidant, phenolic type 2 0.4
Polybutene (1300 MW) 100 23.3
Carbon black, furnace type, FEF ---ll 0.02
Total 472.1 100.0
lb/gal 13
Nonvolatile, % 99

A typical intennediate perfonnance butyl Fig. 4.

tape contains 20-22 % uncured butyl polymer,
20-25 % high molecular weight polybutene, nation glazing. 22 - 26 , 86,91 Figure 5 shows the
and pigmentation from calcium carbonate or application of a patented extruded tape to an
silica, plus zinc oxide or phenolic antioxidants. insulated glass unit in which the spacer and
Partial crosslinking is achieved in the inten- desiccant is incorporated into the sealant. This
sive mixing operation in the presence of high patented product combines these three compo-
surface area fillers. This vulcanization in- nents, typically applied separately, and allows
creases tape strength and elasticity, and re- for installation ofthe tape in a single operation.
duces compression set. Table 10 gives the fonnulation of a typical bu-
High perfonnance elastomeric butyl tapes are tyl hot-melt sealant.
available for large window lite glazing in high-
rise structures and for windshield sealing. Polyisobutylene
These usually contain crosslinked butyl elas- As a homopolymer, polyisobutylene (PIB) is
tomers (20-40%) plus polybutenes,' resinous pennanently tacky. Most of the PIB used in
tackifiers, and reinforcing fillers such as carbon
black and platy talc. Chlorobutyl rubber com-
positions are available for faster and more thor-
ough vulcanization.

Hot Melt. Field-Extruded Sealants. Sev-

eral butyl raw material manufacturers and seal-
ant producers have recently developed butyl
tapes. These are premasticated, high viscosity
thennoplastic compositions that are fed as
talced ribbons into a polymeric sealant appli-
cator (PSA). Within the PSA, the compound is
heated and extruded into the joint opening to
fonn a smooth joint that cools rapidly with ex-
cellent adhesion claimed, even to oily or oth-
erwise poorly prepared surfaces. These hot-
applied, post-fonned butyl tapes have been
successfully used to seal insulated glass units,
automotive windshields (Fig. 4), curtain walls,
concrete pipes, precast concrete structural
joints, and as bedding compounds in combi- Fig . 5.
620 HANDBOOK OF ADHESIVES

Table 10. Butyl Hot-Melt Sealant Table 11. Hypalon-Based Sealant

(Black. Hot Applied). (Gun Grade. White).
lb % weight % weight
Butyl rubber, cross-linked 100 27.8 Hypalon 40 1.7
Carbon black (Statex RH) 100 27.8 Hypalon 30 . 15.7
Naphthenic rubber process oil 120 33.3 Chlorinated paraffin (low viscosity) 17.5
Terpene-phenolic resin ~ ..lL..! Fibrous talc 2.6
Total 360 100.0 Thixotropic agent 2.6
Silica, hydrated, precipitated 5.2
lb/gal 9.5
Titanium dioxide (rutile) 14.0
Nonvolatile, % 99
Talc 8.8
Tribasic lead maleate 7.0
Hydrogenated rosin . 0.3
sealants is employed in the modification of 2-Mercaptobenzothiazole 0.2
other sealants or tapes, primarily of the butyl Tetramethyl thiuram disulfide 0.1
type. The remainder is used in bedding com- Xylol 10.4
pounds in the glazing industry, usually as part Dibutyl sebacate 9.3
of a combination glazing system. Petroleum plasticizer 2.9
The lower molecular weight grades of pm
Isopropyl alcohol J:1
Total 100.0
are used to modify butyl caulks; the higher mo-
lecular weight grades containing butyl elasto- lb/gal 10.9
Nonvolatile, % 88
mers are used in butyl tapes. Both grades go
into pm bedding compounds. Small amounts
of PIB are used in the formulation of insulated
glass sealants. 102 chemical, ozone, oxidation, and heat resis-
tance, good modulus, exterior durability, and
Hypalon abrasion resistance, but poor initial color and
color stability and extended cure time when
Hypalon, Dupont's chlorosulfonated polye~­
compounded for gunning. Applications are
ylene, finds modest use as a sealant for curtam
usually related to oil and chemical resistance,
walls, precast panels, exterior glazing, and roof
e.g., chemical plant service, automotive, ma-
joints. 27 It possesses not only the good me-
rine, concrete pipe seals, and, to a limited ex-
chanical properties of neoprene, but also ex-
tent, lubricant-adhesives for preformed
cellent color stability, exterior durability, and
neoprene highway joint seals.
ozone resistance. Shortcomings as a single
Both one-part and two-part neoprene sealants
component sealant are its relatively poor pack-
are made most commonly using general pur-
age stability, extended cure time to reach ulti-
pose neoprenes of the GN and W types. Two-
mate elastomeric properties, and relatively high
part compositions contain 25-30% neoprene
shrinkage from solvent evaporation. Also, the
plasticized with materials such as dioctyl se-
complex curing system may result in excessive
bacate or resinous plasticizers, stabilized with
post-hardening.
phenolic antioxidants, filled with reinforcing
Hypalon caulks are produced primarily as
pigments such as carbon black and hard clay~,
gun-grade compositions, packed in cartridges
and'modified with cure-rate regulators and aCId
or in bulk. A typical formulation is shown in
acceptors such as zinc oxide and magnesium
Table 11. The cure system comprises tribasic
oxide. Cure accelerators such as polyamines
lead maleate (metal oxide source and acid ac-
(Le., tetraethylene pentamine) are used at 5-10
ceptor) and rubber chemical accelerators MBTS he-
phr based on neoprene. 28 Heat-reactive.p
•
and Thiuram M.
nolic resins are also effective. One such com-
position is shown in Table 12.
Neoprene (Polychloroprene)
One-part compositions contain up to 35 %
Cured neoprene compositions have excellent neoprene. Storage life is extended by reducing
elastomeric properties as well as good oil, the levels of curing agent and by dilution with
 SEALANTS AND CAULKS 621

Table 12. Neoprene-Based Sealant. Table 13. Styrene-Butadiene-Based

parts by weight Sealant.
Component A % weight
Neoprene (Type W) 100 Styrene-butadiene rubber 12
Magnesium oxide 4 Polymerized rosin 19
Antioxidant 2 Hydrogenated rosin, methyl ester 2
Calcium carbonate 150 Aromatic plasticizer 2
Petroleum process oil 30 Clay 17
Amine-modified bentonite 3 Fibrous talc 10
Zinc oxide ---1 Toluol 26
Total, Component A 294 Xylol ..n.
ComponentB Total 100
Butyl phenol-formaldehyde 45 lb/gal 9.5
resin (heat reactive) Nonvolatile, % 60
Xylol 115
Zinc oxide -2
Total, Component B 167
Thermoplastic Elastomers. These are sty-
lb/gal (blended) 1l.5 rene-butadiene-styrene block copolymers
Nonvolatile (blended), % 80
which may have utility in hot-melt sealants.
They process more easily than conventional
solvents such as xylol down to as low as 55 % SBR.
NV.
Other types of neoprene-containing sealants PVC Pressure-Sensitive Tapes. Formu-
include a neoprene/Hypalon gun-grade caulk lated PVC plastisols are used in automotive ap-
and a pressure-sensitive neoprene foam tape for plications. A pressure-sensitive adhesive-
mounting molding and trim on autos, boats, and coated closed-cell PVC tape has replaced butyl
trailers. glazing tape in some glazing applications. 29 ,3o
Other applications include automotive, trucks
SBR and Miscellaneous Elastomers and trailers, mobile homes, steel building erec-
tion, metal door gasketing, and sound deaden-
Elastomers used to a minor extent as the prin-
ing. Both single-face and double-face tapes are
cipal binder in sealants include styrene-buta-
available in various thicknesses, widths, and
diene rubber (SBR), nitrile rubber, and reclaim
densities. The pressure-sensitive adhesive is
rubber. 102
believed to be of the acrylic type.
PVC foam tapes form compression seals in
SBR. This elastomer provides good tack and
combination glazing with polysulfide, silicone,
ease of compounding when used. Formulation
or acrylic sealants. Elongation and resistance to
is in the 12-15% range, along with modified
compression set are excellent, along with good
rosins for increased tack and stabilizers for UV
peel strength. The PVC foam cells must not in-
and ozone resistance; -Because of the high so-
terconnect or there may be wicking of water.
lution viscosity of SBR, large quantities (35-
PVC tapes are easier to place than conventional
40%) of solvents, such as xylol, are required
butyl tapes, and reportedly cheaper to install
to achieve satisfactory extrusion properties in a
than gun-grade caulks or bedding compounds.
gun-grade compound. Consequently, the re-
sulting sealant has considerable shrinkage.
Acrylic Solution
Weathering characteristics are poor. An SBR
sealant composition is shown in Table 13. Acrylic solution caulks have been used in glaz-
ing and small-joint industrial sealing for over
Nitrile Rubbers. These require high solvent 15 years. The original compounds (at 90% NV)
levels to produce gunnable sealants, hence are were extremely difficult to extrude at room
little used. Reclaim rubber goes into asphaltic temperature; cartridges had to be warmed to
sealants. 120°F before gunning. However, this acrylic
622 HANDBOOK OF ADHESIVES

Table 14. Acrylic Solution Sealant Table 15. Acrylic Emulsion Sealant
(Room Temperature Application, (Gun Grade, White).
Gun Grade, Natural Shade). lb gal
lb gal Acrylic solution polymer (55% NV) 430.2 48.2
Acrylic solution polymer (83% NV) 545 62.8 Nonionic surface active agent 9.5 1.0
Xylol 75 10.3 Sodium polymetaphosphate (anionic) 10.7 0.5
Pine oil 6 0.6 Polymeric plasticizer 124.2 14.9
Ethylene glycol 9 1.0 Mineral spirits 26.9 4.1
Calcium carbonate, fine 422 18.7 Aqueous dispersant, polyacrylate type 1.3 0.1
Fibrous talc 17 0.7 Calcium carbonate, fine 692.1 30.7
Talc 96 4.3 Titanium dioxide (rutile) --11.:1 ~
Silica, pyrogenic ~ --1& Total 1,312.6 100.0
Total 1,198 100.0 Ib/gal 13.1
Ib/gal 12 Nonvolatile, % 83
Nonvolatile, % 84.5

up readily, are nonbleeding and nonstaining,

sealant has excellent adhesion to common con- and dry rapidly so that they can be painted soon
struction surfaces without primers, is nonstain- after application. They have low shrinkage, ex-
ing, and has excellent durability and color cellent flexibility, fair recovery, and excellent
pennanence. While extensibility is good, re- UV resistance and color retention. 37 ,38
covery is poor as the polymer is not elasto- A typical gun-grade acrylic emulsion sealant
meric. Later acrylic sealants have been (Table 15) contains about 18% acrylic polymer
fonnulated at lower solids so as to allow extru- solids and 9-10% of a polymeric plasticizer.
sion at temperatures of 50-60°F. This feature Sodium polymetaphosphate is a primary pig-
is beneficial to applicators but, if overdone, can ment dispersant aided by a water-soluble poly-
adversely affect shrinkage and durability prop- acrylate. A nonionic surfactant acts as a wet-
erties. ting agent and emulsifier. Often small amounts
A typical acrylic sealant (Table 14) contains (up to 2 %) of glycols are included for addi-
about 37-40% acrylic polymer solids pig- tional freeze-thaw stability. Mineral spirits
mented with calcium carbonate, talc, and (about 2 %) retards skin formation. Acrylic
fumed silica as a thickening and rheological emulsion caulks are used indoors as bathtub
control agent. 31 Other ingredients include pine caulks, baseboard and trim seams, and out-
oil as a pigment dispersant and penetrating doors for glazing, masonry joints, and roof and
agent for oil or grease on the joint surfaces, siding joints.
ethylene glycol for fumed silica activation, and
xylol for viscosity control and extrusion ease. Polyvinyl Acetate
The high solvent content (10-15%) can cause
Sealants and caulks based on vinyl acetate
considerable shrinkage, moderated somewhat
homo- and copolymers have been on the mar-
by the slow solvent release of the system, re-
ket since the late 1950s. Use of these lower-
sulting in sufficient stress relief to overcome
performance materials has been mostly in res-
joint distortion.
idential areas-bathtub caulking, wall tile
Acrylic solution caulks are available in
joints, wallboard joints, etc. Latex caulks based
caulking cartridges or in bulk. Usage is mostly
on polyvinyl acetate plasticized with dibutyl
in industrial sealing and glazing, including cur-
phthalate, or on one of the newer vinyl acetate-
tainwall joints, concrete roofs, masonry panels,
acrylic emulsion copolymers, have the same
and metal-to-masonry joints such as flashing,
skylights, etc. 32 ,33 ease of application as the acrylic emulsion
caulks but are less flexible, harden on aging,
and have inferior exterior durability. 102
Acrylic Emulsion
A typical polyvinyl acetate caulk, as shown
Acrylic emulsions are easy to apply, adhere in Table 16, contains about 25-28% copolymer
well to most construction joint surfaces, clean solids, with surfactants, modifiers, and pig-
 SEALANTS AND CAULKS 623

Table 16. Polyvinyl Acetate-Based ethyl) ether with sodium polysulfides; small
Sealant (Tub and Tile Caulk, quantities of 1,2,3-trichloropropane are used to
White, Low Shrinkage). produce branching of the LP polymer chains.
lb gal The final product is a thiol-terminated polyfor-
mal with strategically located disulfide link-
Vinyl acetate copolymer emulsion
(65% NV) 537 59.0
ages. 43 The two LPs most used for sealants
Xylol 9 1.3 have the following characteristics:
Hydroxyethyl cellulose solution 125 15.0
(QP 30,000 grade, 2.5% NV in
LP-2 LP-32
water)
Propylene glycol 33 3.8 Mol % cross- 2 0.5
Ultramarine blue 0.3 0.01 linka
Titanium dioxide (rutile) 148 4.2
Calcium carbonate, fine 247 11.0 Molecular 4000 4000
Aluminum silicate -ill- ~ weight
Total 1,222.3 100.0 Viscosity, poise 400 400
Ib/gaJ 12.2 % SH 1.75 1.75
Nonvolatile, % 74 'Mol % of 1,2,3-trichloropropane used in manufacture.

The LP polymers are usually cured by oxi-

dation using higher-valence-state metal oxides
mentation generally similar to the acrylic emul-
or peroxides. (Dichromate and manganese
sion caulks previously described. Total solids
dioxide cure systems are used in aircraft sys-
are as low as 70 % NV; the potential for severe
tems.) Oxides such as lead dioxide react with
shrinkage always exists, although it is reduced
the mercaptan groups to form higher polymers
through utilization of some of the new high sol-
as well as crosslinks through disulfide bridges.
ids vinyl acetate terpolymer emulsions.
Cure is accelerated by sulfur and water, and
retarded by stearic acid.
Polysulfides and Polymercaptans
Lead dioxide has traditionally been the pre-
Polysulfide Sealants. Liquid poly sulfide ferred curing agent, but it cannot be used in
polymers are the base of poly sulfide sealants, white or light-tint compositions. Other curing
the workhorse elastomeric sealants used in con- agents which have been used are manganese
struction, glazing, marine, and aircraft appli- dioxide, tellurium oxide, barium peroxide, cal-
cations for over 35 years. 40-42,84 cium peroxide, zinc peroxide, and dibutyl tin
Polysulfide sealants are now available in one- oxide. Silane adhesion promoters are often uti-
component as well as two-component form, and lized in poly sulfide sealants. 51
as gun-grade materials, packed in cartridges or Lead is toxic; skin contact must be avoided.
bulk. They are elastomers, expanding and con-
tracting with joint movement; adhesion is good, Two-Component Polysulfide Sealants.
with satisfactory resistance to water, dust, Many formulations of two-component polysul-
chemicals and other contaminants or aggres- fide sealants are available. All have a base
sive atmospheres. Hardness can be varied from component containing the LP polymer and an
that of soft rubbers (Shore A = 20) for curtain- activator component containing the curing
wall sealing and high-rise glazing, to hard rub- agent. (Automotive windshield sealants, for-
bers (Shore A = 50+) for pour-in-place floor merly important in the industry, have two ac-
joints and concrete pavement joints which must tivator components.)
resist penetration and standing water. Perfor- A typical construction sealant base compo-
mance life of 20 years or more can usually be sition contains 35-50% LP polymer. Chlori-
expected. nated terphenyl or chlorinated paraffin were
The first manufacturer of liquid polysulfide formerly included as an extender to lower cost
polymers (LP polymers) was Thiokol Chemi- at little sacrifice in elastomeric properties.
cal Corp., Trenton, NJ. Most LPs for sealants However, for health reasons, they have been
are condensation polymers of bis(2-chloro- replaced by phthalate plasticizers. The plasti-
624 HANDBOOK OF ADHESIVES

cizer also improves working properties and rate is accelerated by high temperatures and hu-
plasticity. Phenolic resins or epoxy resins are midities, and vice versa. Joints must be scru-
added at the 2-3% level to improve adhesion. pulously clean to obtain the best adhesion.
Small amounts of stearic acid and sulfur (less Primers are available for use on unsound sur-
than 1 %) are used to control the rate and extent faces, particularly masonry or stone. These are
of polysulfide cure. Pyrogenic silica or amine- often based on chlorinated rubber solutions,
. modified bentonite clays, or combinations of with or without silane adhesion promoters .
the two, are used as thickeners, maintaining Two-component polysulfides are used in in-
slump resistance in vertical joints while the ac- dustrial construction service: curtainwall seal-
tivated system cures. Pigments are chosen ing; building expansion and contraction joints;
which reinforce the rubber while having no ad- precast concrete construction joints; combina-
verse effect upon cure. Coated calcium carbon- tion glazing; insulated glass sealing; highway,
ates are the most popular, together with airfield, and bridge joints, canal and inland
calcined clays and rutile titanium dioxide. waterway joints; automotive windshields; air-
Black compounds use good quality carbon craft construction and fuel-tank sealing; and
blacks such as SRF (see Table 17). various marine construction and repair joints.
Two-component polysulfide sealants cure to
80-90% of their final strength, adhesion, and One-Component Polysulfide Sealants.
elastomeric properties within 16-24 hours. 78 One-component poly sulfide sealants, intro-
While satisfactory overall, they do have defi- duced in 1962, are now made by several com-
ciencies. Although they are always supplied in panies. They are advantageous in that no field
premeasured components, accurate and com- measurement or mixing is required, quality is
plete dispersion on the job is essential. Cure factory-assured, material loss is minimized, and
working time and pot life are not problems as
they are with two-component materials.
Table 17. A Two-Component These materials are formulated in a manner
Polysulfide-Based Sealant similar to that of two-part systems, with some
(Gun Grade, Gray). important differences. The curing agent is an
lb % (weight) alkali oxide such as calcium peroxide (about
2 %) which, upon moisture activation, initiates
Base
54.42
the LP polymer chain extension and crosslink-
Poly sulfide polymer, liquid 100
Phthalate plasticizer 20 10.89 ing reactions. For practical package stability
Calcium carbonate, precipi- 35 19.05 (six months minimum in sealed, aluminum foil
tated, surface treated lined cartridges), the use of bone-dry ingredi-
Titanium dioxide, rutile 10 5.44 ents and the complete exclusion of moisture
Carbon black, furnace 5 2.72
0.54
during processing and packaging is essential.
Stearic acid, single pressed
Organic-modified bentonite 3.0 1.64 Moisture scavengers, such as molecular sieves
clay or barium oxide, are often included as insur-
Fumed silica 2.5 1.36 ance. The total composition contains about 25-
Phenolic resin 5 2.72 35% LP polymer (LP 2 or 32) and about 4-6%
Gamma-aminopropyltri- 0.15 0.08
aromatic solvent (such as toluol) for improved
ethoxy silane
Sulfur, sublimed 0.1 0.05 gunning. A suggested formulation for a one-
Toluene _2_ ~ component sealant is shown in Table 18.
Subtotal, base 183.75 100.00 One-component poly sulfides skin rapidly at
Activator relative humidities above 50 %; the remainder
Lead dioxide, technical 7.5 50.00 of the reaction proceeds slowly into the com-
Stearic acid 0.75 5.00 pound at a rate dependent on temperature, rel-
Dibutyl phthalate 6.75 45.00
ative humidity, and the ratio of joint width to
Subtotal, activator 15:00 100.00
depth. Cure is slow, reaching about 50% oful-
lb/gal, blended 13.5 timate properties in seven days-often as long
Nonvolatile, % 99+ as 30 days if humidity is low. 4547,95
 SEALANTS AND CAULKS 625

Table 18. Polysulfide-8ased Sealant compositions and properties are made available
(Single-Component, Gun Grade, White). by the fonnulator to the end user. Earlier ure-
% (weight) thane compositions had excessively high mod-
uli; cohesive strength was far greater than
Polysulfide liquid polymer (LP-32) 50
Epoxidized soya oil 4
strength of adhesion to the joint substrate, with
Pyrogenic silia 2 resulting adhesive failure. Also, adhesion was
Calcium carbonate, surface treated 5 destroyed readily after exposure to UV through
Titanium dioxide, rutile 22 glass. Primers are now utilized to improve
Hydrated lime 2 adhesion. In addition, compositions have been
Synthetic zeolite 2
Calcium peroxide 4
modified to give lower crosslink densities and
Phthalate plasticizer 2 moduli.
Gamma-aminopropyltriethoxy silane 1 Urethane sealants have good elongation and
Toluol 4-6 recovery, excellent abrasion resistance and tear
Total 100
strength; their resistance to indentation make
Ib/gal 12 them the preferred compounds for floor joint
Nonvolatile, % 96 compounds, highway and airfield joint mate-
Note: Manufactured and packed under anhydrous conditions. rials, and prefonned gasket seals in clay and
concrete pipe. Low temperature performance
(to below -40°C) is superior to that of the
Polymercaptans. Mercaptan-terminated polysulfides. 52, 53, 93, 96
polypropylene oxide polyethers for sealant use
The polyhydroxy components of urethane
were developed in the 1960s. Fonnulation and
sealants are mostly hydroxyl-terminated satu-
curing procedures are similar to those used with
rated polyesters or polyethers. Most polyesters
the LP polymer poly sulfides since both make
used in urethane sealants have been standard
use of the thiol group.
condensation products of dibasic acids (such as
The sealant grade material had a molecular
adipic acid or phthalic anhydride) with glycols
weight of 5000-6000. Considerable interest
and triols (such as propylene glycol, glycerin,
was shown in this material by sealant producers
or trimethylol propane). Polyester-based ure-
because of its lower price than polysulfide.
thane sealants are hard and tough, have rela-
However, polymer quality and cure rates
tively good adhesion in joints, but are deficient
were not reproducible batch to batch, and field
in hydrolytic stability and exterior durability.
experience showed that chemical resistance and
Polyether polyols are usually preferred as the
dynamic sealant properties were inferior to
hydroxyl-rich components of urethane seal-
those of polysulfides. Second generation poly-
mercaptans were introduced in 1974. 8 1,82,94 ants. These are nonnally polypropylene oxide
condensates with molecular weights in the 400-
Polyurethanes 4000 range, hydroxyl-terminated. Triols are in-
corporated in minor proportion to provide for
Polyurethanes are the most versatile polymer crosslinking. Compared to polyesters, poly-
systems used to fonnulate elastomeric sealants. ether urethanes have superior hydrolytic stabil-
Polyurethane sealants are sold both as two- ity, lower moduli, but somewhat inferior
component and one-component gun-grade adhesion.
compositions, packed in cartridge or in bulk. The most common polyisocyanate used in
Applications are similar to those of the poly- urethane sealant production is toluene diiso-
sulfides, including the insulated glass markets cyanate (TDI). The TDI is usually prereacted
and sealing automotive windshields. to give an isocyanate-terminated prepolymer.
Most polyurethane sealant systems are based Other aromatic polyisocyanates used in seal-
on the reaction of polyhydroxy materials (and ants include diphenylmethane diisocyanate
diamines) with polyisocyanates in situ to pro- (MOl) and polymethylene polyphenylene iso-
duce a polyurethane (or urethane-urea) rubber .. cyanate (PAPI). All of the aromatic polyiso-
By varying backbone compositions, NCO/OH cyanates contribute to yellowing of urethanes
ratios, catalyst content, etc., a wide range of on exposure to light.
626 HANDBOOK OF ADHESIVES

Nonyellowing urethane sealants can be made Table 19. Polyurethane-Based Sealant

using aliphatic or cycloaliphatic polyisocyan- (Two-Component, Gun Grade, White).
ates or with compounds where the NCO group parts by
is removed from the benzene ring by at least weight %
one methylene group. These include hexa- Component A
methylene diisocyanate (most frequently as its Polyethylene glycol-isocyanate pre- 100 100
less toxic biuret with water), methylcyclohexyl polymer (2.6% free isocyanate)
diisocyanate, dimer acid diisocyanate, and xy- ComponentB
Antioxidant 0.65 0.5
lene diisocyanate. Since these materials are
Polypropylene glycol (MW = 2(00) 62 47.3
considerably more expensive than TDI, usage Titanium dioxide-rutile 7.86 6.0
is limited. Calcium carbonate filler 49 37.2
The isocyanate-terminated prepolymers used Nonsag agent 10.4 8.0
in most urethane sealants incorporate polyes- Tin catalyst J.M -..kQ
Total 131.72 100.0
ter, polyether or other polyol building blocks.
Curing to elastomeric compositions is achieved lb/gal (blended) 11.5
in two ways: two-component, by the addition Nonvolatile, % 99 +
of a hydroxyl-rich coreactant (polyester or
polyether); or one-component, by water ab-
sorption followed by 'polyurea formation with thanes good candidates for windshield sealants.
elimination of carbon dioxide. They are also used in highway and airfield seal-
ing, aircraft construction, and marine applica-
Two-Component Polyurethane Sealants. tions.
As with polysulfides, many formulations of
two-component urethane sealants are available One-Component Polyurethane Sealants.
to suit the wide varieties of applications and Isocyanate prepolymers with NCO equivalent
product qualities expected by users. Most com- weights of 1000-2000 are used in the formu-
monly, the NCOIOH equivalent ratio is about lation of one-component urethane sealants. A
1.05-1.10. One component is a liquid isocyan- typical gun-grade compounds may contain 30-
ate-terminated prepolymer, pigmented and 60% of prepolymer, pigmented with titanium
filled with titanium dioxide (if white), calcium dioxide, calcium carbonate, and silica, with up
carbonate, talc, or silica. The second compo- to 5 % of dry toluol for easier gunning. Com-
nent is a hydroxyl-terminated polymer, often pounds may also contain molecular sieves to
pigmented as well, containing small amounts absorb unremoved water for improved com-
of a catalyst such as methylene dianiline (which pound stability. As with one-component poly-
also reacts with isocyanate and serves as a flow- sulfide sealants, manufacture of the compound
control agent). Ingredient mixing is done with is carried out with dry ingredients under vac-
heat under anhydrous conditions for maximum uum and heat so as to eliminate all traces of
stability. These compounds have polymer con- water. One suggested formulation is shown in
tents in the 50-70% range. Component mixing Table 20.
in the field must be very thorough. Pot life Since they cure by moisture absorption, one-
range is 1-4 hours; substantially all of the elas- component urethane sealants have joint restric-
tomeric properties are achieved within 24-48 tions and delayed cure characteristics similar to
hours. A typical formulation is shown in Table those of one-component polysulfides, except
19. that urethane sealants cure somewhat faster in
Their applications in industrial construction similar joints because of greater moisture
include vertical joints with high movement re- permeability. Materials are available with
quirements, and horizontal or floor joints where package life of up to one year when well sealed
their hardness, toughness, abrasion resistance, from moisture. Catalysts such as 1,2,4-tri-
and resistance to indentation are important. methylpiperazine can speed cure, but at a sac-
They are suitable for insulated glass sealants. rifice in package life.
Rapid-cure characteristics make the ure- A method can be used for preparing one-
 SEALANTS AND CAULKS 627

Table 20. Polyurethane-Based Sealant. good UV, ozone, and chemical resistance with
Moisture Curable (Single Component. low shrinkage. Also, silicone based materials
Gun Grade. White). display good release and electrical insulation
% weight properties. Silicone sealants can be com-
pounded into low, medium, and high modulus
Titanium dioxide, rutile 2.0
Calcium carbonate, fine 34.5
one-part RTV sealants. Table 21 shows basic
Silica, precipitated 6.0 low, medium and high modulus formulations.
Molecular sieve 1.0 The RTV cure of silicone sealants usually in-
Isocyanate prepolymera 30.0 volves the hydrolysis of dimethyl siloxane in-
Phthalate plasticizer 23.0 termediates and their condensation to
Organosilane, epoxy functional 1.0
UVabsorber 0.5 polysiloxanes. Crosslinking occurs through
Toluol ---.bQ condensation of trifunctional organosilanes,
Total 100.0 usually catalyzed by organometal soaps such as
lb/gal 11.5 dibutyl tin dilaurate. Polysiloxanes containing
Nonvolatile, % 98 vinyl groups can be crosslinked by organic per-
"Prepolymer (3 % unreacted isocyanate): oxides. A variety of one- and two-component
Polypropylene glycol diol (EW = 1000) 67.7 silicone elastomers can be formulated, depend-
Polypropylene glycol triol (EW = 1600) 19.1
Toluene diisocyanate 13.1 ing on application and performance require-
Dibutyl tin dilaurate 0.1 ments. 101 . 105
100.0
NCOIOH = 1.9
One-Component Silicones. The liquid sil-
component sealants which reduces moisture icone prepolymers used in one-component
sensitivity during manufacture and yields im- sealants are usually methyl-substituted polysi-
proved package stability and wet adhesion. The loxanes having more than two blocked, hydro-
polyol is chain-extended with TDI to a molec- lyzable end groups. These groups may be
ular weight of 10,000-15,000 and then sto- acetoxy, ketoxime, alkylamino, or benzamido.
ichiometrically end-capped with 'Y-amino- When the composition is extruded into a joint
propyltrimethoxy silane to react all of the free
NCO groups. In a pigmented one-component Table 21. Silicone Sealants.
urethane sealant, this prepolymer cures by hy-
Component %
drolysis of the methoxy groups and siloxane
polymerization. Basic Low Modulus Formulation (N-Methyl
Acetamide Chain Extender and
Diethylhydroxylamine Crosslinker)l04
Silicones SHanol polymer (4000 cs) 46.0
Silicone rubbers are outstanding in resistance Calcium carbonate 50.0
Methyl vinyl di(N-methyl acet- 3.0
to high temperature, low temperature flexibil- amido)sHane
ity, and exterior dlJ,rability. Two-component Aminoxy sHoxane copolymer 0.7
types have been developed with both heat cured
(HTV) or room-temperature (RTV) cured vul- Basic Medium Modulus Formulation (oxime)
canization.75-77. 101. 104. 105 SHanol polymer (80 mcs) 60-80
Silicone sealants have been used in a number Silicone plasticizer 5·-20
of applications in construction, industrial, and Fumed silica (treated and/or untreated) 2-6
Calcium carbonate (treated and/or un- 20-30
consumer markets. The versatility of silicone treated)
systems is derived from the range of high-per- Oxime crosslinker 5-7
formance properties. These properties include Tin catalyst 0.05-0.1
ease of application with a wide range of rheo- Basic High Modulus Formulation (Acetoxy)
logical properties (including nonsag and pour- Silanol polymer (20 mcs) 80-85
able grades), rapid cure, excellent elastomeric Fumed silica (treated and/or untreated) 6-10
properties (including extension/compression Acetoxy crosslinker 5-7
Tin catalyst 0.05-0.1
and high recovery), good thermal stability, and
628 HANDBOOK OF ADHESIVES

and exposed to atmospheric moisture, the end metal substrates, silicone sealants are widely
groups are hydrolyzed off as acetic acid, etc. used in such construction applications as ex-
Because of the odor of acetic acid and its cor- pansion joints, perimeter sealing, control joints,
rosiveness to metals, limestone, and cement, nonstructural glazing, and structural glazing. 58-
62,99
the ketoxime-blocked silicones are preferred.
The unstable Si -OH segments rapidly con- Due to their dependability, versatility, and
dense, forming Si-O-Si bonds to give a durability, silicone sealants have found use for
three-dimensional structure. The skin is tack- the consumer market. These uses include bath-
free within 30 minutes; the rubber continues to tub caulk, auto sealants, windshield sealants,
cure from the outside in at a rate depending on window sealants, high temperature gaskets, and
humidity and joint dimensions. general household glues and sealants.
Silicone sealants of this type are available as
colorless (translucent) compositions if desired. Two-Component Silicone Sealants.
Silicone polymer content is in the 60-70% These products contain, in the larger compo-
range (40-50% polysiloxane plus up to 20% nent, a hydroxyl-terminated polysiloxane and a
dimethyl silicone or methylphenylsilicone plas- crosslinker such as ethyl orthosilicate. The ac-
ticizer). Pigments and fillers include titanium tivator part is an organometal catalyst, e.g., di-
dioxide, silicas, calcium carbonate, or dried butyl tin dilaurate in paste form. Upon mixing,
clays. Pyrogenic silicas are used for rheologi- cure takes place in the entire mass.
cal control to produce nonslump sealants. The two-part silicones are used in aircraft and
Like the one-component polysulfides or electrical potting and encapsulation. Industrial
polyurethanes, the one-component silicones and construction applications include second-
must be protected from moisture during man- ary seals for high performance insulating glass
ufacture and storage. However, package sta- units and structural glazing, respectively.
bility of the silicones is superior. If a cartridge For special applications, the pendant methyl
is only partially used, the plug of cured rubber group along the polymer chain can be replaced
which forms in the tip retards further moisture with other organic groups. The common sub-
penetration. stitutions are the phenyl, cyanoethyl, and tri-
The wide range of properties has expanded ftuoropropyl groups. Partial substitution of the
the commercial use of one-component silicone methyl groups with phenyl can give silicone
sealants. Examples of industrial applications sealants improved low temperature properties
include: and oxidation resistance. The improvement of
in-place temperature (service temperature) util-
• Form-in-place gaskets for automotive ity will be a function of the percent phenyl in
areas such as valve covers, oil pans, ther- the polymer. For example, the substitution of
mostats, rear axle covers, automatic trans- 5.3 mole percent diphenylsiloxy units will
mission housing, and taillight assemblies; lower the resultant brittle point of the sealant
• Automotive adhesive applications such as from - 85 OF to - 165 of. The addition of a po-
adhering rear view mirrors; lar group such as triftuoropropyl or cyanoethyl
• Gaskets for household appliances such as will increase the solvent resistance of the cured
dishwashers, washing machines, vacuum silicone sealant. These polar groups make sili-
cleaners, electric steam irons, etc.; cone polymers incompatible with nonpolar or-
• Aerospace gaskets for windows and doors; ganic fuels and oils, giving them fuel
• Electronic encapsulation of connectors and resistance. Again, the exact solvent resistance
terminals; is a function of the percent of triftuoropropyl in
• Conformal coatings to protect circuit the polymer.
boards and electrical components;
• Fabric coatings; Fluoropolymers
• Secondary seal for insulating glass.
The expensive ftuoroelastomers are used in
Because of their weathering and movement small volume in high temperature and fuel-re-
capabilities, and adhesive qualities to glass and sistant seals in military aircraft, as well as in
 SEALANTS AND CAULKS 629

automotive, chemical processing, and electri- Sealant Selection

cal applications. The principal fluoroelasto-
Sealant joints cannot be designed until a deci-
mers are copolymers of vinylidene fluoride and
sion is made as to what sealant we desire to
hexafluoropropene. Cure is believed accom-
plished in a two-component system by extrac- utilize. Its ability to expand and contract re-
mains the most important factor in that deci-
tion of HF by reaction with diamines, such as
hexamethylene diamine carbamate, activated sion. Major manufacturers indicate the
movement capacity of a sealant as plus or mi-
with magnesisum oxide and dibasic lead phos-
nus a certain percentage of its designated width.
phite.
Cured fluoroelastomers can withstand pro- For instance, a 1" wide joint utilizing a seal-
longed exposure to high temperatures and re- ant with capacity of ± 25 % indicates that the
tain their elastomeric, mechanical, chemical, sealant can withstand the joint's compression
and electrical properties better than other elas- to i" or its expansion to Ii" without either the
adhesive failure of its bond or the cohesive
tomers. Continuous service at 450°F is com-
(tearing) failure of the sealant.
mon; intermittent exposure at 600°F is
In selecting the proper sealant for a specific
possible. Although resistance to compression
situation, consideration must also be given to
set is excellent at 400-450°F, low temperature
such characteristics as its service life, hard-
properties (including compression set) are poor,
ness, cure time, application parameters, adhe-
compared to silicones and fluorosilicones.
sion to various substrates, weather, stain, and
Phosphonitrilic fluoroelastomers have a
chemical resistance, and rate of recovery. (See
phosphonitrilic backbone with trifluoroethoxy
Tables 22 and 23.)
and heptafluorobutoxy side groups. The rub-
bers are useful in the temperature range from
Movement Capability
-100°F to 300°F, are solvent-resistant and
nonflammable. Low Movement Sealants (Caulks). These
include polybutene, polyisobutene, and oil and
resin-based caulks. These low cost sealants
SEALANT SELECTION, JOINT DESIGN,
have an approximate joint movement capacity
AND INSTALLATION
of only ±5 %, a slow rate of cure (120 days),
In determining the appropriateness of a sealant a low Shore A hardness, a relatively short ser-
or caulk for an application, many factors need vice life (approximately 6 or 7 years on aver-
to be considered. The generic polymer tech- age), and only modest weather or chemical
nology, the physical form, sealant classifica- resistance. Therefore, low movement sealants
tion, specifications and performance properties are primarily utilized in static joints having
are all important features of a sealant or caulk. minimal exterior exposure.
Table 22 outlines some basic performance Applications of low movement sealants in-
properties of the sealant types reviewed in this clude perimeter joints of residential door and
chapter. As seen in Table 22, most of these window frames, siding, or interior duct work.
sealant types are utilized in construction appli- Generally, they require a minimum amount of
cations. As described earlier in this chapter, surface preparation, have good adhesion char-
sealants and caulks can be classified in low, acteristics, and are supplied in one-component
medium, and high movement categories, and cartridges.
selection is primarily decided on the basis of
movement capability, adhesion, life expect- Medium Movement Sealants. These ex-
ancy, and material cost. Table 23 reviews the hibit higher performance properties. The la-
typical applications for these types of sealants texes and butyls have a movement capacity of
and caulks. ± 7.5 %. Hypalon, neoprene, and solvent-re-
The following is a description of the selec- lease acrylics have a movement capacity of
tion of the appropriate sealant, then proper joint ± 12.5 %. Cure time is about 5 days for latexes,
design and installation for construction sealant/ 30 days for Hypalon and neoprene, 120 days
caulk applications. for butyls. Service life is 10 years for most me-
CD
W
o

Table 22. Sealants Selection and Application Guide (Sealant, Caulk, Glazing Compound, by Polymer Type).
Asphalt
Styrene- Acrylic Acrylic Polyvinyl Poly- Fluoro-
Properties Bituminous Oleoresinous Polybutene Butyl Hypalon Neoprene Butadiene Solution Emulsion Acetate Polysuljide urethane Silicone polymer

NV, % by weight 70-90 96-99+ 99+ 74-99+ 85-90 80-85 60-70 80-85 80-85 70-75 90-99+ 94-99+ 98+ 99+
Weight, Ib/gal 9-12 14-20 13-14 10-13 10-11 11-12 9-10 12-13 12-14 12-13 12-15 11-12 10-12 14-16
Max. joint movement, 5 5 5-10 10-15 10-15 10-15 5-10 10-15 5-10 5 25 25-40 25-50 10-20
%±
Recovery after joint P P NAb F-G F P-F P-F F F P-F F G E F-G
movement"
Shrinkage, % 10-20 4 1-20 10-15 10-20 20-30 10-20 10-20 20-25 10 6 2
Life expectancy, exte- 1-2 2-10 5-10 5-15 5-15 5-15 3-10 5-20 2-20 1-3 10-20 20+ 30+ 10-20
rior,e yr
Cure type Evap. Oxidtn. Noncure Evap. Chem. Chem. Evap. Evap. Evap. Evap. Chem. Chem. Chem. Chem.
Practical service temp.
nmge
max. OF ISO 150 180 200 225 210 180 180 180 150 250 250 400 500
min. of 0 0 -40 -20 -25 -25 -10 0 0 0 -40 -40 -90 -10
Adhesion to common G G G-E G F-G F F E G F-G G G F-G F
building mate-
rials, unprimedd
Components, one-part, I,T I,T 1,2 1,2 1,2 2
two-part, tape
aE = less than 10% compression set; G = 10-20%; F = 20-30%; P = <30%.
"NA = not applicable.
'Mild to severe conditions.
dAdhesion of all materials improved with suitable primers.
 SEALANTS AND CAULKS 631

Table 23. Sealant and Caulk Distribution by Polymer Type and Application.
Construction
Indust. Prefab. Insu/. Airfield Aircraft
Polymer Type Resid.' Comm.· Housing b Glass Auto. C Highway" Runways Aerospace' Marini Otherg

Asphalt, bituminous X X X
Oleoresinous X X X X
Polybutene X X X X X
Butylh X X X X X X
Hypalon X X
Neoprene X
Styrene-butadiene; X X
PVC X
Acrylic solution X
Acrylic emulsion X X
Polyvinyl acetate X X
Polysulfide j X X X X X X X X X
Polyurethane X X X X X X X
Siliconek X X X X X X X X X
Fluoropolymer X
Others l X X
'Resid. (residential)-home and architectural maintenance and repair. Indust. Comm. (industrial, commercial)-commercial, professional applications,
OEM (original equipment manufacture), maintenance, and repairs.
bprefabricated housing, modular housing, mobile homes, recreational vehicles, campers.
'Automotive, including truck and trailer, and aftermarket.
dHighways, bridges, canals, dams, interior waterways.
'Including electrical and electronic sealants for aircraft applications.
'Including aftermarket.
"Including pipe seals, undistributed electrical and electronic applications, appliances, chemical processing equipment.
hIncluding polyisobutylene.
'Including nitrile rubber.
iIncluding polymercaptans.
'Including Iluorosilicones.
iIncluding telechelic butadiene copolymers, polypropylene, EPDM (ethylene-propylene-diene polymers), poly(isoxazolines), epoxy resins, poly-
imides.

dium mOvement sealants but up to 20 years for with asphaltic concrete and bitumen. This
neoprene. property encourages their usage in roadway ap-
Sealants having medium performance capa- plications. Finally, solvent-based acrylics have
bility offer a longer life than caulks, along with a movement capability of ±12.5%, minimal
significantly better performance characteris- shrinkage, high strength, good resistance to
tics, but at a higher price. weather and chemicals, and excellent recovery
Medium movement sealants show versatil- of their original shape after compression. These
ity. Latex sealants offer compatibility with la- properties, along with a relatively short range
tex paint in that they are suitable for coating of cure (14-21 days) allow them to be utilized
and provide ease of cleanup. This allows them in some exterior dynamic joint applications.
to be used as an interior sealant under paint fin-
ishes. Butyl sealants have good adhesion to High Movement Elastomeric Sealants.
most surfaces and good resistance to water. These include polysulfides, polyurethanes, and
This leads to their use in such places as door silicones.
thresholds, flashing, metal and vinyl siding, Polysulfides were the first generation of high
and duct end pipe penetrations. performance sealants. They were introduced
Hypalon sealants offer good UV, ozone, and into the construction market in the early 1950s.
chemical resistance. These properties allow However, since the mid-1970s, polysulfides
them to be used in moderately moving exterior are being displaced as building joint sealants
joints around doors and windows or concrete by urethane and silicone products. Polyure-
panels. Neoprene sealants exhibit compatibility thane sealants are the most versatile polymer
632 HANDBOOK OF ADHESIVES

systems used to fonnulate one- and two-part Rubber tubing made of neoprene, EPDM, or
sealants. Nonsag urethane sealants are used for butyl is an excellent but expensive backup ma-
high movement construction joints, while self- terial. In essence, the tubing acts as a dual sys-
leveling, cold-pour-type sealants are used in tem with the sealant, since the partly
horizontal traffic applications. Silicones have compressed tubing will also act as a water bar-
been used in a number of applications in in- rier in case the sealant suffers a loss of adhe-
dustrial, consumer, and construction markets. sion.
Silicone sealants have widespread use as seal- Both open- and closed-cell backups are used.
ant/adhesives for structural glazing due to their The closed-cell backup does not pennit any
extreme high recovery, movement capacity, water to contact the sealant but has been a
and weather resistance. Fig. 6 shows four problem where the backer rod is first com-
structural glazing details in which the glass is pressed into the joint. If the rod is punctured
retained at either two (butt glazing) or four during installation, gas will slowly be released
(stopless glazing) edges. into the uncured sealant, causing surface bub-
The service life of these sealants is 20 years bles. This bubbling can be quite conspicuous if
or more. They have a range of movement from the wall is exposed to sunlight on a hot day
±25% (polysulfides) to +40/ -25% (poly- before the sealant cures. The solution is to use
urethanes) to + 100/ - 50% (low modulus sil- open-cell foam. Open-cell foam is desirable if
icone sealants) extension/comp~ssion. Their a one-part sealant that requires moisture acti-
price can range as much as seven times that of vation is used. Here, the sealant will begin cur-
some low movement caulks. ing from both sides. However, the open-cell
foam may in time become saturated with mois-
BACKUP MATERIALS ture and cause adhesion problems or even frost
fonnation and spalling. Properly vented walls
The primary purpose of the backup material in
would reduce this problem. There is no ideal
the joint is to control the depth of the sealant
solution, and the selection of backup material
in the joint, thus ensuring the proper shape fac-
will depend on the sealant used and job site
tor. Another purpose of the backing is to pro-
conditions.
vide support or reinforcement for the sealant
A word of caution: outgassing of closed-cell
material in horizontal joints, such as floors and
backer rod can be prevented if the installer does
patios. Depending on the type of construction,
not use sharp tools when pushing the rod into
the backup material may be already in the
place. This will prevent rupture to the rod.
joint-for example, the plastic or cork board
joint sometimes used in pavement construc-
tion. 97
SPECIFICATIONS
The backup material must be unaffected by
any solvent contained in the sealant. Backup In the selection of a sealant or caulk, the meth-
material containing asphalt, coal tar, or poly- odology of perfonnance evaluation must be
isobutylene should never be used. These ex- understood. The perfonnance data by the man-
trudable oils are incompatible with some ufacturer must be quantifiable and comparable
sealants and may cause loss of adhesion. It is to other materials. A method must be used to
quite possible that these extrudables may cause detennine the appropriateness of a sealant or
staining of porous substrates. caulk in a specific application. Test methods
Neoprene, urethane, polyurethane, polyeth- and specifications have been established by the
ylene foam, cork board, fiberboards, cotton ASTM, Bureau of Standards, Adhesive and
rope, and jute have all been used as backing Sealant Council, and other agencies.
material. The foams have been the most suc- Table 24 lists important U.S. specifications
cessful materials because they are quite com- for sealants and caulks; Table 25 lists ASTM
pressible with very little spread. The foams are test methods for building seals and sealants; and
readily available in strip fonn, in both round Table 26 is a reference guide for sources of
and rectangular cross sections to fit most joints. sealant and caulk specifications.
 Proglaze
Silicone Sealanl .t== 7 l

SST-800Tope 'f ~
SCR-820
OenseSpacer ~

Ploglaze
SiliCOne Sealanl Proglaze
Silicone
Sea.lant
Progtaze
Silicone Sealan1

Cusrom _
Dense Gasket ...

Butt Glazing Stopless Glazing

Proglaze
Proglaze Silicone Sealant - - - - - - -- - -.....
Silicone Seatanl--------~

g;~s~~pacer ZZ ff.lli
~~!~p.oer ., .. ~

Proglaze
Silicone
Sealanl "'<>glaze
Silicone Sealanl

Poly·Wel
Gasket
SCR·820
Dense Space' 7 1"1 SCR-820 Setting Block
~ 80-90 Ouromeler)

Butt Glazing Stop less Glazing

0)
Co)
Co)

Fig. 6.
634 HANDBOOK OF ADHESIVES

Table 24. Sealant Specifications.

CONSTRUCTION
Federal Specifications
TT-S-00227E Sealing compound elastomeric type, multicomponent (for caulking, sealing, and glazing
(1114/69) buildings and other structures)
TT -S-00230C Sealing compound elastomeric type, single component (for caulking, sealing, and glazing
(10/9170) buildings and other structures)
TT-S-01543A Sealant compound, silicone rubber base (for caulking, sealing, and glazing buildings and
(6/9171) other structures)
TT-C-598B Caulking compound, oil and resin base type (for masonry and other structures)
(3/17/58)
TT-S-OOI657 Sealant compound, single component, butyl rubber based, solvent release type (for build-
(10/8170) ings and other types of construction
ASTM Specifications
ASTM C570-72 Standard specification for oil and resin base caulking compound for building construction
(reapproved
1984)
ASTM C669-75 Specification for glazing compounds for back bedding and face glazing of metal sash
(reapproved
1981)
ANSI/ASTM Standard specification for latex sealing compounds
C834-76
(reapproved
1981)
ASTM C836-84 Standard specification for high solids content, cold liquid-applied elastomeric waterproof-
ing membrane for use with separate wearing course
ANSIIASTM Standard specification for elastomeric joint sealants
C920-79
ASTM C957-81 Standard specification for high solids content, cold liquid-applied elastomeric waterproof-
ing membrane with integral wearing surface
Insulating Glass
ASTM E774-84a Standard specification for sealed insulating glass units
AUTOMOTIVE
AMS-3087E Compound, insulating and sealing, silicone
HIGHWAY/ American Association of State Highway and Transportation Officials (AASHTO)
BRIDGES,
SS-S-200E(3) Sealing compounds, two-component, elastomeric, polymer type, jet fuel resistant, cold
applied
MILITARY SPECIFICATIONS
MIL-A-46106(2) Adhesive-sealants, silicone, room temperature vulcanizing, general purpose
MIL-A-46146 Adhesive-sealants, silicone, RTV, noncorrosivity (for use with sensitive metals and
(2) AMD 3(MR) equipment)
MIL-A-47040(1) Adhesive-sealants, silicone, room temperature vulcanizing, high temperature
(1) (MI)
MIL-C-15705A(1) Caulking compound (liquid polymer polysulfide synthetic rubber formula #112 for metal
enclosures)
MIL-C-46867(MI) Compound: caulking, conductive
MIL-C-47070(MI) Compound, polyurethane
MIL-C-47113(MI) Compound, heat sink, silicone
MIL-C-47121 (MI) Compound, sealing, polysulfide rubber
MIL-C-47164(MI) Compound, plastic polyurethane
MIL-P-4 7170( 1)(MI) Primer, silicone rubber sealant
MIL-P-47216(MI) Primer, polyurethane
MIL-P-47275(MI) Primer, silicone
MIL-S-II030E Sealing compound, noncuring (poly sulfide base)
MIL-S-ll 031 B Sealing compound, adhesive, curing (polysulfide base)
MIL-S-1l388B Sealing compound for metal container seams
 SEALANTS AND CAULKS 635

Table 24. (Continued)

MIUTARY SPECIFICATIONS
MIL-S-12158C(AT) Sealing compound, noncuring, polybutene
MIL-S-14231 C( 1) Sealing compound, joint, two-component, for bolted aluminum or steel petroleum storage
tanks
MIL-S-22473D(4) Sealing, locking and retaining compounds
MIL-S-23586C(3) Sealing compound, electrical, silicone rubber, accelerator required
MIL-S-2869B Sealing compound, synthetic rubber, hose cover repair
MIL-S-3105C Sealing compound, inert (for use in ammunition)
MIL-S-3927C(l) Sealing compound, thread, polymerizing, room temperature
MIL-S-4383B(2) Sealing compound, top coat, fuel tank, Buna N type
MIL-S-45180C Sealing compound, gasket, hydrocarbon fluid and water resistant
MIL-S-46163(1) Sealing, lubricating and wicking compounds-thread locking, anaerobic, single compo-
nent
MIL-S-47122(MI) Sealing compound
MIL-S-47123(l)(MI) Sealant, ablative, silicone base, room temperature curing and primer
MIL-S-47162( I )(MI) Sealant, silicone rubber, room temperature vulcanizing
MIL-S-47165(MI) Sealing compound, high tear strength
MIL-S-47245(MI) Sealant, electrically conductive
MIL-S-48112(MU) Sealing compound, butyl rubber sealant (for use with ammunition)
MIL-S-7916C Sealing compound, thread and gasket, fuel, oil and water resistant
MIL-S-81732( I )(AS) Sealing compound, electrical, high strength, accelerator required
MIL-S-8516E(2) Sealing compound, polysulfide rubber, electric connectors and electric systems, chemi-
cally cured
MIL-S-8660B(4) Silicone compound
MIL-S-8784B Sealing compound, low adhesion, for removable panels and fuel tank inspection plates
Navy
MIL-C-18225D(3) Caulking compound, synthetic rubber base, wooden deck seam application
(ships)
MIL-C-81947A Coating compound, thermal insulation, 3 component, intumescent
MIL-S-15204C(2) Sealing compound, joint and thread, high temperature
(ships)
MIL-S-17377D Sealing compound, boiler casing
(ships)
MIL-S-19653A Sealing compound (wood beddings) fortified
(ships)
MIL-S-23498(1) Sealing compound, bearing preservation, synthetic rubber base
(ships)
MIL-S-24340 Sealing compound, deck, polyurethane (polyester base)
(ships)
MIL-S-2912D(l) Synthetic rubber compound, acid and oil resistant (for lining battery compartments on
(ships) submarines)
MIL-S-81733B(2) Sealing and coating compound, corrosion inhibitive
(ships)
Aircraft

MIL-C-83983 Compound, sealing, fluid resistant

(USAF)
MIL-S-38228(2) Sealing compound, environmental, for aircraft surfaces
(USAF)
MIL-S-7124B Sealing compound; polysulfide, accelerator required, for aircraft surfaces
MIL-S-883 15(1) Sealing compound, aluminum structure, pressure and weather sealing, low density
(USAF)
MIL-S-833 18(1) Sealing compound, low temperature curing, quick repair, integral fuel tanks and fuel cell
(USAF) cavities
MIL-S-83430(3) Sealing compound, integral fuel tanks and fuel cell cavities intermittent to use to 360°F
(USAF) (1 82 0c)
MIL-S-83432 Sealing compounds, adhesive bonded structure
(USAF)
MIL-S-8802D( 1) Sealing compound, temperature resistant, integral fuel tanks and fuel cell cavities, high
AMD2 (USAF) adhesion
636 HANDBOOK OF ADHESIVES

Table 25. ASTM Building Seals and Sealants Test Methods.

1. American Society of Testing and Materials (ASTM C-24)
2. The 1986 Annual Book of ASTM Standard on Building Seals and Sealants in Volume 04.07

3. ASTM C-24 Active Technical Committees. The ASTM C-24 Committee was organized in 1959 to develop standards
for building seals and sealants. Currently, the following 18 technical subcommittees are identified:
C-24.12 Oil and Resin Base Glazing and Caulking Sealants
C-24.15 Hot Applied Sealants
C-24.16 Emulsion Sealants
C-24.18 Solvent Release Sealants
C-24.32 Chemically Curing Sealants
C-24.35 Structural Sealants
C-24.40 Backup Materials
C-24.50 Tape Sealants
C-24.70 Lock Strip Gaskets
C-24.72 Compression Seal Gaskets
C-24.80 Building Deck Waterproof Systems
C-24.82 Criteria for Evaluation of Sealant Testing Laboratories
C-24.83 Statistical Analysis
C-24.84 Insulating Glass Sealant Compatibility
C-24.85 Sealants for Acoustical Applications (inactive)
C-24.86 Solar Collector Seal Applications (inactive)
C-24.87 International Standards
4. List of ASTM C-24 Standards
C-510-77 Test for staining and color change of single or multicomponent joint sealants
(reapproved 1983)
C-570-72 Specification for oil and resin-base caulking compound for building construction
(reapproved 1984)
C-603-83 Test for extrusion rate and application life of elastomeric sealants
C-639-83 Test for rheological (flow) properties of elastomeric sealants
C-661-83 Test for indentation hardness of elastomeric type sealants by means of a Durometer
C-669-75 Specification for glazing compound for back bedding and face glazing of metal sash
(reapproved 1981)
C-679-71 Test for tack-free time of elastomeric type joint sealants
(reapproved 1977)
C-681-84 Test for volatility of oil and resin-based, knife-grade, channel glazing compounds
C-71l-72 Test for low-temperature flexibility and tenacity of one-part elastomeric solvent-release
(reapproved 1983) type sealants
C-712-72 Test for bubbling of one-part elastomeric solvent-release type sealants
(reapproved 1983)
C-713-84 Test for slump of an oil base knife-grade channel glazing compound
C-717-84d Definition of terms relating to building seals
C-718-72 Test for UV cold box exposure of one-part elastomeric solvent-release type sealants
(reapproved 1983)
C-719-79 Test for adhesion and cohesion of elastomeric joint sealants under cyclic movement
C-731-82 Test for extrudability after package aging of latex sealing compounds
C-732-82 Test for aging effects of artificial weathering on latex sealing compounds
C-733-82 Test for volume shrinkage of latex sealant compounds
C-734-82 Test for low-temperature flexibility of latex sealing compounds after artificial weathering
C-736-82 Test for extension/recovery and adhesion of latex sealing compounds after artificial
weathering
C-741-85 Test for accelerated aging of wood sash face glazing compound
C-742-73 Test for degree of set for wood sash glazing compound
(reapproved 1984)
C-765-73 Test for low temperature flexibility of preformed tape sealants
(reapproved 1984)
 SEALANTS AND CAULKS 637

Table 25. (Continued)

C-766-84 Test for adhesion after impact of preformed tape sealants
C-771-74 Test for weight loss after heat aging of preformed sealing tapes
(reapproved 1980)
C-772-74 Test for oil migration or plasticizer bleed-out of preformed sealing tapes
(reapproved 1980)
C-782-74 Test for softness of preformed sealing tapes
(reapproved 1980)
C-790-84 Practices for use of latex sealing compounds
C-792-75 Test for effects of heat aging on weight loss, cracking and chalking of elastomeric seal-
(reapproved 1980) ants
C-793-75 Test for effects of accelerated weathering on elastomeric joint sealants
(reapproved 1980)
C-794-80 Test for adhesion-in-peel of elastomeric joint sealants
C-797-75 Recommended practices and terminology for use of oil and resin based putty and glazing
(reapproved 1981) compounds
C-804-83 Standard practice for use of solvent-release type sealants
C-834-76 Specification for latex sealing compounds
(reapproved 1981)
C-836-84 Specification for high solids content, cold liquid-applied elastomeric waterproofing
membrane for use.with separate wearing course
C-879-78 Methods for testing release papers used with preformed tape sealants
(reapproved 1984)
C-898-84 Guide for use of high solids content, cold liquid-applied elastomeric waterproofing mem-
brane with separate wearing course
C-907-79 Test for tensile adhesive strength of preformed tape sealants by disk method
(reapproved 1984)
C-908-84 Test for yield strength of preformed tape sealants
C-910-79 Standard test for bond and cohesion of one-part elastomeric solvent release type sealants
(reapproved 1985)
C-919-84 Practice for use of sealants in acoustical applications
C-920-79 Specification for elastomeric joint sealants
C-957-81 Specification for high solids content, cold liquid-applied elastomeric waterproofing
membrane with integral wearing surface
C-961-8 Test for lap shear strength for hot applied sealing compounds
C-962-81 Guide for use of elastomeric joint sealants
C-972-82 Test for compression/recovery of tape sealants
C-981-83 Guide for design of built-up bituminous membrane waterproofing systems for building
decks
C-1016-84 Test for determination of water absorption by sealant backup (joint filler) material
C-I021-84 Practice for laboratories engaged in the testing of building sealants
C-2202-84 Test for slump of caulking compounds and sealants
C-2203-84 Test for staining of caulking compounds and sealants
C-2249-74 Predicting the effect of weathering on fact glazing and bedding compounds on metal sash
(reapproved 1984)
C-2376-84 Test for slump on face glazing and bedding compounds on metal sash
C-2377-84 Test for tack-free time of caulking compounds and sealants
C-2450-75 Test for bond of oil and resin-base caulking compounds
(reapproved 1981)
0-2451-75 Test for degree of set for glazing compounds on metal sash
0-2452-75 Test for extrudability of oil and resin-base caulking compounds
(reapproved 1981)
0-2453-75 Test for shrinkage and tenacity of oil and resin-base caulking compounds
(reapproved 1981)
638 HANDBOOK OF ADHESIVES

Table 26. Sources of Specifications. 10. Panek, I. R., "Know Your Sealants. Part I," Build-
ings, (April 1970).
ASTM Specifications 11. Blatt, Maurice, "Ioint Sealing Compound," U.S.
American Society for Testing and Materials Patent 3,806,481 (Apr. 23, 1974).
1916 Race Street 12. Dalton, R. H., McGinley, C., and Paterson, D. A.,
Philadelphia, PA 19103 "Developing a Quality Standard for Butyl-Polyiso-
(215)299-5400 butylene Solvent Release Sealants," Adhesives Age,
AASHTO Specifications 41 (Nov. 1973).
The American Association of State Highway and 13. Berejka, A. I., and Higgins, I. I., "Broadened Ho-
Transportation Officials rizons for Butyl Sealants," Adhesives Age, 21 (Dec.
444 North Capitol Street, NW 1973).
Suite 225 14. Del Gatto, I., "Enjay's New Mayonnaise Butyl,"
Washington, DC 20001 Rubber World, 41 (June 1969).
(202)624-5800 15. "New Butyl Rubbers Offer Advantages as Window
and Construction Sealant," Adhesives Age, 30 (Sept.
Federal Specifications 1969).
Business Service Center 16. Stucker, N. E., "A New Polymer Makes the Scene
General Services Administration (regional offices) [Butyl LM-Insulating Glass]," Glass Digest, 56
7th and D Streets, SW (Nov. 1970).
Washington, DC 20407 17. "Enjay Butyl LM-430-Sealants-Compounding
Military Specifications Guide," Enjay Polymer Labs [now Exxon Polymer
Commanding Officer Labs] EPL-7204-597, March 1972.
U.S. Naval Supply Depot 18. Paterson, D. A., "XL Butyl Rubber Improves Pre-
5801 Tabor Avenue formed Sealant Tapes," Adhesives Age, 25 (Aug.
Philadelphia, PA 19120 1969).
19. Klemm, F., and Leibowitz, L., "Butyls Enter the
ANSI Specifications High Performance Field, " Adhesives Age, 37, (Nov.
American National Standards Institute Inc. 1973).
1430 Broadway 20. Risser, A. I., "Ioint Sealants," U.S. Patent
New York, NY 10018 3,759,780 (Sept. 18, 1973).
(212)354-3300 21. Malloy, F. P., "Preshimmed Tape," Glass Digest,
U.S. Army Corps of Engineers 42 (Feb. 15, 1971).
Chief Specification Section 22. "Extruding Stiffer Sealant Tapes," Adhesives Age,
Box 60 49, (Nov. 1972).
Vicksburg, MS 39180 23. Kutch, E. F., "Hot Melt Butyl Sealant Provides High
Adhesion Properties," Adhesives Age, 33 (Aug.
1973).
REFERENCES 24. Scheinbart, E. L., and Callan, I. E., "A Systems
Design Approach for Butyl Sealant Tape Manufac-
1. Reid, W. I., "What's Ahead for Adhesives and Seal- turing," Adhesives Age, 17 (March 1973).
ants," Adhesives Age, 21 (Apr. 1970). 25. Massalena, I., "Sealing of Extruded Tape," U.S.
2. Cook, I. P., "Construction Sealants and Adhe- Patent 3,767,503 (Oct. 23, 1973).
sives," New York, Wiley-Interscience, 1970. 26. Callan, I. E., "Crosslinked Butyl Hot Melt Seal-
3. "Polymers for Sealing, Caulking Uses Develop a ants," Adhesives and Sealants Council Spring Tech-
Broader End-Use Pattern," Chemical Marketing Re- nical Meeting, March, 1974.
porter, 33 (Feb. 13, 1967). 27. Wormser, E. S., "Hypalons-Overlooked, but of
4. Prane, I.W., "Vehicles for Sealants and Caulking High Performance," Glass Digest, 66 (Dec. 15,
Compounds," Amer. Painti., 96, (Apr. 6, 1964). 1971).
5. Prane, I. W., "Pigmentation of Ioint Fillers," in 28. Purvis, T. A., "Dry Sealing Systems [with Neo-
"Pigment Handbook," Vol. II, p. 151, New York, prene Gaskets]," Glass Digest, 50 (Dec. 15, 1971).
Iohn Wiley and Sons, 1973. 29. Girard, D. G., and Waldenberger, D., "New Ma-
6. Damusis, A. (ed.), "Sealants," New York, Van terial Makes Its Debut [PVC Foam Tapes]," Glass
Nostrand Reinhold, 1967. Digest, 62, (Dec. 15, 1971).
7. Zakim, I., and Shihadeh, M., "Results of a Seven- 30. Sullivan, C., "PVC Foam Tape: New Sealant for
Year Study [on Sealants]," Glass Digest, 68 (Sept. Recreational Vehicles," Adhesives Age, 28, (April
1965). 1973).
8. Keifer, H., "Caulks and Sealants," Amer. Paint J., 31. Rohm and Haas, RC-34, "Acryloid CS-l," Mar.
72 (Aug. 22, 1966). 1967; RC-42, "Room Temperature Gunnable Seal-
9. Amstock, I. S., "Reclassification of Ioint Sealants," ants Made with Acryloid CS-l," Sept. 1967.
Adhesives Age, 18 (Feb. 1964). 32. Fussl, R., "Polyacrylate Dispersions-A New Basic
 SEALANTS AND CAULKS 639

Raw Material for Sealing Compounds in Building," High Temperature Elastomers," J. Elastoplastics, 3,
Kunststoffe, 61, 633 (Sept. 1971). 82 (Apr. 1971).
33. Miller, F. L., "Acrylics [Sealants]-Long Service 58. "Silicone Sealant Waterproofs Spires of Museum
Life," Glass Digest, 7 (Dec. 15, 1971). Towers," Adhesives Age, 27 (Dec. 1972).
34. Gorman, J. W., and Toback, A. S., "Polyurethane 59. "Silicone Adhesive/Sealant Makes Ceramic Range
Polyacrylate Sealant Compositions," U.S. Patent Tops Watertight," Adhesives Age, 32 (Feb. 1973).
3,425,988 (Feb. 4, 1969). 60. Smith, J. C., "Silicone Adhesives for Joining Plas-
35. Lees, W. A., "Self-Hardening Acrylic Sealants and tics," Adhesives Age, 27 (June 1974).
Adhesives," Adhesives Age, 26 (Jan. 1972). 61. Smith, J. C., "[Silicones for] Stringent Glazing
36. Plonchak, M., "Applications Grow for Anaerobic Specifications," Glass Digest, 42 (Dec. 15, 1971).
Sealants and Adhesives," Adhesives Age, 45 (Nov. 62. "Tunnel Walls Sealed with Silicone Sealant." Ad-
1972). hesives Age, 40 (Jan. 1973).
37. Gillis, T., and Schendel, D., "Make Room for 63. "Silicone Rubbers in Automotive Applications,"
Aqueous Acrylic Caulks," Adhesives Age, 34 (Nov. Rubber World, 43 (Apr. 1971).
1971). 64. "Vistalon 404 Sealing Tape," Enjay Polymer Labs
38. Toogood, J. B., "A Latex Producer Looks at the [now Exxon Polymer], AlD-30l, 1970.
Sealant Industry," Adhesives Age, 27 (Nov. 1972). 65. Cantor, S. E., "RTV Adhesive System Based on
39. Rohm and Haas, "Rhoplex LC-40-Acrylic Emul- Ethylene-Propylene Diene Terpolymer," Adhesives
sion Polymer for Caulks and Sealants." Age, 17 (June 1974).
40. Dupler, J. F., Jr., "A Decade of Experience [with 66. "Hycar Reactive Liquid Polymers," B. F. Goodrich
Polysulfides]," Glass Digest, 66 (May, 1965). Chemical Co., 1972.
41. Petrino, D. A., "That All-Important Second Look 67. Dolezal, T. P., Johnson, G. K., and Pfisterer, H. A.,
[Polysulfides], " Glass Digest, 40 (Dec. 15, 1971). "Liquid Dibromopolybutadiene in Adhesives and
42. Panek, J., "Polysulfide Sealants for Plastics," Ad- Sealants," Adhesives Age, 30 (July 1971).
hesives Age, 32 (Nov. 1973). 68. Richard, J. C. m, "New Polymer Offers Advantages
43. Bertozzi, E. R., "Chemistry and Technology of for Elastomeric Sealants," Adhesives Age, 22 (July
Elastomeric Polysulfide Polymers," Rubber Re- 1970).
views, 114 (Feb. 1968). 69. Lieff, M., "Epoxy-Based Materials-An Aid to
44. Amstock, J. A., "The Single Component Compound OSHA Compliance," Adhesives Age, 22 (July 1980).
[Polysulfide]," Glass Digest, 70 (May, 1964). 70. MacDonald, N. C., "Standard Test Methods for Ad-
45. Santaniello, A. F., "Polysulfide Sealant Meets Needs hesives," Adhesives Age, 21 (Sept. 1972).
of World Trade Center," Adhesives Age, 32 (Nov. 71. Hann, G., "Sealant Specificiations from the Produc-
1972). ers' Standpoint," Adhesives Age, 24 (Mar. 1973).
46. Gallagher, J. P., "Recreational Vehicles-A New 72. "Developing Testing Standards for Building Joint
Market for Polysulfide-Based Sealants," Adhesives Sealants-Job of ASTM Committee C-24," Adhe-
Age, 39 (Nov. 1971). sives Age, 47 (Nov. 1973).
47. Box, J. A., "A Thorn in the Side [Insulating Glass]," 73. Karpati, K. K., and Handegord, G. 0., "A Rational
Glass Digest, 52 (Sept. 15, 1971). Approach to Building Sealant Testing," Adhesives
48. Harries, R. W., "Role of Adhesives and Sealants in Age, 27 (Nov. 1973).
the Autqmotive Industry," Adhesives Age, 45 (Sept. 74. Jema!, R., "Viscosity Measurements in Adhesive and
1970). Sealant Systems," Adhesive Age, 37 (May 1974).
49. Wolf, R. F., "Rubber Use in 1972 Autos," Rubber 75. Karpati, K. K., "Mechanical Properties of Sealants.
Age, 69 (Oct. 1971). I. Behavior of Silicone Sealants as a Function of
50. Petrino, D. A., "L-I011 Tri Star Places New De- Temperature," J. Paint Technol., 44(565), 55 (Feb.
mands on Air6ift Sealants and Adhesives," Adhe- 1972).
sives Age, 15 (Feb. 1972). 76. Karpati, K. K., "Mechanical Properties of Sealants.
51. "UCC and USM Corp. Jointly License Sealant II. Performance Testing of Silicone Sealants as a
Technology," Adhesives Age, 54 (Sept. 1970). Function of Rate of Movement," J. Paint Technol.,
52. Bedoit, W. C., Jr., "Urethanes in the Seventies," J. 44(569), 58 (June 1972).
Cellular Plastics, 110 (May, June 1971). 77. Karpati, K. K., "Mechanical Properties of Sealants.
53. Swanson, F. D., and Price, S. J., "Chemistry of Ur- m, Performance Testing of Silicone Sealants," J.
ethane Adhesives with Silane Coupling Agents," Paint Technol., 44(571), 75 (Aug. 1972).
Adhesives Age, 23 (June 1973). 78. Karpati, K. K., "Mechanical Properties of Sealants.
54. Hale, W. F., and Conte, L. B., Jr., "New Inter- IV. Performance Testing of Two-Part Poly sulfide
mediates for Urethane Sealants," Adhesives Age, 29 Sealants," J. Paint Technol., 45(580), 49 (May
(Nov. 1971). 1973).
55. NASA, "Elastomeric Sealants [in Aerospace Pro- 79. Skeist, I. (ed.), "Handbook of Adhesives," 1st Ed.
gram]," in "Adhesives, Sealants, and Gaskets," New York, Van Nostrand Reinhold, 1962.
Chapter 3, SP-5066, 1967. 80. Yaroch, E. J., "The Curtainwall's Chief Problem,"
57. Pierce, O. R., and Kim, Y. K., "Fluorosilicones as Glass Digest, 48 (Feb. 1966).
640 HANDBOOK OF ADHESIVES

81. Kenton, I. R., "Polythiol-Based Sealants," U.S. ing Properties of Sealants," J. Eng. Mechanics, 111,
Patent 3,798,192 (Mar. 19, 1974). 882-892 (Iuly 1985).
82. Doss, R. C., and Marrs, O. L., "New Polymercap- 93. Oxley, C. E., Elastomerics, 111,29-32 (Nov. 1979).
tan Polymer for Elastomeric Sealants," Adhesives 94. Lamb, C. M., and Williams, R. P., "New Poly-
Age, 25 (Nov. 1974). mercaptan One-Component Sealant," 22, 44-46
83. "Silicone Building Sealant Handles Cold Weather (Nov. 1979).
and Ioint Movement," Adhesives Age, 18 (Nov. 95. Ghatage et al., "Polysulfide Sealants," Rubber
1974). Chem. Technol., 54, 197-210 (May/Iune 1981).
84. Bethke, I. I., and Ketcham, S. I., "Polysulfide Seal- 96. Feldman, D., "Polyurethane and Polyblend Seal-
ants for Corrosion Protection of Spot-Welded Alu- ants," Polymer Eng. Sci., 21, 53-56 (Ian. 1981).
minum Ioints," Adhesives Age, 29 (Nov. 1974). 97. "Sealants Beads Precisely Applied," Machine De-
85. Devine, A. T., "Sealants: A Comparative Evalua- sign, 55, 8 (Oct. 20, 1983).
tion of Performance in Two Typical Ioint Configu- 98. Panek, I. R., and Cook, I. P., "Construction Seal-
rations," Adhesives Age, 37 (Nov. 1974). ants and Adhesive, " 2nd Ed., New York, Iohn Wiley
86. Toogood, I. B., "Sealants: A New Market for Hot and Sons, 1984.
Melts," Adhesives Age, 46 (Nov. 1974). 99. Elias, M., "Silicone Sealant Technology, Markets
87. Day, R., "Common-Sense Guide to Caulks and Continue to Grow," Adhesives Age, 8 (May 1986).
Caulking," Popular Science, 107 (Sept. 1974). 100. "Editorial Advisory Board 1985 Review/1986 Fore-
88. "Sealant Performance Characteristics," Strucutral cast," Adhesive Age, 17 (Jan. 1986).
Sealant Newsletter, No. 18, Ian. 1968, Thiokol 101. Noll, W., "Chemistry and Technology of Sili-
Chemical Corp. cones," New York, Academic Press, 1968.
89. Bouchey, G. I., "ASTM C-24 Sealant Report: Task 102. Skeist, I. (ed), "Handbook of Adhesives," 2nd Ed.,
Group Examines Glazing for Insulating Glass Units, " New York, Van Nostrand Reinhold, 1977.
Adhesives Age, 27 (Iuly 1984). 103. Cochran, H., and Lim, C., "The Effect of Fumed
90. Karpati, K. K., "Quick Weathering Test for Screen- Silica in TRV -1 Silicone Rubber," presented at the
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32 (March 1984). cal Society.
91. Armstrong, I. S., and Duffy, I. W., "Advantages of 104. Toporcer, L. H., and Crossan, I. D., "Low Modulus
Urethane Insulating Glass Sealants," Elastomerics, Room Temperature Vulcanizable Silicone Elasto-
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92. Anderson, I. B., "A Method for Finding Engineer-
 38
Pressure-Sensitive Adhesives for
Tapes and Labels
SAMUEL C. TEMIN
Technical Consultant
Walpole, Massachusetts

Pressure-sensitive adhesives (PSAs) are mate- properties led to an explosive growth in their
rials which in dry fonn are aggressively and use. From a post-World War II value of less
pennanently tacky at room temperature and than $100 million the industry has expanded to
finnly adhere to a variety of dissimilar surfaces a current dollar volume, at the manufacturer's
upon mere contact without the need of more level, of about $3 billion. 3 Tapes account for
than finger or hand pressure. l They are widely roughly 60% of this market, with labels, in-
used in familiar, everyday products such as cluding decals, taking about 30%. The remain-
masking tapes and office tapes, finger bandages der is utilized for decorative and protective
and labels. sheets, sanitary napkins, floor tiles, various
The true PSA does not require activation by medical applications, sun control films, EMI
solvents or heat and adheres finnly to a wide shielding and numerous specialty items. The
variety of surfaces. Despite their aggressive PSA market additionally requires a significant
tackiness, "they can be handled with the fin- dollar volume of release coatings, to provide
gers and removed from smooth surfaces .with- surfaces to which the PSA has low adhesion for
out leaving a residue. " 1 handling and transfer of products.
The earliest commercial PSAs of importance Originally PSA products were manufactured
were blends of natural rubber (NR) and wood by drying a solution of the adhesive on a suit-
rosins. 2 The rosin, subsequently categorized as able backing. In the 1970s, in response to cost
a member of a class of materials called tacki- increases in solvents and regulatory restrictions
tying resins, imparted to the rubber the neces- regarding emissions, the industry turned to
sary degree of tackiness. With the NR/rosin water-based (emulsion) PSAs and 100% solid
blends, largely in response to a need for mask- compositions or so-called hot melt pressure-
ing parts to be protected in painting operations, sensitive adhesives (HMPSAs). These market
the PSA industry had its origins. In time other forces have had a profound effect on the selec-
elastomers were utilized and the original wood tion of PSA materials.
rosins were chemically modified to provide a Although rubber-based adhesives still consti-
large variety of tackifiers. Hydrocarbon-based tute the largest component of the PSA market,
tackifiers were added and other elastomeric NR has been supplanted by the styrene-iso-
polymers, particularly polyacrylates, came into , prene-styrene (S-I-S) block copolymers as the
use after World War II. dominant hydrocarbon elastomer in this cate-
The availability of PSAs with improved gory because, to a large extent, the S-I-S

641
642 HANDBOOK OF ADHESIVES

polymers lend themselves to hot melt fonnu- are applied to the backing using either a hot
lations; in contrast, NR adhesives are still melt coater, a calendar, or an extruder. For
mostly solvent-based. The utilization of latex most purposes the final coating is relatively
vehicles based on hydrocarbon elastomers is thin, of the order of 2-3 mils in thickness, but
still relatively minor and is largely restricted to it may be as thick as 12 mils. In general, the
styrene-butadiene emulsions and some natural 100% solids adhesive lend themselves better
rubber latex. However, in the case of acrylic than solutions or latices to heavier coatings.
PSAs, emulsions now surpass solution adhe-
sives in volume consumed. Drying Lines. Oven drying lines represent
These trends are expected to continue, with large capital investments, of the order of sev-
water-based and hot melt fonnulations gradu- eral million dollars, and the same line is fre-
ally supplanting solution polymers. A newer quently used to handle both solutions and
technology, radiation polymerization or cure of latices. The metering equipment may be either
PSAs, at present is of minor industrial impor- reverse roll coaters, which offer maximum flex-
tance, although at least two of the major pro- ibility, or knife-over-roll coaters, which are less
ducers of PSA products are reported to operate expensive. For thin films a wire-wound rod to
manufacturing lines utilizing electron beam ra- remove excess material can be used. Because
diation. UV radiation use may grow in time. of coating difficulties encountered with latex
vehicles such devices as an air knife or flexible
CONSTRUCTIONS blade are sometimes used with these products.
Coating of tapes is often directly onto the
Pressure-sensitive products basically consist of
backing. Label adhesives, in contrast, are al-
an adhesive coated on a backing or carrier.
ways coated on a release liner which is then
Most often the backing is a flexible film, foil,
laminated (nip rolls) to the paper or other back-
or fabric, although many products utilize rigid
ing and used or sold in this construction.
supports or have the adhesive directly coated
The drying step of necessity must be rela-
onto the fonn or object that is to be bonded to
tively slow to avoid bubbles, etc., and the web
another surface. A typical construction is
speed in commercials ovens is usually re-
shown in Fig. 1. stricted to 25-50 yards per minute. Hot air
ovens are the most common type of dryer, al-
Manufacture
though the air flow is often supplemented by
PSAs are applied to backings in several ways infrared heating. For solvent operations the
depending on the nature of the adhesive. So- modern oven either incinerates the solvents, for
lutions or latices are coated on a moving web fuel value, or pennits recovery of the solvent
of backing or release liner, in a continuous op- by condensation or by absorption on activated
eration including drying in an oven. If the ad- charcoal. 4 The energy requirements for drying
hesive is coated on a release paper or liner, it latices are actually less than for solvents since
can be subsequently laminated or transferred to less hot air is required; the air volume must be
the desired backing and the liner retained or re- large to avoid an explosive concentration of va-
moved. Hot melts, or 100% solid adhesives, pors in the case of solvents.
In almost all cases the adhesive is coated on
wide-width material and then slit into narrow
widths for tapes, which are subsequently wound
into rolls, or diced or otherwise cut into the
shapes desired for other products.

Hot Melt Coating. HMPSAs are heated to

achieve a bulk viscosity suitable for the equip-
ment used and then conveyed to a roll-backed
Fig. 1. PSA tape construction. 1, release coating; 2, web. The tenn hot melt coater refers to equip-
backing; 3, primer; 4, adhesive. ment that has viscosity limitation, while an ex-
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 643

truder can handle materials of quite high ket on an area basis. At the thickness most
viscosity. Accordingly the adhesives suitable commonly used, about 5-6 mils, paper is much
for hot melt coating are restricted in molecular less expensive than films but subject to delam-
weight. The most popular machines pump the ination. Accordingly, for tape purposes the pa-
molten polymer from a reservoir through a slot per is strengthened by impregnation with a
die, although other devices are also used. polymeric saturant such as a styrene-butadiene
Extrusion coating, although currently prac- or acrylic latex. Often the paper is creped to
ticed only by a few large PSA manufacturers, enhance its comformability to rough surfaces.
appears to be of growing importance because it Paper tapes are used for masking, packaging,
permits utilization of high molecular weight electrical insulation, identification and splic-
compositions. For rubber-based adhesives the ing, with masking tape for the automotive in-
equipment provides for in-line mixing of rub- dustry taking the largest volume. In many
ber and tackifier. For acrylic adhesives twin- applications, such as packaging, paper is being
screw extruders can devolatilize solutions or replaced by films, particularly polypropylene
emulsions and deliver 100% solids through the film. The paper backing used for labels is sel-
slot die. Both hot melt coater and extruders are dom latex-impregnated. A large amount is clay-
capable of delivering over 1000 pounds an hour coated to permit better printing quality.
of adhesive. Film backings are stronger than paper per unit
Hot melt machines require a much smaller thickness and offer additional advantages in-
capital investment than extruders, and narrow cluding transparency and water resistance. Cel-
width coaters are used by label manufacturers lophane was the first film used for a PSA
and for smaller scale tape operations. Extruders product but has now been replaced by cellulose
are justified only in the case of a single large- acetate for transparent office and household
volume product. tape. Oriented polypropylene is used in enor-
mous volumes, approaching that of paper, for
Calendering. This older technique, highly diaper tapes, strapping tapes, and other pack-
capital intensive, is of declining importance for aging applications. Other widely used films are
PSAs. Because it is still a preferred process for polyester, for electrical and packaging appli-
thick coatings, calendering is used for pipe cations as well as decorative sheets, and poly-
wraps, where the adhesive thickness may be as vinyl chloride for electrician's tape, finger-
much as 12 mils. Calendering is also used for bandages, medical products, decorative sheets
making fabric-backed duct tapes, where heavy and labels. Polyethylene is little used except as
applications are required to compensate for the thick films for corrosion protection tapes for
adhesive buried in the backing, but it is doubt- underground transmission pipes. Among the
ful if new production of PSAs will utilize cal- lesser used films are those of nylon, polyimide,
endars. metallized polyester, fluorocarbon, and poly-
urethane-all of which fit some special niche in
Backings the market place.
Many films are reinforced with fibers or lam-
Because of the myriad applications found for inated to fabric, an important segment of the
PSA products, a large number of backing ma- duct tape market, and metal for nameplates.
terials or carriers are needed to satisfy end-use Fabric or cloth backings are used for medical
requirements. For tapes and labels thin and tapes, finger bandages and electrical tapes.
flexible materials such as paper, films, fabrics, Other specialty backings include metal foils and
and foils constitute the major share of back- foams.
ings. For other products, such as floor tiles or
name plates, the backing can be rigid and thick.
Release Coatings and Liners
Other backings, for example Velcro strips, can
be intermediate in rigidity. Release coatings are an essential feature of PSA
Paper is the most widely used backing and, technology. Self-wound tapes often require an
in fact, constitutes about 80% of the label mar- abherent or antistick coating on the reverse side
644 HANDBOOK OF ADHESIVES

of the backing to pennit facile unwind of a roll. tackifier, which nonnally constitutes 35-50%
Labels and many specialty products are always by weight of the adhesive. These tack-enhanc-
backed with an antistick or release-coated liner; ing materials are also used with other types of
some tapes are also wound with a release in- elastomer and thus constitute an important, and
terliner. The release liner is most often coated even essential, raw material in fonnulating
with a polymeric material of low surface en- PSAs.
ergy or composed of a film, also of low surface
energy, to which the PSA adheres poorly. Note Tackifiers
that if the backing does not have good adhesion
Tackifiers were originally produced from the
to the PSA but is primed or chemically altered
rosin found in wood. The wood rosins derived
to provide good anchorage of the adhesive, then
from aged tree stumps, or naval stores, contain
no release coating is required.
various unsaturated acids, e.g., abietic and lev-
The release coating, applied as a very thin
opimaric, as a major constituent. To obtain
film to the reverse side of the backing (see Fig.
more aging stability and compatibility with base
1), can be a silicone or an alkyd or copolymer
polymers, these acids have been modified by
containing long aliphatic hydrocarbon constit-
hydrogenation, disproportionation, and esteri-
uents. Thus, ethylene bis-stearamide, for ex-
fication (Fig. 2) with glycerol or pentaerythri-
ample, can be added to a paint vehicle or, less
tol; little unmodified rosin is used today.
commonly, used alone. The .copolymers are
Partially hydrogenated rosin esters are increas-
crosslinkable emulsions of an acrylate or vinyl
ingly utilized.
acetate containing a monomer like stearyt ac-
Wood turpentine, also from tree stumps, is
rylate. Other polymers or materials that pro-
the source of another important group oftack-
vide a low energy hydrocarbon moiety, which
ifiers. Cationic polymerization of dipentene and
tends to concentrate in the surface, are used to
a- and /3-pinene, the major constituents of tur-
a lesser extent.
pentine, yields the terpene tackifiers (Fig. 3).
Silicone coatings represent about one-quarter
Tall oil, a byproduct of the paper industry,
of tape release coatings (in area) but com-
has now surpassed naval stores as a rosin
pletely dominate the release liner field. The
most common liner substrate is kraft paper or,
to a limited extent, polyethylene-coated paper.

~-'~~
Silicone vehicles may be either solutions (by
far the most common), or emulsions of self-
crosslinking poly(dimethylsiloxane) polymers

1~
which are coated and oven dried in a continu-
ous operation. Solventless or 100% solids coat-
ings have also been developed. Electron beam
cured coatings, also solventless, may be ac- REACTION
WITJ.l
E51ERIFICATION
DIMERIZATION
1
ESTERIFICATION

cepted in the future but at present represent a MALEIC

ANHYDRIDE
very small part of the market. In-house produc- Fig. 2. Chemistry of rosin ester tackifiers. Rosin actually
tion of release liners is conducted by many PSA contains other components besides abietic acid.
tape and label manufacturers but most purchase
liner stock from paper companies.

ADHESIVE SYSTEMS
<~- PINENE

0(- PINENE
Natural rubber, a hydrocarbon elastomer, was (""" ""["TEN,) 3>
the first material utilized in making PSAs and
is still widely used today. The tenn rubber- n n
based now includes many new synthetic elas- MW: 750-3500 NlW:600-1000
tomers as well as natural rubber (NR). With all LImIT-COLORED DARK.

rubber-based PSAs an essential ingredient is a Fig. 3. Chemistry of polyterpene tackifiers.

 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 645

source. The tall oil rosins are very similar to properties, and plasticizers such as petroleum
the wood rosins and similarly modified. oil or low MW polyisobutylene. Antioxidants
Lower cost tackifiers, derived from oligo- are always added to protect the unsaturated
merization of unsaturated petroleum fractions, backbone from oxidative degradation. Some
are now the most heavily used for PSA manu- typical formulations are given in Table I.
facture. Both the C s and the C9 fractions are NR latex is used for PSAs to a small extent.
utilized; the former has greater industrial im- Here the tackifier must be in the form of an
portance on the basis of broader compatibility aqueous dispersion.
with PSA base polymers. Synthetic polyisoprene, chemically similar to
Tackifiers with aromatic content, particularly NR, has the advantage of not requiring milling
a-methyl styrene and vinyl toluene copolymers like NR in order to prepare solutions. Never-
and coumarone-indene resins, are of significant theless, its use in PSAs is about one-tenth that
industrial value. of NR because of costs and poorer cohesive
Tackifiers are all low molecular weight ma- strength than NR. For these reasons and be-
terials, ranging from about 300 to about 3000. cause of competition from other elastomers, its
Some are liquids but the most widely used tack- usage is not expected to grow.
ifiers are brittle solids having ring and ball soft-
ening points of about 6O-115°C. For most Block Copolymers. The hydrocarbon elas-
effective behavior the tackifier should be close tomer enjoying the greatest volume in PSAs is
in solubility parameter to the elastomer with an A-B-A triblock copolymer where A is poly-
which it is blended. s Thus aliphatic hydrocar- styrene and B is either a poly isoprene or
bon tackifiers are not indicated for use with the polybutadiene unit. These polymers are trade-
polar acrylic PSAs. marked "Kraton" by Shell Chemical Com-
For use with latex adhesives, the tackifiers
are produced as aqueous dispersions. It is im-
portant here that the dispersants used be com- Table 1. Typical PSA Formulations
patible with the surfactant in the polymer Based on NR.
emulsions. A. General Purpose: Clear
Milled pale crepe 100
Rubber-Based Adhesives Poly terpene (MW 750) 90
Antioxidant 2
Natural Rubber. Natural rubber (NR), all Heptane 350
cis-I,4-polyisoprene, is available as the natural B. General Purpose: Pigmented
latex, but the major raw material for PSAs is Milled pale crepe 34
the recovered solid, or baled gum rubber. The Cs hydrocarbon resin (s.p. 95°C) 34
principal types of NR used for PSAs are pale Dixie clay 20
Titanium dioxide II
crepe or ribbed smoked sheet, which is less ex- Antioxidant
pensive but of darker color. The baled rubber (Can be calendered)
must be masticated to lower its molecular C. Surgical Tape
weight before use. Milled smoked sheet 100
Most NR-based adhesives are sold as solu- Rosin ester (s. p. 95°C) 90
tions, usually about 35 % solids, in C6-C 7 ali- Lanolin 20
phatic hydrocarbons, often blended with some Zinc oxide 50
Antioxidant 2
toluene. With this elastomer almost any tacki- (Solvent to coatable viscosity)
fier can be used, but terpenes and C s hydrocar-
D. Masking Tape
bon types are favored. Tack (see below) reaches
Milled pale crepe 100
a maximum at 50-70 parts tackifier per 100 Polyterpene (s.p. 115°C) 41
parts (phr) NR, depending on the tackifier. Calcium carbonate 58
Often a mixture of tackifiers gives better prop- Resole phenolic 51
erties. The PSA composition often includes Antioxidant 2
Hexane/toluene (70/30) 450
fillers such as clay to lower costs and alter
646 HANDBOOK OF ADHESIVES

pany, the only domestic producer. By far the Table 2. Typical PSA Formulation Using
more popular copolymer is that in which the Steron 840A.
midblock is composed of isoprene units; this Stereon 840A 47.0
material yields adhesives of higher tack than Hydrogenated rosin ester (s.p. 100°C) 31.5
those with butadiene midblocks. The copoly- Naphthenic oil 30.0
mers have an overall molecular weight of about Antioxidant 1.5

100,000 with about 15-30% by weight of

polystyrene. 6
These triblock copolymers develop a domain ter 0, are often used. One tackifier, with 0 be-
structure; the polystyrene blocks from various low 9, is compatible with the midblock while
polymers aggregate into domains which func- the other, 0 above 9, is compatible with the
tion as thermolabile crosslinks. On heating high-Tg end blocks. Midblock tackifiers are
above the glass transition temperature Tg of the mostly Cs hydrocarbon resins and terpenes. The
amorphous polystrene end units, the material endblock tackifiers, such as a-methylstyrene
behaves as a typical thermoplastic and may be polymers or coumarone-indene resins, are of
pumped or extruded. On cooling, the polysty- high Tg and reinforce or stiffen the polystyrene
rene domains reform and the copolymer be- domains. Oils, included in many formulations
haves like a crosslinked rubber. Similarly, the to lower the melt viscosity, can have little
copolymer may be dissolved like a thermoplas- aromatic character to avoid entering and soft-
tic and on evaporation of the solvent regain the ening the polystyrene domains. Typical for-
domain morphology and behave again as if mulations using Kraton block copolymers are
crosslinked. The thermolability of the "cross- given in Table 3.
links" permit formulation of the Kraton as
HMPSAs. Currently, the triblock-based adhe- Styrene-Butadiene Random Copolymers.
sives make up almost 100% of the HMPSA The SBR preferred for PSA usage differs from
market. the SBR used primarily as an elastomer. The
Block copolymers are also widely used in the former is emulsion polymerized at a higher
form of solution adhesives. Although higher temperature and thus has a broader molecular
cost than NR, their low MW permits making weight distribution and a gel fraction, both at-
higher solids content solutions which have ob- tributes having advantages for PSAs. The con-
vious economic and ecological advantages. sumption of SBR in this field is now about the
Hydrogenation of the diolefinic midblock of same as that of NR.
a S-B-S copolymer gives an elastomer, desig-
nated Kraton G, which is favored for HMPSA Table 3. PSA Formulations Based on
applications, in spite of lower tack than the S-I-S Block Copolymers.
S-I-S copolymer, because of greater resistance A. Solution Formulation
to oxidative breakdown. Since poly(isoprene) Block copolymer (Kraton 1107) 100
degrades primarily by chain scission while Hydrogenated rosin ester (s.p. 104°C) 84
poly(butadiene) tends to crosslink, mixtures of Liquid hydrogenated rosin ester 35
S-I-S and S-B-S polymers are sometimes used Antioxidant I
Hexane/toluene (70/30) 180
to minimize the effects of degradation.
A similar block copolymer targeted for the B. Hot Melt
Block copolymer 100
hot melt market has recently been introduced
Cs hydrocarbon resin (s. p. 95°C) 100
by Firestone. This product, Stereon 840A, is a Naphthenic oil 40
multiblock styrene-butadiene copolymer. It has Antioxidant 2
a higher styrene content and somewhat lower C. Higher Shear Hot Melt
MW than the Kratons. A typical PSA formu- Block copolymer 100
lation using Stereon is given in Table 2. Cs hydrocarbon resin (s.p. 95°C) 100
The tackification of the triblock copolymers Coumarone-indene resin (s.p. ISS°C) 60
differs from that of other elastomers in that two Naphthenic oil 40
Antioxidant 4
tackifiers, of quite different solubility parame-
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 647

Most of the SBR used in PSAs is obtained as Table 5. PSA Formulations Based on
gum rubber and compounded as solvent adhe- PIB.
sives. The major utilization is in label manu- A. Removable Label
facture. Preferred tackifiers are rosin esters and PIB (MW 2 million) 100
{:l-pinene resins; the C s hydrocarbon resins are Polybutene (MW 1200) 70
not used. Typical solution formulations are Liquid hydrogenated rosin ester 35
Cs hydrocarbon resin (s.p. 100°C) 45
shown in Table 4.
Antioxidant
Recently SBR latexes have been promoted for Heptane 1000
PSAs but the higher cost of tackifier disper-
B. Medical Tape
sions and the competition of the more oxida- PIB (MW > I million) 100
tively stable acrylic PSAs have limited their PIB (MW 55,000) 30
growth. What SBR latex is used is found mainly Zinc oxide 50
in the label and decal area. Hydrated alumina 50
USP white oil 40
Phenolic resole 50
Polyisobutylene and Butyl Rubber. The Antioxidant
homopolymer of isobutylene, PIB, available (Solvent to coatable viscosity)
commercially in a wide range of MWs, has the
C. Vinyl Floor Tile
advantages of a saturated backbone and low Butyl rubber (MW 450,000) 100
permeability to water and gases. PSA compo- PIB 20
sitions consist of a high MW polymer, Mv of Terpene phenolic resin 70
from 725,000 to over 2,000,000, blended with Mineral spirits 360
a low MW PIB which functions as a plasticizer
as well as providing a portion of low MW
PSAs is for removable labels, where low tack
chains to promote wet-out of surfaces to which
and adhesion are desirable. Typical formula-
the adhesive is applied. The preferred tackifiers
tions containing PIB are given in Table 5.
are C s hydrocarbon resins and polyterpenes.
Butyl rubber is a copolymer of isobutylene
Because PIB is a low energy polymer, for
with a minor amount of isoprene (0.8-2 mole
adhesion to more polar surfaces, rosin esters
%). Unlike PIB, butyl can be crosslinked to
can be used. Most PIB adhesives are solvent
improve the otherwise poor cohesive properties
based, with petroleum fractions (naphthas)
of this class of adhesive. The major use for BR
being suitable solvents. A major use of PIB
is in anticorrosion wrap for gas ~nd oil trans-
mission pipes. The backing for this tape con-
Table 4. PSA Solution Formulations sists of a thick polyethylene or PVC film,
Based on SBR. loaded with carbon black. The adhesive mass,
A. General Purpose Tape which is quite thick (up to 12 mils) not only
~R 100 contains the usual tackifiers, of which many can
Hydrogenated rosin ester (s.p. 104°C) 75 be used, but also a high concentration of par-
Antioxidant 2 ticulate filler. This tape lends itself favorably
Toluene 180
to calendar manufacture. A typical formulation
B. Removable Label Stock for a pipewrap adhesive is given in Table 6.
SBR (54 Mooney Viscosity) 100
Hydrogenated rosin ester (s. p. 105°C) 50
Plasticizing oil 37
Table 6. Typical Formulation for
Antioxidant 2
Toluene 200 Calenderable Pipewrap Adhesive.
C. Masking Tape Butyl rubber (MW 350,000) 100
SBR (54 Mooney Viscosity) 100 Poly butene (MW 900) 100
C9 hydrocarbon resin 150 Carbon black 90
Bromomethyl phenolic resole 20 Talc or clay 200
Zinc resinate 5 Process oil 50
Antioxidant 2 Cs hydrocarbon resin (s. p. 105°C) 75
Hexaneltoluene (60/40) 275 Amorphous polypropylene 50
648 HANDBOOK OF ADHESIVES

Reclaim Rubber. Rubber recovered from number of comonomers have been mentioned
scrap rubber goods, primarily by digestion or in patents, acrylic acid is the most popular po-
mastication at elevated temperatures, consists lar comonomer; others, such as acrylamide,
of soluble hydrocarbon, crosslinked rubber, and acrylonitrile, hydroxyethyl acrylate, and cer-
about 30 % carbon black, plus minor amounts tain amine-functional monomers, have found
of oil, tackifiers, and curative residues. The commercial utilization.
fQbber content of reclaim derived from tires is A so-called modifying monomer, such as vi-
a mixture of SBR and NR, while butyl reclaim nyl acetate or ethyl acrylate, is very frequently
is derived from inner tubes. One 'of the princi- included in acrylic PSA compositions to in-
pal virtues of reclaim is price. It is used for crease the Tg (see the Theory section, below).
black friction tape but to a larger extent for duct Typical recipes for acrylic PSAs are given in
tapes and pipewrap tapes. Table 7.
Acrylics, by virtue of their saturated back-
Ethylene-Vinyl Acetate Copolymers. bone, far surpass the rubber-based PSAs in
EV A copolymers having a vinyl acetate con- terms of aging stability. The acrylics are also
tent of 40 % or higher have some utility in colorless and can be readily tailored to suit spe-
PSAs. These copolymers, which also require cific applications by adjustment of the mono-
high levels of tackifiers, were at one time the mer ratios. As a generalization, acrylics adhere
base materials for HMPSAs but have been al- better to polar surfaces than rubber-based PSAs
most completely displaced by the triblock co- but, correspondingly, less well to low energy
polymers. Although somewhat lower in cost surfaces. 8 Although acrylic PSAs do not dis-
than styrenic block copolymers, EV A has been color or lose adhesive properties on outdoor ex-
unable to compete successfully because of low posure, their tack and peel strength, again as a
tack and poor shear strength, especially at el-
evated temperatures.
Table 7. Typical Compositions of
Acrylic PSAs.
Acrylics A. General Purpose Tape
2-Ethylhexyl acrylate 75
Poly(acrylate esters), often called acrylics, have Vinyl acetate 20
grown from their first introduction in the mid- Acrylic acid 4
1950s to account for about one-quarter of the N-Methylolacrylamide
domestic PSA market. The pioneering research B. Conformable, High Tack Adhesive
in this field by Ulrich7 revealed that the nor- Isoocty I acrylate 95.5
mally tacky polymers of certain acrylic esters Acry lic acid 4.5
could be converted to useful adhesives by the Hydrogenated rosin ester (s.p. 50.0
85°C)
incorporation of up to about 10% of a polar
monomer. The acrylate esters of C4-C 12 alco- C. Firm, Repositionable Adhesive
hols, giving homopolymers having a Tg of Isooctyl acrylate 57.5
Methyl acrylate 37.0
about -50°C to about -75°C, are the major Acrylic acid 7.5
constituent of the PSA.
D. Self-Crosslinkable Adhesive
For economic reasons the dominant esters
2-Ethylhexyl acrylate 89.5
worldwide are butyl and 2-ethylhexyl acrylate. Dimethylaminoethyl methacrylate 7.0
The 3M Company, the largest tape producer in Acrylic acid 3.0
the U.S., is reported to manufacture for captive Glycidyl methacrylate 0.5
consumption the ester of isooctyl alcohol de- E. Post-Crosslinkable Adhesive
rived from the OXO process. Other acrylate es- 2-Ethylhexyl acrylate 72.5
ters, such as decyl and isodecyl acrylate, and Vinyl acetate 18.9
Ethyl acrylate 5.2
certain methacrylate esters, such as lauryl
Maleic anhydride 3.4
methacrylate, give rise to the requisite low- Tg
homopolymer but are currently too expensive Add 0.3 metal alkoxide or acetylacetonate to coating so-
lution
for commercial consumption. Although a large
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 649

generalization, are somewhat less than that of compatible pendant chain forms domains in a
the best rubber-based adhesives. Another sig- manner analogous to the morphology generated
nificant difference is that acrylics do not require in S-I-S copolymers. One method to provide
tackification to provide excellent physical the requisite pendant chain consists of grafting
properties. Nevertheless, many commercial of, for example, styrene or methyl meth-
acrylic PSAs contain tackifiers, most often acrylate to a preformed conventional acrylic
rosin esters, to increase peel adhesion and tack. polymer.16 Another method involves copoly-
Because acrylics can be free of antioxidants and merization of a monomer, that is, a low MW
tackifiers, they are generally regarded as less polystyrene chain terminated with a methacryl
irritating to the skin and are often preferred for group. A recently introduced product is Arco
medical applications. 9 Chemical Co. 's Chemlink 4500 Macromer
Although the acrylics were originally avail- monomer, which, when copolymerized with an
able only as solution adhesives, the rising cost acrylate ester and a polar monomer, provides
of solvents and the amendments to the Clean pendant chains of polystyrene. 17 Typical for-
Air Act in the 1970s created strong motivation mulations using this macromer are given in Ta-
for water-based forms. Today acrylic emul- ble 8.
sions volume exceeds that of acrylic solutions, Acrylic PSAs are used for some labels and a
and the trend toward the emulsions is expected wide variety of tapes, particularly transparent
to accelerate in the future. Once offered com- office, strapping, transfer, medical, and metal
mercially, \0 hot melt acrylic PSAs are no longer foil tapes.
on the market except for a minuscule amount
ofRMPSA material designed for post-radiation Silicones
curing. It has been extremely difficult to de-
The use of silicone-type PSAs is restricted be-
velop compOSItIOns with adequate shear
cause of their high cost, in spite of the excellent
strength at the low molecular weights required
adhesion to surfaces of both high and low sur-
for hot melts.
face energy and the ability to function accept-
Solution adhesives are limited in MW be-
ably at a temperature range of over 500°C. The
cause of the effect of MW in increasing solu-
base raw materials for producing silicone PSAs
tion viscosity. In contrast, since MW of the
come primarily from Dow Coming and Gen-
polymer has no effect on latex viscosity, this
eral Electric Corp.
factor does not operate with latex adhesives.
The two basic components of a silicone PSA
Often, however, some chain transfer agent is
are a resin and a gum, somewhat analogous to
incorporated in the emulsion recipe to lower
MW of the polymer in order to obtain better tackifier and elastomer in organic adhesives.
The resin is derived from reaction of silicic or
tack. To compensate for the low MW of solu-
tion adhesives, it is common practice to effect polysilicic acid (hydrosol) with something like
crosslinking of the dried adhesive in the oven trimethyl chlorosilane to convert part of the OR
drying line. Melamine resins are used II as well
as the soluble derivative of a multifunctional Table 8. Typical PSA Formulations
metal, e.g., aluminum acetyl acetonate l2 or a Using Macromer.
titanium alkoxide,13 which loses its ligand and A. Untackified
effects salt crosslinks with the carboxyls in the Chemlink 4500' 15
polymer on drying. Some latex polymers are 2-Ethylhexyl acrylate 80
Acry lic acid 5
also crosslinked e.g., by incorporating some-
thing like zinc acetate. Of increasing impor- B. Tackified
tance are the self-curing compositions where Chemlink 4500' 15
1-Decy I acry late 82.9
the crosslinking mechanism is built into the Acrylic acid 2.1
polymer. 14.15
A new approach to achieving augmented co- Hydrogenated rosin ester (s.p. 85°C) 97.0
hesive strength without crosslinking is based on Trioctyl trimellitate (plasticizer) 16
a polymer with pendant high- Tg chains. The in- 'Arco Chemical Co.
650 HANDBOOK OF ADHESIVES

groups to trimethylsiloxane groupS. The con- masking and insulation where high tempera-
centration of residual Si-qH groups is less tures are encountered. Special high perfor-
important than the MW of the resin, which is mance silicone tapes include those with
preferably less than 5000. The gum is a high polyimide and poly(tetrafluoroethylene) as
MW polysiloxane with tenninal OH groups. backings.
Both all-dimethyl and dimethyl-diphenyl poly-
siloxanes are used. The inclusion of diphenyl
Miscellaneous Polymers
siloxane units, nonnally 6 or 12 mole percent
of the gum, results in higher tack and peel Other than the hydrocarbon elastomers and
adhesion in the resulting PSA. The simplest acrylics, and to a smaller degree silicones, little
method of PSA preparation is mixing resin and success commercially has attended efforts to
gum in a suitable solvent, typically toluene. utilize other polymers for PSAs. The patent lit-
The solution can be used for coating as is, or erature describes a number of water solubles,
heated to induce more Si-O-S fonnation, suitably crosslinked, as the base ingredient for
both intra- and intennolecular, which gives a repulpable adhesives on paper backings used to
product with higher cohesive strength. The splice rolls during papennaking opera-
physical properties of the PSA are a function tions. 19 ,20 The patent literature also reveals ef-
of resin/gum ratio, type of gum, and amount of forts to utilize polyurethanes,21 polyurethane-
heating given the blend prior to coating. The acrylic hybrids,22 ionomers,23 and polyester
effect of the resin/gum ratio, using an all di- block elastomers,24 among others, but only re-
methyl gum, is illustrated in Fig. 4. 18 An ad- pulpable adhesives have reached the market-
hesive based on a partial diphenyl gum would place. Two systems that have achieved
have higher tack and peel adhesion values. mentionable commercial success are described
Silicone PSAs find application almost exclu- below.
sively in tape fonn. Polyester film is widely
used as backing particularly for masked printed Vinyl Acetate Copolymers. Available only
circuit boards during plating operations, for as emulsions for PSA applications, the use of
electrical insulation and paper splicing tapes. vinyl acetate copolymers is still relatively small
Glass cIotti-backed tapes are preferred for and confined almost entirely to pennanent la-

,,
/
90
" 1200

IJNU;fALVZED TACK.
ADIlESION (q/cm)
C02/in)
800
70

400

50

R(SIN TO GUM RATIO

Fig. 4. Effect of resin-to-gum ratio in silicone adhesives on tack, adhesion and shear strength. 18
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 651

bels. Some of the emulsions are used as such ergetics of the adhesive and adherend (basic to
and some blended with an acrylic latex before all adhesion phenomena), while resistance to
application. Vinyl acetate copolymer adhesives debonding forces is, in the case of PSAs, a
are produced that have an excellent balance of function of the viscoelastic behavior properties
tack, peel strength, and shear resistance; as of the adhesive. Unlike structural adhesives,
with acrylics, adhesive strength builds with there is no phase change from liquid to rigid
time. The only domestic producer, Air Prod- solid in the case of PSAs. Both surface ener-
ucts, does not reveal the composition of its getics and especially viscoelastic properties are
PSAs but patents25 indicate that they may be basic to the understanding of PSA behavior. In
roughly 1: 1 copolymers of vinyl acetate and what follows there is a brief discussion of sur-
dioctyl maleate containing some acrylic acid. face energetics but viscoelastic behavior is cov-
ered in the discussion of the three principal
Poly(Vinyl Alkyl Ether) Blends. Vinyl criteria by which PSAs are evaluated: tack, peel
ethyl ether polymers, available from Union adhesion, and resistance to shear.
Carbide and GAF, are used in medical prod-
ucts because of high moisture vapor perme- Surface Energetics
ability, valuable for patient comfort during long
term application to the skin. Also of some small In order to maximize bond strength between
use are PSAs based on poly (vinyl isobutyl adhesive and adherend it is necessary that the
ether). The technology here involves blending liquid (adhesive) wet and spread over the solid
high and low MW polymers, as illustrated in to achieve close contact between the surfaces,
Table 9, analogous to the approach with pm. that is, to eliminate voids or gaps at the inter-
Again, the low MW polymer provides for face. Although PSAs are fairly viscous at room
spreading on the adherend surface and the high temperature, experience shows that intimate
MW polymer provides cohesive strength. The contact, which means flowing into the pits and
major drawback with this category of adhesive, crevices of the solid surface (which is never
not readily crosslinkable, is poor shear resis- microscopically flat) is obtained at short times
tance. under moderate pressure. Thus the ability of the
PSA to flow into the aspersities of the solid sur-
face and achieve the desired intact interface is
THEORY determined to a large extent by the relative sur-
The adhesive properties of PSAs, like other ad- face energies of the two phases.
hesives, are governed by two basic considera- Surface tensions are readily determined for
tions, namely the ability to wet and spread on liquids, unlike solids. To ascribe surface en-
an adherend surface and the ability to resist de- ergy values to solids, the concept of critical
tachment from that surface. Making a good surface tension 'YC' as developed by Zisman,26
bond is to a h!f~e extent, but certainly not en- is utilized. As a generalization, a liquid will
tirely, dependent upon the relative surface en- spread on a surface which has a higher surface
tension or free surface energy than that of the
liquid.
Table 9. PSA Formulations Based on These surface energies are the basis for cal-
Poly(Vinyl Alkyl Ether). culating the thermodynamic work of adhesion,
WA , which also represents the work required to
A. Poly (Vinyl Isobutyl Ether) Type
PVmE MW 100,000 180 separate two surfaces. It must be stressed that
PVmE MW 40,000 585 WA is far smaller than the force required to re-
PVmE MW 10,000 135 move a PSA tape from a substrate; the experi-
Antioxidant 5 mental peel force includes significant
B. Poly(Vinyl Ethyl Ether) Type contributions from the bulk viscoelastic prop-
PVEE Red. vise. 0.3 50 erties of the adhesive and the backing, as
PVEE Red. vise. 4.0 25 pointed out later. Nevertheless WA and peel
__ Zinc
_resinate
_ _ _ _ _ _ _ _ _ _ _ _ _ _5 force can be correlated.
652 HANDBOOK OF ADHESIVES

WA can be expressed by two classical equa- forces; the latter are probably not simply di-
tions: pole-dipole interactions but are better ascribed
to acid-base interactions. 3o The key point here
WA = 'Ys + 'YL - 'YSL (1) is that interfacial tensions depend on polarity,
that is, on the difference in polarity between
WA = 'YL(1 + cos 8) (2) adhesive and adherend; if only dispersion
forces are operative, 'YSL is zero. Thus the ef-
Where 8 is the contact angle, 'YSL is the inter- fective energy of a solid surface really depends
facial surface tension and 'Ys and 'YL are the sur- on the intractions possible with the liquid. This
face energies or surface tensions (neglecting for concept explains instances of specific adhe-
simplicity that their measurement actually in- sion, where an adhesive bonds more strongly
volves an interface with vapor) of solid and liq- to one surface than a second, both of which
uid, respectively. The first equation, applicable have equal 'Ys or 'Yc values but different polar
when the contact angle is zero ('YL < 'Ys), em- components 'Y~ of that energy. Expressed an-
phasizes that adhesion increases to the point other way, for optimum thermodynamic wett-
where 'YL is close to 'Ys and then decreases. ability, when the surface tensions of the two
(When 'Ys is greater than 'YL, the 'YSL will not be . phases are similar, matching of the polarity of
minimum.) It also reinforces the experimental the two phases is very important.
observation27 that 'YSL is the most important cri- On the basis of surface energetics it is un-
terion of bond strength. The second equation derstandable, not only that PSAs do not bond
(Young-Dupre), applicable when the contact as well to solids of low 'Y c' but also why the
angle is not zero, points out that as 8 ap- more polar acrylic PSAs bond better to polar
proaches zero, WA approaches 2'YL' This leads surfaces like glass and rubber-based PSAs bond
to the conclusion that for maximum WA , 'YL better to surfaces of lower polarity like poly-
should be maximum, consistent with a low to olefins.
zero contact angle.
Thus, based on thermodynamic considera-
Tack
tions, maximum bond strength is approached
when the adhesive has a surface energy close To the layman the not clearly defined property
to but not exceeding that of the adherend. Al- of tack is often equated with stickiness and as-
though it is sometimes claimed that maximum sessed by touching a PSA surface with a finger.
adhesion for a particular adhesive increases ASTM defines tack as "the property of a ma-
continuously as the 'Yc value of the substrate in- terial which enables it to form a bond of mea-
creases, this statement is only true when the 'YL surable strength immediately on contact with
of the liquid is higher than that of all the sub- another surface. ,,31 The time of bond forma-
strates involved. The predicted maximum in tion is thus a factor in tack, as is the force to
bond strength with increasing 'Y c of the adher- unbond after contact, since the definition speaks
end has been observed experimentally by of measurable strength. In other words, tack in-
Toyama28 in the case of PSAs, both rubber- volves both a bonding and an unbonding force.
based and acrylics. Toyama found 'YL for the The quantitative value of tack will depend on
adhesives to vary from 30 dynes/cm2 for a PIB- the method of testing; the pressure used in
based adhesive to about 36 dynes/cm2 for a NR- making contact of the PSA with a surface, the
based adhesive, a figure somewhat higher than time of contact, and the rapidity of removal all
that found by Dahlquist,29 and a plot of peel greatly influence the observed value. Note that
force vs. 'Y c for adherends showed a broad max- the term pressure-sensitive arises because the
imum at values of the adherends within 1 or 2 strength of the bond is influenced by the con-
dynes/cm2 of the PSA value. tact pressure.
The simplistic discussion above neglects the To effect a good bond immediately, that is,
very important fact that surface energies are in short times of contact, the adhesive must not
made up of contributions from both dispersion only have favorable surface energetics relative
forces (roughly van der Waals forces) and polar to that ofthe substrate, as discussed earlier, but
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 653

also a low viscosity and a low elastic modulus can make greater contact (enhanced wetting and
or high deformability. spreading) with an adherent surface during the
Low viscosity need not be a characteristic of time defined by the tack test than can the un-
all the polymer in a PSA, but some fraction of tackified rubber. PSAs have viscosities in the
the chains must be of sufficiently high mobility range of 106_108 poises at ambient tempera-
at the temperature of application to permit wet- ture. 33
ting the surface of the adherend in a short time. The other component of tack, the force to un-
To function properly, therefore, the PSA must bond, is discussed more fully in the next sec-
have a low Tg ( -lO o e to -40 o e is typical), tion (Peel Adhesion) and emphasis in the
which implies high segmental jump frequency, consideration of tack is placed on the bonding
and have a low enough viscosity to wet, which process.
really means to spread over the adherend, in a Tack can be related to modulus, as shown by
short time. Dahlquise4 in an experiment in which tack and
Sheriff,32 using rubber-tackifier blends over the complex tensile modulus E* of a PSA were
a range of concentrations, found that at low fre- both measured as a function of temperature. E*
quencies (using a Weissenberg rheogoniome- at 1 cycle / sec was found to drop with temper-
ter) both the in-phase shear modulus G 1 and the ature until, at the temperature where the tack
in-phase component of the dynamic viscosity values become appreciable, it was below 107
." 1 of the elastomer were lowered as tackifier dynes/cm2. At about 35°e, where tack was
was added. At high frequencies, on the other maximum, the modulus approached 106
hand, both G1 and ." 1 for the tackified blends dynes / cm2. Kraus35 concluded, in work with
were higher than that of the rubber, as illus- tackified styrenic block copolymers, that to
trated schematically in Fig. 5. Lower frequen- achieve satisfactory bonding the tensile storage
cies are equivalent to longer times and bonding modulus E' at 35 Hz must not exceed about 107
times, albeit short, are long compared to the dynes/cm.
times of peeling or unbonding. Accordingly, Bates36 has developed a procedure to express
the lower viscosity and more compliant PSA tack as an energy term.

,. ,

,.',,'
5.4 " :3
--- , ,,
2

',-
5.9
L~ G' " ,
LOG n'
(N/m~) ,,
, 0 (N/yn~)

4.6 -I
B.'
~,'
,,
,
.,,,
-2

,,
4.2 -3

-3 -z -I 0 2 :3
L~ WOI'.t
Fig. 5. Schematic master curves comparing in-phase shear modulus and dynamic viscosity with frequency of NR and
tackified NR. A and D, natural rubber; B and C, natural rubber tackified with 50% hydrocarbon resin.
654 HANDBOOK OF ADHESIVES

Peel Adhesion
Quantification of peel adhesion involves mea-
surement of the force required to remove the PEEL t /~
adhesive, obviously on some backing, from a FORCE I /A
specified surface at a specified rate of peel. ,/
Whereas in tack measurement the bonding and
unbonding occurs within seconds of each other,
adhesion tests are conducted after a specified PEEL RATE ~
but considerably longer dwell period of the ad- Fig. 7. Schematic plot showing effect of peel rate on peel
hesive on the test surface. Moreover, since sig- force. A, region of cohesive failure.
nificant pressure is used to enhance contact of
the tape with that surface, there is the impli-
cation that a good bond has been achieved (al- figures, and a maximum in adhesion near the
though this obviously will not occur if the point where there is change to adhesive failure.
adhesive has a higher surface energy than the It is evident that in the region of slow peel or
adherend or if the adhesive has low compliance high temperature, where the adhesive under-
and/or high viscosity), and the force required goes viscous deformation to split and leave a
to unbond will be a measurement of the vis- residue on the test surface, there is a different
coelastic deformation of the adhesive. Many failure mode than in the high rate of peel or
workers have indeed related peel adhesion to lower temperature region, where the adhesive
viscoelastic responses of the adhesive under the exhibits a higher degree of elastic response or
conditions of peeling. 37-39 rubbery behavior and parts cleanly from the
Plots of peel adhesion versus temperature ,40 surface.
Fig. 6, are almost inverse to the plots of peel Using time-temperature superposition, and
adhesion versus rate of peel, shown schemati- the shift factors of the WLF equation,4Oa it is
cally in Fig. 7. Both curves show a region possible to construct master curves relating
where cohesive failure dominates, A in both pulling rate to peel force,41-43 adjusted to some

1000

ADI-IE.SION
(9)
o {'Oo

· •I
·\A
I

\
.
\
I
200 \
\
\ ,,

2 40 GO
TEMPERATURE. (0c.)
Fig. 6. Schematic plot showing effect of temperature on peel adhesion of PSA. A, region of cohesive failure.
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 655

is attained at about 40% by weight of tacki-

fier. 45
Cohesive Strength
The internal strength of the adhesive mass or
its resistance to flow or creep under an applied
load is referred to as the cohesive strength.
PSTC defines cohesive strength as "the ability
of the adhesive to resist splitting;' ,46 upon de-
formation, the extended fibrils of a PSA47 with
low cohesive strength will rupture (split), lead-
o ing to a residue on the adherend surface.
-4 4 8 Cohesive strength can be equated with shear
LOG JtO'T (cmfr,e,) resistance and is most frequently assessed by a
Fig. 8. Schematic master curve relating temperature and holding power test, that is, the measurement of
peel rate of a typical PSA in accordance with the WLF the time for a tape to creep a specified distance
equation. or to fall from a test panel when a static load is
applied in the plane of the backing (see Test
Methods). The shear resistance of the amor-
chosen temperature, usually 296°K. A typical
phous polymer is thus a function of the viscous
master curve is shown in Fig. 8. A comparison
component of its viscoelastic response to the
by Aubrey and Sheriff44 of curves of storage
shear force and can be shown to be related to
modulus G 1 and frequency of deformation with
the steady -state flow viscosity. 48
the peel force vs. peel rate curves, using NR-
To limit the viscous flow of a PSA, that is,
based adhesives, showed that the transition
to increase its cohesive strength, it is necessary
from viscous to rubbery behavior occurred at
to increase the molecular weight and conse-
the same log G1 value regardless of the com-
quent chain entanglement contributions or to
position of the PSA. As noted below, increas-
provide some crosslinking. (The obvious ex-
ing the Tg of the adhesive results in a shift of
ception to this generalization occurs in the case
the mas~r curve to the left along the frequency
. 45 Th'IS study confirms that peel force is of the domain polymers.) The increase in MW
aXIs.
or the extent of crosslinking permissible in
dependent on the viscoelastic state of the ad-
PSAs is limited by the need, as pointed out ear-
hesive; a characteristic of simple viscoelastic
lier, for the polymer to have a high compliance
materials is that their moduli increase with in-
during the bonding stage. In the absence of
creasing rate of deformation.
crosslinking some portion of the polymer must
An objective in the formulation of commer-
possess very high MW (over 1 million) to min-
cial PSAs is to achieve a peel force at ambient
imize flow, while some portion must consist of
temperatures near the inflection point between
material that must have short-time compliance.
viscous and rubbery behavior, but on the rub-
In the case of crosslinking it is found that a gel
bery (clean interfacial separation) side, at a peel
fraction concentration of 30-50% is suitable for
rate close to that used in the standardized tests.
a good balance of properties in a high shear
Since the transition from viscous to rubbery
adhesive. 49
behavior occurs near the glass transition tem-
The shear resistance of adhesives is, of
perature, it is evident that the point on the peel
course, temperature dependent and evidence of
force versus peel rate curve at which there is a
high cohesive strength often involves measur-
change from cohesive to interfacial separation
ing holding power at elevated temperatures.
will depend on the Tg of the adhesive. For prac-
tical purposes it is desirable to formulate the
TEST METHODS
PSA to have a Tg that will yield a maximum in
rubbery or clean peel at the test method rate of Sources for standardized test methods for eval-
pulling. For NR-tackifier blends, the target Tg uating PSA products are The American Society
656 HANDBOOK OF ADHESIVES

for Testing and Materials (ASTM) and the probe to make contact with the PSA, holds it
Pressure-Sensitive Tape Council (PSTC). In there for a preset time of contact, variable in
addition a large number of test methods are of- 10 steps from 0.1 to 100 sec, and then with-
fered by the U. S. Government,SO foreign agen- draws the probe at a controlled speed, which
cies, and organizations representing various can be varied in steps from 0.02 to 2 cm/sec.
segments of industry. Tape manufacturers in The adhesive, on some backing, is attached to
descriptions of their products most often refer the flat bottom of an inverted metal cup with a
to results given by ASTM and PSTC test meth- hole in the bottom through which the probe en-
ods. ters. Thus, the contact pressure can be varied
Both peel adhesion and shear resistance tests by using cups or annular weights of various
utilize tape specimens, while tack testing can masses. The probe material can be varied, but
be performed on specimens in other shapes as a stainless steel probe is almost always used.
well as on tapes. In peel and shear tests a stain- The most commonly reported test conditions
less steel panel with a specified surface rough- are 100 g/ cm contact pressure, 1 sec contact
ness is used as a test surface. S1 time, and 1 cm/sec withdrawal speed (100, 1,
1).
Tack Testing Probe tack value is the force required to re-
move the probe, as measured by a mechanical-
Although tack testing using a flat probe (probe force gauge, under the specified conditions of
tack) is almost universally the choice in scien- test. This force will depend, as discussed ear-
tific literature, industry literature frequently re-
lier, on how good a bond is made in the first
fers to a rolling-ball tack test. place and on the rheological behavior of the ad-
Probe tack conditions are set forth by
hesive when the bond is broken. For example,
ASTMs2 and the Polyken Probe Tack Tester,
a highly compliant PSA, which can achieve a
shown schematically in Fig. 9, is the most
good bond quickly, will give a higher tack
commonly used instrument. In this device, de-
value at short contact time than will a PSA of
veloped by Hammond,s3 a 5 mm diameter flat-
higher modulus or viscosity; this distinction
ended rod, connected to a load cell, constitutes
might not be observed if longer contact times
the probe: The instrument mechanically lifts the
were used in the test. The ability of the Polyken
Probe Tack Tester to vary test conditions per-
mits it to be used for research purposes as well
as comparative testing.
Probe tack values increase somewhat with
adhesive thickness but reach a constant value
at thicknesses above 0.25 mm. S3 The values are
also influenced by the nature of the backing,
because some of the force measured in bond
breaking involves energy expended in defor-
mation of the backing, and by the roughness of
the adhesive since more time is required for a
rough adhesive to make intimate contact with
the probe.
Experimental values of probe tack are ex-
pressed in terms of gram force, with all con-
ditions specified. Values of 500 g (for 100, 1,
1 conditions) are considered good. Some very
o tacky adhesives, particularly rubber-based
types, give values as high as 1500 g.
Fig. 9. Schematic of Polyken probe tack tester showing
The rolling ball tack test consists of a ball
detail of contact area. I, backing; 2, adhesive; 3, weight; rolling down an inclined ramp and contacting a
4, carrier; 5, probe; 6, timing control. firmly held horizontal tape strip butted against
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 657

the end of the ramp. The distance the ball rolls tape itself. It is measured as the force resisting
on the tape before stopping is the experimental peeling of tape at 90° from a standard surface
value of tack. The test has a long history and upon which it has been applied under no other
many variations have been explored;54 many pressure than the weight of the tape itself. ,,57
versions are still in use, so that conditions for The PSTC test method for quick stick, also
the test may differ among laboratories. Even known as the Chang Test,58 utilizes a special
between the two standardized versions of jig to permit pulling the tape, laid "without
ASTM 55 and PSTC,56 which are supposedly pressure," from a test panel at 12 in. jmin at a
identical, there is a slight difference in the slope constant 90 ° angle of peel. Unfortunatel y, as a
of the ramp.54 Fig. 10 is a schematic drawing tape is pulled from a flat surface there is a zone
of the PSTC apparatus. of compression just before the point where the
Variables explored in the test include the size adhesive parts from the surface. 59 The resultant
and weight of the ball, its velocity at the end force has the effect of pressing the tape against
of the ramp and the shape of the ramp. The the panel so that the condition of using "no
current standard methods use ~ inch diameter pressure" is violated. Further, a stiff backing
steel balls (which are carefully cleaned before could prevent the adhesive making good con-
reuse to remove any adhesive residues), a ramp tact with the test surface. Essentially, then, this
which is inclined 22 ° from the vertical and a test resembles a typical peel test and is often
release point on the ramp, which determines the not a measure of quick stick, as the term is de-
velocity, about 6 inches from the bottom. fined, or tack.
Using PSTC Test Method No.6, rolling ball
tack valves for commercial adhesives vary from
Peel Adhesion Testing
about 0.1 inch to about 10 inches; anything un-
der 1 inch is considered evidence of a tacky The force required to remove a tape from a sur-
PSA. face depends on the angle of peel, the rate of
The term quick stick is also frequently pulling (see Fig. 7), the roughness and surface
equated with tack; it is defined by PSTC as: energy of the test surface, the pressure with
"Ability of tape to adhere to a surface in- which the tape is applied to that surface, the
stantly, using no pressure other than weight of time of dwell before the test is started, and, as
discussed earlier, the mode of failure (see Fig.
6). Moreover, the nature of the backing effects
the values obtained. 57 For valid comparisons
between tapes, therefore, it is essential that the
conditions of peel testing be specified and, if
adhesives are to be evaluated, the backings of
the tapes be the same. Nevertheless, if condi-
tions of a standardized test are followed, the
test can be of great practical and theoretical
value.
The PSTC procedure60 specifies angle of peel
(180°) and rate of peel (12 in.jmin), and ap-
plication pressure is controlled by passing a
standardized rubber-covered roller over the

cl--J, jj
one-inch wide tape specimen, placed on the
clean steel panel, five times in each long direc-
tion. The peel test according to PSTC is to be
conducted within one minute of bonding, al-
though many laboratories run the test also after
Fig. lO. Schematic of PSTC rolling ball tack tester. 1,
V-shaped trough; 2, release mechanism; 3, leveling bub- long periods of dwell. Today almost all testing
ble; 4, tape specimen; 5, ~" diameter steel ball; 6, base utilizes a constant rate of extension machine,
curve; 7, angle of 21 °30'. such as an Instron (Canton, MA).
658 HANDBOOK OF ADHESIVES

Yalues are expressed as ounces per inch viscosity to permit establishment of a good
(most specimens are one inch wide). Accept- bond will often fail suddenly (pop off) and
able tapes, depending on end use, may have leave no residue on the panel.
peel values as low as 25 oz. lin. while tapes What constitutes acceptable shear resistance
designed for use in high shear applications give for a tape depends, of course, on the intended
values as high as 100-150 oz./in. use for the product. Thus various weights can
be attached in the test and the temperature of
test can be varied also. The most commonly
Shear Resistance Testing
reported test weight is 1000 g, for a 25 x 25
The classical test for shear resistance consists mm area of contact. Holding at room temper-
of attaching a weight to a strip of tape attached ature (70°F) for over 1000 hours would be
to a vertical panel and noting time for failure considered evidence of adequate cohesive
of the bond. Since this "holding power" test strength. For many tapes, designed to be used
is highly dependent on the area of adhesive at higher temperatures, the holding power test
contacting the test panel, the PSTC test61 spec- is conducted at some elevated temperature;
ifies a one inch square surface bonded to a steel 100°F or 150°F are frequently used in individ-
panel. A rack holds the panels 2 ° from vertical uallaboratories.
so that the back of the panel forms an angle of A related test, involving measuring shear re-
178° with the extended piece oftape (Fig. 11) sistance as a function of temperature
in order to avoid any peel-back forces. Failure (S.A.F.T.), is often used to compare adhe-
can be defined as slippage of the tape by a cer- sives; here the vertical tape with attached
tain distance or complete separation of the tape weight is left in an oven while the temperature
from the panel. In the latter case a device to is raised (usually 40°F/hr) and the time and
automatically time the fall of the weight can be temperature at which the tape unbonds are re-
used. corded. Higher temperatures at which failure
The manner of separation of the tape can be occurs obviously indicate greater shear resis-
instructive; an adhesive of low cohesive tance.
strength or poor resistance to creep will split or
leave residue on the panel, while an overly Miscellaneous Tests
crosslinked adhesive or one too high in bulk
Many additional tests, too numerous to discuss
in detail here, are conducted by users and pro-
ducers to assess tape performance in some par-
ticular application. Many, of course, are
modification of the more popular tests de-
scribed above but presumably measure more
accurately the resistance of the tape to forces
encountered in some special application. For
example, there is a test for holding cardboard
panels at 90° to each other under stress62 which
is of value for packaging tape. Many others
have been developed by the Federal govern-
ment, by automotive manufacturers, or by as-
sociations serving the needs of some industry.
Other tests measure such things as adhesion of
the tape to its backing, the difficulty in un-
winding a roll of tape,63 and behavior of the
tape under various environmental conditions.
Fig. 11. Schematic of PSTC holding power test. 1, plate; PSTC alone offers over 30 test methods and
2, one square inch of tape contacting plate; -3, weight; 4, hundreds more could be culled from sources
absorbent pad. mentioned above.
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 659

APPLICATIONS the patient. Because of the presumed need for

high water vapor transmission in skin applica-
The versatility of pressure-sensitive products is
tions to avoid maceration due to accumulated
so enonnous that complete tabulation of all
moisture, many tapes utilize porous backings
their uses is virtually impossible. Every sector
such as fabrics, both woven and nonwoven, and
of the economy uses PSAs in one fonn or an-
perforated films. Other backings include trans-
other. All that can be indicated here are some
parent film and foams. An interesting use em-
of the major applications.
ploying reinforced backings is wound-closure
strips to replace sutures for minor incisions in
Tapes
the skin.
As pointed out earlier, tapes constitute the
dominant usage fonn ofPSAs. Some ofthe im- First Aid and Health Care. Many of the
portant tape applications include packaging, tapes used in hospitals are available in drug and
masking, splicing, electrical insulation, heat- general stores. The largest volume item is the
ing and air conditioning duct sealing, holding finger bandage, available with plastized vinyl
or bundling, mounting, and attaching medical and cloth backings, which are mostly flesh-col-
and first aid products to skin. Many consumer ored but can be decorated or transparent.
uses for tapes, familiar to the layman, parallel A very large tape market of many millions of
industrial uses. For example, masking tape is square yards is for diapers. The common dis-
used for painting both in the home and in in- posable diaper is secured with tapes mounted
dustrial plants. Frequently, the same tape may on attached release liners which adhere to the
be used for more than one application, al- diaper's polyethylene backing.
though manufacturers prefer to offer products Feminine sanitary napkins are held in place
for specific industries or end use application, by PSA tapes. The size of this market is limited
even though this may mean only minor differ- by the popularity of tampons, which do not re-
ences in adhesive or backing for various prod- quire fastening to the wearer.
ucts. In the sporting goods industry, considered
High volume uses of tape are presented be- here as in the health field, there is appreciable
low, organized by industry. use of strapping tapes designed to prevent in-
jury as well as to support injured joints or mus-
Packaging. The highest volume application cles. These athletic tapes, with defonnable
of tapes is in packaging. Much tape is used in cloth backings to facilitate ease of wrapping and
the manufacturing and sealing of corrugated easy tear, must also have adhesive masses that
boxes and in tear strips for cartons. An impor- pennit facile removal. The sports industry also
tant backing for such tape is oriented polypro- consumes tapes for wrapping hockey stick
pylene film, which has largely replaced blades and baseball bat handles.
unplasticized vinyl film and paper tapes. Also
of importance are reinforced tapes, mainly with Graphic Arts and Office Products. Tapes
polyester film backing, which have reinforcing used as graphic art aids are usually sold through
fibers embedded in the adhesive. A large art or office supply stores. Many of these prod-
amount of tape distinguished solely by being ucts have symbolic patterns or designs printed
inexpensive, such as paper masking tape, is on the backing; their use eliminates redrawing
used for less demanding packaging operations. the design or symbol. Very narrow tapes in
Freezer tapes for the food industry require low various colors are used for bar graphs, con-
Tg adhesives to pennit application at low tem- struction layouts, etc.
peratures. The product of greatest volume in the office
area is the well known clear tape, once known
Hospital Usage. Tapes have myriad uses in as cellophane tape, usually consisting of an
the hospital; they cover and protect wounds, acrylic PSA on acetate film.
hold down dressings, intravenous needles, and In the photographic and electronic areas light-
surgical drapes, and restrict joint movement by blocking tapes, called stripping tapes, utilize a
660 HANDBOOK OF ADHESIVES

transparent red film backing to pennit viewing Construction. Duct tapes for constructing
of the underlying surface while blocking out and insulating heating and air conditioning duct
wavelengths of light to which the photographic work are a high volume item in the building
emulsion is sensitive. industry. Much duct tape uses a cloth rein-
forced polyethylene backing, but a widely used
Electrical Industry. In addition to the fa- version is a high shear aluminum foil tape.
miliar electrician's tape, usually a black adhe- Other tapes are used for temporary holding of
sive with a stretchable film backing, there are various assemblies until a pennanent adhesive
many tapes used by equipment manufacturers cures. Additionally, tape is used by painters and
for insulation in transfonners and motors. electricians during construction. Also, PSA on
These products require PSAs of low conduc- a foamed backing is used for weatherstripping
tance. The tapes are rated in tenns of temper- and to plug gaps in place of a sealant.
ature resistance. For highest temperature ex-
posure, silicone PSAs must be used with
specialty backings like glass cloth, polyvinyl Miscellaneous. Lead foil-backed tapes are
fluoride, Teflon, or polyimide film. Tapes are used in electroplating, x-ray plate masking, golf
also used to insulate soldered joints, to secure club construction and sound dampening. Dou-
wire ends and, with fabric backings, to cushion ble-faced tapes are used to splice material from
and protect assemblies of wires. Harness tape the end of one roll to the start of the next roll
is used to bundle a group of electrical wires. in industries where a web of material is fed
Specialty products for the electronics indus- continuously to some operation. For the paper
try include aluminum foil-backed tapes for industry, a paper tape with a water-dispersible
antistatic shielding and copper foil tapes for adhesive is used to provide for repulpability of
electrostatic shielding of circuit boards and mi- the scrap paper. Masking tapes are used for
crowave components. painting of everything from small appliances to
railroad cars. For decoration and marking pur-
Automotive Industry. Tapes are used for poses, stenciling tapes are used. Many prod-
decoration of automobile bodies, to secure body ucts, such as tools, use tape to protect edges
side molding, and for electrical harnesses, but and surfaces during shipping. Reinforcing tapes
by far the largest use is for masking of surfaces are used in manufacture of wallets, handbags,
during painting. Because such masking tapes and shoes.
must resist solvents and baking cycle temper-
atures, as well as peel cleanly later, crosslinked
Labels and Decals
rubber-based adhesives are widely used.
Manufacture of label stock, the precursor as-
Corrosion Protection. Although steel un- sembly of backing or facestock, adhesive, and
derground transmission lines are often pro- release paper prior to printing and die cutting,
tected by coal tar or fusion bonded epoxy is similar to tape manufacture, but the proper-
coatings, a large volume of polyethylene tapes ties desirable for the facestock include print-
as well as some vinyl-backed tapes are used for ability as a major consideration. Labels earlier
corrosion protection. Pipes of large diameter, were classified as pennanent, removable, or
such as oil line pipes, are usually machine- freezer types but in tenns of applications are
wrapped in the field just prior to placement in usually categorized as industrial, data process-
the ground. The tapes are unusual in that the ing, or office retail.
backing is from 12 to 15 mils thick and the bu- Industrial labels produced as roll stock are
tyl-based adhesive is approximately of the same used for identification, description, and adver-
thickness. For the pipeline industry the rolls are tising of the product as well as pricing and con-
18 in. wide and contain up to 800 feet of tape. stitute by far the largest part of the label
There is a reduction currently in domestic pipe- business. Huge quantities of labels are con-
line construction but appreciable amounts of sumed by the medical-phannaceutical, toilet-
pipewrap are exported. ries-cosmetics, consumer, automotive, and
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 661

durable goods industries. In addition to pri- clean peel is essential; paper and polyethylene
mary labeling, secondary labels are applied to . are common backings.
advertise specials and to apply price tags. Ma- Reflective signs used outdoors for traffic con-
chines are available, for example for the food trol and direction signs indoors are mounted or
industry, to weigh an item and print weight, attached with PSAs.
price, and unit price on the label. Although An important article of commerce is wood-
secondary labeling is almost entirely PSA- grained vinyl sheet, used both for automotive
based, primary labeling of bottles, etc. com- interiors and station wagon bodies. The printed
petes with the much less expensive water-acti- vinyl is used for decorative attachment to many
vated glues. However, PSA label use is other surfaces.
expected to grow on the basis that PSA label Hospital usage of nontape PSA products is
application is less capital intensive and is much fairly extensive. Wound dressings of all kinds
more rapid. and sizes are held in place with PSAs. A rela-
Electronic data processing labels, printed by tively new product consists primarily of a
computers, are almost entirely with paper fa- transparent and elastomeric polyurethane film
cestock. Information of many kinds, including of high moisture vapor transmission rate coated
addresses, is printed on these labels. with adhesive. Among other uses the material
In the office category, a relatively smaller can be applied to the skin and surgical inci~ions
market, both blank and preprinted labels are made through it under sterile conditions. PSA-
used for inventory control, inspection, filing held devices are used for ostomy seals and for
and many other pUIpOses. In retail stores, the transdermal drug delivery; in the latter case the
stamping of prices on containers or packages drug may be contained in or go through the ad-
has been largely replaced by paper labels. hesive. Disposable electrocardiogram elec-
Although paper facestock dominates the la- trodes are held in place with PSAs. Used both
bel business, a sizable fraction of labels and in the hospital and at home are elastic bandages
decals utilize more expensive backings of held in place by the PSA coating on one side.
polyester and calendered PVC backings. Typ- Com pads and bunion protective cushions, sold
ical applications of the more resistant film in the drug store, consist of form-cut foam or
products are for labeling of shipping cartons moleskin pieces held to the skin by PSAs.
and for attaching nameplates and emblems for 3M's "Post-it" notes are pads of small paper
appliances and office equipment. Decals, hard sheets with a strip of adhesive along the top of
to distinguish from labels in terms of function, the back of each sheet. The small sheets of pa-
frequently have facestock that is transparent per which take ink or pencil inscriptions can be
film or brightly colored and reflective metal attached repeatedly to letters, reports, book
foils. Some transparent label stock is used to pages, etc., without tearing the paper on re-
cover and protect other labels or printing. moval. The adhesive consists of tacky, cross-
linked acrylic microspheres which make "point
contact" with the paper. See U. S. Patent
Other Products
3,857,731 (1974). This relatively new product
PSA-based products other than tapes and labels competes very successfully in spite of higher
fall in this category. Such products include cost with the older practices of attaching notes
sheet goods but also consist of individual items to paper by staple or paper clip. In the graphic
that utilize PSAs for attachment to another sur- arts office or shop a small amount of film sim-
face. Although not as large a business as tapes ilar in construction to the tapes described be-
or labels, the dollar volume of these products fore but of larger size is consumed; the film
is many hundreds of millions of dollars. For sheets can be cut into pieces of any desired size
many products a release liner is an essential or shape.
component. A fairly large market exists for decorative
A large market exists for PSA-coated sheets shelf and drawer coverings. Used to a large ex-
used to protect plastic or polished metal sur- tent by the homeowner, these vinyl sheets
faces during transportation. An adhesive for which can be cut to size from a roll offer pro-
662 HANDBOOK OF ADHESIVES

Table 10. Adhesive Thicknesses for whereas calendered coatings are generally over
Various PSA Products. 4 mils in thickness. Further, cloth or other po-
Approximate Coatings rous or nonsmooth backings often require a
Product Thickness (mils) heavier coating weight to compensate for the
Paper labels 1.'0
adhesive that penetrates into the backing. Table
Paper transfer tape 1.'0 10 gives typical adhesive thicknesses for var-
Plastic labels and decals 1.'0-1.5 ious products.
PVC finger bandage 1.5-2.'0
Silicone electrical tape 1.5-2.'0 REFERENCES
Diaper tape 1.5-2.'0
Polyester packaging tapes 2.'0-3.5 I. "Glossary of Terms Used in Pressure Sensitive Tape
Polypropylene strapping base 2.5-4.'0 Industry," Pressure Sensitive Tape Council (pSTC),
Acetate office tape 2.5-3.'0 Glenview, IL 1959.
Aluminum foil duct tape 2.5-3.5 2. Drew, R. G. (to 3M Co.), U.S. Patent 2,156,38'0
Printable computer tape 3.'0 (May 2, 1939).
Porous hospital tape 3.'0-4.'0 3. "Pressure Sensitive Adhesives Market," New York,
Trainers tape 4.'0-5.'0 Frost and Sullivan, 1984.
Velcro strip 5.'0-7.'0 4. Anon., Adhesives Age, 21(3}, 4'0 (1978).
Glass-reinforced polyester tape 5.'0-7.5 5. Kodama, Y., Proceedings, PSTC Technical Semi-
Film labels and decals 1i>.'O nar, 1983, p. 14.
Paper masking tape 6.'0-7.'0 6. Harlan, J. T., and Petershagen, L. A., "Thermo-
Coated cloth packaging tape 12.'0 plastic Rubber (A-B-A Block Copolymers) in Adhe-
Corrosion protection tape 12.'0-15.'0 sives," in "Handbook of Adhesives," 2nd Ed., I.
Skeist, ed., Chap. 19, p. 304, New York, Van Nos-
trand Reinhold Co., 1977.
7. Ulrich, E. W. (to 3M Co.), U.S. Patent Reissue
tection of surfaces while serving an aesthetic 24,9'06 (Dec. 13, 1960).
purpose when placed on furniture, shelves, etc. 8. Fries, J. A., Int. J. Adhesion, 2, 187 (1982).
Also used in the home are floor tiles coated with 9. Krug, K., and Marecki, N. M., Adhesives Age,
26(12}, 19 (1983).
a PSA. Most floor tile manufacturers make vi-
10. Sanderson, F. T., and Gehman, D. R., Proceedings,
nyl tiles which are backed with a thick PSA PSTC Technical Seminar, 198'0, p. 87.
coating, usually of an inexpensive composition 11. Groff, G. L. (to 3M Co.), U.S. Patent 4,396,675
based on something like atactic polypropylene (Aug. 2, 1983).
or EV A because the tile experiences little of 12. Milker, R., and Czech, Z., Adhaesion, 29(3}, 29
(1985).
shear forces after placement. Also available for
13. Blance, R. B. (to Monsanto Co.), U.S. Patent
flooring installations are carpet and wood 3,532,7'08 (Oct. 6, 197'O).
squares coated on the back with a PSA. 14. Knapp, E. C. (to Monstanto Co.), U.S. Patent
Lightly metallized polyester films are placed 3,284,423 (Nov. 8, 1966).
over windows to help reduce the sunlight pass- 15. Ley, D. A., and Burkhard, H. (to Amer. Cyanamid
Co.), U.S. Patent 4,522,973 (June 11, 1985).
ing through the window. Most of these solar 16. Sunakawa, M., Takayamo, K., Matsuoka, N., and
radiation control films are coated with a PSA Moroshi, Y. (to Nitto Electric Ind. Co., Ltd.), U.S.
for attachment. Patent 4,500,683 (Feb. 19, 1985).
The ubiquitous "Velcro" is often attached to 17. Milkovich, R., and Chiang, M. T. (to CPC Inter-
surfaces via PSAs. For example, car interior national, Inc.), U.S. Patent 3,786,116 (Jan. 15,
1974).
head liners are secured to Velcro pieces at-
18. Simoneau, E. T., G. E. Corp., private communica-
tached to the car roof by a shear resistant PSA. tion, 1986.
19. Gleichenhagen, P., and Wesselkamp, I. (to Beiers-
dorf AG), U.S. Patent 4,413,'082 (Nov. 1, 1983).
Adhesive Mass Thicknesses
2'0. Ohhaski, I., Mori, T., and Shimojo, S. (to Nippon
The weight or thickness of adhesive masses ap- Synthetic Chern. Ind. Co., Ltd.), Japanese Patent 76
06,236 (Jan. 19, 1976); C. A. 84, 165830t (1976).
plied to various backings depends both on the
21. Anderson, R. L. (to Anchor Continental, Inc.), U.S.
method of application and the intended use of Patent 4,049,601 (Sept. 2'0, 1977).
the product. Thus coatings applied by oven- 22. Lee, Y. S. (to B. F. Goodrich Co.), U.S. Patent
drying are generally thin, roughly 1-3 mils, 4,214,061 (July 22, 198'O).
 PRESSURE-SENSITIVE ADHESIVES FOR TAPES AND LABELS 663

23. Agarwal, P. K., and Makowski, H. S. (to Exxon Re- position of Peel Rate, Temperature and Molecular
search and Eng. Co.), U.S. Patent 4,359,547 (Nov. Weight for T-Peel Strength of Polyisobutylene," in
16, 1982). "Adhesion and Absotption of Polymers," Vol. 12A
24. Japan Atomic Energy Research Institute, Japanese L. H. Lee, ed., pp. 439-453, New York, Plenum,
Patent 81,167,716 (Dec. 23, 1981); C. A. 96, 1980.
144139g (1982). 43. Gent, A. N., J. Polym. Sci .• Pt. A-2. 9, 283 (1971).
25. Lenney, W. E. (to Air Products), U.S. Patent 44. Aubrey, D. W., and Sherriff, M., J. Polym. Sci .•
4,507,429 (Mar. 26, 1985). Polym. Chem. Ed.• 18, 2597 (1980).
26. Zisman, W. A., Adv. Chem. Ser., 43,1 (1964). 45. Aubrey, D. W., "Pressure Sensitive Adhesives-
27. Mitta1, K. L., Polym. Eng. Sci., 17(7),467 (1977). Principles of Formulation," in "Developments in
28. Toyama, M., and Ito, T., Polymer-Plast. Technol. Adhesives," Vol. I, W. C. Wake, ed., Chap. 5, p.
Eng., 2(2), 161 (1973). 140, London, Applied Science, 1977.
29. Dahlquist, C. A., "The Significance of Surface En- 46. Pressure Sensitive Tape Council, "Glossary of Terms
ergy in Adhesion, " in •• Aspects of Adhesion 5, " D. Used in Pressure Sensitive Tape Industry," 7th Edi-
J. Alner, ed., pp. 183-200, London, University of tion, 1976, PSTC, 1201 Waukegan Road, Glenview,
London Press, Ltd., 1969. Illinois 60025.
30. Fowkes, F. M., et aI., J. Polym. Sci., Polym. Chem. 47. Kaelbe, D. H., Trans. Soc. Rheology, 9(2), 135
Ed., 22(3), 547 (1984). (1965), Fig. 9.
31. ASTM DI878-61T, ASTMBull. No. 221,64 (1957). 48. Woo, L., "Study on Adhesive Performance by Dy-
32. Sherriff, M., Knibbs, R. W., and Langeley, P. G., namic Mechanical Techniques," paper presented at
J. Appl. Polym. Sci., 17,3423 (1973). the National meeting of American Chemical Society ,
33. Ref. 28, p. 179. Seattle, Washington, March 1983.
34. Dahlquist, C. A., "Tack," in "Adhesion, Funda- 49. Ref. 45, p. 132.
mentals and Practice, The Ministry of Technology, " 50. Particular specifications can be obtained for the is-
Chap. 5, p. 143, New York, Gordon and Breach, suing Federal Agency or Department or the Com-
1969. missioner, Federal Supply Service, General Services
35. Kraus, G., Rollman, K. W., and Gray, R. A., J. Administration, Washington, D.C.
Adhesion, 10(3),221 (1979). 51. Pressure Sensitive Tape Council, "Test Methods for
36. Bates, R., J. Appl. Polym. Sci., 20, 2941 (1976). Pressure Sensitive Tapes," 7th Edition, 1976, Ap-
37. Aubrey, D. W., "Viscoelastic Basis of Peel Adhe- pendix B, p. 11. See Ref. 46 for address.
sion," "Adhesion 3," K. W. Allen, ed., Chap. 12, 52. ASTM D 2979-71 (Reapproved 1982), "Annual
pp. 191-205, London, Applied Science, 1978. Book of Standards," Vol. 15.06 (1983), p. 254.
38. Yarnamato, S., Hayashi, M., and Inoue, T., J. Appl. 53. Hammond, Jr., F. H., "Polymer Probe Tack
Polym. Sci., 19,2107 (1975). Tester," ASTM Special Technical Publication No.
39. Gent, A. N., and Hamed, G. R., Polym. Eng. Sci., 360, 1964, pp. 123-124.
17, 462 (1977). 54. Johnson, J., Adhesives Age, 26(12), 34 (1983).
40. Bright, W. M., "The Adhesion of Elastomeric Pres- 55. Ref. 52, ASTM D 3121-73 (Reapproved 1979).
sure-Sensitive Adhesives: Rate Processes," in 56. Ref. 51, Test Method No.6.
"Adhesion and Adhesives, Fundamentals and Prac- 57. Ref. 51, Test Method No.5.
tice," J. Clark, J. E. Rutzler, Jr., and R. L. Savage, 58. Chang, F. S., Rubber Chem. Technol .• 20, 847
eds., pp. 130-138, New York, John Wiley and Sons, (1957).
Inc., 1954. 59. Johnson, J., Adhesives Age, 11(4),20 (1968).
4Oa. Williams, M. L., Landel, R. F., and Ferry, J. D., 60. Ref. 51, Test Method No.1.
J. Am. Chem. Soc., 77, 3701 (1955). 61. Ref. 51, Test Method No.7.
41. Aubrey, D. W., Welding, G. N., and Wong, T., J. 62. Ref. 51, Test Method No. 14.
Appl. Polym. Sci., 13,2193 (1969). 63. Ref. 51, Test Method No.8.
42. Tsuji, T., Maskuoka, M., and Nakao, K., "Super-
 39
Bonded Abrasives
WILLIAM F. ZIMMER, JR.
Consultant to
The Norton Company
Punta Gorda, Florida

Modern civilization would not be possible and amount of abrasive and the choice and
without bonded abrasive products. By the year amount of bond. Since this is a discussion of
1825 sand, emery, and even diamond were adhesives, other sources should be consulted
being bonded together with shellac for use in for information about abrasives. 2
abrasive sticks and wheels. Rubber bonded In a bonded abrasive product the prime role
wheels were introduced in 1857, the sodium of the bond is that of a structural adhesive. The
silicate and the vitrified bond just after the Civil function is to hold the abrasive particles in some
War,l and the phenolic resin bond in 1923. The desired spatial relationship and to provide me-
metal bond was introduced for diamond wheels chanical strength and integrity to the compos-
in 1940. ite. Other functions may be designed into the
Bonded abrasive products have a three-di- bond, however; it is upon these other functions
mensional structure consisting of abrasive par- that the complexity of bonded abrasive tech-
ticles, a bonding agent, and porosity. Each of nology depends. The bond may be required to
these three elements may be varied in amount provide a strong, tough, thermally resistant
in a precisely controlled fashion to alter the be- wheel for very difficult grinding jobs when rug-
havioral characteristics of the abrasive article ged durability is needed. Again, it may need to
in predictable ways. Bonded abrasive articles be friable or thermally sensitive or weak for free
may take the form of sticks, wheels, wheel seg- and fast cutting action, good finish, or low me-
ments, and variously shaped cylinders, cones, tallurgical damage to the work. It may need to
balls, etc., to which are affixed metal rods for resist water or alkaline coolants.
insertion into chucking devices of power tools. In the grinding of many metals, reaction of
A bonded abrasive article, being three-dimen- the freshly cut metal surface with air forms an
sional in concept, operates sacrificially during oxide layer which can effectively prevent adhe-
use, with retention of sharpness until all the us- sion of the metal surface to the abrasive, to the
able portion has been worn away. In contrast, bond, or to itself. This facilitates the abrasive
a coated abrasive product must be discarded process. Substances which can react more rap-
when its single abrasive layer loses its sharp- idly with fresh metal surfaces than does air, or
ness. which can melt and cover the surface with a
protective layer, are called active grinding aids.
The most common ways such substances are
THE ROLE OF THE BOND
used is in the oils or water-based coolants for
The grinding quality of a bonded product in any wet grinding and as impregnants or fillers in the
given application is determined by the choice bond of the abrasive article for dry grinding.
664
 BONDED ABRASIVES 665

Through careful selection of fillers and filler quirements for the finished part of dimensional
combinations, the grinding quality of the accuracy, finish, and surface condition of the
bonded product may be greatly improved. Fill- part. This information leads to the selection of
ers known to be effective are cryolite, fluor- the grinding wheel composition which includes
spar, fluoborates, sulfur, iron disulfide, kind, size, and shape of abrasive; volumetric
polyvinylidene chloride, polyvinylchloride, tin, proportions of abrasive, bond, and porosity;
and compounds of lead and antimony. Active bond composition; fabrication process; and af-
fillers cannot be incorporated into metal or vi- tertreatments and/or mechanical inclusions.
trified bonds directly because of the nature of. Rubber, shellac, and alkyd resin bonds are
these bonds and their high temperature pro- inefficient. However, they are used for fixed
cessing. However, wheels which contain ac- feed, fixed force, and cutoff operations on ap-
cessible and interconnecting porosity may be plications where there are requirements for very
impregnated after manufacture with various good finish, no metallurgical damage to the
materials to strengthen them, to provide lubri- part, where only limited power is available, or
cation, or to provide active grinding aids. Thus perhaps very fast cutting is required.
epoxy resins, fats, waxes, graphite, and sulfur Phenol-formaldehyde (resinoid) bonded
are frequently incorporated into vitrified wheels wheels represent by far the largest part of or-
and occasionally into organic bonded wheels. ganic bonded products. These are standard for
Organic bonds such as phenolic lend them- dry, rough, fixed force, or constant power
selves conveniently to the incorporation of par- grinding in foundries and steel mills. Here high
ticulate active fillers such as iron pyrite, speeds are the rule and toughness and durabil-
polyvinylidene chloride, cryolite, and potas- ity are required. Speeds of 16,000 surface feet
sium compounds such as potassium sulfate or per minute are common. Resinoid wheels are
potassium fluoborate. widely used in cutting-off operations, where
strength with flexibility (break resistance) is re-
quired. The trend toward higher speeds has
APPLICATION
been more rapid in cutoff than in any other type
The widespread commercial use of both coated of grinding. There is also a trend to substan-
and bonded abrasives has been very dependent tially higher rotational speed and grinding
on machine development, although these tools speeds in drill grinding and camshaft grinding.
evolved on the basis of hand methods which Vitrified bonded wheels make up roughly half
are still in use. A grinding wheel (or a coated of all those produced, although the recent trend
abrasive belt) must be mounted on a machine, toward higher speeds is causing some shifting
however simple or complex, in order to have it toward resinoid bonds. Vitrified bonds are
perform its basic function. standard for most fixed feed operations because
Existing wheel grinding machinery ranges of their dimensional stability and predictabil-
from low or even fractional horsepower and ity, their utility in wet environments, their free
hand operation on light equipment such as a cutting nature, and their friability, which al-
dental drill or a 1~-3 horsepower portable lows them to be readily shaped or "dressed"
grinder up to roll, centerless, or slab grinders to maintain grinding geometry or sharpness.
powered by as large as 200-300 and even up The brittleness of these bonds and their heat
to 500-600 horsepower motors. Paper pulp shock sensitivity precludes their use in many
grinders may be powered by motors as large as applications such as cutoff.
10,000 horsepower. The use of metal bonds is reserved for the
Grinding operations may be sorted into four most difficult grinding operations, where max-
main categories: fixed feed, fixed force, con- imum strength, durability, and thermal resis-
stant power, and cutting off. The choice of bond tance is required and exotic abrasives such as
type and wheel specification for a given oper- diamond are justified as the abrasive. Most of
ation is determined by the specifics of the op- this is fixed feed operation. Metal bonded cut-
eration, the available power, speed, wet or dry off wheels, represented by metal bonded dia-
environment, and work material; and by re- mond segments brazed to the periphery of a
666 HANDBOOK OF ADHESIVES

steel disk, are used for very difficult cutting op- liquid resins or monomers, rubbery or plastic
erations, especially on nonmetallics such as ce- intennediates, and particulate solid resins. Ad-
ramics, carbides, and cennets, stone, and ditives such as catalysts, accelerators, plasti-
reinforced composites. cizers, coreactants, and processing aids are
frequently included, and various mixing tech-
ORGANIC BONDED PRODUCTS niques are used both for bond and mix prepa-
ration. Usually the main bond components are
The organic bond grouping includes a number
blended first, after which the abrasives and
of subsystems based on very different polymers
bond are combined into a mix for molding.
and curing mechanisms. Th~re is little use in
In a typical procedure for making a mix, the
the bonded abrasive industry for bonds of a
abrasive is wetted in a mixer with a liquid wet-
thennoplastic nature, partly because of an un-
ting agent which may be either a coreactant, a
desirable tendency for thennoplastics to smear
plasticizer, or a solvent for the resin. T~en a
and also because of the superior ability of ther-
powdered resin bond is added and the mIxture
mosetting systems to resist time dependent
stirred so that the powder may be coated onto
changes such as creep and environmental stress
the wetted abrasive particles to fonn a dry mix-
crazing.
ture. The degree of pickup of the powder onto
Commercially available organic bonds in-
the wetted abrasive granules is detennined by
clude ones based on phenolic and modified
the proportions of liquid and powder used. Su~h
phenolic resins, alkyds and polyesters, shellac,
a mix is relatively free-flowing and can be dIS-
polyurethanes, epoxies, and rubbers such as
tributed readily and uniformly in a cold
natural, synthetic natural, GRS, Neoprene, and
compression mold.
acrylics. Further, polyimide bonds find use in
Plastic or rubbery ingredients for bonds re-
diamond and cubic boron nitride products.
quire more vigorous mixing than simpl~ stir-
These bonds provide a very wide range of
ring can provide. Kneaders, banbu.ry ml~ers,
composition and of thennomechanical proper-
or roll mills are used to blend bond mgredlents
ties. The relatively low curing temperatures
and to prepare the abrasive mix for such bonds.
range up to 225°C, except for those few bonds
Mixes which cannot be spread or packed into a
containing refractory polymers like the poly-
mold readily may be rolled out into sheets,
imides, which may reach approximately
much like the sheeting of rubber compounds,
400°C. These relatively low curing tempera-
from which product shapes may be cut. Some
tures pennit inclusion of thennally sensitive
few bonding systems are liquid, and these may
materials which could not survive the process-
be poured into molds with or without vacuum
ing conditions for metal bonds (650°C) or vi-
treatment to remove bubbles.
trified bonds (up to 1250°C). Moreover, the hot
Compression molding to thickness, to pre-
versus cold strength of cured organic bonds can
determined pressure, or to closed mold is the
be manipulated through choice of composition
main molding method for most products. Mixes
and curing conditions in such a way that grind-
for cold molding must be fonnulated to provide
ing properties can be varied differently from
greenware strength for product between mold-
mechanical strength. Additionally, the higher
ing and curing and to allow the porous green
strength obtainable with organic bonds allows
wheel to be cured without becoming distorted
the use of organic bonds at very high and effi-
through evolution of volatiles which may cause
cient centrifugal speeds not economically or
swelling or through slumping because of a bond
technically feasible for either vitrified or metal
which is too low in viscosity at temperatures
bonds.
before geometry is fixed by the cure.
Stronger and more dense products can be ob-
Organic Fabrication Methods
tained by hot compression molding, usually in
Organic bonds contain varying amounts of a flash mold. For phenolics, a press platen tem-
finely divided (usually mineral) filler dispersed perature of about 165°C is usually ~sed. Such
in a thennoset polymer matrix. The matrix is a hot molding cycle can be used eIther to fix
derived from combinations which may include the wheel geometry into a partially cured con-
 BONDED ABRASIVES 667

dition for subsequent oven cure, or it can be find use in resins for phenolic bonds, the back-
used to provide the sole curing cycle for the bone of the phenolic abrasive bond system is
product. the phenol-formaldehyde reaction product,
In recent years there has been an industry either as a resole or as a powdered novolak
trend to simplify the production of abrasive crosslinked with hexamethylene tetramine. For
products and to reduce production costs through maximum strength and rigidity over a broad
development of liquid casting systems. Com- temperature range, this polymer system has lit-
mercial processes and products have been de- tle competition. No other system has been able
veloped based on polyurethane bonds and more to match its structural and thermomechanical
recently on epoxy bonds. Much remains to de- properties on a cost/performance basis.
velop the potential of such liquid abrasive The high compatibility of both the phenolic
bonds for the abrasives industry. resin intermediate and of the crosslinked ma-
terial with a wide range of organic and poly-
meric substances has permitted further wide
Bond Characteristics
variation to be built into bonded abrasive prod-
Shellac. Shellac bonds are not the form of ucts. Materials such as epoxies, various rub-
shellac most people know as a solvent-based bers, polyvinyl chloride, polyvinyl formal, or
coating. Shellac bonds for abrasive products polyvinyl butyral may be combined with the
have been subjected to extensive baking for phenolic material either in the resin kettle or
long time (days) in order to convert the shellac later in preparing the abrasive bond or mix.
by ester condensation reactions into a strong, Such modifiers can provide greater toughness
tough, relatively water resistant bond which has and water resistance and can impart a softer
special thermally sensitive properties. This grinding action and higher bond quality while
toughness, good adhesive properties, and high rotational strength and break resistance are re-
thermal sensitivity provides a very fast and free- tained.
cutting action. This gives a high quality of cut,
absence of heat damage to parts ground, and Epoxy Bonds. During the past twenty years
high luster finish unmatched by any other bond or so numerous companies have developed
system. Its fast wearing characteristics and lim- commercial bonded abrasive products based on
ited strength range are causing it to be replaced the epoxy resin system. Cold or hot pressed
by rubber and other organic bonds. products based on powder mixes have been
developed from powdered epoxies used in
Rubber. Rubber products combine many of powder coating technology. Examples are
the cutting characteristics of shellac with the powderable resins based on bisphenol-A and on
greater strength, water resistance, and heat re- brominated bisphenol-A. Other examples are
sistance available in the rubber bond. Most products prepared by casting of liquid epoxy
rubber bond systems are of the high sulfur hard mixtures of abrasive, fillers, and sometimes
rubber type. However, physical properties of bond-softening agents such as plasticizers and
the rubber bond can range from soft and elas- hollow materials such as polystyrene beads or
tically conformable to high modulus with high phenolic or glass microballoons. Liquid casting
tensile strength. These differences can be of abrasive wheels seems particularly attractive
achieved through appropriate choice of rubber for wheels of large or complex shape difficult
types, sulfur content, coreactants, and fillers. to form by compression molding. Such liquid
The rubber system lends itself readily to the in- systems also seem of special attraction for very
corporation of active grinding aids either as fill- small or complex shaped wheels containing
ers or as integral components of the polymer very fine abrasives. Such products could be
structure (such as organic halogen and sulfur made in reactive injection-molding-type oper-
compounds) . ations.
The variety of both liquid and powderable
Phenolic. Although substituted phenols and materials available and their wide range of
agents other than formaldehyde occasionally cured properties along with relatively low costs
668 HANDBOOK OF ADHESIVES

make epoxy resins attractive for adaptation for VITRIFIED PRODUCTS

use as abrasive bonds. The epoxy bond should
be viewed as generally lying above shellac, Vitrified bonds are very widely used in the
alkyd, and rubber in bond strength and heat re- metalworking industry, especially for machin-
sistance but below that offered by the phenolic ery manufacture. The basis for this glass type
bond system. bond is a fusible clay, feldspar. 3 Refractory
materials and fluxing agents are added to pro-
duce the desired composition. The dried clay
Specialty Bonds. The polyurethane system and other bond ingredients are pulverized,
can be formulated over a wide range of cross- screened, and blended to form the dry bond.
linking densities and mechanical and thermal This is added to the water wetted abrasive in a
properties. Little use has been found for this mixer to coat each abrasive particle with the
system in bonded abrasives. A bond based on bonding medium. The resulting mix is pressed
this system was developed perhaps twenty years cold in compression molds to form the basic
ago and found some commercial success in the wheel shape.
rough grinding of large milling rolls, where To provide mechanical strength sufficient for
deep cuts, high wheel speeds, and high stock handling of the unfired wheels, various organic
removal rates are found. Some usage was also polymeric materials may be used to wet the ab-
developed in other high speed grinding'opera- rasive, such as starch paste, dextrin, and urea-
tions. However the business was not a com- or phenol-formaldehyde resin. During firing,
mercial success, and such products are no these organic substances decompose to yield
longer available. carbonaceous char residues which provide tem-
Other bond systems have been based on al- porary binding strength for the wheel until the
kyds, unsaturated polyester resins, and poly- glass bond sinters or melts and develops its own
vinyl alcohol. Although such bonds can be for- vitreous strength. These residues must then
mulated to be strong, they have usually found bum off to leave no unwanted discoloration or
application where a very mild or free-cutting deterioration of the bond.
action is required or where an extremely fine After air drying, the cold pressed green wheel
abrasive is required. Examples are knife grind- is fired in a kiln, either batch or continuous, to
ing, hypodermic needle pointing, the finishing about 1250°C for the appropriate time.
of rotogravure and milling rolls, and the cutting The original vitrified bonds tended to have a
off of very difficult-to-grind materials. limited range of firing conditions under which
The great variety of high performance poly- satisfactory product could be made. The cur-
mers now available, especially those designed rent trend is to make bonds from glasses which
for use at temperatures beyond the range of or- have a broader firing range and which result in
dinary organic materials, has encouraged much greater uniformity in the product.
effort in evaluation of these for bonded abra- Silicate bonded wheels, wherein the bond
sive utility. Of these, only the polyimide fam- consists essentially of sodium silicate with fill-
ily has found its way into abrasive usage. The ers, are mixed, spread into molds, and tamped
polyimides, polymaleimides, and polyamide- to compact. These are fired at considerably
imides have many useful properties such as lower temperatures (about 260°C) and are not
high strength retention at high temperatures, as strong as vitreous bonds. They are used when
toughness, resistance to a wide variety of sol- very free-cutting action is required and when
vents, and abrasive resistance or lubricity. Be- the machine conditions (such as low rotational
cause of high cost and difficult fabrication speed) permit. Very large wheel diameters can
requirements, these materials have found only be made with such a bond system. The silicate
very specialized application where their unique bond has been replaced largely by stronger and
properties can be used to advantage. Two such more versatile products.
applications are polyimide bonded diamond The oxychloride bond, a mixture of magne-
wheels used in cam and in drill flute grinding. sium chloride and magnesium oxide, has had
 BONDED ABRASIVES 669

some minor success. This bond sets cold and perature during use, so a water resistant and/or
requires no bake. Like the silicate bond, this heat resistant cement may be chosen.
system provides a soft, free-cutting action. Probably the largest adhesive operation for
However, it is not resistant to attack by cool- bonded products is the cementing of abrasive
ants, and this has seriously restricted the utility wheels or segments, especially vitrified bonded
of this bond system.4 products, to a steel plate for mounting on spe-
cially adapted grinders. Such an adhesive joint
may need to withstand complex thermome-
METAL BONDED PRODUCTS
chanical and environmental stresses during use.
Metal bonded wheels are made nearly exclu- One common method for this adhesive appli-
sively with diamond for very severe applica- cation has been to use a rubbery bond based on
tions where high mechanical strength is a rubber compound. Such bonds have been re-
required. Electroplated cubic boron nitride placed largely by the use of resilient cements
products are also finding applications, espe- based on epoxy resins. The epoxy resin system
cially of very difficult to grind and very hard can be formulated to provide very elastic bonds
steels. either with use of an external plasticizer or,
Metal bonded products are produced by mix- preferably, through internal plasticization with
ing the abrasive with powdered metal and cold epoxy or hardener components. For plate
pressing the mix into the desired shape, after mounting of wheels when a very rigid and/or
which it is sintered in an inert atmosphere. Al- heat resistant bond is required, specially for-
ternatively, the abrasive are mixed with metal mulated filled phenolic adhesives can be used.
powder and hot pressed. Products are even pre- Both epoxy and phenolic adhesives, when
pared by cold pressing the diamond and metal properly formulated and cured, can provide ad-
powder mixture and subsequently infiltrating, hesive bonds superior to the bond in the bonded
with molten metal. Another method is electro- abrasive product itself.
plating, wherein the abrasive is affixed to a The second largest use of adhesive on fin-
metal mandrel by means of a metallic layer ished product is probably that for mounted
electroplated around the particles of abrasive to wheels and abrasive points. Small abrasive
lock them in place. The bonds employed vary shapes are frequently fitted with metal man-
from soft bronze through steel bonds to very drels for mounting in chucks like a drill bit.
durable cemented carbide bonds. Organic-type Although organic bonded materials may have
adhesives have virtually no use in metal bonded metal mandrels molded in, the high firing tem-
abrasive products except for some applications peratures for vitrified products preclude this
for attaching diamond-containing sintered metal technique, and the metal mandrels must be in-
rims to either metallic or nonmetallic cores. serted and cemented in place afterward. These
products may be exposed to severe mechanical
abuse and high temperatures during use. Cop-
MISCELLANEOUS ADHESIVE USES
per oxide-phosphoric acid cement has been
The bonded abrasive article, after it is formed used widely here. Other cements have included
and fired, may still be incomplete or unusable low melting alloys, phenolic resins, and epox-
in that state. The use of adhesive materials to ies.
bond such articles together or to other materials Pulpstones are used in the paper industry to
is common, and a wide variety of adhesive sys- grind wood into pulp and are of a large diam-
tems have been used. eter (to 6 ft). Once installed, they must provide
Such adhesives are frequently room temper- years of trouble-free service in a hot aqueous
ature curing, not only for simplicity of use but environment and so must be sturdily con-
also because the adherends may be of very dis- structed. Vitrified segments, each containing a
similar materials such as vitrified bonded ab- metal bolt cemented in place with a phenolic
rasive and steel. The product may be used in a resin, or perhaps an epoxy resin, are arranged
wet environment or be exposed to high tem- into an annular ring affixed to a metal rein-
670 HANDBOOK OF ADHESIVES

forcement cage and separated from one another Grinding wheels with accessible porosity
with a layer of resilient material, such as a rub- may be impregnated with liquid curable resins
ber compound. Phenolic resin and epoxy com- to strengthen the product or to reduce abrasive
pounds have also been used for this purpose. action on machine mounts. Such an impregna-
After the abrasive ring has been fabricated, the tion of a vitrified wheel for example with an
wheel is completed by casting a concrete core epoxy resin can greatly increase not only the
inside. compressive strength but also the rotational
Room temperature curing systems such as burst strength of the wheel and allow higher
unsaturated polyesters and epoxies are fre- operating speeds to be specified.
quently used to cement threaded bushings into
wheels. Inorganic materials such as litharge and
sulfur cements and low melting metals are used REFERENCES
for anchoring and bonding operations.
1. Pinkstone, William G., "The Abrasive Age," Lititz,
Injection molding compounds are occasion- Pennsylvania, Science Book Service, Sutter House,
ally used to form bushings and mounting pads 1974.
on abrasive wheels. 2. Coes, L., Jr., "Abrasives," New York, Springer-Ver-
Rubber and cellulosic-type solvent cements lag, 1971.
3. Houghton, P. S., "Grinding Wheels and Machines,"
are used for attaching gaskets and blotters.
p. 16, London, E. & F. N. Spon Ltd., 1963.
Water based adhesives such as sodium silicate, 4. Lewis, Kenneth B., and Schleicher, William F., "The
starch, dextrin, and latex are used for a variety Grinding Wheel," 3rd Ed., Cleveland, Ohio, The
of applications such as labeling. Grinding Wheel Institute, 1976.
 40
Coated Abrasives
ANTHONY C. GAETA
Carborundum Abrasives Co.
Niagara Falls, New York

A coated abrasive consists of a backing sub- surface, while bonded abrasives are designed
strate coated with an abrasive mineral (grit), for total cut and breakdown, thus exposing new
which is bonded to the backing using an ad- abrasive particles to continue the grinding pro-
hesive system. There can be several layers of cess.
adhesives used in the manufacturing process.
The primary adhesive coat, called the make HISTORY
coat, is used to bond the grain onto the back-
ing. A top coat of adhesive is applied after the The first coated abrasive made goes back to the
make coat and grain coating. This is called the 13th Century, when the Chinese used crushed
size, since it is used to reinforce the grain and seashells as an abrasive grain and bonded them
insure an adequate abrasive bond. Reactive fill- to parchment paper with natural gums. I Other
ers are also incorporated into the size formu- forms of coated abrasives were made by apply-
lation to enhance the grinding performance of ing abrasive minerals to animal skins, leather,
coated products. etc., and as time passed, animal hide glues and
The backing substrate, especially if it is fin- varnishes were used to bond grain to paper and
ished cloth, may also contain several layers of cloth.
adhesives and fillers, which are used to impart Today's coated abrasives have advanced
to the backing its desired body and other re- from a simple smoothing and polishing func-
quired properties. tion to complex heavy stock removals where
Coated abrasives are made in a wide range rates of 5-7 in. 3 fmin per linear inch of belt
of grit sizes, ranging from as coarse as 16 grit width are not uncommon, thus rivaling tradi-
to very fine micron and submicron sizes. They tional grinding wheel applications. Since mod-
are also made available in a wide array of dif- ern backing designs have been improved to
ferent shapes and sizes. The most common in- keep pace with advancements made in abrasive
cludes sheets, disks, rolls, flap wheels, and materials, coated abrasives are now able to
belts. compete effectively in some of today's most
Coated abrasives are different from bonded demanding abrasive applications.
abrasive wheels in that coated products have Modern day abrasive grits have also pro-
abrasive grain coated on their surface, as op- gressed from natural minerals to synthetic
posed to bonded products, which are com- abrasives, which include alumina-zirconia and
prised of mainly abrasive grain bonded together ceramic aluminum oxide abrasives. Conven-
to form the actual shape of the product. Coated tional aluminum oxides are still widely used;
abrasives are designed to be used only on their however, these new abrasive materials are

671
672 HANDBOOK OF ADHESIVES

much tougher and greatly improve the ability uct needs to meet increasingly tougher appli-
to effectively abrade large amounts of material. cations or special finishing requirements.
Silicon carbide still is widely used in the tra- Specifically, of the various backing types,
ditional applications where razor-sharp hard- greige goods (raw cloth substrate from the cloth
ness is required. mill) can produce many different types of fin-
In order to take advantage of the new abra- ished cloths. Furthermore the same greige
sive grit materials, new and improved bond goods may be finished differently to create a
systems had to be developed. Subsequently, backing with completely unique properties.
adhesive systems have also come a long way, Backings may also be classified by their weight
progressing from fish and animal hide glues to and the type of weave used to make them. For
urea-formaldehyde resins, epoxies, phenolic, example, a backing could have a plain, twill
and radiation-curable systems. This evolution (drills and jeans), sateen or knit construction.
has placed a continuing demand on the adhe-
sive systems used in the manufacturing of
Cloth Filling Adhesives Systems
abrasive products.
Adhesives used in cloth filling range from plain
BACKINGS animal hide glues and starch based systems to
complex thermoset and radiation-curable sys-
Types of Backing
tems. Extensive use is also made of latex sys-
Coated abrasive products can be made on a tems of various polymer and copolymer blends,
wide variety of backing types. There are five which impart to the backing good adhesion and
general groups of backings used in the coated flexibility not obtainable with glue- or starch-
abrasive industry: paper, cotton cloth types, based systems. Typical latex systems used for
vulcanized fiber, synthetic fabrics and films, cloth filling are based on synthetic rubbers, vi-
and any combination of these laminated to- nyls, or acrylics. These systems are often mod-
gether. Generally speaking, paper-type back- ified with fillers such as calcium carbonate and
ings are used when strength and toughness are thickening agents to give the backing its desir-
not required, but low cost is essential. Cotton able properties.
cloth backings are used where greater strength Radiation-curable resins are also finding use
and heat resistance are required and cost is as cloth filling systems. Both ultraviolet- and
again a significant consideration. Vulcanizedfi- electron-beam-curable systems are used today
ber backings are used for disk application and offer some unique properties. One advan-
where the backing must be stiff and have good tage of these systems is that they are energy
strength in all directions. Typical fiber that is efficient, that is, they require minimal amounts
coated is 0.030 in. (30 mils) in thickness and of energy to be polymerized. Another impor-
is used primarily for portable grinding appli- tant advantage is that radiation-curable resins
cations. Synthetic fabrics are usually polyester, are in effect 100% solids. By using reactive
polyester-cotton, rayon, or polyester-nylon monomers (instead of solvents) as diluents to
blends, while films are usually polyester. The cut viscosities of the base oligomers, airborne
synthetic materials have the greatest physical emissions can be virtually eliminated. A third
strength and toughness, and are used in the advantage is that these systems cure immedi-
most demanding applications where perfor- ately after exposure to the radiation, requiring
mance is the most important consideration. The no heat. However, reactions are exothermic
use of these backing materials requires that the during polymerization.
end user have good control over his or her op- The most commonly used radiation-curable
erations, so that these premium products are resin systems for cloth finishing are based on
utilized to their fullest. The last group involves acrylated epoxies, acrylated urethanes, and
combination of the above in order to meet spe- patented hybrid systems which form interpe-
cial requirements that none of the other back- netrating networks. 2 Mixtures containing 25-
ings would meet alone. Usually these 40% phenolic or other heat-curable resins are
combinations are used where the abrasive prod- particularly useful.
 COATED ABRASIVES 673

ABRASIVES grit is incorporated into the adhesive system and

slurry coated onto the backing. However, this
Abrasive Types
technique is restricted to very fine particle sizes
Modem day coated abrasives utilize a wide and is used only to a limited extent.
range of abrasive minerals. Typical abrasive
grits are: emery, crocus, garnets, fused white Gravity Coating. Grain may be delivered to
aluminum oxide, light brown and brown alu- the backing during the coating process by using
minum oxides, high-temperature aluminum ox- a vibrating tray, or some sort of feed rolls, in
ides, zirconia alloy abrasives, ceramic oxide which the abrasive is dropped by gravity onto
types, and silicon carbides. These abrasives the make adhesive. This method distributes
vary considerably in cost and physical proper- grain in a random manner, with no particular
ties. orientation. The process is easy to perform and
is primarily used for applying a base coat of
Versatility of Various Grains grain before the electrostatic process.
Each abrasive type has its own area of prime
Electrostatic Coating. This is the most
importance. For example, silicon carbide is
widely used method for placing abrasive onto
used to grind glass, wood, and certain metal
the web of a coated abrasive. The abrasive is
alloys, but is generally not recommended for
applied to a moving grain belt, which brings
ferrous alloy applications, except for certain
the grit into an electrostatic field. At the same
white cast irons. Alumina-zirconia abrasives,
time the backing is passed through the field,
on the other hand, can be used on a broad range
above the abrasive. The grain particles pick up
of materials.
an electrostatic charge and are propelled away
Generally, during a grinding operation the
from the grain belt onto the backing. This pro-
abrasive grains are exposed to temperatures as
cess leaves the abrasive standing upright, per-
high as the melting point of the material being
pendicular to the backing. The interesting fact
ground (-600-IS00°C). For example, wood
here is that the sharper end of the grit is left
products do not melt, so usually we are looking
pointing up away from the web. This fact is
for an abrasive which is sharp and tough, and
one of the primary reasons that coated abra-
will retain a good cutting edge. Metals and their
sives work so well, because the sharpest part
alloys pose a different problem: because of the
of the grain is exposed to the workpiece, as op-
high temperature involved during grinding, the
posed to grinding wheels in which the grain is
abrasive grains tend to react with the metals,
randomly oriented.
the atmosphere, and the adhesive system.
Therefore, one of the primary criterion for se-
BOND SYSTEMS
lecting an abrasive type is its reactivity with the
material being ground. The most common types of adhesives used to-
Abrasive grits are selected to give the best day in coated products are hide glues, var-
performance under specific operating condi- nishes, urea-formaldehyde, radiation-curable,
tions. In addition to the type of material being and resole phenolic resins. Depending on the
ground, other factors must be considered when severity of the applications, the make and size
selecting an abrasive type: operating speed bond formulations are modified to suit the job
(sfpm), in-feed rate and pressure, whether at hand. Combinations of the above systems are
grinding is being done wet or dry, machine used to achieve special properties which may
types, workpiece configuration, etc. give certain products economic and perfor-
mance advantages.
Methods of Application
Essentials of Adhesive Systems
The abrasive grits may be applied to the back-
ing using gravity coating, electrostatic coating, Glue binders are used primarily for paper and
or both. In some cases the abrasive material some cloth products that are inexpensive, light
may be applied by a third method, in which the duty in application, and are used dry. The an-
674 HANDBOOK OF ADHESIVES

imal glues used are obtained in a dry granulated phenol) resin. Phenolic systems require tht:r-
form, and are prepared in water. Hide-based mal curing, which takes place by polycon-
animal glues are the most widely used in the densation reaction at temperatures in the neigh-
abrasive industry, and may be modified with borhood of -200-250°F. These resins can be
fillers, plasticizers, dispersing agents, etc. B-staged in the maker and sizer ovens prior to
Other glues such as bone and fish generally do final curing, or taken to complete cure in spe-
not have the jelling properties that hide glues cially designed sizer ovens.
possess. Radiation-curable resins also go into make
Glues are easy to apply, and reach a jelled and size formulations. One big advantage of
consistency on cooling slightly from their these resins is that they cure almost immedi-
heated state during application. This fast jell- ately through a free radical mechanism after
ing aids in anchoring the grain in place, and being exposed to high energy radiation. In the
provides abrasive products with good grain ori- case of ultraviolet curing systems, photoinitia-
entation. Animal glues are economical to use, tors are used to enhance the generation of free
which is of prime importance on most paper radicals, which in tum allow the reaction to
products. propagate, thus polymerizing the resins. Elec-
Varnishes are used extensively in the manu- tron beam curing methods do not require initi-
facturing of waterproof paper products. These ators, because the high energy electrons
products require waterproof bonds with some generate free radicals on being absorbed by the
degree of flexibility. The spar varnishes used resin itself. Curing of radiation curable systems
today are primarily phenolic-modified tung oils. is usually carried out under nitrogen. If these
They are typically made by blending approxi- resins are irradiated in air, curing is inhibited
mately equal parts of tung oil with a resole phe- on their surface because atmospheric oxygen
nolic resin, along with dryers, usually cobalt terminates the free radical mechanism by the
and manganese naphthenates. Varnish cures by formation of peroxidic structures which are
oxidizing with atmospheric oxygen, which more stable than the radicals generated by ir-
causes the coating to polymerize. radiation, thus ending the propagation.
Urea-formaldehyde systems are used in Typically, coated abrasives -are manufac-
products that require more demanding proper- tured on making machines which employ fes-
ties. These systems are used on both paper and toon curing ovens, which require large amounts
cloth products. Urea bonds impart better heat of floor space. Disadvantages of festoon curing
resistance and more strength than either glue or areas include the formation of stick marks or
varnish adhesives. The urea resins are usually defects caused by suspension rods, and binder
obtained in a liquid form, and are catalyzed by and abrasive migration. Radiation-curing sys-
additions of ammonium chloride or other acid tems eliminate the need for festoon curing
catalyst. The fillers must not interfere with the ovens and the defects associated with their use.
acid catalyst. Typically, calcium carbonate is Because of their rapid curing, there is no need
avoided, but other fillers such as calcium sul- to hang coated material on rack sticks in long
fate are acceptable. ovens to facilitate curing.
Phenolic resins are used in paper-, cloth-, and Another advantage of radiation curable sys-
synthetic-backed products. These bond sys- tems is that they improve the sharpness of the
tems give the greatest strength and heat resis- abrasive product by curing immediately, thus
tance compared to conventional adhesives. anchoring the grain particles in place in the best
Today's high performance coated abrasive possible orientation. Thermal cure systems first
products would not be possible without the use tend to reduce in viscosity as they are exposed
of phenolic resins. The typical systems are base to heat; thus, some loss in grain orientation is
catalyzed and water miscible, having water tol- possible through resin and grain migration.
erances in the range of 50-300 %. Most phe- Radiation-curable systems are likely to be
nolic make !IDd size bonds are blends of two or based on acrylated epoxy resins, acrylated
more resins, usually a high (e.g., 1.8) and a polyurethane resins, acrylated epoxy-novolak
low (e.g., 1.1) F/P ratio (formaldehyde-to- resins, and acrylated isocyanurate resins.
 COATED ABRASIVES 675

Formulation of Coating Systems APPLICATIONS

Materials Being Abraded
The binders used in the manufacturing of coated
abrasive products can be complex. The adhe- Coated abrasives can be effectively used on a
sive systems used in premium coated products wide variety of materials, including wood and
must be able to withstand considerable heat, wood products, plastics, paints, glasses,
anchor the abrasive grit onto the backing, de- leather, rubber, metals and their alloys, and
liver grinding aids if present, and have a usable composites. The range of materials that can be
plot life of several hours. This means that fill- processed with coated abrasives is virtually un-
ers must be well dispersed, additives must be limited.
balanced to give good wetting, with no foam-
ing, and have the proper rheology to be coated
Power Demands
without sagging during curing. Typical fillers
may include: calcium carbonate, cryolite, po- Power demands may vary from hand opera-
tassium fluoroborate, potassium cryolite, cal- tions utilizing minimal effort to abrasive plan-
cium sulfate, and zinc stearate. Other filler ers that consume several hundred horsepower.
systems may be used to promote rheological Because of the wide variety of applications and
changes, flatting, nonslip, or antiloading prop- the vast array of finishing and stock removal
erties. requirements, there are many types of coated
abrasive designs and products on the market.

Use of Statistically Designed

Characterization
Experimentation
Most coated products are used at grinding
Many variables are involved in designing a speeds ranging from 1500 to 11,000 sfpm (sur-
coated abrasive product, and some way is face feet per minute). In-feed pressures vary
needed to identify and study their effects. Sta- from less than 1 psi to as high as 800 psi.
tistically designed experimentation is the best Coated abrasives are individually formulated
way to fine tune coating formulations, enabling to work under the specific constraints of certain
the optimization of product performance. applications, such as wet or dry grinding, car-
For example, it is found that blending two bon steels, exotic aerospace alloys, wood fin-
different surface-active agents improves their ishing, wood planing, antistatic, antiloading,
effectiveness. Through the use of designed ex- and polishing applications.
perimentation, one can easily determine the op-
timum levels of each agent, in conjunction with
Contact Wheels
defoamers, dispersants, etc. Combinations of
reactive fillers may yield a eutectic mixture with An often overlooked element of application is
a lower melting point, requiring less energy to contact wheels which are used to drive and sup-
activate. During grinding of metals and their port the abrasive belt products while control-
alloys, many chemical reactions are taking ling the degree of aggressiveness and finish
place simultaneously which affect the perfor- required. Wheels can be made from a variety
mance of coated abrasives. Binder-metal reac- of materials, such as steel, aluminum, rubber,
tions occur when reactive fillers are used to urethane, and cloth. The most common types
enhance performance. A statistically designed are rubber coated aluminum wheels, serrated
experiment can determine an antagonistic and/ on their surface. A soft rubber contact wheel
or synergistic effects of formulation compo- will allow the coated abrasive products to cut
nents on product performance. Mathematical smoothly, but be less effective in removing
models and computer graphics enable the de- stock than a harder rubber wheel. The serra-
sign engineer to predict the interaction of the tions are designed to improve the coated abra-
components and their effect on product perfor- sives' aggressiveness. This usually extends the
mance. life of the coated products by reducing the level
676 HANDBOOK OF ADHESIVES

of glazing, and by allowing the abrasive prod- Splicing of Coated Abrasives

uct to break down more easily, thus enabling
Splices are used to join the ends of coated ab-
the operator to use the product with less effort.
rasives so that endless belts, or sleeves, can be
Serrations are used to increase the effective unit
fo~ed. The two most commonly used types of
pressure on the abrasive surface.
sphces are laps and butts. Lap splices are
The ratio of land width to the width of a
formed by overlapping the ends the abrasive
groove machined in the surface of the contact
material, after preparing each end and applying
whe~l, known as the land-to-groove ratio, de-
the proper adhesive. This is followed by a hot-
termInes how aggressive a given wheel will be.
pressing operation that sets the adhesive. Butt
A contact wheel with higher ratio of land to
splices are less complicated and are manufac-
groove will be less aggressive and give a better
tured by applying an adhesive to each end of
finish.
the prepared backing, butting the ends to-
The angle of serration can also be varied to
gether, and taping them with a special rein-
increase or decrease the aggressiveness of the
forced splicing tape. This also is followed by
wheel; however, most wheels are used with a
hot-pressing. Within these basic splice types,
45° angle of serration. Contact wheels can
there can be many variations depending on the
greatly affect the way a given coated abrasive
final application.
product functions, thus giving even more ver-
The adhesives used to make splices are usu-
satility to coated products.
ally polyurethanes. Favored crosslinkers are the
There are also many applications where con-
trifunctional isocyanates, to give the splice ad-
tact wheels are not utilized, but depend on some
hesive its final heat resistance. After hot-press-
other means of support, for example, platen or
ing, the splices require about 24 to 48 hours to
slack-of-web grinding methods, as well as
attain their maximum physical properties.
hand, disk, and roll operations.
Flexing of Coated Abrasives
Versatility of Coated Products Since coated abrasives are composed of a sub-
strate coated with grain and bonded with a ther-
Outside of basic design, any given coated prod-
moset make and size resin system, such as
~ct can.be ~odified by changing its flexing or
phenolic or urea-formaldehyde, they tend to be
Its apphcation environment, including backup
very stiff. Flexing is used as a means of im-
pad or contact wheel, the land-to-grove ratio
parting various levels of flexibility or confor-
the operating speed, and the type or concentra~
mity to coated products. Flexing causes the
tion of lubricant if the operation is wet. One
coated material to break up, forming many
significant advantage this provides coated ab-
small inslands separated by controlled cracks in
~sives over bonded abrasives is versatility: a
the bond which act as hinges, enabling the
gIven coated product can be adapted to a wider
coated abrasive to flex, without dislodging the
range of applications than a given bonded prod-
very stiff and brittle thermosetting resin sys-
uct.
tems used to make the product. A flexible bond
Once a product is coated, it can be converted
system might satisfy the flexibility require-
into any size or shape desired, up to the width
ments but would not have sufficient heat resis-
of the jumbo roll of coated abrasive. It is even
tance to be effective in many applications.
poss~ble to exceed the width of the jumbo by
Also, flexible adhesives generally lack the sup-
making segmented or sectional wide belts.
port for the abrasive grit to function aggres-
These sectional belts contain more than one
sively.
splice, and are fabricated from panels cut in the
cross rather than the running direction of the
PSA Products
belt. Belts can be manufactured in width rang-
ing from!" to 68" in single splice belts, and to Pressure sensitive adhesives (PSAs) are used
130" width in sectional belts. extensively to manufacture a special form of
 COATED ABRASIVES 677

disks and sheets known as PSA-backed prod- pair body damage in used vehicles. The wood
ucts. These coated abrasive products have their industry is an excellent example of their use in
backings coated with a PSA, which enables the shaping and finishing.
disks or sheets to adhere to various backup pads
without the use of any mechanical means. Machine Methods
These adhesives have medium to high tack
Coated abrasives are used on a wide range of
properties, meaning that they develop a bond
different machines. Machine applications can
immediately upon being applied to another sur-
be classified by how the workpiece is fed into
face with low pressure.
the unit or by the type (shape) of abrasive. Ma-
PSA systems include hot-melt, emulsion,
chines vary from hand-held sanders to disk
solvent-based, and radiation-curable types. Hot
grinders, platen grinders, backstand, semiau-
melt and radiation systems are 100% solids and
tomatic, and automatic grinding machines. In
require no solvents, thus eliminating the need
addition, there are through-feed machines and
for devolatilization or solvent recovery sys-
computerized gantry grinders for cleaning up
tems.
large metal alloy plates. Coated abrasives can
also be utilized on computerized numerically
Markets
controlled machines for abrasive machining,
There are many market areas in which coated sophisticated metal parts.
abrasives are used: automotive, industrial met- In many applications, coated products can
als and fabricators, sporting goods, wood, re- remove material faster, cooler, and at a lower
tail, furniture, aerospace and transportation, cost, while providing a better finish than other
just to name a few. For example, the planer methods of material processing. Coated abra-
belt markets utilize coated abrasive belts to sive products are in existence today because of
plane rough lumber down to finished size, in- their unique ability brought about through com-
stead of traditional knife planers. The advan- binations of abrasives, backings, and adhesive
tages of abrasives are that they can cut faster, systems.
last longer than knives, and are not as sensitive
to being damaged by nails or hard items some- REFERENCES
times found in boards. 1. "Coated Abrasives-Modern Tool of Industry,"
Today more and more coated products are Cleveland, Ohio, Coated Abrasives Manufacturers' In-
being employed in industry to shape products stitute, 1982.
2. Caul, Lawrence D. and Forsyth, Paul F. (to Carborun-
as well as finish them. In the automotive mar- dum Abrasives), "Resin Systems for High Energy
kets, coated products serve to finish cars and Electron Curable Resin Coated Webs," U.S. Patent
trucks during manufacturing, as well as to re- 4,588,419, May 13, 1986.
 41
Adhesives for Building Construction
ROBERT S. MILLER
Corporate Vice President
Franklin International, Inc.
Columbus, Ohio

Glues and sealants have been used in construc- BASIC CONSIDERATIONS IN

tion since Biblical times; but the synthetic ad- ADHESIVE SELECTION
hesives achieved prominence only after World
Selection of an adhesive starts with the answers
War II. Even in recent decades, however,
to five basic questions:
changes have been dictated by new adhesive
materials and new building materials. 1. What do we want the adhesive to do for
Today, many types of adhesives are in use us? Start by listing all of the requirements
throughout industry, including the construction expected of the adhesive formulation: the
industry. Some adhesives require sophisticated drying time, the ultimate strength needed
application techniques while others can be put in the bonded assembly, the years of ser-
in place by trowel, brush, spray, or spot appli- vice expected, the conditions to which the
cation. This chapter will concentrate on the lat- bonded assembly will be subjected, etc.
ter, since most construction applications are 2. Is it reasonable or practical to expect all
carried out at the job site, or at best under rather of our basic requirements to be fulfilled
nontechnical factory applications. Thus in this by an adhesive formulation? For exam-
chapter we will be looking at the factors in- ple, most adhesives will not perform sat-
volved in selecting an adhesive for a particular isfactorily when subjected to constant
application, whether it be under factory con- submersion under water. Neither will
trolled conditions, by the builder at the job site, most of the adhesives encountered in the
or even by the novice do-it-yourselfer. construction industry perform continu-
Areas to be examined where adhesives are ously at extremely high temperatures in
commonly used include a variety of materials excess of 300 or 400°F. It is necessary to
for floors, subfloors, walls, and ceilings. In ad- write down all the factors which, al-
dition, we will look at the match between ad- though desirable, could be sacrificed if
hesives, construction materials, and substrate necessary.
to which they will be bonded. Toward the end 3. Will you be limited by available equip-
of the chapter we shall seek to determine why ment, plant layout, production require-
adhesives sometimes do not perform well. In ments, construction design, special job
short, this chapter will take an elementary and site tools, etc. in adhesive selection?
practical approach to the use of adhesives in 4. Will insurance rates, local building
construction, leaving the more technical con- codes, OSHA, or other government agen-
siderations to other chapters in this book. cies restrict your adhesive selection?

678
 ADHESIVES FOR BUILDING CONSTRUCTION 679

5. What effect will the cost of the adhesive cannot be used to bond two nonporous
formulation, the necessary special equip- surfaces. To bond two nonporous sur-
ment required, alterations in construc- faces, one must consider a product that
tion design, etc. have in the initial can be predried and perfonn either as a
selection of a suitable formulation? contact-type cement or a pressure-sensi-
tive adhesive. Other alternatives are cat-
The answers to these basic questions will help
alytically cured systems and hot melts.
narrow the vast field of available fonnulations
to those several to be evaluated further accord- The degree of porosity of the substrates will
ing to (1) application, (2) perfonnance, and (3) also have a great effect on the drying rate. Both
cost. wood and gypsum wallboard are porous, but
the drying time will generally be more rapid on
APPLICATION the more porous gypsum wallboard.
Here the main considerations are: Some applications may depend on the ab-
sorption or penetration of the adhesives into
1. Nature of the substrate and the materials some of the pores of the materials being
being bonded. What is the texture of the bonded. An extreme example is a paper honey-
surfaces-are they smooth, rough, un- comb, where the pores are quite large and deep.
even, out of plumb, etc.? A surface that The adhesive bed must be sufficiently thick to
is relatively uneven cannot be bonded to bond to the edges and sides of the honeycomb
a very smooth surface with a low viscos- pores. Certain types of cinder block also de-
ity adhesive. If one must bridge certain velop superior bonds as there is a degree of ab-
irregularities that are quite common in sorption or penetration into the surface by the
construction, then heavier viscosity for- adhesive. Where there is high absorption, the
mulations are needed. fonnulation must be sufficiently viscous to as-
The surfaces being bonded may not be dusty, sure that there is adequate adhesive at the in-
dirty, oily, greasy or wet. The strength of the terfaces.
bonded assembly will never be any greater than
3. Preferrred systems of application. The
the weakest link. When a piece of wood is cov-
nature of the materials being bonded will
ered with sawdust, if it is bonded to a concrete
many times dictate the preferred method
substrate, the application is doomed to failure
of application. Large surfaces may re-
at the sawdust layer.
quire a spray or roller coat application.
The adhesive must be compatible with the
Thin plastics or fabrics may require also
surfaces being bonded. Polystyrene foam is at-
a roller or spray. Other. applications call
tacked by some solvent based adhesives. Also,
for an extrusion, while even others will
plasticizers can migrate between adhesive and
lend themselves better to trowel, spot,
vinyls, or other plastic substrates.
spatula, brush, or other types of applica-
It is important also to consider the internal
tion.
strengths of the materials being bonded. Most
4. Methods available for application. Any
wood fractures internally at shear strengths of
one of the preferred systems of applica-
200-400 psi. Thus it makes no sense to select
tion may have available a number of dif-
an adhesive that would develop shear strengths
ferent systems of varying sophistication.
of 1000 psi or more. The bond between a low
Where an application would require ex-
density blanket-type fiberglass and a concrete
trusion, for example, a factory controlled
or metal surface need be no stronger than the
situation may dictate a capital expendi-
bond holding the glass fibers together.
ture for automatic equipment. At the other
2. Porosity of the suifaces. Most adhesives end of the scale, the do-it-yourselfer
must depend on the release of either a would find a cartridge his best method of
solvent or water to accomplish drying and extrusion, with a caulking gun. Often an
setup of the glue line. Such adhesives application system already in use can be
680 HANDBOOK OF ADHESIVES

adapted to another application, thus re- 3. Glue line resilience required. On films of
ducing cost. fabrics, plastics, etc., a very resilient glue
5. Desired or required viscosity. One should line may be Qeeded. Even on many rigid
not attempt to brush a heavy mastic prod- substrates and adherends, it is desirable
uct when the required viscosity is much to maintain a certain degree of resiliency
thinner. in the glue line to assure impact resis-
6. Drying requirements. The rate of drying, tance. Bonded assemblies of materials
or speed of set, is an important factor, that are somewhat mobile and are being
particularly if no auxiliary drying meth- moved from place to place also require
ods are available. In this event one must flexibility and/or resilience of the glue
choose between rapid-drying solvent- line. Thus, in factory built construction
based materials versus the slower-drying that is moved to other locations, the ad-
emulsions and certain other solvent hesive should resist racking or other
blends. However, if special drying equip- movement that could have an adverse ef-
ment (infrared, forced air, etc.) is avail- fect on the glue line. There are all de-
able, this, too, will have an effect on the grees of hardness and of resilience.
selection. Normally, special drying 4. Resistance to water, moisture, humidity,
equipment would be encountered primar- and light. In some applications, particu-
ily in factory applications rather than on larly those with surfaces exposed to the
the construction job site. elements, excellent water resistance is
desired. Ultraviolet light from sources
PERFORMANCE such as the sun can be very detrimental
to some adhesive formulations, particu-
In the selection process, applications and per-
larly SBR and other elastomers.
formance characteristics are most often consid-
5. Resistance to oils, greases, and solvents.
ered simultaneously. The following are
Special formulations may be needed.
probably the most commonly used perfor-
6. Resistance to acids, alkalines, and chem-
mance criteria.
icals in general. Again, special formula-
1. Minimum tensile, shear or peel strength tions are available for special
at specified temperatures. For the most environmental conditions.
part, only one of these types of strength 7. Aging. In the construction industry, life
evaluation need be considered. There is expectancy is important. The adhesives
no need for adhesives to develop strengths industry has come to rely more and more
far in excess of the internal strength of on the oxygen bond test (ASTM-D-572)
the weaker of the materials being bonded. as an indicator of relative life expectancy
2. Minimum and maximum service temper- of a given formulation. As a general rule,
atures. Many formulations perform sat- only adhesives that can withstand expo-
isfactorily at temperatures ranging from sure to 500 hours or more in the condi-
-lOoF to + 150°F. However, if the ap- tions encountered in this test procedure
plication requires performance at temper- should be considered for construction ap-
atures that will exceed 200°F, there is no plications. If after 500 hours exposure an
point in evaluating adhesives designed for adhesive specimen is not hard and brittle,
performance in these lower ranges. Ex- then it can generally be counted on to
treme cold temperatures, -30°F. and perform satisfactorily for many years.
colder, pose an added problem in that 8. Weathering. Adhesives are generally not
many formulations become very brittle at subjected to the conditions that are nor-
these temperatures. Also a consideration mally considered in weathering tests,
is whether exposure to the upper and since the adhesive is not ordinarily ex-
lower temperature limits is to be at a sus- posed to ultraviolet light. Sealants, how-
tained rate or intermittent on a cyclical ever, may well be subjected to ultraviolet,
basis. either on the perimeter or through glass
 ADHESIVES FOR BUILDING CONSTRUCTION 681

or other transparent or semitransparent will reduce initial costs, technical service

surfaces, and then the weathering factor from the manufacturer is much more cost
must be considered. Weathering tests in- effective, greatly reducing the chance of
volve temperature and humidity cycling, future adhesive problems, which can be
as well as ultraviolet exposure. extremely costly in time, replacement,
9. Color requirements. Color may be a fac- call-backs, and loss of business.
tor for a number of reasons, for example, 4. Application consideration. There are, of
matching the colors of the materials being course, certain applications that require
bonded, preventing adhesive shadows specific types of adhesive. Again, avail-
from showing through opaque surfaces, able equipment may limit adhesive
masking excess squeeze-out in inacces- choice, and special adhesives can be very
sible places such as dark tongue and expensive. Generally speaking, however,
groove wood joints, and identification. the performance requirements are much
more rigid than application requirements.
5. Coverage. There are a number of factors
COST CONSIDERATIONS that affect coverage, hence cost. Gener-
ally speaking, lower viscosity adhesive
The third major factor of consideration in the
formulations will yield higher coverages
initial adhesive selection process is cost. You
than the heavier viscosity formulations,
will notice that references to cost have gener-
thus reducing the cost per square foot.
ally been set aside until last. While of impor-
However, the nature of the application
tance in some specialty applications, cost
may be such that a lower viscosity adhe-
generally is less significant than either appli-
sive is unsuitable.
cation or performance criteria. The factors that
most commonly affect cost are the following: Application techniques and methods will also
have a great effect on coverage, as will design
1. Initial cost. Unfortunately, the inclina-
of the application system, its efficiency, and
tion is often to put cost of the material per
cleanliness.
gallon or per pound before any other con-
As pointed out before, the nature of the ma-
sideration. In most cases this can lead to
terials being bonded, the demand placed upon
problems. While it certainly must be
adhesive performance and the application
taken into consideration, the base cost of
methods used or available all combine in the
the adhesive generally is not one of the
initial selection process. These factors dictate
initial selection factors that is evaluated,
the type adhesives that will be candidates for
and would come further down the line. It
your application. It is then that cost factors en-
will again go hand in hand with applica-
ter into consideration and efficient coverage will
tion and performance considerations, but
play its role.
generally will follow them in order of
consideration.
Coverage Data
2. Performance requirements. Cost will be
greatly affected by the performance re- Mastic type formulations are generally applied
quirements. In most cases as these re- by either an extrusion or by some type of trowel
quirements are raised, so will be the cost application or variation thereof. Extrusions can
of the adhesive. Performance will gener- either be with the utilization of some type of
ally have a much greater influence on cost automatic equipment or by common cartridge
than any other consideration. gun extrusion.
3. Service requirements. Technical exper- The data in Table 1 may be of help in esti-
tise, experience in the industry, and rep- mating coverage of mastics. The figures are
utation for quality and service should be modified by other variables that affect coverage
prime considerations in selection of an such as inconsistencies or human error in hand
adhesive supplier and formulation. While applications, temperatures at point of applica-
lower cost adhesives or reduced usage tion, efficiency of application systems, clean-
682 HANDBOOK OF ADHESIVES

Table 1. Volume of Extruded Bead Length vs. Bead Size.

Bead Size, in. diam.
Volume 1"
Ii 3 "
16 1" ~"
16 i"
Small Cartridge 123 ft 54 ft 3~ ft 19~ ft 13~ ft
(10 ft. oz.)
Small cartridge 129 ft 57 ft 32 ft 2~ ft 14 ft
(10.5 ft. oz.)
Large cartridge 355 ft 158 ft 89 ft 57 ft 39 ft
(29 ft. oz.)
1 U.S. gallon 1,569 ft 597 ft 392 ft 251 ft 174 ft
(128 ft. oz.)
5 gallons 7,845 ft 3,485 ft 1,960 ft 1,255 ft 870ft
(Pail)
52 gallons 81,588 ft 36,244 ft 20,384 ft 13,052 ft 9,048 ft
(Drum)
In approximate figures, 1000 lineal feet of extruded adhesive bead will require:
~ gallon at A" diameter bead
;i gallons at!" diameter bead
5. gallons at ~. diameter bead

liness of the system, etc. Glue patterns are Table 3. Trowel Coverages.
shown in Table 2. Approx. Coverage
Trowel (sq. ft per gal.)
Trowel Coverage Square notch trowel
Hand trowels change coverage with build up of (Notches f6" wide X i" deep
X -&" o.c.) 34
dried adhesive on the trowel edge, with the an- Sawtooth trowel
gle at which the trowel is held, and with wear (Notches f6" wide X i" deep
in contact with an abrasive surface such as con- x -k" o.c.) 54
crete for a prolonged period of time. Table 3, Serrated
based on a clean trowel held at an approximate V-notch trowel
(Notches -k" wide x i" deep
45° angle, shows typical coverage. See Fig. 1. x ~" o.c.) 66
(Notches -k" wide x -k"
Other Types of Applications and Their deep x 16" o.c.) 41
Coverage (Notches -k" wide x -k"
deep x -&" o.c.) 54
Here again, there are so many variables that it
is most difficult to state precise coverage fig-
ures. Since coverage is greatly affected on cer- ical solids content of a product of this type
tain applications by the viscosity of the would be in the range of 30-50%.
adhesive, the solids, the cohesion within the
material, etc., an arbitrary viscosity of 8,000-
COMMON ADHESIVE APPLICATIONS
10,000 cps has been selected in Table 4. Typ-
IN THE CONSTRUCTION INDUSTRY
Table 5 shows some of the most widely avail-
Table 2.
able types of adhesive and the substrates and
facing surfaces on which they are commonly
:r_
used. Do not rely on this table alone. Use it in
:r IIIrIp conjunction with a performance, application,
and cost analysis.
_1eIIf/III1n1t. 32' 4(/' 42' ..... 5O'Ar' Table 6 shows some of the general charac-
/IqcI.oz.@W_ 2.8 3.3 3.4 3.8 4.1
/IqcI. oz. @ '/1' _
/IqcI.oz.@W_
10.5
23.5
13.1
28.4
13.7
30.8
14,4
32.3
18.5
37.1
teristics of the most commonly used adhesives
by type, and can be particularly useful in the
 ADHESIVES FOR BUILDING CONSTRUCTION 683

treatment and/or preparation of the subfloors

prior to installing any type flooring over them.
In most remodeling or refurbishing jobs
around the home, the existing floor will act as
the subfloor for the new flooring material.
However, in conventional stick-type construc-
tion, or the finishing of an attic, basement, or
garage, or when rooms are added to existing
construction, a subfloor of some type must be
installed to receive the finished flooring mate-
rial. In the addition of rooms or new construc-
tion work, adhesives can playa very important
part.
Since the mid-1960s the American Plywood
Association has been carrying on an intensive
program to perfect subfloor systems that would
Fig. I. (Top) Typical V-notch spreader used with tiJe- improve floor quality and perfonnance while
board adhesives. (Bottom) Typical notched trowel used to
using less material. The APA's present system
apply floor mastic.
is based on recently developed gluing tech-
niques and adhesives that firmly and penna-
evaluation of the perfonnance criteria of a par- nently secure the structural plywood
ticular fonnulation. Both Table 5 and Table 6 underlayment to wood joists. The resulting
are quite general but can assist in zeroing in on bond is so strong that floor and joist behave as
the best possible fonnulation. integral T-beam units. This combination of
joist, plywood and adhesive increases stiffness
when compared with conventional floor con-
FLOORING struction. For instance, stiffness of the joist is
increased significantly (about 25% with 2" x
The first major category of construction . ele- 8" joist and~" plywood) when a single layer of
ments to be examined is flooring. Among the plywood underlayment is glued to the framing
major choices for floor coverings are wood, re- joist. Gluing the tongue and groove joint be-
silient surfaces, rigid surfaces (ceramic tile, tween panels approximately doubles the in-
slate, and brick), and soft fabric materials such crease in stiffness (to about 50% in the case
as carpeting. All of these floor coverings can mentioned). Thus, glued floors not only deflect
be easily installed with the proper adhesives. less under traffic but tests show better resis-
Before discussing some of them more specifi- tance to long tenn deflection than nailed-only
cally, however, we need to address two very floors. There are many other benefits to the use
important subjects. One is the use of the Amer- of the APA Glued Floor System, not the least
ican Plywood Association Glued Floor System of which is the virtual elimination of squeaks
in basic construction work and the other is the in the floors. Extensive testing undertaken by
the APA also indicates that the glued floor sys-
tem will provide many economies while in-
Table 4. Spray, Brush and Roller
creasing and improving the structural
Application.
perfonnance of the entire unit. The increased
Spray equipment used was spacing to 24" on center from conventional 16"
Binks #62 gun/#365
needle/67 pb air cap. 66 floor joist will save nearly one-third of the
Fluid tip/55 lb. line pres- framing members required and result in higher
sure and 8 lb. cup pressure. 250-350 sq. ft/gal strengths than conventional nailing on 16"
Brush coverage-medium coat 175-225 sq. ft/gal spacing. Tests have also found that spans can
Roller coverage-Carpet be increased considerably by the various sized
Stipple Roller 300-350 sq. ft/gal
framing members. The design of a typical
 Table 5. General Selection Practices by Type of Adhesive.
Substrates (Back Up Surfaces)
01
Concrete CID
~
Brick, Cinder Concrete Gypsum Gypsum Particle
Facing Surfaces Stone Block (Poured) Board Plaster Hardboard Metal Board Plywood Wood ::r::
Brick Veneer D,b,e D,b,e D,b,e B,D,f,h,m B,D.f,h,m B,D,f,h,m D,b,e,k B,D.f,h,m B,D,f,h,m B,D,f,h,m
»
Z
Carpet B,f,h,m B,f,h,m B,F,H,M B,f,h,m B,f,h,m B,f,h,m B.f,h,m B,F,H,M B,F,H,M B,F,H,M C
lIII
Ceramic, Slate B,c B,c B,c,f B,F,c,h B,F,c,h B,F,c,h B,c B,F,c,h B,F,c,h B,F,c,h 0
Quarry Tile 0
;III:
Chalkboard & B,d B,d B,d,f,h,m B,d,f,h,m B,d,f,h,m B,d,f,h,m B,d,f,h,m B,d.f,h,m B,d,f,h,m B,d.f,h,m
0
Cork "II
Cove Base D,L,b,h D,L,b,h D,L,b,h D,L,b,h D,L,b,h D,L,b,h D,b,h D,L,b,h D,L,b,h D,L,b,h »C
Cultured B,D B,D B,D B,D,h B,D,h B,D,h B,D B,D,h B,D,h B,D,L
Marble
::r::
m
Furring Strips B,D B,D B,D B,D,f,m B,D,f,m B,D,f,m B,D B,D,f,m B,D,f,m B,D,f,m til
Gypsum B,D B,D B,D,f,m B,D,a,f,m B,D,f,m B,D,a,f,m B,D B,D,a.f,m B,D,a,f,m B,D,a,f,m <:
m
Wallboard til
Hardboard B,D B,D B,D,f,m B,D,a,f,m B,D,a,f,m B,D,a.f,m B,D B,D,a.f,m B,D,a,f,m B,D,a,f,m
Paneling
Insulation B,D B,D B,D B,D,f,h,m B,D B,D,f,h,m B,D B,D,f,h,m B,D,f,h,m B,D,f,h,m
Board
Metals B,D,k B,D,k B,D,c,k B,D,h,k,m B,D,h,k,m B,D,h,k,m B,C,D,E,K B,D,h,k,m B,D,h,k,m B,D,h,k,m
Marble B,D,k B,D,k B,D,k B,D,k B,D,k B,D,k B,D,c,k B,D,k B,D,k B,D,k
Wood Parquet B,D,h,k B,D,h,k A,B,d,h,k A,B,d,h,k B,D,h,k A,B,d,h,k B,D,c,e,h,k A,B,d,h,k A,B,d,h,k A,B,d,h,k
Plastic b,c,d,e b,c,d,e b,c,d,e D,E,c,b D,E,c,b D,E,b,c b,c,d,e A,D,E,b,c A,D,E,b,c A,D,E,b,c
Laminates
Plywood & B,a,d,f,m B,a,d,f,m B,a,d,f,m A,B,d,f,m A,B,d,f,m A,B,d,f,m B,D,f,m A,B,d,f,m A,B,d,f,m A,B,d,f,m
Paneling
Polystyrene A,B,F,H,M A,B,F,H,M A,B,F,H,M A,B,F,H,M A,B,F,H,M A,B,F,H,M B,F,H,M A,B,F,H,M A,B,F,H,M A,B,F,H,M
Foams
Polyurethane A,B,D,F, A,B,D,F, A,B,D,F, A,B,D,F, A,B,D,F, A,B,D,F, B,D,h A,B,D,F, A,B,D,F, A,B,D,F,
Foams H,M H,M H,M H,M H,M H,M H,M H,M H,M
Subftooring B,D B,D B,D B,D,a,m B,D,a,m B,D,a,m B,D B,D,a,m B,D,a,m B,D,a,m
Tileboard B B B B,I B,I B,I B,d B,I B,I B,I
(Wallboard)
Plastic Tub & B B B B,f,h,m B,f,h,m B,f,h,m B B,f,h,m B,f,h,m B,f,h,m
Showers
Vinyl Floor F,h,m F,h,m F,h,m F,h,m F,h,m F,h,m F,h,m F,h,m F,h,m F,h,m
Materials
Wood Flooring, B,c,d,k B,c,d,k B,c,d,k B,d,k B,d,k B,d,k B,d,k B,d,k B,d,k B,d,k
Strip & Plank
Wood/Plywood B,D,k B,D,c,f,h,k B,D,a,c,f, A,B,F,d,h, A,B;F,d,h, A,B,F,I,I, B,D,c,e,k A,B,F ,1,1 ,M, A,B,F,I,I,M, A,B,F,I,I,M,
h,k,m k,m k,m M,d,h,k d,g,h,k d,g,h,k d,g,h,k
ADHESIVE TYPES:
a. Polyvinyl Acetate e. Nitrile (Solvent) i. Animal Glues m. EthyleneNinyl Acetate
b. SBR-(Solvent) f. Latex emulsions j. Resorcinol Capital Letters-Most
c. Epoxies g. Hot Melts k. Polyurethanes commonly used
d. Neoprene rubber (Solvent) h. Acrylics (Latex) 1. Resin/Rosin Based Lower Case Letters-May
also be used
 Table 6. General Characteristics of Adhesive Types.
Shear
Stability of Adhesive Types for Various Surface Conditions
Temperature Strength
Service Range at Resistance Resistance Initial Tack
Systems of Application Range In 70 Deg. F to Oils Resistance to Acids, or Cohesive Porous Porous Non-porous
Curing or Methods of Temperature Degrees F In Psi and Resistance to Alkalies, Wet Strength to to to
Materials "Setting" Application 'F (a) (b) Greases to Water Weathering Chemicals Strength (Dry) Porous Non-porous Non-porous
Polyvinyl Water Evap. Brush, Spray, 35' to 100' -20' to 180' 100 - 4000 G P-E P-F P-F F E E G P
Acetate Heat, Roller Flow
Pressure
SBR Solvent Evap. Brush, Spray, 0' to 120' -20' to 200' 50 - 700 P-F F-G F-E P-F F-G F-G G G G
(Butadiene Roller, Ext.
Rubber) Trowel
Epoxies "Catalyzed" Brush, Flow 40' to 100' -20' to 350' 50 - 5000 E G G-E G-E F-G E G E E
Curing Roller
Agents Extrusion
Neoprene Solvent Evap. Brush, Spray, 0' to 120' -40' to 300' 20 - 500 G-E G-E G-E G G-E G-E G G E
Rubber Heat Roller,
Extrusion
Nitrile Rubber Solv. Evap. Brush, Spray, 0' to 120' -40 to 300' 20 - 500 E G-E G G-E G-E G G G E
Heat Roller
Extrusion
Latex Water Evap. Brush, Spray, 40' to 100' -30' to 200' 50 - 300 P-F P-G P-G P-F P-F F-G E G P l>
C
Emulsions Roller, Ext. :I:
Trowel m
rJ)
Hot Melts Heat Loss Brush, Flow 140' to 350' -20' to Melt 20 - 500 P-F G F-G F-G F-G F-G G G G <:
Extrusion m
rJ)
Acrylics Water Release Brush Flow 0' to 100' -40' to 400' 10 - 300 F-G F-G G-E F-G P-G F-G G-E F-E F-E
."
(Latex) or X-link Ext., 0
Trowel 21
Spray 111
c:
Animal Glues Water Evap. or Brush, Flow 70' -20' to 200' 500 - 4000 G P P-F F P-F E E G P r=
Heat loss Roller C
Extrusion 2
C)
Resorcinol Water Release, Brush, Flow 70' -20' to 250 1000 - 4000 G E G G F E E G P
C')
Heat Roller 0
Pressure Z
rJ)
Polyurethanes Solv. or Water Brush, flow 40' to 120' -40' to 300' 20 - 700 F-G F-E G-E G F-G F-G G G G -I
ReI., X-link Ext., Spray 21
c:
Resin/Rosin Solvent Trowel 40' to 100' 0' to 180' 20 - 200 P-F F-G P P G-E G-E G G G C')
Release Extrusion -I
Eva Latex Water Evap. Brush, flow 35' to 100' -20' to 200' 50 - 500 F-G F-G F-G F-G P-G F-G G G F-G
0
Z
Ext., Spray
0)
Trowel IX)
C1I
Notes: (a) Dependent on nature of materials being bonded such as thermal conductivity. thickness. required strengths at given temperatures. etc.
(b) Varies with type of materials being bonded. method of application. thickness of bond line. etc: E == Excellent; G == Good: F == Fair P == Poor
686 HANDBOOK OF ADHESIVES

subfloor system using the American Plywood moisture conditions that may exist underneath
Association Glued Floor System is shown in the slab. Just because a slab is above grade, it
Fig. 2. is not necessarily totally moisture free. In new
From an adhesive point of view, the APA construction the builder/contractor should al-
specification is quite strict in spelling out the ways insist that some form of plastic vapor bar-
performance characteristics of adhesives for use rier with proper drainage be used underneath
in this system. As a matter of fact both the APA the slab prior to pouring of the concrete. While
Glued Floor System and HUD-FHA, in their wet surfaces on concrete may not necessarily
Use of Materials Bulletin #60, require indepen- be harmful to the adhesive, they may be quite
dent outside laboratory testing for the conform- detrimental to the flooring material itself.
ance of these adhesives to AFG-Ol carried out A practical test to determine the presence of
with field samples of adhesives procured at ran- moisture in a concrete slab, whether it is new
dom. This is one of the very few specifications or has been down for a number of years, is the
in the construction industry that has built-in following. A piece of polyethylene sheet ap-
quality assurance for the user. It is highly rec- proximately 36" square should be taped to a
ommended that the APA Glued Floor System clean surface of the slab with a standard duct
be thoroughly investigated and considered in tape applied completely around the perimeter.
basic construction and remodeling work. If moisture is present in the slab, it will gen-
erally show up within 48 hours as condensation
underneath the polyethylene film. In this event,
Treatment of Subfloors
one should thoroughly check out the source of
There are many existing subfloors or substrates the moisture and attempt to eliminate it prior to
that can be used as surfaces for applying fin- installing any type of flooring material.
ished flooring materials. However, these sur- It also stands to reason that it will be most
faces often may also be the source of serious difficult to achieve a satisfactory bond on con-
problems if they are not properly addressed and crete that is loose, flaky, or spalled in any way.
treated. Before attempting to install any floor- Occasionally, curing agents have been used in
ing material, the subfloor should be thoroughly the concrete that may have a tendency to rise
examined to make certain that it will provide a to the surface and create salts that are most dif-
suitable and satisfactory base. ficult to bond to. In this event these salts should
be removed before attempting to adhere any
Poured Concrete. This is probably one of type flooring material. All cracks or rough areas
the most common surfaces to which modern on the concrete should be patched prior to pro-
day flooring materials are bonded. One of the ceeding with flooring installations. Naturally
most common problems with concrete is the the surface should also be free of any dust, dirt,

Tile, Carpet, Unoleum, or other

non-slruclural flooring.
Leave 'h," space al all end and
edge joinls.

Single layer of APA

underlaymenl T&G plywood->r~_
(lnlerlor, or Interior with
exterior glue)_
6d deformed shank or 8d
common nalis spaced 12" all
bearings or closer il required
by codes_

Tongue'" Groove edges (or

provide edge blocking).

Fig. 2. APA glued floor system (Courtesy of American Plywood Association).

 ADHESIVES FOR BUILDING CONSTRUCTION 687

''!(n" • 2'//' or 1112" Flooring nailed and finished flooring installations. Flooring is gen-
.004 [ StriP Flooring. bonded.
Polyethylene erally the last piece of finish work to be done
Film (lap edges 1". 2" strips n~16"• O.C.
2" treated slrlps
on any construction project; thus the subfloors
.
over sleepers). with 4d nails. laId In adhesive
f:±
.
~ take much abuse during the construction pro-
.t" .
: I! r- Io.r. ~ ~on~ri'e S.~ab . ~ _: .
cess and need attention to make certain they
n,. ~.;~~:~,~:~*.~:\O~~" , ,~ ~':i .:\~.~ .:V:~. -:\Y?~~~~:l;.j .. :~".~ ~'~' will be receptive to a good bond.
Fig. 3. Laying strip floors over a concrete slab. Existing Floor Surfaces. Often it is desir-
able to apply a new flooring material over an
older existing floor. In most cases this can be
Plywood accomplished, provided the potential problems
are addressed. For example, on existing vinyl
tile or vinyl sheet floors there is often a buildup
of wax and dirt that would interfere with bond-
ing. These floors should be stripped of all wax
and dirt. One should also be certain that these
existing floors are well bonded and have not
delaminated from the subfloor with the old ad-
hesive.
Fig. 4. Insulated floor over a concrete slab. When old existing floors are removed, all
traces of old adhesives on the subfloor must be
oil, or grease prior to installing finished floor- removed. Often these older adhesives are not
ing. compatible with newer adhesives that would be
Concrete slabs are occasionally damp or have used to put down modern floors; there can be a
some moisture content or may be exposed to migration of plasticizers between the two ad-
moisture conditions. A system to provide a va- hesives, resulting in a glue line that will never
por barrier when wood floors are put down over set up or develop a strong bond.
concrete is shown in Fig. 3. The sleepers may Questions regarding the treatment of these
be bonded to the concrete slab with construc- subfloors can be answered by the manufactur-
tion type adhesives. Occasionally asphalt cut- ers of the flooring material and the adhesive as
backs are also used for this purpose. well as the flooring system dealer or distribu-
In the event that it is desirable to insulate the tor.
floor underneath a plywood subfloor, foam in-
sulation can be placed between sleepers that Floors
have been installed over slabs, as shown in Fig.
Wood Floors. Wood floors probably were
4, with the aid of either construction adhesives
first installed in the mid-II th Century, and have
or asphalt cutbacks.
been a leading flooring material ever since. To-
day both hardwoods such as oak, birch, beech,
Wood Subfloors. While plywood is still
and maple, and softwoods such as pine and fir
probably one of the most common subfloor sur-
are used for wood flooring. A number of dif-
faces made from wood, we are beginning to see
ferent types of wood floors are installed with
other types of composition subfloors: particle
adhesives; among these are solid block par-
board, flake board, wafer board, etc. Most of
quet, laminated parquet, solid finger block,
these types of surfaces are treated like ply-
strip, and plank-type flooring.
wood. Large gaps between the subfloor and the
Fortunately most of the wood floors installed
floor should be filled with a suitable wood filler.
today utilize a very narrow range of adhesives,
All nails must be flush with the surface and not
which greatly simplifies the selection decision.
protruding. Since these subfloors are generally
These are as follows:
in existence during all other phases of construc-
tion, they may accumulate dirt and dust which 1. Asphalt cutbacks. Until a few years ago
must be cleaned prior to making any further the majority of wood floors installed with
688 HANDBOOK OF ADHESIVES

adhesives utilized these asphalt cutback ceed the internal strengths of the wood,
fonnulations. Unfortunately, their and they are unnecessarily expensive as
flammability posed an extreme hazard to well as difficult to use. Furthennore, there
the workmen as well as the structural ele- have been a number of failures because
ments during installation. While there still the bond strengths were so high that de-
are some examples of this type material lamination occurred when the floor con-
being used today, the liability that the tracted and expanded and there was no
user is exposed to has virtually elimi- accommodating resiliency in the glue
nated this as a selection. The chief reason line.
for their use was basically economic, in It should be always kept in mind that wood
that the asphalt materials were generally and water are inimical. There should never be
quite low in cost. However, they nor- any attempt made to install any type wood
mally did not develop the strengths that flooring if water or moisture is present. The
were desired, and this, coupled with the presence of moisture has most probably been
hazard involved, prompted most users to the single largest problem with installing wood
switch to the nonflammable, chlorinated flooring.
solvent SBR (butadiene-styrene rubber)
fonnulations. Resilient Flooring. Practicality, conve-
2. Chlorinated solvent systems. Most adhe- nience, ease of application, and long wear are
sive-installed wood flooring today uti- a few of the reasons why resilient flooring con-
lizes this type of material. They are tinues to be one of the most popular choices of
nonflammable because they utilize 1,1,1- homeowners everywhere. With the tremendous
trichloroethane or other chlorinated sol- variety of materials, designs, and colors avail-
vent with a base such as butadiene-sty- able it is possible to create virtually any floor
rene rubber. High strengths are achieved, scheme that strikes the fancy.
yet the material remains sufficiently resil- Resilient floors generally are manufactured
ient to allow nonnal expansion and con- in two basic types: sheet material and tiles. The
traction of the flooring and the substrates sheet materials are generally available in con-
without delamination. In virtually all tinuous rolls up to 12' and larger widths. One
cases the adhesives are applied by of the key advantages of sheet flooring is the
notched trowel. huge reduction in seams in the finished floor;
3. Polyvinyl acetate systems. It is not un- another is the beautiful wall-to-wall sweep of
common today for the finger block floor- color and design. These sheet or roll goods of
ing materials, particularly those that are resilient materials, including carpeting, are in-
unfinished, to be installed with a fonn of stalled with latex emulsion-type adhesives,
PV A adhesive. While these products are which are nonnally troweled over larger areas
water based materials, they dry ex- and remain open long enough to pennit shifting
tremely rapidly and will nonnally not and adjustment of the roll goods into position.
cause any warpage problems in the finger It is important that the recommendations and
block types of flooring. Some of the for- instructions of both the flooring manufacturer
mulations will dry sufficiently within and the adhesive manufacturer be followed.
three to five hours to allow the installer Adhesives must be of good quality to insure a
to begin sanding operations to smooth the long lasting installation. Certain types of foams
surface prior to finishing. Generally, un- present in foam-backed sheet goods may not be
finished finger block installed with poly- compatible with some of the adhesives that are
vinyl acetate adhesives requires the skill generally sold for roll goods application. In the
of an experienced contractor. event a particular piece of sheet goods or car-
4. Epoxy resins. Installations are occasion- peting is foam backed, one should detennine
ally made with epoxies, but, the strengths absolutely that the adhesive used is compatible
these adhesives develop generally far ex- with these foams by means of a test on scrap.
 ADHESIVES FOR BUILDING CONSTRUCTION 689

Also, the recommended notched trowel for the Rigid or Hard Material Flooring. Ceramic
installation must be used to achieve the proper tile, ceramic mosaic tile, quarry tile, slate, and
laydown. marble are all examples of the more rigid floor-
Resilient Tile. These tiles are commonly ing materials. All can be installed with adhe-
based on vinyls. Good quality mUltipurpose la- sives. The subfloor or substrate is likely to be
tex emulsion adhesives very similar to those either a concrete slab or plywood or similar
used for roll goods are also satisfactory for re- composition wood material. Once again it is
silient tile installations. However, since most important that these subfloors be clean, dry, and
of these resilient tiles are in either 9" x 9" or free from dust, dirt, oil, grease, etc. Most in-
12" x 12" pieces, they can also be installed stallations of these rigid substrates utilize sim-
with lower-viscosity pressure-sensitive adhe- ilar adhesives.
sives. Some of these are referred to in the trade Ceramic or Ceramic Mosaic Tile. Ceramic
as clear, thin spread adhesive. These adhesives tile is thin compared to other rigid flooring ma-
can be applied by either a brush, trowel or roller terials and calls for smaller notched trowels for
coat over rather large areas. Generally they are spreading the adhesive on the substrate. Exces-
allowed to dry to a point where they become sive amounts of adhesive should be avoided and
pressure sensitive; then the tile is placed into the tile should not be moved around after it has
position in the adhesive bed, and bond is im- been imbedded in the adhesive. These practices
mediate. These pressure-sensitive formulations tend to cause the adhesive to push up into the
have exceptionally high green grab, so that one joints and make it difficult if not impossible to
can walk on the floor during and immediately properly grout the tile after the adhesive has
after their installation. For the do-it-yourselfer, set. Solvent-based SBR and nitrile formula-
the installation of vinyl tiles with these low- tions as well as SBR latex emulsions are com-
viscosity, clear, thin spread adhesives is vir- monly used. It is important to select a
tually foolproof, even for the most inexperi- formulation that dries quite rapidly and that will
enced individual.! enable grouting the tile within a 24-48 hour pe-
A common finishing item for various types riod. This requirement favors solvent systems
of flooring are vinyl and rubber cove base trims. over the slower drying. latex emulsions. Since
Generally, resin-type adhesives are used for the grouting process involves pressure on the
these cove bases, extruded in parallel strips ap- tile, for example by standing on it, it is impor-
proximately I!" to 2" apart along the back of tant that the adhesive develop strong bonds
cove base. Alternatively, cove base can be in- quickly to avoid shifting of the tiles during
stalled very efficiently with neoprene contact grouting.
cements. The cove base is first put into position Quarry Tile. Quarry tile may also be in-
without any adhesive, and a light pencil mark stalled with adhesives, and because of its thick-
made along the top edge of the cove onto the ness and size, calls for larger notched trowels
wall surface. The neoprene contact cement is for spreading the adhesive. Here again the ad-
then brushed in the space below the pencil mark hesive must develop its strength quite rapidly
as well as on the back side of the vinyl or rub- to permit grouting of joints. The selection of
ber cove base, the solvent is allowed to evap- grouts with adhesive-installed flooring systems
orate, then cove is pressed into position for is critical. These floors tend to have some de-
immediate bond. gree of movement and deflection. Therefore,
Wood trim pieces are sometimes placed on rigid setting grouts will have a tendency to
hard wall surfaces such as poured concrete or crack out of the joints. It is recommended on
concrete block. These wood moldings can be adhesive-installed floors that the grouts utilize
bonded with SBR solvent-based adhesive, ex- a latex base in order to provide resiliency.
truded from cartridge onto the back of the cove Gauged Slate. Slate is generally available
base and then pressed into position. A common either gauged or ungauged. Most slate is cut
form of this adhesive is referred to as construc- into random pattern designs and installed in this
tion adhesive. fashion. Adhesive installations of slate can only
690 HANDBOOK OF ADHESIVES

be accomplished with gauged slate, which has finished surface or an excellent backup surface
been unifonnily sized by grinding down to for other wall covering products. Adhesive-in-
standard thicknesses. Ungauged slate is gen- stalled gypsum wallboard has many advan-
erally installed on a thick bed of portland ce- tages, to be discussed later. Construction
ment rather than adhesives, because it is quite adhesives or panel-type adhesives are most fre-
uneven. In installing gauged slate, the grout quently used, many specifically labeled for
must again have a resilient base to allow for gypsum wallboard installations.
movement and deflection. Paneling is one of the most common wall
Marble. Adhesives for marble are similar covering materials applied with adhesives. Pre-
to those for other rigid flooring materials. finished plywoods, solid woods, and prefin-
However, there is another potential considera- ished hardwood are but a few types of paneling.
tion with marble: the translucency of some Some of these require specific adhesive for-
marbles may pennit dark-colored adhesives to mulations, while others can utilize the general
show through. Therefore, the adhesive must be panel adhesives. Some forms of prefinished
rather light in color. plywood and hardboards are applied directly to
There will be from time to time new rigid gypsum wallboard' surfaces using adhesives
flooring materials. Usually they will be bonded troweled over the entire surface of the panel-
with an elastomer, solvent-based SBR (buta- ing. The adhesives used must have longer
diene-styrene rubber). However, it is not un- working times than are normally found in car-
common to find some emulsions (water based tridge extrusions of panel adhesives. These
systems) that are satisfactory. Some of the trowel-type products are called tileboard ad-
larger rigid flooring pieces may have a degree hesive and are suitable not only for prefinished
of warpage. Therefore, it becomes imperative hardboard but also for other types of paneling.
that the correct notched trowel be used to pro- It is not uncommon to find flooring materials
vide the optimum thickness of adhesive be- used as wall covering, for example, wood par-
tween the substrate and the flooring material. quet flooring and carpeting. They require dif-
ferent adhesives from those used on floor
WALL AND CEILING ELEMENTS installations, with sufficient green strength to
hold the flooring material in a vertical position.
The use of adhesives for installing wall mate-
Ceramic and mosaic tiles also require special
rials has grown immensely since the end of
adhesives. Latex emulsion formulations are
World War II. A rather wide variety of adhe-
generally used, troweled onto the wall surface
sives are designed for the various wall cover-
prior to the installation of the ceramic or mo-
ings according to the specific requirements of
saics.
each.
Another unusual type wall covering material
On poured concrete walls or masonry walls,
is the plastic laminates found on countertops.
it is becoming common to utilize some form of
These are quite commonly installed on wall
insulation such as polystyrene foam, polyure-
surfaces for backsplashes. This requires a more
thane foam, or fiberglass before installing the
viscous adhesive than the contact cements that
finished wall covering. Polystyrene foam may
are normally used on countertop work, because
require special adhesive formulations that do
of uneven wall surfaces.
not attack it.
Furring strips also may be installed directly
Backup Surfaces or Substrates for Wall
to concrete and masonry walls to provide a
Covering Materials
backup surface for the installation of finished
wall covering. Such applications on furring As with floors, it is important to have accept-
strips generally utilize a high quality construc- able substrates to which to bond the finished
tion adhesive. wall covering. Many walls are out of plumb
Gypsum wallboard is quite frequently in- and require some type of furring or adjustment
stalled with adhesives direct to furring strips or in order to be receptive to a plumb finished
studs. This wall covering can provide either a wall. Other walls may have moisture problems,
 ADHESIVES FOR BUILDING CONSTRUCTION 691

dusty or dirty surfaces, or loose, scaly paint thatwall covering, particularly over exterior ma-
does not provide a good surface to which to sonry or poured concrete walls. Polyurethane
apply wall coverings. foams are generally not harmed by the solvents
contained in adhesive formulations commonly
Concrete and Masonry-Type Substrates. used for wall coverings. However, polystyrene
A word of caution about poured concrete walls. foams are very susceptible to attack from sol-
Often the forms for making these walls are vent-based systems unless the formulation is
coated with oils or other mold releases to pre- specifically developed for the installation of
vent the concrete from adhering to the form. If polystyrene foams. Therefore, adhesive for the
these are not removed from the cured concrete polystyrene foams must be selected cautiously,
wall surface, it will be difficult to get any ad- whether the foam is to be bonded to a substrate
hesive to adhere. Therefore, one should be cer- or a finished paneling material is to be bonded
tain that these walls have been thoroughly directly to the foam.
cleaned and are free from any oils or mold re- Generally, any uneven substrate or backup
leases. Masonry construction, on the other surface should be furred out prior to applying
hand, generally does not utilize oil or mold re- additionai wall covering, but panel-type adhe-
lease materials, but does have a problem of sives may bridge some minor irregularities.
mortar squeezing out from the joints, creating
an uneven surface. This can generally be cor- Types of Adhesive for Wall Coverings
rected quite easily by thoroughly wire brushing
prior to application. In the event moisture is Construction Adhesives. Unfortunately
present, steps should be taken to eliminate it the commercially available adhesives labelled
from the masonry or concrete walls prior to "construction" range in quality from poor to
putting on any other wall covering. If the mois- excellent. One way to be assured that the con-
ture problem is not addressed prior to the in- struction adhesive is of acceptable quality is to
stallation of the wall covering, it will most look for the hallmark on the label that the prod-
probably persist and worsen as time goes on, uct is certified to comply with the American
providing a very inadequate surface for wall Plywood Association's specification AFG-Ol,
covering installations. a very rigid test.
The label information must be read carefully.
Existing Plaster or Gypsum Wallboard Do not assume that a product can be used on
Surfaces. On older construction there is a polystyrene foams unless this is stated. The la-
good possibility that there are a number of coats bel will also indicate if it is satisfactory to use
of paint over the surface of the gypsum wall on treated lumber. Some of the treated lumber
board or plaster. Before any wall covering can available today requires special adhesives for
be bonded to these surfaces, one must make ab- good bonding results, but the better quality
solutely certain that the paint is well bonded construction adhesives will perform satisfacto-
and that it will not be softened by any ingre- rily. Virtually all construction adhesives would
dient of the adhesive formulation. This gener- be satisfactory for panel installations directly to
ally can be determined by applying some studs or furring strips. These adhesives are
adhesive over the paint in an obscure spot and generally available in cartridge containers for
allowing it to dry for 24 hrs to determine extrusion of beads. They have the advantage of
whether it has good bonding properties with the bridging framing irregularities. Here again,
painted surface. It goes without saying that all though, you can not expect miracles on this
loose and scaly paint must be removed before bridging characteristic and most manufacturers
an attempt is made to bond anything to the sur- will state on their label the minimum and max-
face. imum bead size that should be used.
Many high quality construction adhesives can
Plastic Foams. It is becoming common to be used on exterior applications other than
use either rigid polystyrene or polyurethane wood decks. Many spot applications on sur-
foam as a backup material for certain types of faces that are normally difficult to secure by
692 HANDBOOK OF ADHESIVES

nails or other mechanical fasteners can beser- the area around the adhesive for solvent attack
viced by these construction adhesives. Some or softening of the foam.
that are specifically formulated for high tem-
perature work, such as the neoprene-based Gypsum Dry Wall Adhesives. Gypsum
mastics, are suited for metal building use. wallboard has been installed with adhesives
However, in roof applications on metal build- since the 1950s. The use of adhesives results
ings, temperatures become quite severe, even in a great reduction in the number of nails that
exceeding 200-250 o P in the summer. are necessary, and at the same time virtually
eliminates nail popping. Racking strengths are
Panel Adhesives. Panel adhesives are gen- greatly enhanced if the gypsum wallboard is
erally formulated specifically for the installa- bonded to the stud walls. At the same time,
tion of either prefinished plywood paneling or there is less need for spackling and finishing
hardboard paneling of some type. They do not the nail heads. The mastics used in this appli-
have the high performance requirements- cation will again bridge framing irregularities
either high temperature or high shear strength- in the stud walls and result in more level and
of the better construction adhesives. Neverthe- flat wall surfaces than nailing to bowed or
less, most panel adhesives used today would warped studs. Today most good installations of
actually fracture the wood they are bonded to gypsum wallboard are made with quality ad-
before they would delaminate internally. They hesives.
are typically high-viscosity mastics.
Ceramic and Mosaic Wall Tile Adhesives.
Tileboard Adhesives. These viscous adhe- These adhesives are generally emulsion sys-
sives are generally applied by a notched trowel tems with a long working time as well as a high
spreader. They would be used on large sheets degree of green grab that prevents the tile from
up to 4' x 8' where the entire back of the sheet sliding down a vertical surface. All ceramic tile
would be troweled and then placed into posi- cements today are troweled by notched trowel
tion on the existing wall. These adhesives re- spreader, whose notch spacing is recom-
quire certain characteristics not normally found mended by the adhesive manufacturer on the
in panel adh~sives. They must have a long label.
working time in order to avoid the drying out
of the mastic too severely before installation; Wood Glues. While wood glues are nor-
but they still must have an adequate amount of mally thought of in relationship to furniture and
green grab or tack to hold the panel in position cabinet making, they have become ilIlportant in
when it is placed on the wall. This type of construction also. Most finish carpenters utilize
product is used to apply paneling over existing one of the various types of wood glues on trim
wall surfaces, which must first be suitably around doors, windows, base board or other
treated. Trowels used for these applications types of trim in the finishing process of con-
should be frequently cleaned to avoid buildup struction, whether residential or industrial.
of adhesive on the notches, as this would result White glues, based on polyvinyl acetate, are
in too little adhesive being applied on the sur- of course quite common, but there is a trend
face. toward the aliphatic resin yellow wood glues
for this finish work. Not all yellow-colored
Foamboard Adhesives. Poamboard made glues are based on aliphatic resin. One advan-
from polystyrene foam or bead board is very tage of the aliphatic resins is their built-in heat
susceptible to solvent attack or solvent etching. resistance, which allows them to be sanded
Thus many of the available solvent-based con- where the white glues would gum up the sand
struction and panel adhesives are unsatisfactory paper. Also, they dry quite rapidly, faster than
for the installation of foams. The adhesive un- most white glues. The true aliphatic resin can
der consideration should be tested by placing a be detected by the fact that it has a tacky char-
bead of adhesive between two pieces of foam acteristic normally not found in white glues.
overnight, then breaking it apart and inspecting Liquid hide glues, while still available, are
 ADHESIVES FOR BUILDING CONSTRUCTION 693

passing out of vogue in construction applica- Water base contact cements will generally
tions because of their slow drying characteris- require greater pressures for ultimate bond
tic. Generally speaking, white glues and strengths than can normally be accomplished
aliphatic resin wood glues greatly outperform on the job site. As a result, they are relegated
the liquid hide animal glues on construction ap- to the cabinet shops and areas where controlled
plications. conditions and uniform pressures can be ap-
plied. They tend to be absorbed into the sub-
CEILING TILE APPLICATIONS strate, resulting in a "starved" glue joint.
Thus, in the event a water base cement is used,
Several years ago, virtually all acoustical ceil- adequate thickness of adhesive is essential.
ing tile was installed with adhesives. Today, Many times this may require two or even three
most installations are drop-in types with grid coats of the contact cement. Of course, both
systems. There still are some instances how- the plastic laminate and the substrate need to
ever where the acoustical tile is still bonded to be coated.
the ceiling, requiring a special kind of adhesive Solvent base contact cements are among the
or mastic formulated from low molecular most hazardous adhesives to use on the job site.
weight tackifying resins. Frequently, adequate ventilation is difficult to
When adhesives are applied to the back of a achieve and accumulation of vapors can result
12" x 12" ceiling tile in golf ball size globs, in fire and/or explosion. This characteristic be-
there is a dead load placed on the adhesive bond came such a problem a few years ago that the
from the weight of the tile. Generally, these
federal government, through the CPSC (Con-
ceiling tiles are tongue-and-grooved, and this
sumer Products Safety Commission), banned
accentuates the problem. Thus, the adhesive. is contact cements with flash points below 20°F
required to have a high degree of cohesive
from the consumer markets. This ruling has re-
strength to hold the tile in position and not al-
sulted in broader acceptance of chlorinated sol-
low it to sag away from the ceiling. This co- vent contact cements. The small increase in
hesive characteristic is not available in most price is well worth the reduction in hazard from
adhesive formulations, except for the resin- flammability and explosion. Chlorinated con-
based mastics. Consequently, most acoustical tact cements resemble flammable contact ce-
tile cements are formulated from resin base
ments in both application and ultimate
rather than rubber base. Mastics deficient in co- properties.
hesive strength will fail. Cultured and/or acrylic based marble coun-
tertops are not necessarily installed over ply-
FLAT HORIZONTAL SURFACES
wood or particleboards; some are bonded to
In today's construction, flat surfaces may in- framing members of countertop construction
volve plastic laminate, cultured marble, or with high quality construction adhesive. While
acrylic countertop. Formerly, most of these some of the SBR construction adhesive would
products were installed on plywood. Today, work satisfactorily, the traditional mastics have
however, various types of hardboard, particle been of the neoprene class. They are extruded
board, or wafer board provide suitable sub- from cartridges onto the cabinet framing, and
strates. bridge the framing irregularities that are gen-
Contact adhesives are preferred for the plas- erally present. Because of the translucency of
tic laminate materials. Contact cements are cultured and acrylic marbles, it is generally de-
available in three types: water base, flammable sirable to select mastics that are light in color
solvent base, and chlorinated solvent non- to avoid shadowing through the counter top.
flammable base. The vast majority of these
contact cements utilize neoprenes as the basic
SPECIALTV ADHESIVES
elastomer. Attempts have been made by some
manufacturers to formulate acrylic contact ce- A number of adhesives, glues, and cements
ments, but as of this writing none of these are with unique properties are used in the construc-
in general use in the construction industry. tion industry for special applications. The ros-
694 HANDBOOK OF ADHESIVES

ter will undoubtedly grow in the future, and the curtain wall construction. While they can be
list below is by no means all-encompassing. prepared in low viscosity, most of the products
for the construction industry today would prob-
Cyanoacrylate Adhesives ably fall into the heavier mastic classification.
They have uses similar to general construction
Sometimes referred to as "super glues," these
adhesives, and are in fact often referred to as
remarkable adhesives provide extremely high
construction adhesives. Blended with phenolic
strength and quick setting times. Cyanoacrylate
resins, they are superior in heat resistance, oil
adhesives, like their cousins the anaerobics,
resistance and strength to the lower-priced SBR
cure in the absence of oxygen. Thus, they are
construction adhesives.
best suited for the bonding of nonporous sur-
faces such as plastics, glass, metal, plastic lam-
Polysulfide Adhesives
inates, etc. Extreme caution should be used in
their handling, because setup time is so rapid While polysulfides are better known as caulk-
that smears of the adhesive on fingers can result ing materials, they are also strong, water-re-
in gluing fingers together. sistant adhesives with great flexibility. They are
formulated as one-part systems that cure or set
Epoxy Adhesives by reaction with moisture from the atmosphere.
They have not been readily available. Sulfide
These products are more generally used in
odor is a problem, especially for the do-it-your-
manufacturing than in the construction industry
seIfer.
and particularly on the job site. Generally two-
part systems, they utilize curing agents that will
Silicone Adhesives
impart their own particular characteristics to the
cured formulation. Many types of curing agents Silicone rubber is also used primarily as a
are available for epoxies. Some of the amine caulking material. However, its tough rubbery
curing agents can cause dermatitis, and cause consistency will lend it to various construction
violent reactions with evolution of heat. Usu- applications in the future and more silicone
ally, however, epoxy systems available over the based adhesives will be sold over the counter.
counter utilize polyamide curing agents that are
much easier and safer to handle. Thorough and Hot Melt Glues
complete mixing of the curing agent and epoxy
These glues, based on ethylene-vinyl acetate
is imperative to develop optimum properties.
copolymer, polyamide, polyethylene and other
Thus the epoxies are difficult to use in job-site
resins, are generally applied from electric glue
construction.
guns. They have rather sharp melting points
that render them liquid at one temperature and
Resorcinols
solid when they cool a few degrees. They are
Resorcinol-phenol-formaldehyde is one of few excellent where quick bonds are desirable.
totally waterproof adhesives available today. However, they are best suited to spot applica-
Again, this is a two-part system that has limited tions rather than larger areas. One must work
life after mixing the two components. The re- fast with these formulations because once they
sorcinol adhesives cure at ambient temperature begin to cool, they set up very quickly, gen-
above 45°P; they can thus be used to build erally within a matter of seconds.
large wooden arches that must be totally water-
proof. PROBLEMS AND TROUBLE SHOOTING
Very few building products are totally infalli-
Nitrile Rubber (Acrylonitrile-Butadiene
ble and completely trouble free. Adhesives are
Rubber) Adhesives
certainly not immune to problems. Unfortu-
These were developed in the 1930s as Buna-N nately, when something has not been properly
adhesives, suitable for the fabrication of air- bonded, the adhesive is blamed where in fact
craft structures. They have had some use in in most cases some other factor has caused the
 ADHESIVES FOR BUILDING CONSTRUCTION 695

problem. Thus it is necessary to be cognizant terials being bonded, a trial should be made
of the potential sources of trouble. The condi- with scraps of the adherends. After 24 hours,
tions outlined below are but a few that seem to the substrates should be pried apart and the
occur more frequently than others. bond and surfaces examined.

Freeze-Thaw Stability Materials Unreceptive to Bonding

Latex or emulsion adhesives contain water, and Unclean Surface. This is one of the most
may freeze. While many are called "freeze- common causes of adhesive failure. Dust, dirt,
thaw stable" by virtue of hydrophilic organic loose scaly paint, oil, grease, etc. must be re-
constituents, others can be harmed by freezing. moved. Never clean with gasoline or fuel oils
The signal to the user is the notation on the as they leave an oily residue. If you use sol-
label, "Keep from freezing." Fortunately, it is vents for cleaning, be careful to observe all rec-
generally not possible to use a product that has ommended safety precautions.
been damaged by. freezing. If it is not freeze- Sometimes it is necessary to clean walls,
thaw stable, the adhesive may coagulate upon ceilings or floors with a strong detergent or
freezing and cannot be removed from the con- agent such as trisodium phosphate. All waxes
tainer. Adhesives that are freeze-thaw stable must be removed from old existing floors be-
can generally go through a number of cycles of fore any attempt to adhere a new material. If
freezing and thawing without damage. there are any loose tiles or floor depressions of
any type, they should be removed and the area
Improper Storage of Product of depression leveled with a latex concrete
Adhesives should be stored at room tempera- bonder or floor leveling compound.
ture for 24-48 hours prior to use during the
Tolerances Too Great (Too Much Gap Fill-
colder winter months. Even those that are not
ing). Another common cause of failure on
harmed by freezing have a tendency to thicken
adhesive installation is gaps or dips in the
when cold and are hard to use.
subfloor. Even smooth-troweled concrete that
Some adhesives are packaged in fiber con-
tainers such as cartridges. These can be dam- is clean and dry can sometimes cause problems
aged and weakened if stored in a damp area, through puddling. For example, if a concrete
and the adhesive may lose solvent and become floor, even a new one, is hosed down with
water, some puddles of water accumulate in the
heavy or even hard. Sometimes this is unde-
low areas. Should one be putting down a rigid
tectable until one tries to use the adhesive.
flooring material such as slate, quarry tile, or
Incorrect Product for Application wood parquet, it is possible that a gap would
form between the flooring and the subfloor as
Adhesives partially utilized for one project may the flooring would tend to bridge over the low
be quite unsuitable for another. Also, a leftover points. In severe cases the adhesive that was
adhesive may be irretrievably changed in com- troweled onto the subfloor may be prevented
position and physical characteristics. from coming into contact with the flooring, and
Adverse Effects of Adhesive on the an inadequate bond would be developed. These
Adherend low places in floors as well as all cracks should
be leveled and filled with a suitable latex-con-
It is important that the materials being bonded crete underlayment before any attempt is made
and the adhesive or glue be compatible. The to install flooring. Mastic-type adhesives will
sensitivity of polystyrene foams to attack by perform some gap filling functions; but all too
certain solvents has been mentioned. Adhe- often too great a burden is placed on the mastic
sives tend to bleed through some thin or porous to fill too large a gap.
surfaces. The solvents used in various adhesive
formulations may harm the plastics and inter- Surfaces Not Dry. One final problem which
fere with bonding. If there is doubt about the may cause interference with bonding is a moist
effect that an adhesive may have upon the ma- surface. Most adhesives are not designed to
696 HANDBOOK OF ADHESIVES

bond to wet surfaces. Damp masonry walls and are dissipated less rapidly. Metal or glass
concrete slabs are particularly troublesome. surfaces will not permit the drying or re-
Even though a wall or floor may appear dry, lease of solvents as quickly as will wood
surface water can seep through masonry walls or similar surfaces. In general the open
during heavy rains and hydrostatic pressure can or working time will not be nearly as long
develop in floors. Adhesives and glues are not on porous materials as on nonporous ma-
waterproofing compounds, and should not be terials.
used for this purpose even if they are called 3. Temperature and humidity conditions.
rubber based, waterproof, or water-resistant. Higher temperatures result in a more rapid
release of the solvents, thereby shorten-
ing the open or working times. However,
Improper Application of Adhesive or Glue
humidity also plays an important role.
Incorrect Amount. All too often an attempt Even if the temperatures are high, solvent
is made to install wall or floor covering with an release under high humidity conditions
insufficient amount of adhesive. Even if the could be extremely slow, resulting in a
trowel notch size is correct, it may be partially much longer open or working time. Of
clogged, or held at the wrong angle, or worn course, the presence of air flow or wind
down from long use on concrete. would also tend to shorten open times.
4. Waiting period too long. While anyone
Adhesive Too Dry Before Assembly Made. or a combination of the above factors
Several factors may cause poor bonds as a re- could create problems, probably none are
sult of excessively dried adhesive: the size of as common as just plain waiting too long
the bead from a cartridge; the size of the after the adhesive is applied to make the
notches on the trowel; failure to wet the sub- assembly. On any job it is wise to occa-
strates; ambient temperature too high and hu- sionally pull apart an assembly shortly
midity too low; and too long a waiting period after it is made just to make sure that there
before assembly. is wet adhesive transfer from one surface
to another.
1. Trowel and cartridge application. The
open or working time of most adhesives
Adherends Improperly Positioned,
is one of the variables that is generally
Clamped, or Braced During Drying. Po-
controlled by the manufacturer through
sitioning is very important. In the case of con-
formulation. A bead extruded from a car-
tact cements there is no second chance to
tridge will generally have a shorter open
position the substrates, since bond is instanta-
or working time than a troweled material.
neous. In other types of installations the cor-
The manufacturer will recommend on the
rection of improper positioning can result in too
label the exact bead size or notch trowel
much adjustment, thereby wiping adhesive
size for optimum results. Too small a
from one of the substrates, resulting in a starved
bead or notch can greatly reduce the open
joint, a bond with inadequate adhesive.
or working time, thereby causing the ad-
Improper clamping or bracing can also create
hesive to be too dry to develop a satisfac-
problems. Not having the assembly in close
tory bond.
enough contact during drying or curing will re-
2. Nature of substrates. Surfaces differ in
sult in an unsatisfactory bond.
porosity or absorbency. Particle board is
made from different wood species, some
Bonded Assembly Improperly Set, Cured,
more porous than others, so that solvents
or Dried
or water are absorbed more readily,
thereby shortening the open or working Many good bonds are destroyed by moving the
times. Steel-troweled concrete is also far assembly about before the adhesive or glue has
less porous or absorbent than regular ma- had an opportunity to adequately cure, dry, or
sonry concrete, and as a result, solvents set. There is wide variation in the curing or
 ADHESIVES FOR BUILDING CONSTRUCTION 697

drying characteristics of different kinds of glues ularly in roof and ceiling applications, that they
and adhesives. Some good wood glues cure in were never designed to tolerate. Some adhe-
a matter of minutes, while a so-called fast- sives have poor metal adhesion yet bond well
drying rubber mastic might take 12-24 hours to wood and other surfaces. Strengths are also
to develop a satisfactory bond. The directions to be considered. It makes no sense, for ex-
on the label or manufacturer's instruction sheet ample, to use an epoxy adhesive that will de-
must be followed. velop thousands of pounds per square inch of
strength when even one of the substrates will
Adhesive or Glue Did Not Meet fracture with only a few hundred psi or less of
Performance Requirements of Bonded shear stress.
Assembly
Where and how is the final bonded assembly Have Not Read the Manufacturer's
going to be used? This is a key question that is Instructions
sometimes overlooked. All too often the final A thorough reading of the manufacturer's label
assembly will stand outdoors in all kinds of and directions would go a long way towards
weather, yet a waterproof adhesive has not been preventing some of the trouble areas that are
selected. Many manufacturers are inclined to occasionally encountered. After all, the cost of
take some poetic license in describing their the adhesive or glue is only a minute part of the
products as "water resistant" or "water- total cost in terms oftime, labor and materials.
proof." lithe product is to be used outdoors,
the label should not only state "waterproof"
but also describe the conditions under which BIBLIOGRAPHY
the adhesive can be used and will perform.
Most wood glues are not waterproof and should Miller, Robert S., "Home Construction Projects with Ad-
hesives and Glues," Franklin International, 2020 Bruck
not be exposed to exterior conditions. St., Columbus, OH 43207, 1983. Installation proce-
Temperature is another consideration. Many dures for all types of flooring are elaborately detailed in
adhesives are exposed to temperatures, partic- this book.
 42
Adhesives in the Electrical Industry
LEONARD S. BUCHOFF
Consultant
Huntingdon Valley, Pennsylvania

The use of adhesives in the electrical industry thermal conductivity, application methods, cure
is rapidly expanding bepause adhesives are temperature, and environmental exposure.
being developed having characteristics suited Epoxies are the most widely used adhesives
to the unique needs of electrical/electronic because of their versatility, excellent adhesion,
market. Also the electrical industry has gained compatibility, ease of application, good elec-
faith in the reliability of adhesives. trical properties, and resistance to weathering.
Some of the major recent developments in the Silicones are used where flexibility, wide tem-
adhesives used in the electrical industry are: the perature range, high frequency, high humidity,
emergence of specially tailored surface mount and/or atmospheric contamination are encoun-
adhesives; the increased use and proliferation tered. Hot melts can be used where their lower
of polyimides; the purification of die attach ad- strength and limited temperature range can be
hesives and other materials coming in close tolerated and rapid assembly is important.
contact with IC dies; and the use of high mo- Acrylics are used because of their excellent
lecular weight epoxies in sealing flat panel dis- electrical properties, stability, good aging char-
plays. acteristics, optical clarity, and rapid curing.
Adhesives are used in the electrical/elec- Urethane adhesives have flexibility, toughness,
tronic field in a variety of ways, from holding and strength from cryogenic temperatures to
microcircuits in place to bonding coils in mam- 125°C. Precoated polyvinyl butyral produces
moth electrical generators. Failure of adhesives bonds which are tough and are easily fabri-
could cause computers to stop functioning, cit- cated. Ceramics and glasses of many compo-
ies to black out, or missiles to misfire. sitions form high temperature and hermetic
In addition to mechanically fastening, adhe- seals. Adhesives are available as one-part liq-
sives in electrical applications are required to uids, two-part liquids, powders, solvent solu-
conduct heat, conduct or isolate electricity, tions, films, thermoplastic rods, and preformed
provide shock mounting, seal, and protect sub- pellets.
strates. Properties required for various appli-
cations cover the range from life of a few MICROELECTRONICS
seconds to many years. Operating temperatures
Die Bonding
are from -270°C to 500°C. Adhesives are
used in quantities of less than a microgram to Three major uses of adhesives in microelec-
more than a ton. The adhesive choice is gov- tronics are die bonding, bonding circuit ele-
erned by these considerations plus strength, ments to substrates, and sealing electronic

698
 ADHESIVES IN THE ELECTRICAL INDUSTRY 699

packages. The processing tempemture of the tain less than 50 ppm ionic impurities. Table 1
adhesive is much lower than the tempemtures lists the epoxy components and their affect on
required by eutectic bonding, which degmded the properties of the cured adhesives. Table 2
chip properties. In die bonding, a microdrop of gives properties of a typical die attach adhe-
adhesive as small as 0.003" in diameter is dis- sive. The adhesives must be capable of with-
pensed onto the substrate in a precise location. standing subsequent fabrication stress, such as
The integmted circuit chip is placed accumtely the 400°C encountered in thermal compression
into the adhesive, which is then heat cured. The lead bonding.
amount and location of the dispensed adhesive Some chips are very sensitive to gaseous at-
are critical; too much will result in a bond line mospheric contamination. Solvents and some
which is excessively thick. The viscosity and curing agents, e.g., amines and fluorides have
surface tension must be high enough to hold the been reported to affect CMOS and other ICs.
chip in place and the adhesive must not thin out All organic adhesives release water vapor in
to the point where it will flow and insulate cir- hermetically sealed packages. The level of
cuit pads. Thinning (reduction in viscosity) water vapor must be kept below 15,000 ppm to
would allow filler settling and the chip swim- avoid chip deteriomtion. Adhesives are avail-
ming out of its proper location. One- and two- able that contain getters to bind the water and
part specially formulated epoxies and poly- thus eliminate this problem. As other chemi-
imide adhesives are used for die attachment. cals are also released from the adhesives on ag-
Polyimides became popular as die bonding ing, and different chips have varying degrees
adhesives a few years ago because the then of sensitivity to contaminants, each circuit must
available epoxies contained ionic contamina- be checked with the chosen adhesion formula-
tion that caused failures. Polyimides are inher-. tion.
ently "cleaner" than epoxies because of their Besides holding the chip in place, the die
method of manufacture. Polyimides are stable bonding adhesives generally must conduct heat
at much higher tempemtures than epoxies but from the chip to the heat sink. This requires a
they always are applied out of solvent solution high thermal conductivity and minimum of
and require much higher cure tempemtures. The voids in the bond line. Electrically conductive
epoxy formulations now in use genemlly con- adhesives are used where the back of the chip

Table 1. Constituents of Epoxy IC Adhesives.

Base Resin
1. Bisphenol A-epichlorohydrin resin (bis A), most widely used, liquid at room temperature
2. Novolak epoxies-good for high temperatures, brittle, semisolid, or solid at room temperature
3. Solid bis A resin-for preforms and films

Curing Agents
1. Dicyandiamides plus accelerators-one-part systems, long shelf life, l50°C cure
2. Acid anhydrides plus accelerators
3. Aromatic substituted ureas

Fillers
Aluminum oxide, boron nitride, magnesium oxide, and silica; particle size, 1-2 microns
Reactive Diluents
(lower viscosity of mix)
Butyl glycidyl ether, phenyl glycidyl ether

Solvents
1. Butyl cellusolve-for screening
2. Xylene and MEK-for spraying
700 HANDBOOK OF ADHESIVES

Table 2. Typical Epoxy Die-Attach Adhesive Properties.

Storage Life: One-component system-6 months
Curing Cycle: One-component-l hour at 125·C, 30 minutes at 150·C, or 24 seconds at
270·C
Two component-15 minutes at 120·C
Resistivity : 10 12 ohm-cm at 150·C
Tensile Strength: To gold surface-l,OOO psi
Outgassing: 24 hours at 125·C under 10- 6 Torr.
Maximum weight 10ss-1 %
Maximum condensibles-O.l %
Temperature: Exposure without permanent loss of properties:
4OO·C for 5 minutes
150·C for 1,000 hours
Repairability ; Adhesive bond sufficiently weakened at 200·C to 250·C to permit nondestruc-
tive chip removal
Specifications: Curing agents prohibited-primary and secondary amines
Chemicals prohibited-those that release excessive water and/or ammonia
Ionic contamination-less than 50 ppm of chlorine, sodium, and potassium

contains a circuit connection, e.g., grounding. Ceramic frits and metal solders are also used
(Electrically conductive adhesives are covered to seal IC packages when hermetic seals are re-
in another section of this book.) quired. The ceramic is applied to the substrates
out of a suspension. The solvent is evaporated
Component Attachment and the binder burned out. The cover is then
put in place and the glass frit is melted to pro-
The next level of microelectronic adhesive duce the bond. Properties of the ceramic and
bonding is adhering the IC packaged chip, ca- glass are given in Table 3.
pacitors, and resistors to hybrid circuits. Epox-
ies with properties similar to die bonding PRINTED WIRING BOARDS
adhesives are used. In multichip applications
the adhesive is often screened onto the ceramic The necessity to resist 250°C soldering tem-
substrate. Film adhesives with and without perature limits the adhesives that can be used
glass cloth carriers are also used. The film is to bond copper foil to laminated printed wiring
solid, semi-cured epoxy which is cut to the chip boards. The copper foil can be bonded during
package size. On heating, the epoxy melts and the lamination operation if the base resin has
then sets during the curing cycle. sufficient adhesive strength. If the foil is ap-
Solvents used in the manufacture of the films plied to the cured board it is first coated with a
are not always completely removed. During the B-staged epoxy or thermoplastic and then heat
cure cycle, solvents can form gas pockets pro- bonded. A film of B-staged epoxy or polyvinyl
ducing inferior, porous bonds. In some circuits butyral can be used in place of the precoat.
the solvents can affect the electrical character- Copper foil is adhered to polyester film based
istics of the component. flexible circuitry with a thermoplastic polyester
adhesive. This produces a bond having lower
operating temperature than the other adhesives
Package Sealing
cited. When polyimide film such as DuPont's
Film adhesives are also used to seal integrated Kapton is used as the high temperature flexible
circuit packages. The film, cut in the form of a circuit substrate, a thermoplastic FEP Teflon
frame, is positioned on the bonding ledge, the coating or epoxy, acrylic, or polyimide adhe-
lid is put in place and the unit is heated to melt sive is used to bond the foil.
the adhesive and cure it. This process assures When printed circuit assemblies are sub-
the correct amount of adhesive in the proper jected to shock or vibration, components must
place and minimizes adhesive runout. be held in place with circuit board coatings or
 ADHESIVES IN THE ELECTRICAL INDUSTRY 701

Table 3. Glass/Ceramic Sealing.

Types
I. Stable glass-melts and solidifies without phase change, like thennoplastic plastics, most contain about 70% lead
2. Devitrifying glass-melts and crystallized to a high temperature ceramic, has low coefficient of thennal expan-
sion, not transparent, low temperature processing-430 to SOO C.

Uses
In cathode ray tubes, IC packages, liquid crystal displays, and gaseous discharge tubes
Die attach

How Applied
1. From a slurry: (a) glass powder suspended in amyl acetate or butyl carbitol with nitro-cellulose or ethyl cellulose
binder; (b) slurry is screened onto substrates or deposited by other methods; (c) solvent evaporated below 2OO·C,
(d) binder burned off at lS0-3oo·C; (e) glass is fused at 4S0·C for one hour
2. Perfonn-dry and ready for fusion

adhesives. Highly filled epoxies cured at low strength. Phenyl modified silicones are used as
temperature with amines are often used. Ther- impregnant up to 220°C. They offer excellent
mal cycling can crack bonds if the thermal coef- penetration into the interwinding fabric and
ficient of expansion of the adhesive differs moisture protection. For 185°C operation,
greatly from that of adjacent objects. It may be polyesters based on isophthalic acid or tere-
necessary to cushion glass components with a phthalic acid or RTV silicones are used. Where
soft silicone rubber interface before bonding to high voltage insulation up to 155°C is re-
prevent their cracking. quired, epoxies cured with anhydrides of di-
basic acids are the impregnants of choice.
B-staged epoxies and polyesters in glass cloth
LARGE EQUIPMENT are used to bind and tie armatures, transformers
and coils together. This reinforced material re-
The physical and electrical requirements for
places previously used steel bonding, which
generators, transformers, and other large
had to be carefully insulated to eliminate short-
equipment are becoming increasingly strin-
ing other electrical components. Acrylic resins
gent. They must operate at elevated tempera-
on glass cloth or Nomex is used in hermetic
tures for 20 to 40 years in hostile environments.
and general purpose motors because of their re-
Current surges which displace coils and high
sistance to DuPont's Freons, solvents, and oils.
rotational speed put physical stress on the
equipment. The size of many pieces of equip-
Pressure Sensitive Adhesives
ment preclude the possibility of curing in ovens
and the heat conduction of copper and other Pressure sensitive adhesive tapes are used for
metal makes local heating impractical. Room holding and anchoring lead wires to the outer
temperature setting adhesives overcome these wrap of transformer coils, capacitor wrapping,
difficulties. protection of leads and coils, and other similar
Often components such as coils are bonded applications. Adhesive transfer films are used
and insulated before assembly. High voltage to hold insulating material in position. Natural
insulation around coils is formed from fabric rubber based pressure sensitive adhesives have
impregnated with epoxy, polyester, or silicone poor solvent resisitance unless they are cross-
varnishes. Glass or polyester cloth is wound linked. Many modifications are possible. Syn-
into the coils. The cloth acts as a spacer which thetic rubber has better stability than natural
is subsequently impregnated by the resin. The rubber and better solvent and ozone resistance.
resulting reinforced fabric bonds the coil into a Acrylic pressure sensitive adhesives have the
strong monolithic structure with high dielectric best balance of properties. They maintain their
702 HANDBOOK OF ADHESIVES

excellent electrical properties and solvent resis- SURFACE MOUNTING ADHESIVES

tance after aging at high temperature and can
On printed wiring boards containing surface
be crosslinked if desired. Silicones are only
mounted and through-hole attachments, it is
pressure sensitive adhesives suitable for 180°C
necessary to secure the chip components to the
operation. Also, they can be applied at lower
bottom of the board before soldering. A num-
t~mperature than the others. Adhesive tape
ber of specialized adhesives have been devel-
backing include films of polyester, polyethyl-
oped to do the job. These adhesives hold the
ene, polyvinyl chloride, polyimide, polytetra-
components in their correct positions through
flourethylene and others.
board handling, cleaning, flux application, and
It is important to check the compatibility of
soldering, and must not weaken or change
the pressure sensitive adhesive with the magnet
shape during these exposures.
wire used to be sure that there is no deteriora-
The adhesive has minimal function after the
tion of the wire enamel and reduction of di-
soldering application, but it must not reduce the
electric strength. High sulphur and chlorides
reliability of the circuit by becoming conduc-
will adversely affect the copper wire especially
tive during environmental exposure, or put
in the presence of humidity and polution.
stress on the components during thermal cy-
cling or mechanical handling. On the other
Bonded Mica hand, if component replacement is necessary,
Shellac or alkyd resin is used to bind mica the adhesive should soften sufficiently at sol-
splittings to produce mica board. This is dering iron temperature to allow part removal.
pressed into shapes used as insulation in elec- Many of the currently available adhesives
tric motors, generators, and transformers. Mica have the required cured properties for use in
tape is used as insulation in motors and gener- component staking, but do not have the nec-
ator coil slots. Mica tape is fabricated by bond- essary application properties. High speed ad-
ing mica flakes to glass cloth or tissue paper hesive dispensing equipment requires adhesives
with shellac or silicone resin. with extended pot life and smooth flow char-
acteristics. The formed adhesive mounds must
retain their shapes without slumping and must
Displays
have enough green strength to hold the com-
Bonding and sealing liquid crystal displays ponents in place through the curing cycle. The
must be done in a carefully controlled way with adhesive must not string or tail as the dispen-
carefully selected materials to assure moisture sing tip is withdrawn. The resin component
exclusion and no deterioration of the liquid must not migrate onto contact pads where it
crystal component. Thermoplastic, high mo- would cure and interfere with soldering. The
lecular weight epoxy resins without catalyst are adhesive should cure rapidly with heat and/or
widely used as the sealing medium. Some man- UVexposure.
ufacturers use a O.OOOS" thick polyester film Several types of adhesives have been for-
spacer coated with B-staged epoxy. Glass seals, mulated to have the properties required to at-
described in Table 3, are used in liquid crystal tach surface mounted components. Some of the
displays and gaseous discharge displays. typical products are listed in Table 4 with their

Table 4. Typical Surface Mount Adhesive.

One-Pan UV-Curing
One-Pan Epoxy Frozen Epoxy Methacrylate"
Storage life at room temp. 3 months 4 hours 6 months
Cure time: 150·C 3 min 5 sec 40 sec
120·C 10 min 10 see 2 min
'Can be cured with UV lamp alone if light can reach entire body of adhesive. Exposed adhesive can be partially cured in 10-30 seconds
with UV and the completely cured with heat.
 ADHESIVES IN THE ELECTRICAL INDUSTRY 703

properties. These adhesives can be applied by Films-Supported or Unsupported

silk screening, dispensing from a single tube or
Examples. B-staged epoxy, rubber phenolic
multiple tubes, or pin transfer.
and polyvinyl butyral.
FORMS OF ADHESIVES AVAILABLE
Advantages. Precise amount and shape ap-
Two-Part Systems plied to correct location, accurate spacing of
adherents and control of spreading.
Examples. Epoxy, polyurethane and sili-
cone.
Disadvantages. Expensive, mating sur-
faces must be parallel, heat and pressure re-
Advantages. Very long shelf life, very fast
quired.
cure and room setting possible, properties can
be varied by using different curing systems.
Applications. Sealing IC packages, cement-
ing copper foil to printed wiring boards.
Disadvantages. Short pot life, excess mixed
material is wasted, possibility of improperly
proportioned or mixed adhesive producing in- Preforms - Solid Shapes That Melt to
ferior results. Viscous Liquid and Cure with Heat
Example. B-staged epoxy cylinders.
Applications. General use, cementing com-
ponents to printed circuits.
Advantages. Accurate amount of adhesive
put in optimum position, controlled flow, no
One-Part Liquids - Heat Curing waste, high speed production.
Examples. Epoxy and polyimide.
Disadvantages. Expensive, carefully con-
Advantages. No mixing, no pot life prob- trolled heat cycle required.
lems, and no waste.
Applications. Sealing caps on vacuum tubes
Disadvantages. Necessity for high temper- and sealing switch terminals.
ature cure, shelf life and storage conditions are
critical. Thermoplastic

Applications. IC chip bonding and impreg- Example. Ethylene vinylacetate based hot
nation. melts.

Advantages. Very rapid application and

One-Part Liquids-Moisture Curing
setting, no waste and inexpensive.
Examples. RTV silicones and poly sulfide
rubber. Disadvantages. Heated application equip-
ment necessary, bonds have moderate strength,
Advantages. Excellent adhesion to a vari- not useful at high temperature.
ety of substrates including silicones, room tem-
perature setting, and ease of use. Applications. Tacking wire in place, bond-
ing voice coil to speaker cone.
Disadvantages. Acetic acid given off by
some silicones, need of permeable adherend.
Pressure Sensitive Adhesive
Applications. Cementing silicone gaskets in Examples. Rubber or acrylic PSA on
place, sealing wire harnesses. polyester tape.
704 HANDBOOK OF ADHESIVES

Advantages. Instant adhesion at room tem- Solvent Systems

perature, substrate supplied with adhesive, eas-
Examples. Rubber, rubber phenolic, acrylic.
ily removed.
Advantages. Rapid application, inexpen-
sive, wide range of bonding methods and sub-
Disadvantages. Limited temperature, low strates.
strength, creep.
Disadvantages. Solvent removal neces-
sary, high cure shrinkage.
Applications. Securing transformer coil in Applications. Labels and insulation lami-
place, positioning lead wire to coil. nation.
 43
Conductive Adhesives
JUSTIN C. BOLGER
Consultant
Amicon I. C. Assembly Materials
W. R. Grace & Co.
Lexington, Massachusetts

Polymeric materials are normally excellent in- between $5 and $8 per troy oz. * vs. about 30<;:/
sulators. Most of the resins, such as epoxies, oz. for powdered copper. The price of silver
that are used in today's best adhesives are has stabilized during the past nine years, and
prized for their ability to insulate metals and silver continues to offer advantages in conduc-
other surfaces from both heat and high electri- tivity stability which cannot be matched by
cal voltages. But for many important industrial copper or other lower cost metal powders.
applications, particularly in the electronics in- Figure 1 shows the mechanism for current
dustry, it is necessary that an adhesive be able flow through a metal-filled polymer. If enough
to conduct either heat or electricity, or both. metal particles are added to form a network
Conductive adhesives, therefore, owe their within the polymer matrix, electrons can flow
conductivity as well as their cost and most other across the particle contact points, making the
physical properties to the incorporation of high mixture electronically conductive. Even under
loadings of metal powders or other special fill- the most favorable circumstances, current flow
ers of the types shown in Table 1. occurs only over the small area of the contact
points, so the conductivity of even the best cur-
rent silver-filled products is two orders of mag-
ELECTRICAL CONDUCTIVITY
nitude lower than the conductivity through pure
Table 1 shows the electrical conductivity val- silver.
ues and densities for pure silver, copper, gold Figure 1 also shows the resistances which are
and other metals; for the best current electri- introduced at the particle contact points by sur-
cally conductive adhesives and coatings; and face oxide layers, or by layers of absorbed or-
for oxide-filled and unfilled insulation resins. ganic molecules. It is this surface oxide layer
Although a large number of metals might be that rules out the use of most metals in conduc-
considered, in powdered form, to make con- tive plastics. Aluminum powder is widely used
ductive adhesives, most high performance con-
ductive products today are based on flake or
*Prices for silver, gold, and platinum are normally quoted
powdered silver. Silver has the disadvantage of in newspapers and elsewhere in dollars/troy oz. One pound
being relatively expensive, currently selling for equals 14.5 troy oz. One troy oz. equals 31.1 grams.

705
706 HANDBOOK OF ADHESIVES

Table 1. Electrical Conductivity of Metals, Conductive Plastics and Various

Insulation Materials at 25°C.
p = Volume
Specific Gravity Resistivity
Material g/cm3 ohmcm
Silver 10.5 1.6 X 10- 6
Copper 8.9 1.8 X 10- 6
Gold 19.3 2.3 X 10- 6
Aluminum 2.7 2.9 X 10- 6
Nickel 8.9 10 X 10- 6
Platinum 21.5 21.5 X 10- 6
Eutectic solders 20-30 X 10- 6
Conductive glass adhesive I X 10- 5
Best silver-filled epoxy adhesives I X 10- 4
Graphite 1.3 X 10- 3
Nickel-filled epoxy adhesives I X 10- 2
Graphite or carbon-filled coatings 102-10 1
Oxide-filled epoxy adhesives 1.5-2.5 10 14 _10 15
Unfilled epoxy adhesives l.l 10 14 _10 15
Mica, polystyrene, and other best dielectrics 10 16

in the adhesives industry as a reinforcing filler Gold-Filled Adhesives and Silver

and as a decorative pigment, but aluminum Migration
powder cannot be used to make electrically
conductive plastics because of the oxide film Gold filler is sometimes specified for electronic
which insulates the particle contact points. Only assembly operations, despite the much higher
metals such as silver and gold, which form both price and lower electrical conductivity com-
thin and relatively conductive oxides, can be pared to silver-filled adhesives. Gold-filled ad-
used in powdered form to provide stable resis- hesives are still required by some military
tivity values less than about 0.001 ohm/em. specifications issued in the early 1960s.

Current path
Surfactants or other adsorbed organic layer

.
:. :.'\l
\.'

/ .' 1
<~),f /

YV
/-j-~
~._ ",:y,/fY
. "- /

Fig. 1. Current flow path between metal particles in conductive adhesives. Adsorbed or-
ganic molecules and oxide films prevent or impede passage of electrons across particle
contact points.
 CONDUCTIVE ADHESIVES 707

The justification for gold is that it avoids an mer coating or potting compound over the sil-
effect called silver migration which occurs with ver-based ink or adhesive, to eliminate any
silver-filled acrylics, epoxies, and other resins. direct diffusion path for ion migration. In the
Silver migration is dependent on the fact that electronic industry, silicone gels and coatings
all polymeric materials are permeable to water are most often used for this purpose because of
to some extent. In the presence of moisture, their ionic purity and their flexibility over a
silver ions may be leached out of the cured broad temperature range.
resin, and redeposited elsewhere in the circuit.
To test for silver migration, a constant DC
Low-Cost Conductive Adhesives
voltage is applied between a silver-filled ad-
hesive and a nearby conductor, such that the In efforts to avoid the use of pure silver to pro-
adhesive is the anode, and the voltage gradient vide conductivity, a number of lower cost con-
between the conductors is on the order of 1 volt/ ductive adhesives have appeared on the market
mil. Moisture vapor condensed on the interven- during the past 20 years. Some of these prod-
ing surface can permit silver ions to migrate ucts are based on nickel or carbon powders,
toward the cathode and form a conductive path others on copper that has been precleaned by
of metallic silver which short-circuits the de- an acid wash, to remove some of the surface
vice. Migration has traditionally been more of oxides, or which has been plated with a thin
a problem in hybrid than in monolithic ICs, be- surface coating of silver. For RFI shielding and
cause the adhesive fillet may approach other other low-cost applications that do not require
conductors on the hybrid substrate. high electrical conductivity or exposure to el-
There is no significant difference in silver evated temperatures, some of these copper or
migration for epoxies as compared to other nickel-filled adhesives have proven adequate.
thermosetting resins or to conductive glass ad- But copper-filled resins may not retain stable
hesives. Silver ions can be extracted from all electrical conductivity at elevated temperature
glasses and polymers with almost equal case. due to continued growth of oxide on the parti-
Increasing Tg (glass transition temperature) of cle surfaces. A copper-filled epoxy will typi-
the adhesive has a slight, but not important, ef- cally increase in resistivity by a factor of 100
fect on reducing migration. Whether or not an after 48 hours in air at 150°C. Silver-coated
adhesive is "clean" (low Cl-, Na +, and other glass beads, although more stable than silver-
extractable ions) also has no significant effect coated copper, have both rheological and con-
on preventing silver migration. Previously it ductivity limitations.
had been speculated that it was necessary to Much of the technology involved in conduc-
have ions present in the water film on the sur- tive plastics involves the metal particle size and
face to "connect the cell" and initiate silver shape. Silver is normally used in the form of
ion transport. very small flakes. To minimize cost (Le., silver
A lower cost alternative to gold-filled inks or loading), anisometric particles, such as rods or
adhesives is to substitute a silver-palladium al- flakes, are used to give a higher number of con-
loy for the pure silver filler used as the conduc- tact points and higher conductivity than would
tor. When the alloy content of Pd exceeds about spheres or cubic particles. But these flakes tend
30 %, migration is retarded· long enough to to orient parallel to the adherend surfaces dur-
comply with Mil. Std. 883B, with no signifi- ing many bonding and coating processes. For
cant loss in conductivity, and with relatively bonding applications where electrical conduc-
small increase in cost relative to pure silver tivity perpendicular to the bond line is re-
filler. Nickel-powder-filled adhesives offer an- quired, this orientation can reduce conductivity
other way to avoid migration, although at con- and be a disadvantage.
siderable sacrifice in electrical conductivity Voids due to air bubbles or to solvent bub-
relative to gold or silver. bles are a frequent quality problem in the bond
The best chemical method is to use a poly- line. These voids are undesirable because they
708 HANDBOOK OF ADHESIVES

increase electrical and thennal resistivity and must conduct heat but not electricity in order
can also decrease bond strength. For this rea- to bond power devices and other heat-generat-
son, the modern trend is to specify single-com- ing components to heat sinks, and to other
ponent, solvent-free, silver-filled adhesives, metal surfaces, where the adhesive must permit
which are premixed and pre-degassed by the high transfer of heat plus electrical isolation.
adhesive manufacturer before shipment to the Heat-conductive coatings include spray-ap-
customer and which contain no air bubbles, plied coatings for corrosion protection as well
solvents, or other volatiles which can cause as high-voltage insulation.
voids. Table 2 lists thennal conductivity values for
several metals as well as for beryllium oxide,
Comparison of Conductive Adhesives to aluminum oxide, and several filled and unfilled
Solder resins. Fig. 2 shows the thennal conductivity
Increasingly, silver-filled adhesives are being for an epoxy resin as a function of volume frac-
used to replace tin, lead, and silver-based sol- tion of heat-conductive filler.
ders. A number of reasons account for this in- Beryllium oxide is the most heat conductive
crease in use of conductive adhesives: dielectric material and is frequently used in sin-
tered fonn as a heat sink, but it is generally not
1. Electrically conductive adhesives give used to make heat-conductive adhesives be-
stronger and tougher bonds than most cause of the toxicity and high cost of powdered
solders. Aluminum powder, which is beryllia.
used as the filler in many high perfor- Alumina is inexpensive, provides excellent
mance epoxy adhesives, nonnally gives strength, and can be added to epoxy and sili-
very high bond strengths as measured by cone resins in very high concentrations before
ASTM-I002. Silver-filled adhesives, al- the viscosity becomes excessive. It is, how-
though generally considerably lower in
strength than the best aluminum-filled
structural adhesives, are nevertheless still Table 2. Thermal Conductivity of
much stronger and tougher than most sol- Metals, Oxides, and Conductive
dered joints. Adhesives.
2. Epoxy adhesives wet and bond to almost
Thermol Conducllvlly ., 2S'C
all surfaces and can be used with virtually (Btu/hr'F 1t'lIt)

any combination of metals, glass, ce- Silver 240

Copper 220
ramic, or plastic. Conventional solders Beryllium oxide 130
Aluminum 110
only wet certain metals. Other surfaces, Steel 40
Eutectic solders
such as silicon or alumina or tantalum ox- Aluminum oxide
20-30
20
ide, cannot be soldered without gold plat- Best sliver-filled epoxy adhesives 1 t04
Aiuminum·fllled (50%) epoxy 1102
ing or other costly surface modifications. Epoxy filled with 75% by wI. AI,O, 0.8 to 1
3. Conductive adhesives cure at much lower Epoxy filled with 50% by wI. AI,O,
Epoxy filled with 25% by wI. AI,O,
0.3 to 0.4
0.2 to 0.3
temperatures than are required for solder Unfilled epoxies 0.1 to 0.15
flow and permit use in contact with heat- Foamed plastics
Air
0.01 to 0.03
0.015
sensitive components. Two-component
conductive epoxies cure at room temper-
Table lor ConY8r.lon 01 Thttrmal Conductlvlly Unit.
ature.
g cal/cm2 sec °Clem w/cm J DClem Blulft'hr'F/fI Btulfl'hr" Flln
4. Conductive adhesives eliminate the need
1.0 4.19 242
for solder flux and for flux removal after 0.23 1.0 58
2900
890
4.13 x 10-' 0.0173 1.0 12.0
bonding. 3.44 x 10-' 1.44 x 10-' 0.083 1.0

THERMAL CONDUCTIVITY
Heat lransfer
formula:
k =
thermal conducllvlty
AT = temperature drop aeross material
= q = heat flow/unit area
Metal-powder-filled adhesives conduct both
q kAT
x = material thickness
heat and electricity. Some adhesives, however,
 CONDUCTIVE ADHESIVES 709

10'
x = Filler limit for usable viscosity
lf 100
1:
.e
:::II
i 10
~
!
C;
:::II
'1:1 1.0
C
0
u

.
ii
E
.!
0.1
' " A1,O,·fllled epoxy
BeO·fllled epoxy
~

0.01
0
Volume fraction finer
Fig. 2. Thennal conductivity increases as filler loading increases, but loading is limited
by mixture viscosity to a maximum of 40-50% by volume.

ever, abrasive and may cause wear and other and x = 3 mils = 0.0075 cm
damage to dispensing equipment. Alumina-
filled high k adhesives are processed to remove = qx = 20 X 0.0075 = 9.40C
AT k 0.016
grits or other large particles that can prevent the
attainment of very thin bond lines. Minimum = AT across interface
bond thickness is almost always desirable be-
cause heat flow is proportional to the ratio of An unfilled epoxy adhesive, with a conductiv-
ity of about 0.1 in the same units would cause
thermal conductivity to bond thickness.
a AT, for the same device, bond thickness, and
The best current 100% solids epoxy adhe-
power level, of almost 100°C.
sives contain about 70 % aluminum oxide by
Frequently, a permanent adhesive is undesir-
weight and give thermal conductivities in the
able, because some components must be ca-
range of 0.8-1 in the English units shown in
pable of easy and repeated removal from ~eat
Table 2. For convenience, a conversion chart
sinks or other mounting locations. Mechamcal
is included in Table 2 to permit conversion to
fastening methods, such as screws, leave an
any other set of units. The k values for the best
undesirable air gap between the component and
alumina-filled epoxies are 10-12 times greater
the heat sink, and cause heat buildup. Highly
than for unfilled epoxy resins, but are still much
filled silicone compounds, frequently referred
lower than for pure metals or solders. Never-
to as thermal greases, are used to eliminate this
theless, heat flow is adequate for bonding most
air gap. Special thermoplastic silicone re~ins
components. For example, an adhesive with a
are used which do not harden or crosslInk.
thermal conductivity of 0.91 and a bond thick-
Hence, the device can be removed and replaced
ness of 3 mils would be able to transfer about
for maintenance purposes. The thermal grease
20 W/cm2 of surface area, with a AT only about
must not decompose, give off volatiles, or per-
10°C above the heat sink temperatures:
mit any silicone bleed even after long-term ex-
posure to high temperatures. The filler,
k = 0.91 Btu/hr ft2 °F/ft
normally zinc oxide, must have a maximum
= 0.91 X 0.0173 particle size under 1 mil to permit a tight fit.
The best current thermal greases meet these re-
= 0.016 W/cm2 °C/cm (Table 2) quirements and provide the thermal conductiv-
If q = power/area = 20 W/cm2 ity of about 0.9 as in the above example.
710 HANDBOOK OF ADHESIVES

DIE ATTACH ADHESIVES can cause no loss in function or reduction in

expected life time of the finished device.
Silver-filled epoxy and polyimide die attach ad-
hesives are used worldwide to bond dies to the
Viscosity and Flow Properties
substrates of hybrid and monolithic integrated
circuits (ICs), light emititing diodes (LEDs), Die attach adhesives are creamy, thixotropic
and other devices. A conductive adhesive per- pastes which must be dispensed rapidly and
mits large cost savings over previous die attach without dryout, stringing, or other flow prob-
methods involving gold-silicon eutectic solder. lems, to permit high yields and high production
The adhesives bond to bare silicon, to gold, to rates. Most ICs are made by dispensing a very
copper, to alumina, and to other surfaces with- small, but carefully shaped, droplet of adhesive
out requiring the prior gold metallization on the lead frame or other substrate, using au-
needed for eutectic bonding, and without re- tomatic die bonding equipment. The adhesive
quiring any scrubbing or bake-out. must have enough green strength to prevent
Solder bonding requires process tempera- chip movement before cure, must form a proper
tures over 300°C. Adhesives, however, cure at fillet height and shape, and must not permit any
much lower temperatures and provide yield im- resin bleed before or during cure.
provement with LEDs and other heat sensitive
devices. Moreover, epoxies have more useful Hot Strength and Thermal Stability
flexibility than solder or glass and are, there-
Die bond adhesives must generally develop
fore, less likely to cause cracking of large dies
high hot strength after a short cure period in
during cool down. Fig. 3 shows the most
order to resist displacement of the die during
widely used method for packaging integrated
subsequent wire bonding. Adhesive tempera-
circuits. The low cost plastic (epoxy) packages
tures may reach 300°C during some wire bond-
called P-DIPs (plastic dual inline packages) are
ing operations. Modem epoxies and polyimides
used in high volume consumer products, such
retain sufficient strength to resist transverse
as games, calculators, watches, TV, radio, and
forces during wire bonding.
audio equipment.
High Purity Adhesives For Other
Die Bond Adhesive Performance Electronic Assembly Operations
Requirements
Conductive adhesives are used for many other
The properties needed for a successful die bond electronic assembly operations, in addition to
adhesive depend on the nature of the final IC die attach. Epoxy paste adhesives are used for
or other device, but generally can be divided capacitor and other component attach in hybrid
into performance requirements needed for high components or on printed circuit boards. In
speed, high yield production, and reliability re- general, these electronic assemblies require
quirements needed to insure that the adhesive high purity adhesives which do not give off im-

Gold wire

Epoxy molding CPO

Conductive
~ _ _ _ _ _ _• ___ adhesive

' - - - - - - - - - - - - Plated lead frame

Fig. 3. Most widely used method for packaging integrated circuits-low cost plastic pack-
ages called P-DIPs (plastic dual inline packages).
 CONDUCTIVE ADHESIVES 711

purities or contaminants which may cause cor- sives with exceptionally high strength and
rosion or other problems elsewhere in the toughness. For this reason, dicyandiamide has
circuit assembly. Outgassing of water or other been used for over 30 years to make one-com-
potentially corrosive vapors is a particularly se- ponent epoxy paste adhesives, plus tape and
vere reliability problem in military, medical, film adhesives, used in aircraft assembly and in
and other high reliability circuits packaged in other high strength adhesive assembly opera-
nonpenneable metal or ceramic packages. All tions. To pennit cure at temperatures below
organics, including all epoxies, give off water 180°C, dicyandiamide is nonnally used with
and organic vapors both during and after cure. an accelerator, such as the chlorinated urea
Vapors given off during cure are primarily sol- compound shown in Table 3. During cure, this
vents or low molecular weight diluent resins combination of epoxy, dicy, and urea reacts to
used to reduce viscosity. If these vapors can produce byproducts which include ammonia
escape to the atmosphere, volatiles released and other low molecular weight amines, and
during cure pose no long-tenn reliability prob- these byproducts continue to be released for
lem unless excessive use of solvent causes long periods after cure. Ammonia plus water
foaming of the adhesive or lifting of the bonded vapor causes alkaline attack of aluminum me-
part. tallization and aluminum bonding pads.
After the adhesive is cured' and the die is Epoxy B in Table 3 is cured with a Lewis
packaged, any further release of volatiles by the acid salt, the monoethylamine salt of boron tri-
adhesive is generally undesirable, particularly fluoride (BF3MEA). The first gold- and silver-
if the volatiles can combine with water vapor filled one-component epoxy die attach adhe-
to cause corrosion. Table 3 shows two epoxy sives, which were sold in the U.S. in the early
fonnulations which are representative of the 1970s, contained this curing agent. When
best one-component silver-filled epoxies used heated to 150°C, BF3MEA liberates BF3 gas,
for electronic assembly up to about 1980. which serves as an acid catalyst to cure the
Epoxy A in Table 3 is cured with a latent amine epoxy.
known as dicyandiamide (dicy):

H NH
I ~ BF3 is a strong acid and, in the presence of
N=C-N-C
moisture, is corrosive to aluminum and other
"NH2 metals. Since it is not chemically bound into
the epoxy network during cure, BF3 vapor can
Dicyandiamide is a crystalline, water soluble continue to be released from the cured epoxy
powder, which decomposes without melting at after packaging.
ca. 150°C. It does not react with epoxy resins The epoxy resin shown in Table 3 in Epoxy
at ambient temperatures but, when heated B is RDGE (resorcinol-diglycidyl ether). This
above its melting point, reacts to yield adhe- was once widely used in conductive epoxies

Table 3. Composition of First-Generation One-Component Epoxy Die Attach

Adhesives.
Epoxy A Weight % EpoxyB Weight %
Epon 828" 5.0 RDGE 27.6
Dicyandiamide 2.0 BF3MEA 0.8
Urea accelerato~ 1.4 Solvent 2.8
Butyl glycidyl ether 2.8 Silver powder 68.8
Silver powder 68.8 100.0
100.0
'Shell Chemical Co.
"24-dichlorobenzene urea
712 HANDBOOK OF ADHESIVES

because of its low viscosity and high strength adhesives is to use an inorganic (i.e., glass)
after cure. But RDGE is now known to be a binder. Conductive glass adhesives are now
strong carcinogen, and most adhesive formu- being used for die attach in CERDIPS (ceramic
lators and users now prohibit its use. dual inline packages) and other high reliability
The resins, solvents and curing agents used IC products. A conductive glass adhesive typ-
in modem conductive epoxy adhesives are cho- ically consists of silver powder and a low melt-
sen to minimize residual vapors which can be ing lead borate glass powder, plus solvent,
released after cure. Modem epoxy adhesives binder resins, and other additives. To form the
generally consist of high purity Bis-A epoxies bond, the adhesive is first dried at approxi-
cured with a phenolic. novolac resin. These mately 100°C to drive off the solvent, and then
mixtures do not contain boron or fluorides, and fired at 400-430°C to bum off the rest of the
generate less ammonia or other corrosive va- organics and melt the glass powder to form a
pors than epoxies available before 1982. permanent, completely inorganic bond. Be-
cause of the high thermal conductivity of the
Chlorides and Other Extractable Ionic glass, these silver-glass adhesives have three to
Impurities five times higher thermal conductivity, and up
to ten times higher electrical conductivity, than
Ionic impurities such as CI- , Na +, and K + can
the best silver-filled epoxies or polyimides.
cause corrosion of Al bond pads and other me-
Future production advances should result
tallization, loss in oxide dielectric strength in
from new epoxy adhesive types that permit a
FET circuits, and other problems in high reli-
variety of B-staging methods. These adhesives
ability (high reI) ICs. Until recently, most con-
can be applied as a thin film, for example, on
ductive epoxy adhesives contained very high
the back of the wafer before die separation, can
levels of extractable chloride ions and other
then be B-staged to a dry, nontacky film, and
ionic impurities. The adhesives of Table 3, for
later bonded directly to LED or IC substrates.
example, would. typically yeild over 600 ppm
Rapid cure (5-10 sec) of these B-staged adhe-
Cl- and over 200 ppm Na +, after a 24 hour
sives can be accomplished above 300°C.
extraction in neutral water at 100°C.
Polyimide resins are inherently lower in
Conductive Tape Adhesives
chlorides than epoxies. For this reason, many
IC manufacturers have chosen to use conduc- Another way of automating assembly is to use
tive polyimides, rather than epoxies, for high the epoxy adhesive in the front of a silver filled
reI assembly operations, even though polyi- or oxide filled tape. These tapes are made by
mides are more expensive, give lower bond impregnating the epoxy adhesive into a glass
strengths, and are more difficult to cure and to mesh support, B-staging to form a tack-free
process than epoxy adhesives. film, and then slitting the tape into rolls or die-
Recently, the major U.S. and Japanese resin cutting the tape into custom-made preforms. In
manufacturers have made available new, highly production, the user places a preform under the
purified epoxy resins which contain much less part to be bonded, or uses a machine to chop
extractable and hydrolyzable chlorides than the or punch preforms from a roll of tape. In either
best epoxy resins prior to 1980. Adhesive for- case, the tape provides precise control of bond
mulators now use these high purity epoxy res- thickness, eliminates voids, and avoids an ex-
ins to produce conductive adhesives, coatings, cessive fillet. The tapes can be cured very
and encapsulants which yield chloride levels of quickly, at temperatures over 160°C, and the
10 ppm or less and sodium levels of 5 ppm or controlled thickness of the bond reduces ther-
less. mal stresses due to thermal expansion mis-
Another approach to formulating high purity match between bonded part and the substrate.
 44
Structural Adhesives in the
Aerospace Industry
ROBERT E. POLITI
Engineered Materials Department
American Cyanamid Company
Havre de Grace, Maryland

Adhesives are used extensively by the aero- The requirements that perhaps most clearly
space industry for bonding structural compo- define the characteristics needed in a truly
nents of aircraft (both military and structural adhesive are those specifying maxi-
commercial), missiles, and satellites. Sealants mum limits on creep under sustained load.
are used in joints around windows, in fuel MMM-A-132, for example, specifies that lap
tanks, etc.; hot melts and pressure sensitive ad- shear creep at 75°F can not exceed 0.015 inch
hesives are utilized in aircraft interiors (pri- in 192 hours under a 1600 psi load. Limits set
marily in fabricating decorative panels); while on creep at higher temperatures help define the
thermosetting adhesives are used to bond load service temperature limitations of the specific
bearing structural components. adhesive. Similarly, Mil-A-25463 sets strin-
This chapter deals exclusively with structural gent limits on creep deflection under load on
adhesives employed in the fabrication of load bonded sandwich structure. For all practical
bearing components of the aircraft. In general purposes the need for creep resistance makes it
the adhesives currently in use will meet the re- mandatory that thermosetting adhesive be uti-
quirements of the Mil-A-25463 and/or MMM- lized in aircraft structure. Thermoplastics hav-
A-132 military specifications. Mil-A-25463 es- ing the required resistance to creep even at
tablishes requirements for adhesives for bond- 180°F have melting points that are so high that
ing sandwich structure comprised of metal they would be very difficult to process.
honeycomb and metallic skins, while MMM- Aircraft company specifications will usually
A-132 establishes requirements for adhesives require that the adhesive meet the requirements
for bonding metal-to-metal airframe structure of one or both of the military specifications. In
(i.e., metal skins to metal skins or metal skins addition, further more stringent requirements
to metallic spars or stringers). Both specifica- are established that are deemed critical to the
tions define the structural requirements of ad- particular application. For example, in the case
hesives having service temperature ranges of of an adhesive used for bonding engine na-
-67°F to + 180°F, 300°F, and 500°F. In ad- celles, requirements for strength retention after
dition, requirements for strength retention are thousands of hours' exposure at temperatures
specified after prolonged exposure to salt spray, of 300°F or higher would be specified. In the
humidity, and various aircraft fluids such as jet case of an adhesive used in a satellite, a limit
fuel, anti-icing fluids, and hydraulic oils. would be established on outgassing under the

713
714 HANDBOOK OF ADHESIVES

ultra-high vacuum conditions that prevail in a minum skin-balsa wood sandwich structure,
space environment. Consolidated studied bonded aluminum-skin-
to-aluminum construction, while Martin
EVOLUTION OF BONDING IN THE worked with sandwich structure consisting of
AEROSPACE INDUSTRY
aluminum skins bonded to aluminum honey-
comb. The types of adhesives evolved to sup-
The first applications of adhesives for bonding port these activities were vinyl-phenolic,
aircraft structure probably date back to about epoxy-phenolic, and nitrile-phenolic film ad-
1920, when light-weight airframes were fabri- hesives. All of these early adhesives containing
cated with plasticized nitrocellulose-impreg- phenolic functioned via a condensation reac-
nated fabric stretched over a framework of tion, and water was evolved during heat cure.
wooden stringers. The wood adhesives used for As a result very high pressure was required to
these applications were first based on casein, minimize porosity in metal-to-metal bonds,
then urea formaldehyde resins, and finally while in sandwich structure perforated hon-
phenol formaldehyde resins .. eycomb was used to permit the escape of the
As aircraft structure shifted from wood to condensation volatiles. In the case of hon-
aluminum, more sophisticated adhesives capa- eycomb assemblies, edge sealing of the bonded
ble of withstanding higher stresses were re- panels was required to prevent ingestion of
quired. De Bruyne of Aero Research Ltd. in moisture, salt spray, and other hostile fluids en-
Britain is generally credited with doing the pi- countered in service. If the edge seal was de-
oneering work that led to the development of fective or became damaged in service, large
the first commercially important adhesive for amounts of water would be ingested into the
metal bonding. This system, known as Redux, panels as a result of altitude cycling.
was first used by De Havilland and Bristol in The next major improvement in aerospace
the mid-1940s. The Redux process involved adhesives occured in the late 1950s with the
applying a liquid phenolic resin to the surface introduction of adhesives based on epoxy res-
to be bonded, covering the liquid with excess ins. Since these adhesives crosslink via an ad-
powdered vinyl resin, allowing the resin time dition reaction, no volatiles are released during
to wet out, and then shaking off the excess heat cure. This made low pressure bonding
powder. Under the influence of heat and pres- possible and the use of nonperforated honey-
sure the vinyl dissolved in the phenolic resin comb feasible in sandwich structure. Other im-
prior to initiation of the crosslinking reaction, provements followed that resulted in more
resulting in a bond having substantially greater durable bonded structure. These include the de-
toughness than that obtained with the unmodi- velopment of corrosion inhibiting adhesive
fied phenolics previously used to bond wood. primers in 1968, corrosion resistant aluminum
Fortunately, the ratio of phenolic resin to vinyl honeycomb in 1969, and the phosphoric acid
powder was reasonably noncritical, and relia- anodizing process for preparing aluminum for
ble bonds could be obtained using this system. bonding in 1974.
Although Redux is still in use today, it has The most recent development is the sharp in-
largely been displaced by adhesives supplied in crease during the past decade in the use of non-
film form. The advantages of film adhesives metallic composites as structural components.
over the Redux system are twofold: (1) they are These materials are prepared from so-called
supplied at exactly the desired weight, and (2) "prepregs" based on undirectional or woven
the formulation is precisely controlled (i.e., the fabrics composed of aramid, glass, or carbon
ratio of phenolic resin to vinyl resin). As a con- fibers, and for the most part impregnated with
sequence the aircraft manufacturer is less de- thermosetting epoxy formulations. To keep
pendent on the skill of the individual applying pace with this development, compatible adhe-
the adhesive. sives have been designed that can be either (1)
Work by de Bruyne was closely followed by co-cured with the prepegs, or (2) used to bond
activity at Chance-Vought, Consolidated Vul- cured composite to itself, to metallic sub-
tee, and Martin. Chance-Vought explored alu- strates, or to honeycomb.
 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 715

ADVANTAGES AND TYPES OF sion that stiffness (i.e., high modulus) is an un-
BONDED STRUCTURE desirable trait in an adhesive for most
applications. As a general rule the adhesive
The primary advantages of bonded over me- modulus should be as low as possible consis-
chanically fastened structure are lighter weight tent with resisting creep under the applied load.
and improved resistance to fatigue. Both of Since both heat and absorbed moisture reduce
these attributes are critical to the Aerospace In- the modulus of adhesives, data on the modulus
dustry and are responsible for the extensive use at the maximum service temperature under wet
of bonding by the industry. conditions will be required before selection of
Bonding results in weight savings by making an appropriate adhesive. This subject is dis-
it possible to reduce the thickness of metal or cussed in much greater detail in two papers by
composite sheet materials (i.e., skins, doub- R. B. Krieger. I •2
lers, etc.). In joining materials of this type to- Another type of bonded structure in common
gether, mechanical fasteners have an inherent use by the aerospace industry is the honeycomb
disadvantage because the discontinuous nature sandwich panel, consisting of thin skins bonded
of the joint results in local stresses at the points to a hexagonal honeycomb core. This type of
of attachment. This results in stress concentra- structure is very weight efficient, as it has an
tions, skin buckling between attachment points, extraordinarily high stiffness-to-weight ratio.
low strength in tension loading, and premature There is no economical way of fabricating
failure due to fatigue in the areas of high stress structures of this type except by bonding. Fig.
concentration at the points of attachment. The 1 depicts a section of a honeycomb sandwich
net result is that with mechanical fasteners it is panel. Design flexibility on this type of panel
not possible to design joints based on the is practically unlimited. Thickness of skins,
strength properties of the thin skins. Bonded thickness of honeycomb, diameter of the hex-
joints, because they are continuous in nature, agonal cells, honeycomb foil gauge, and thick-
reduce local peak stresses. This makes it pos- ness of the facing adhesive can all be varied to
sible through proper design to realize the ulti- meet specific design requirements. Moreover,
mate strength properties of thin sheets. additional skins, doublers, spars and various
Factors that must be considered in design are other types of reinforcements can be bonded
modulus of the adhesive, bond line thickness, into areas subjected to high stress levels. The
and depth of overlap. The use of low modulus efficiency of honeycomb structure derives from
adhesives reduces peak stresses at the edge of the fact that most of the weight is concentrated
the joint, as low modulus adhesives strain in the skins at the top and bottoms of the panel,
(elongate) more under applied shear stresses where it is most needed to carry tension and
than do high modulus adhesives. The net result compression loads. In addition to preventing
is that shear loads can be carried farther back buckling by stabilizing the skins over their en-
from the edge of the joint, resulting in more tire surface, the honeycomb serves to uni-
uniform stress distribution. The magnitude of formly transmit shear loads to the skins. As was
shear strain under an applied load is propor-
tional to bond line thickness. Therefore, in-
creasing the bond line thickness has about the
same effect on stress distribution as decreasing
adhesive modulus. Once the modulus of the ad-
hesive and bond line thickness have been es-
tablished, the designer is in a position to decide
on the appropriate bond line overlap depth be-
cause he now knows how far back into the joint
the applied load will be carried. The optimum
depth of the joint will, of course, also depend
on the modulus and thickness of the substrates.
It should be apparent from the above discus- Fig. 1. Honeycomb sandwich construction.
716 HANDBOOK OF ADHESIVES

the case with skin-to-skin bonds, the elimina- EXAMPLES OF BONDED STRUCTURE
tion of localized stress concentrations caused
Figure 2 gives some indication of the degree to
by mechanical fasteners permits the fabrication
which bonding is utilized in a modern aircraft.
of very light weight panels having excellent re-
Body skins and tear straps account for most of
sistance to fatigue. Honeycomb is available in
the bonding on the fuselage. The interior floor
densities ranging from less than 2 lb to over 40
panels consist of skins bonded to honeycomb
lb per cubic foot to withstand the shear loads
core. Access doors and bulkheads are also
required by specific designs.
bonded. Flaps, spoilers, and leading edge slats
The skin-to-skin bond and the honeycomb
on the wings and empennage are bonded. En-
sandwich bond can involve either metallic or
gine struts as well as acoustic engine cowl
nonmetallic composite substrates or a combi-
panels are also bonded.
nation of the two. Bonding is a very attractive
Honeycomb details used in a bonded acous-
method of joining composite materials because
tic engine nacelle are shown in Fig. 3. The fi-
their ability to withstand local stresses caused
nal assembly will have solid outer skins but the
by mechanical fasteners is quite poor when
inner skins will be perforated in order to reduce
compared to metals. This is especially true of
noise levels.
composites in which the fiber orientation is uni-
Figure 4 illustrates a bonded honeycomb hel-
directional in order to increase stiffness along a
icopter blade. This application requires the ul-
specific axis.
timate in fatigue resistance. Some of the early
In the case of bonded high modulus compos-
blades made with mechanical fasteners had fa-
ites, failure at low load levels due to interply
tigue lifes of less than 100 hours. Bonding re-
delamination within the composites is a com-
duced stress concentrations to the point that
mon problem. The use of low modulus adhe-
fatigue life now exceeds several thousand
sives minimizes this problem.
hours. The steel spar bonded into the leading
High modulus composites designed for high
edge of the blade contributes to its rigidity as
temperature service tend to have relatively low
well as making it more capable of withstanding
impact strength. Dramatic improvements in
impact loads. Multiple layers of bonded doub-
impact strength can be achieved through the use
lers at the root end of the blade serve to rein-
of so-called interleaf films. These are based on
force it where flexure stresses are the greatest.
zero flow, low modulus adhesives that will not
Finally, Fig. 5 is a cross section of a typical
mix with the composite prepreg during cure.
honeycomb sandwich trailing edge wing flap.
Since there is no intermixing, the modulus of
Note the use of high density honeycomb to
the prepeg resin is not reduced and the stiffness
reinforce the area adjacent to the spar caps used
of the structure is preserved.
for attachment to the main wing structure.
A final use of adhesives for composite struc-
ture is as a surfacing ply. In this application a
PHYSICAL FORMS OF ADHESIVES
low flow adhesive is applied to the composite
surface prior to cure in order to produce a cos- Although film adhesives account for the over-
metically smooth surface that is ready for whelming bulk of structural adhesive used by
painting without further finishing operations. In the aerospace industry, expandable and syntac-
addition, surfacing ply adhesives as well as in- tic adhesive foams, paste adhesives, and ad-
terleaf films have been effective in reducing the hesive primers are all necessary parts of a
porosity of composite skins. This has led to complete bonding system.
their applications in "wet wings" to prevent Film adhesives are usually supplied coated
fuel leakage and in composite skin sandwich on nonstick release paper. Depending on the
structure to prevent moisture penetration. tack level of the specific adhesive, a polyeth-
Composite bonding and the use of interleafs ylene liner may also be utilized. Most but not
to improve impact resistance are discussed in all film adhesives contain a fabric carrier. This
more detail in papers by R. E. Politi and K. R. carrier makes the adhesive less fragile during
Hirschbuehler. 3 .4 handling and also serves as a means of con-
 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 717

LAMINATED EDGE
COVER PANELS ---.-....

=
TEAR STRAPS
LAP SPLICE

STRUT FAIRING

_ = BONDED AREA

Fig. 2. Schematic showing bonded areas. (Courtesy Boeing Co.)

trolling the thickness of the bond line. In the depth to which the honeycomb core foil pene-
early years of bonding, cotton and nylon fab- trates into the face bond adhesive. This in turn
rics were frequently used as carriers. In order dictates how great a shear load the adhesive is
to improve resistance to high humidity condi- capable of transferring to the face sheets. For
tions, most of the adhesives developed during very light weight sandwich panels used in the
the past 10-15 years are supported by more construction of satellites or other lightly loaded
water resistant fabrics based on fiberglass or structure, very light weight adhesives are suit-
polyester fibers. Depending on the handling able. For heavily loaded panels fabricated with
characteristics required, tack levels can vary relatively thick face sheets and high density
from nontacky to agressively tacky. honeycomb, thicker and heavier adhesives are
Thickness ofthe adhesive is varied to suit the required. It should also be apparent from Fig.
specific application. For example, when the 1 that precise control of flow of the adhesive is
substrates to be bonded are smooth and uni- required. The adhesive must flow sufficiently
form in thickness a light weight adhesive of to give good fillet formation but must not run
about 5 mils in thickness is usually selected. down the honeycomb cell walls from the top
For assemblies having large or variable gaps, face.
adhesives up to 15 mils or higher in thickness Expandable foams are used to splice pieces
are utilized. Examination of the honeycomb of honeycomb together or to splice the honey-
panel pictured in Fig. 1 makes it obvious that comb to edge members of the sandwich panel.
adhesive thickness is a critical factor that must These foams expand prior to gelation during
be considered in the design of sandwich struc- heat curing. Low density high expansion foams
ture. The size of the adhesive fillets and thick- are suitable for lightly loaded structure, while
ness of the face bond adhesive determine the lower expansion foams of 30-40 lb per cubic
718 HANDBOOK OF ADHESIVES

Stainlc s Leading Edg:.c.::C:.!ap:.-_ _ _ _ _ _ _~

Melal Spar
Fig. 4. Bonded helicopter blade.

of the aircraft structure. The cross section of a

sandwich panel shown in Fig . 6 illustrates how
syntactic foam is used to provide better holding
power for a threaded fastener.
Syntactic foams are also available in sheet
form, generally at thicknesses of 20-40 mils.
Since it is impractical to machine conventional
honeycomb down to this thickness range, this
form of syntactic foam has found use in very
thin sandwich structure fabricated with com-
posite skins.
Aerospace paste adhesives are usually thix-
otropic in nature. A major use is as a gap filler
in areas where the mismatch is so great that the
use of film adhesives becomes impractical.
Other uses are in joints where pressure cannot
easily be applied or as high density potting
Fig. 3. Honeycomb engine nacelle details.
compounds where syntactic foams do not pro-
vide sufficient strength. Pastes are also utilized
foot density are used in heavily loaded struc- as fairing compounds in areas such as wing-to-
ture. engine pylon joints to provide aerodynamic
Syntactic foams are generally supplied in smoothness in order to reduce drag in flight.
paste form as either one-part heat cure or two- Both one-part heat cure and two-part room tem-
part room temperature cure systems. These perature cure pastes are utilized by the indus-
systems usually contain hollow glass micro- try.
spheres, and most commonly have densitie.s in Adhesive primers are an integral part of a
the 40 lb per cubic foot range. The major use complete adhesive system. Although it is pos-
of these paste foams (also known as potting sible to obtain excellent adhesion to casually
compounds) is to provide local reinforcement cleaned (e.g., solvent wiped) metals, these
of honeycomb panels where mechanical fas- bonds are seldom durable when exposed to
teners such as threaded bolts are to be inserted hostile environments such as salt spray or 100%
in order attach the bonded panel to another part humidity conditions. In the case of aluminum,

hem_MiIlCd par Cap

~High Densily Core
======'mTI~TflFT::Y::::;:::~/~-- .0 I O· Adhesive Thickness

67
\
.2" Wide
Metal-lo-Melal

Fig. 5. Trailing edge flap .

 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 719

Table 1. Effect of Salt Spray on

Strength Retention.
Lap Shear, psi
Exposure
Time B~ 123 Primer B~ 127 Primer
Initial 5875 5680
30 days 3490 5890
90 days 1460 4970
Fig. 6. Potting compound used for local reinforcement of
180 days o 4480
honeycomb.

titanium, and many other metal alloys, special BR@ 127 corrosion inhibiting primer. Both
treatments are required to provide a stable primers are manufactured by the American Cy-
bonding surface. Aluminum alloys such as anamid Company.
2024-T3 and 7075-T6 account for most of the The data show that in the case of the BR@
bonded metallic structure in aircraft and this 127 corrosion inhibiting primer approximately
discussion will be limited to primers for these 80 % of the initial strength is retained after 180
alloys. days' exposure. In the case of the BR@ 123
Three surface treatments for aluminum are in there is no residual strength after 180 days, with
wide use: (1) chrome-sulfuric acid etching, (2) all of the loss due to bond line corrosion.
chromic acid anodize, and (3) phosphoric acid It should be pointed out that alcad aluminum,
anodize. All of these impart a controlled oxide because of the sacrificial nature of the clad
layer to the surface of the aluminum that is suit- coating, is much more susceptible to bond line
able for bonding. Unfortunately these oxide corrosion than bare alloys. For example, in
layers will hydrolyze if the panels are stored for similar tests run with 2024-T3 bare aluminum,
prolonged periods of time. One function of an the differences in performance between BR@
adhesive primer is to prevent hydrolysis of 127 and BR@ 123 are much less pronounced,
these oxide layers. Most aircraft companies with retentions of original strength after 180
specify that the surface treated metal must be days exposure being about 95 % and 70 %, re-
primed within 8 hours. In reality the actual safe spectively.
storage time is inversely proportional to the rel-
ative humidity. Under extremely low humidity
CHEMICAL TYPES OF ADHESIVE
conditions storage times of several days do no
apparent harm. However, since bond shop hu- As previously pointed out, film adhesives ac-
midity limits are generally set at a maximum of count for the major share of structural adhe-
65 % RH, limiting the time between surface sives consumed by the aerospace industry.
treatment and priming to 8 hours appears to be Therefore, this discussion of chemical types of
prudent. adhesive, after making some general comments
Many of the primers developed during the on other types, will be limited to film-type ad-
past 20 years contain corrosion inhibitors. hesives.
These primers have a second function: to fur- In most cases the resins, curing agents, etc.,
ther improve hydrolytic stability at the adhe- used in adhesive foams are similar to those used
sive to metal interface and prevent corrosion in film adhesives. Expandable adhesive foams
during exposure to salt spray. Table 1 shows will obviously differ in that they will contain a
the difference in strength retention of 2024-T3 blowing agent, while syntactic foams will con-
alclad aluminum lap shear coupons exposed to tain hollow microballoons to reduce density.
salt spray. Both sets of coupons were bonded One-part heat cure pastes will contain liquid
with a 250°F cure elastomer modified epoxy resins instead of solid resins. Two-part room
adhesive. One set of coupons was primed with temperature cure epoxy paste adhesives are
BR@ 123 primer (a non-corrosion inhibiting generally cured with active amine curing
primer) while the other set was primed with agents, while one-part epoxy pastes, adhesive
'o,j
N
o

Table 2. Structural Properties of Various Types of Film Adhesives.

Lap Shear at Indicated Temp., ksi
Adhesive Metal Peel, Sandwich peel,
Type Cyanamid Designation -67°F 75°F 180°F 250°F 300°F 350°F 400°F 500°F Ihlin. width in. Ib/in. width
Two-phase toughened FM~ 73 (0.085 psf) 6 6 4 1.5 70 40
Epoxy FM~ 87 (0.085 psf) 6 6 4 3 70 40
FM~ 300 (0.10 psf) 5 5 4.5 4 3 30 20
Nitrile-epoxy duplex FM~ 61 (0.075 psf) 3.5 3 2.8 2.7 1.6 15 25
Nylon-epoxy FM~ 1000 (0.08 psf) 7 7 3.5 2.2 140 80
Vinyl-phenolic FM~ 47 (0.075 psf) 3.5 4.5· 4 2 10-15 20
Vinyl-epoxy FM~ 96 (0.075 psf) 3 3.7 4 4 2.5 1.4 10-15 15
High temp. epoxy FM~ 400 (0.10 psf) 4 4 2.8 2 0.8 10 15
FM~ 350 NA (0.10 psf) 4 4 3.5 10 8
FM~ 355 (0.10 psf) 3.3 3.1 3.6 3.2 2 10 8
Nitrile-phenolic FM~ 238 (0.05 psf) 4 4 3 2.5 1.7 70
Epoxy-phenolic H~ 424 (0.135 psf) 3.2 3.5 2.7 2 <10 10
Bismaleimide FM~ 32 (0.10 psf) 2.8 2.8 3 3 2 <10 6
Addition reaction FM~ 35 (0.135 psf) 3 3 3 2.7 <10 6
poly imide
Condensation reaction FM~ 36 (0.10 psf) 3 2.8 2.7 2.7 <10 7
poly imide
 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 721

foams, and film adhesives favor the use of la- complete product line, this has not limited the
tent amines. coverage of this subject. In most but not all
Table 2 lists the major types of film adhe- cases similar adhesives are available from other
sives in use today together with typical me- sources.
chanical properties. Because many types of peel
and shear tests are in use by industry, in order Vinyl-Phenolic
to avoid confusion the specimen configuration
of each of the tests referred to in this table is This was one of the earliest types of structural
illustrated in Figs. 7, 8, and 9. Most of the ad- adhesive used by the aerospace industry. Vi-
hesives shown in this table are available in var- nyl-phenolics are still in use today because they
ious weights and thicknesses. The data in Table are reasonably low in price and are excellent
2 are representative of the heaviest weight ad- for applications involving bonding metal skins
hesives commonly in use for each type. Lap to wood. FM® 47 adhesive is representative of
shear and metal peel values do not vary much this type. The major disadvantage of this type
with weight, but sandwich peel values would is that crosslinking occurs via a condensation
be considerably lower for lighter weight adhe- reaction. As a consequence the volatiles given
sives. Comments regarding service tempera- off during heat cure result in porous bond lines.
ture apply to heavily loaded structure and take This type of adhesive may be stored at room
into account degree of creep under sustained temperature and is cured at 350°F. Service
load. In many cases these adhesives are suit- temperature is limited to slightly above 180°F.
able for use at higher temperatures in lightly
loaded structure. Epoxy-Phenolic
In every case the properties shown apply to
a specific American Cyanamid adhesive, be- This type of adhesive also cures via a conden-
cause the author is most intimately familiar with sation reaction. Therefore, as was the case with
that product line. Since Cyanamid offers a very vinyl-phenolics, volatiles evolved during cure
complicate processing. A major advantage of
this type of adhesive is that excellent strength
at high temperature can be obtained with cure
temperatures as low as 250°F. Oxidative sta-
bility during long term exposure at high tem-
peratures is relatively poor, but strength
retention after short time exposure to tempera-
tures as high as lQOO°F is excellent. For this
reason this type of adhesive has been exten-
0.50 ± .005"
sively used in bonding on missiles. This system
12.5 ± .125 mm)
has limited stability at room temperature, and
shipping and storage at OaF is recommended.

Nitrile-Phenolic
These adhesives are used exclusively for sheet-
to-sheet bonding because they are extremely
low flow and are not suitable for bonding to
0.063" honeycomb. Strength retention is good up to
(1.6 mm) 250°F and fair at 300°F. Metal peel is excel-
lent at room temperature. However, the glass
transition temperature is relatively high, result-
ing in poor metal peel at low temperatures.
Recommended cure temperature is 350°F. Be-
Fig. 7. Lap shear specimen. cause of their low flow, high pressure bonding
722 HANDBOOK OF ADHESIVES

Test
Load

Plate

Roller

Steel Roller
I" Oiam.
~ ... 025" Face
2024- T3
12" long

Specimen width
.... y be I" or 1/2" 1 5/16"

rest Value is
expressed in lb •.
per inch width

Test \
Load

Fig. 8. Floating roller metal peel.

(100 psi +) is required for optimum perfor- Vinyl-Epoxy

mance.
FM® 96 is one of the early adhesives that is
representative of this type. It has moderate
Early Epoxy Adhesives
strength at temperatures up to 300°F. Oxida-
Aerospace adhesive manufacturers were quick tive stability is excellent which led to its use in
to exploit epoxy resins. Starting in the early areas of the engine nacelle and other hot spots
1950s, a succession of epoxy and modified where continuous exposure to temperatures up
epoxy adhesives were developed and commer- to 300°F are involved. Some improvement in
cialized. The major advantage of epoxy based toughness over unmodified epoxies is achieved
adhesives was that crosslinking occurs via an through modification with a high molecular
addition reaction. As previously stated this weight vinyl resin. As a result moderate metal
made low pressure bonding possible and per- peel and sandwich peel values can be achieved.
mitted the use of nonperforated honeycomb. This type of adhesive can be shipped and stored
 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 723

. .
CLAMP A --.,--.--_

(9):.
I I
BOLT'
HOLEj@l
I
.
I

r---1

SANDWICH SPECIMEN

3.000 ±.01

12.000
APPROX

1.000-
APPROX

·CLAMP B

~,
CUM!' B
II----------+--li $-
--,.
~
:~
~ .,
BOLT
HOLE ~: I
L___ A.J
SECTION A-A

Fig. 9. Honeycomb climbing drum test fixture.

at room temperature. Cure temperature is temperatures up to 300 o P. This adhesive is sta-

350 o P. ble at room temperature. Recommended cure
temperature is 350 o P.
Nitrile.Epoxy Duplex
Nylon-Epoxy Adhesives
This type of adhesive, exemplified by PM® 61,
consists of a high flow epoxy layer coated over Nylon-epoxy adhesives are the toughest class
a low flow nitrile-epoxy layer. In sandwich of structural adhesive available. Lap shears in
panels the high flow epoxy side is placed excess of 7000 psi are obtainable. Sandwich
against the honeycomb and gives excellent fil- and metal peel values are also extremely high
let formation, while the low flow rubber epoxy about 140 in. lb/in. and 80 lb/in., respectively.
side placed against the skin enhances peel. Because of the high concentration of nylon this
Metal peel is fair, while sandwich peel values adhesive is quite susceptible to plasticization by
are fairly high. Strength retention is good at absorbed moisture. Por this reason, perfor-
724 HANDBOOK OF ADHESIVES

mance under long term sustained loads at high Tg of the epoxy and that of the elastomer. The
humidity and elevated temperatures (e.g., exact Tg of the adhesive will depend on the ra-
100% RH and 140°F) is not as good as most tio of elastomer to epoxy and their relative Tg's.
other types of epoxies. Nevertheless this type Since some elastomers have Tg's below O°F,
of adhesive has proved to be extremely durable the Tg of highly modified systems can be
in properly designated structures and is unsur- sharply reduced, the net result being a signifi-
passed in resisting constant fatigue stresses. cant reduction in the ability of the adhesive to
Recommended cure temperature is 350°F and withstand high temperatures.
the service temperature limit is 180°F. This ad- Current toughening technology involves
hesive film may be stored at room temperature. blending the epoxy with an initially compat-
ible elastomer that precipitates into small, uni-
formly dispersed particles during the cross
More Recent Epoxy Adhesives
linking reaction. Fig. 10 is a photomicrograph
Over the past two decades significant advances illustrating such a two-phase system. Since the
have been made in developing epoxy based ad- high softening point epoxy is the continuous
hesives having improved performance. These phase, the Tg of the adhesives remains un-
improvements were made possible by (I) the changed, while the dispersed elastomer parti-
discovery of unique methods of toughening ad- cles lower the modulus and toughen the
hesive and (2) the availability of new multi- adhesive. It is theorized that toughness and peel
functional epoxy resins. are improved because the ductile dispersed par-
The toughened epoxy adhesives previously ticles stop crack propagation initiated by ap-
discussed are single-phase systems in which the plied stresses.
crosslinked epoxy resin is plasticized by a com- The earliest epoxy adhesives were based on
patible elastomer. Because these are single- difunctional bisphenol resins. As the epoxy
phase systems the glass transition temperature manufacturers introduced more functional res-
(Tg) , which is roughly equivalent to the soft- ins, first the epoxy novolacs and then a series
ening point, will fall somewhere between the of high functionality specialty resins, aero-

Fig. 10. Two-phase toughened epoxy.

 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 725

space adhesive manufacturers were able to uti- 400°F. It is an unfilled adhesive and, there-
lize them in fonnulating adhesives having fore, is suitable for applications requiring radar
higher service temperatures. In many cases transparency. This type of adhesive has also
these high temperature adhesive are two-phase found application in bonding high temperature
toughened systems containing dispersed elas- composites.
tomers. FM@ 350 NA is a 350°F curing adhesive with
good strength retention at 350°F and excellent
Two-Phase Toughened Epoxies oxidative stability. For this reason it is suitable
for engine nacelle applications involving thou-
These adhesives currently account for a major
sands of hours exposure to temperatures of
share of structural adhesives consumed by the
300-350°F. An unsupported version of this ad-
aerospace industry. FM~ 73 and FM~ 87 are
hesive is available that can be reticulated (i.e.,
representative of 250°F cure adhesives of this
heat shrunk) on honeycomb core. This process
type that have service temperature limits of
results in the adhesive fonning a bead on the
180°F and 250°F, respectively. Both adhe-
honeycomb cell edges. The honeycomb can
sives have controlled flow and have excellent
then be bonded to perforated metal skins with-
metal peel and sandwich peel. FM® 300 is a
out plugging up the holes. This type of struc-
350°F cure adhesive having good strength re-
ture is used to fabricate acoustic panels used in
tention up to an operating temperature of
engine nacelles to absorb sound and thereby
300°F. Contrasting it with a single-phase sys-
meet FAA standards for pennissible noise lev-
tem such as FM~ 96 makes the advantages of
els.
a two-phase system obvious; FM~ 300 has bet-
Both FM@ 355 and FM@ 350 NA adhesives
ter 300°F strength and higher metal and sand-
are two-phase systems. As a result, even though
wich peel (both toughness related properties).
metal peel and sandwich peel are modest, they
Because of this balance of properties and its
are higher than those obtainable with unmodi-
controlled flow, this adhesive has been exten-
fied high temperature epoxies.
sively used for bonding composites and as a
surfacing ply to impart smoothness and reduce
Bismaleimides
porosity. A zero flow version of this adhesive
is effective as an interleaf material to improve BMI adhesives are suitable for long tenn ex-
the impact resistance of composite structure. posure to temperatures up to 400°F and short
All three of these adhesives must be kept at tenn exposure up to 450°F. They have excel-
O°F for extended storage periods. Storage up lent electrical properties, making them espe-
to about 10 days at a maximum shop tempera- cially suitable for high energy radomes.
ture of 90°F during processing is permissible. Systems currently available are quite rigid and
for this reason have low metal peel and sand-
High Temperature Epoxies wich peel properties. They are addition reac-
tion systems, so no volatiles are given off
The properties of three high temperature epoxy
during cure. This simplifies processing and
adhesives are summarized in Table 2. FM~ 400
makes possible nonporous bondlines with low
is a high temperature adhesive containing alu-
bonding pressures. These systems are usually
minum powder as a reinforcing filler. This ad-
cured for several hours at 350°F under pressure
hesive has excellent strength retention at
and then postcured at 4oo-450°F with or with-
temperatures up to 400°F. However, oxidative
out pressure.
stability at this temperature is not outstanding.
For this reason the major application for this
Polyimides
type of adhesive is in high speed military air-
craft rather than in engine nacelles where long Two types of polyimides (PIs) are currently in
tenn exposure to high temperatures is required. use. Condensation PIs were the first type intro-
Metal peel values are modest while sandwich duced. They are based on the reaction product
peel values are fairly high. of aromatic diamines and aromatic dianhy-
FM~ 355 also has good strength retention at drides, and are capable of withstanding pro-
726 HANDBOOK OF ADHESIVES

longed exposure to temperatures of 500-600 oP (3) control of bond shop environment, (4) con-
and short tenn exposure to temperatures up to trol of bonding process, and (5) verification of
lOOOoP. In addition to the condensation vola- quality of the adhesive bond.
tiles, processing is further complicated by the
presence of high boiling solvents needed to Surface Preparation
make the adhesive pliable and capable of flow.
A wide variety of substrates are utilized by the
To facilitate removal of volatiles these adhe-
aerospace industry in fabricating bonded struc-
sives are generally processed under high vac-
tures. These include aluminum, stainless steel,
uum conditions. Condensation PIs can be cured
and titanium alloys as well as thennosetting and
under pressure at 350 oP. After about two hours
thennoplastic composites. Most metallic sub-
at 350 0 P they develop sufficient green strength
strates are prepared for bonding by immersing
to pennit post curing at 500-600 oP without
them in caustic and/or acidic solutions to re-
pressure.
move mill oils, etch the surface, and in some
Addition reaction PIs are also based on aro-
cases deposit a controlled oxide layer. In the
matic diamines and dianhydrides, but in addi-
case of aluminum, which is the most widely
tion have Nadic imide end groups. These
used metal, the most commonly used surface
systems also contain solvents to make the ad-
preparation methods are chrome-sulfuric acid
hesive film pliable. Curing of these adhesives
etching, chromic acid anodizing, and phos-
initially proceeds via a condensation reaction at
phoric acid anodizing. Nonmetallic substrates
low pressure. However, unlike the conven-
depending on their specific composition, rna;
t~onal condensation reaction PIs, after comple-
be grit blasted, sanded, roughened through the
tion of the condensation reaction and removal
use of a removable peel ply, etched with acids
of solvent, these adhesives are still thennoplas-
or bases, flame treated, plasma etched, etc. De-
tic. ~t this point the temperature and pressure
tails on suitable surface treatments for widely
are lDcreased to densify the bond line and the
used substrates are generally available from the
Tg is increased via an addition reaction through
adhesive suppliers.
the Nadic end groups. Typical processing. con-
In the case of metal substrates primers are
ditions are (1) heat from room temperature to
usually applied to protect the surface from con-
400 0 P in 1 hour under light contact pressure;
tamination and hydrolysis as well as to enhance
(2) hold 30 minutes at 400 oP; (3) increase
the durability of the bond. Primers are usually
pressure to 100 psi and increase temperature to
spray applied. Depending on the specific primer
550 oP, hold at 550 0 P for 2 hours. This pro-
the thickness can vary from 0.1 to 2 mils. Prior
cessing method results in void-free bonds.
to application of the adhesive, the primer is air
The oxidative stability of addition reaction
dried or heat dried to remove solvents and in
PIs is not quite equal to that of the condensa-
some cases heat cured.
tion type. Por prolonged exposure about 500 0 P
As a class, high peel elastomer modified
is the limit, but short tenn strength retention is
epoxy adhesives are very dependent on primers.
good up to 600 oP.
Initial bond strength to metals can be excellent
PI adhesives have excellent electrical prop-
without primer, but durability in a humid en-
erties and are suitable for high temperature ra-
vironment win invariably be poor. Por exam-
domes. They are also used in very hot areas of
ple, lap shear specimens of PM® 73 bonded to
engine nacelles.
unprimed titanium failed in about 3 days under
a 1000 psi load at 140 0 P and 100% RH. Spec-
PROCESSING CONSIDERATIONS
imens primed with BR® 127 primer did not fail
This section describes processing procedures after being subjected to these conditions for 1
and some of the more important factors that im- year.
pact on the quality and durability of bonded Contamination of the surface, improperly
structure. Topics covered include (1) surface maintained acid solutions, inadequate rinsing,
preparation, (2) proper storage and handling, and other factors can also result in adhesive
 STRUCTURAL ADHESIVES IN THE AEROSPACE INDUSTRY 727

bonds having poor durability under humid con- ing high temperature bonding, resulting in po-
ditions. An accelerated test that is effectively rous bond lines.
used by many aerospace companies to verify
that surface preparation has been adequate to
insure durability is the wedge test. In this test Bonding Procedures
a wedge is driven between two strips of bonded
Flat panels of uniform thickness are frequently
substrate material. After allowing the specimen
bonded in heated platen presses. However,
to stabilize for one hour the crack length is re-
most bonded aerospace assemblies are con-
corded and the specimen is placed in a cabinet
toured. For this reason, bonding is usually car-
maintained at 140°F and 100% RH for one
ried out in heated, pressurized autoclaves. In
hour. Crack growth under these conditions
the autoclave process the assembly is supported
should be very slight and should be primarily
by a tool of the required contour, wrapped with
due to cohesive failure rather than failure be-
several layers of glass or polyester bleeder
tween the adhesive and the substrate. Fig. 11
cloth, and then enclosed in a impermeable heat
illustrates a wedge test specimen frequently
resistant bagging film. This layup is then placed
used in process control for bonded aluminum
inside a pressurized autoclave and the inside of
structures. (The technique is, of course, appli-
the bag is vented either to the atmosphere or
cable to other substrates).
connected to a vacuum pump. The autoclave is
then pressurized to the desired level by com-
Storage and Handling
pressed air, nitrogen, or other relatively inert
Most structural adhesives are based on polar gas.
resins and, therefore, will absorb moisture The function of the bleeder cloth is to absorb
when exposed to humid conditions. For this adhesive flash and provide an unrestricted path
reason, the rolls of adhesive are packaged in so that entrained air or reaction volatiles can be
vapor barrier bags to prevent moisture absorp- removed. In the case of condensation reaction
tion during shipping and storage. In the case of polyimides the bag should be vented to rela-
adhesives that are stored at OaF, the rolls should tively high vacuum conditions. This is critical
be thawed out for about 16 hours before re- because it is necessary to depress the boiling
moving the vapor barrier bag in order to avoid point of the high boiling point solvents used to
condensing water on the surface of the adhe- flexibilize the film before gellation of the ad-
sive. hesive occurs.
The need to avoid exposure of the adhesives Heatup rates may be anywhere from 1 to
to high humidities is well recognized by the in- 10°F per minute to the final bond temperature.
dustry, and for this reason the humidity in most Slow heatup rates are sometimes specified for
bond shops is not allowed to exceed 65 % RH. assemblies having variable thickness in order
Less well recognized is the need to limit the to maintain uniform temperatures throughout
exposure to humidity of certain types of com- the bond cycle and thereby minimize heat dis-
posite substrates during storage prior to bond- tortion and locked-in thermal stresses.
ing. Relatively small amounts of moisture Bonding pressures of about 40 psi are em-
absorbed by these substrates will vaporize dur- ployed with most addition reaction adhesives.
However, pressures as low as 15 psi may be
used with some light weight sandwich panels
to prevent crushing the honeycomb, while 100
psi pressure may be used in bonding large body
skins together in order to reduce voids by com-
I 0.75 Initial ~a I pressing any entrained air. The use of nontacky
Crack
Length
or one-side tacky adhesives has been found to
~a = Crack Growth After Exposure be effective in reducing voids in large area skin-
Fig. 11. Wedge test specimen. to-skin bonds. By pulling vacuum on the as-
728 HANDBOOK OF ADHESIVES

sembly to remove entrained air, voids can be method has been largely displaced by sophis-
virtually eliminated. ticated devices capable of detecting very small
voids through the use of ultrasonic sound
Verification of Bond Quality waves.
In order to verify that the bonding process is REFERENCES
under control, process control panels are fre-
quently bonded along with the production as- 1. Krieger, R. B., "Stress Analysis of Metal to Metal
semblies and then tested to determine bond Bonds in Hostile Environment," 22nd National SAMPE
strength. Lap shear, metal peel, or sandwich Symposium, Vol. 22, April 1977.
2. Krieger, R. B., "Fatigue Testing of Structural Adhe-
peel panels are the type most frequently used sives," 24th National SAMPE Symposium, Vol. 24,
for this purpose. May 1979.
The bonded assemblies are then subjected to 3. Hirschbuehler, K. R., "An Improved Performance In-
nondestructive tests designed to determine the terleaf System Having Extremely High Impact Resis-
presence of voids. Some adhesives are formu- tance," SAMPE Quart., 17(1), (October 1985).
4. Politi, R. E., "Factors Affecting the Performance of
lated to be x-ray opaque in order to simplify Composite Bonded Structure," 19th International
void detection. Tapping the surface with a coin SAMPE Technical Con(erence, Vol. 19, October 13-
will detect very large voids. However, this 15.
 45
Adhesives in the Automobile
Industry
G. L. SCHNEBERGER P.E.
Training Resources Inc.
Flint, Michigan

The automotive use of adhesives is nearly as 2. High production rates (some lines are de-
old as the industry itself. The early wood and signed for 100 cars per hour) with short,
canvas bonding agents have been replaced by unvarying times for each operation.
fonnulations capable of holding metal, glass, 3. Minimal cleaning of surfaces, which are
plastics, rubber, and a variety of fabrics to subject to sudden or gradual contamina-
themselves, to each other, and to painted sur- tion.
faces. They are routinely used in structural, 4. Low tolerance for health and safety haz-
holding, and sealing applications. Automotive ards.
adhesives have become increasingly sophisti- 5. Cure times, pressures, and temperatures
cated and capable over the past twenty years. which are somewhat variable and which
This trend has been driven by a need to bond may need to be compatible with paint
new weight-saving and/or corrosion-resistant bake schedules or low material heat dis-
materials in an ever more health and cost con- tortion temperatures.
scious environment. The most significant trends 6. A desire to avoid complex measuring and
since the previous edition of this Handbook mixing.
have been the increased use of plastics and gal-
vanized steel, a shift toward the robotic appli-
cation of adhesives and sealants, and the use of Once these requirements have been met and
nondestructive testing and statistical quality the joint is made, adhesive bonds must perfonn
control techniques. for the life of the car under severe conditions.
No other mass produced product approaching
UNIQUE AUTOMOTIVE the complexity of a modem automobile is ex-
REQUIREMENTS pected to function from -40°C (-40 0 P) to
over 90°C (200 0 P), endure exposure to chang-
Automotive adhesives must meet a number of
ing temperatures, salt water, fuel, oil, high hu-
requirements which are more or less indepen-
midity, vibration, impact, detergents, and dust.
dent of joint performance. They must be usable
Adhesives have been able to meet these re-
under conditions which include:
quirements and do it with life-of-the-car dura-
1. A largely unskilled workforce, often with bility, a real tribute to both the automotive and
a high turnover rate. the adhesives industry.

729
730 HANDBOOK OF ADHESIVES

STRUCTURAL ADHESIVES These plastisols, while not thermosetting, are

able to function as structural adhesives because
Structural adhesives, for the present purposes, of the large bond areas and the relatively low
may be defined as those which transmit signif- loads involved. Furthermore, they endure vir-
icant mechanical loads. They are typically ther- tually no peel or cleavage stress, and the tensile
mosetting and are generally epoxies, phenolics, loads involved are cyclic rather than static.
polyurethanes, polyesters, or some variation Thus the problem of cold flow is not signifi-
thereof, although certain plastisols are an im- cant.
portant exception. Epoxies are used to bond various car and
Structural adhesives have come into use be- truck body panels. The adhesive is set up via a
cause they reduce stress concentrations, pro- four second induction heat cycle. Final cure
vide smooth contours, increase service life or occurs in the paint oven.
performance, or because they are the only The double shell method of roof construction
structural assembly method available at reason- uses only about half as many metal stampings
able cost. Table 1 lists the common automotive as the traditional welded assembly and gives a
uses of structural adhesives. The resins listed rigid, vibration-free product. The plastisol is ef-
are generic and may be modified from time to fective because it requires minimal surface
time at the request of the supplier or the user. preparation and because bond line thickness is
One of the oldest applications listed in Table not critical.
1 involves bonding hood inner and outer panels. The use of adhesives for bonding brake lin-
Automotive hoods and roofs have ~. tendency ings was introduced in 1949. This technique is
to "oil can" or flutter at high speeds unless also used for disk brake pads, clutch facings,
they are stiffened with an inner reinforcing and transmission bands. Brake linings use a ni-
member. The hood inner members are adhe- trile-phenolic film adhesive, as shown in Fig.
sively bonded to avoid unslightly weld marks. 1. The assembly is cured under heat and pres-
"Hershey drops" of plastisol adhesive are used sure. This process, which has produced mil-
in the assembly of hood inner and outer panels. lions of bonded brake shoes with an outstanding
The outer panel is often hem flanged around the performance record, illustrates the skillful for-
periphery of the inner panel to immobilize the mulation of an adhesive for a specific perfor-
parts until they cure in the paint oven. Modem mance need. Brake linings must withstand
plastisols are able -to absorb thin films of oil impact and high shear stresses at temperatures
from the metal as they cure. This ability to bond which can exceed 149°C (3()()OF). The film ad-
through oil is of immense value in an industry hesive used combines the high heat and shear
where thorough cleaning before assembly is resistance of phenolics with the excellent im-
traditionally a problem. pact behavior of nitriles.

Table 1. Common Automotive Structural Adhesive Applications.

Use Resin Comments
Body and roof reinforcement panels viny I plastisol bonds through oil
Double shell roof viny I plastisol bonds through oil; prevents flutter
Hood inner and outer panels vinyl plastisol bonds through oil; prevents flutter
Brake shoes nitrile-phenolic resists heat and impact
Clutch and transmission bands nitrile-phenolic resists heat and impact
Window sealants polysulfides, urethanes best available method
Plastic bumpers urethanes improves performance
Disc brake pads phenolic heat resistant
FRP body panels urethane, polyester used over twenty-five years
(sports car and truck)
Radiator tanks epoxy replaces solder
Plastic load floors polyolefin electromagnetic cure
Hood hem flanges vinyl plastisol reduces flutter
 ADHESIVES IN THE AUTOMOBILE INDUSTRY 731

simultaneously with a crosslinking poly sulfide

material. The latter technique, of course, re-
sults in a more rigid product and is a truly ad-
hesive process.
In recent years, polyurethane adhesives have
replaced the polysulfide resins for windshield
and backlite installation. The urethane material
gives a more rigid assembly which is still able
to damp out vibration adequately. The process
used to install windshields and backlites ac-
tually involves two adhesives. A hot-melt
product is used to secure a rubber molding of
small cross section (called a dam) to the outside
edge of the inner face of the glass. A two-part
urethane is then dispensed as a bead on the glass
just inside the dam. Next the glass is pressed
Fig.!. Adhesive-bonded brake shoes have been used for into place in the body opening, whereupon the
many years. urethane deforms and wets the steel surface.
The rubber dam prevents the urethane from
oozing out onto the exterior body surface. The
Disk brake pads must endure temperatures in
urethane cures spontaneously and yields a very
excess of 180°C (355°F), so the adhesive used
rigid, leakproof glass-to-metal bond.
is primarily phenolic. It is sprayed on the
Anaerobic retaining compounds are used in
cleaned shoes and then heated to remove sol-
a number of structural applications. These in-
vent. The adhesive-coated shoe is placed in a
clude dipstick tube retention and various press-
die where it contacts the uncured brake pad ma-
fitted engine block and bearing assemblies.
terial. The entire assembly is then heated at
Two additional structural applications are the
172°C (310°F) under 6895 kPa (1000 psi) for
use of a two-part urethane in the fabrication of
12 minutes to effect the cure.
SMC car and truck body parts and the attach-
Epoxies have traditionally been little used by
ment of sun hoof hinges to glass panels. The
the automotive industry because of their cost
SMC applications save weight and consider-
and the need for fairly clean surfaces. They are
ably reduce the time and labor involved in drill-
employed only when their durability, strength,
ing and riveting. Galvanic corrosion and air and
or processing ease justifies the additional ex-
water leaks are also reduced.
pense. They have been used to bond roof rail
retainers and to form roof-to-quarter panel
joints. They are slowly coming into wider use
HOLDING ADHESIVES
as one-part formulations.
Another automotive application of structural For the purpose of this discussion, holding ad-
adhesives is that of glass-to-metal assembly. hesives are those whose primary function is to
The windshield (front window) and the backlite attach one material to another without trans-
(rear window) are large, often curved, glass mitting significant structural loads. A holding
panels which must be secured to the steel body adhesive may sometimes be subjected to a fairly
openings. The adhesive used must exclude air, heavy load, but the ability to carry this load is
dust, and water and also absorb mechanical vi- not essential to the structural integrity of the
bration which might crack the glass. Ideally the automobile. An example of this would be the
glass-to-metal assembly should contribute to interior rear view mirror mounting button,
the strength of the body as a unit. Tradition- which is bonded to the windshield with poly-
ally, these glass panels have either been sealed vinyl butyral (Fig. 2). If the mirror is bumped,
with butyl rubber tape and mechanically se- the bond may need to withstand significant
cured or else they have been sealed and held cleavage stress; but the attachment of the mir-
732 HANDBOOK OF ADHESIVES

Table 2. Typical Holding Adhesive

Applications.
Interior:
Trim panel fabric water base pressure
sensitive
Door panel fabric epoxy spray
Ceiling fabric solvent cement
Carpet adhesive polyethylene hot melt
Sound deadener pads solvent cement
Weatherstripping solvent cement
Wiring harness clips vinyl plastisol
Instrument gauge polyamide hot melt
springs
Hem adhesives polyamide hot melts

Exterior:
Body side molding acrylate pressure sensitive
Wood grain decals acrylate pressure sensitive
Fig. 2. Interior rear-view mirror holding buttons are
Stripping decals acrylate pressure sensitive
bonded to the glass.
Weatherstripping acrylic foam tape
Vinyl roof pressure sensitives
Mirror-to-metal frame silicone
ror to the glass is not part of the essential body Plastic headlamps two-part urethane
structure. Various locking anaerobics
Because of their lower strength require- applications
ments, holding adhesives often utilize thermo-
plastic resins. Hot-melt and pressure-sensitive
products are particularly popular because of the Solvent cements of the neoprene or SBR type
assembly speeds which are possible. are used in automotive interiors to fasten roof
It is convenient to group holding adhesives linings, sound deadener pads, and rubber
as interior or exterior, based on their use inside weatherstripping to doors or door openings. Hot
or outside the passenger compartment. Exterior melts of the polyamide type are used as carpet-
adhesives in general are subject to more severe to-floor adhesives and to anchor instrument
environmental exposure and mechanical load- gauge springs.
ing than their interior counterparts. Exterior holding adhesives (Table 2) are pri-
Typical interior holding adhesive applica- marily ofthe acrylate pressure sensitive or neo-
tions are listed in Table 2. One of their major prene solvent cement type. They are chosen
functions is to retain vinyl or ABS films against because of their durability in service, their low
interior door or sidewall trim panels. The ABS temperature flexibility, and their speed and ease
or vinyl sheet material is often vacuum drawn of use. Hot melts are used in exterior applica-
into recesses in the door or trim panel. It may tions to a lesser extent, particularly in subas-
have a tendency to pop loose and creep away semblies such as lamp housings or vinyl roofing
from concavities or from the backside of the seams.
panels. This behavior, which may be expected Vinyl roofs (Fig. 3) have traditionally been
whenever the sheet material is under tension, attached with neoprene solvent cements. To-
is overcome by the use of adhesives such as day, the trend is toward pressure sensitive for-
epoxies which do not cold flow and which be- mulations. The fabric is positioned on the roof
gin to cure when heated in the vacuum forming and pressed downward and outward by hand
operation. For panels where there is less ten- from the center to remove any wrinkles and air
sion on the sheet material, hot melts or solvent bubbles. Outside edges are generally secured
cements may be used. An example is the use under exterior body moldings. Any seams
of a hot melt hemming adhesive to secure plas- which exist in the vinyl fabric are usually
tic sheet when it is wrapped over the edge of a bonded with a hot melt in ·a prior manufactur-
door or trim panel. ing step.
 ADHESIVES IN THE AUTOMOBILE INDUSTRY 733

Fig. 3. Vinyl roofs are attached by adhesive. Fig. 5. A bonded body-color door handle insert reduces
the need for painting.

A second important group of exterior adhe-

sives are those used for attaching trip strips decorative stripes. Their use means that stripes
(Fig. 4), and wood grain vinyl sheeting to var- like those shown in Fig. 7 can be used without
ious body panels. These adhesives are primar- costly paint masking and curing operations. At-
ily of the acrylate type because of the high tack tachment of insignia and script is significant and
and good low temperature flexibility of these challenging from the manufacturing point of
resins. Fig. 5 shows a door handle insert which view. Considerable savings are possible be-
is of the same color as the body. This color cause separate stocks of parts differing only in
match is achieved by the use of colored pres- the location of mounting holes need no longer
sure-sensitive tape applied to the recessed por- be maintained. The entire hole piercing opera-
tion of the handle. tion can also be eliminated.
Miscellaneous script and insignia are gener- Wood grain decals are popular as options on
ally attached with adhesives (Fig. 6), as are some vehicles. These vinyl materials use an ac-

Fig. 4. Bonded trim strips are widely used in the auto

industry. Fig. 6. Bonded automotive script.
734 HANDBOOK OF ADHESIVES

Fig. 7. Adhesive attachment of stripes reduces the need Fig . 8. A preapplied threadlocking compound on a
for paint masking. threaded part.

rylate adhesive and are applied over a thin film position. When the fastener is screwed into
of dilute soap solution. The soapy water film place, the compound will be spread out over
permits the vinyl material to be positioned by the thread surface and effective locking will re-
sliding it around on the surface. The soap and sult. Locking compounds are widely used in lo-
water is then worked out from beneath the vi- cations where vibration loosening is a problem.
nyl with a squeegee, and adhesion results. Oil pan screws and door interior hardware fas-
Two additional types of holding adhesives are teners are typical examples. As the demand for
worthy of mention because their unique prop- more reliable assembly increases, the use of
erties have made them valuable in the auto- locking compounds, anaerobic or otherwise,
motive industry. These are silicone adhesives will also increase.
and locking compounds.
A silicone adhesive is used by most, if not
SEALING ADHESIVES (SEALERS AND
all, U.S. manufacturers to attach the exterior
GASKETS)
rear view mirror to its frame. This is an appli-
cation where vibration would make mechanical These compounds' primary function is to seal
fasteners unsuitable. Low temperature impact out air, dust, or water in order to reduce cor-
and fatigue resistance factors are such that rosion or improve comfort. In many cases they
many adhesives would be inadequate. Room may also function as holding adhesives. Their
temperature vulcanizing silicones, however, low strength generally precludes their use in
have sufficient high temperature flexibility to structural applications. Typical sealing adhe-
do an excellent holding job. sives are listed in Table 3.
Anaerobic locking compounds are unsatu- A great many sealer applications are not vis-
rated polyester monomers such as dimethacry- ible in a modern automobile body. Low vis-
lates whose cure (polymerization) is inhibited cosity, rubbery sealers are used in virtually all
by atmospheric oxygen. When oxygen is ex- metal-to-metal body joints prior to spot weld-
cluded from the bond line, as in the case of ing. Many ofthese materials contain gas-form-
threaded fasteners, the resin reacts and the re- ing chemicals which decompose when heated
sulting bulk solid locks the parts together. to give a foamy seal which is able to seal out
Figure 8 illustrates a threaded part with a moisture, air, and dirt. They also reduce gal-
portion of encapsulated locking compound in vanic corrosion.
 ADHESIVES IN THE AUTOMOBILE INDUSTRY 735

Table 3. Typical Automotive Sealing Adhesives.

(Sealers and Gaskets)
Type Description Use
Weldable Low viscosity, may be heat expand- Between metal to be welded. Inside hem
able, thennoplastic, stretchy flanges. Seals out water, reduces corro-
sion.
Hot melt Polyolefin Inside box sections which are difficult to
reach after assembly.
Body sealers Bituminous Seal around fire wall, interior body joints
and body drain hole plugs. Prevent air
and water leakage.
PVC Used under exterior paint where cohesive
strength need not be high.
Epoxy Use as plastic body solder.
Gaskets Silicones As fonned-in-place gaskets which can re-
sist heat, cold, and fluids.

Hot melt sealants of the polyethylene type THE FUTURE

may be used in locations which are difficult to
The years ahead hold considerable promise for
reach after assembly. A stick or rod of the seal-
automotive adhesives. Currently available
ant may be placed in a door or rocker panel at
products will probably experience a gradual in-
a convenient time during the assembly process.
crease in acceptance, particularly in the areas
When the body is heated in the primer bake
of body structural, hot melt and pressure sen-
oven, the sealant melts and flows by gravity
sitive holding adhesives. While it is risky to
into the joint to be sealed.
predict the future, it seems reasonable to antic-
A number of other body sealers are extruded
ipate additional product development in the fol-
over welded joints to keep moisture out and re-
lowing directions:
duce corrosion. Bituminous materials are one
example of such sealers. These materials have 1. Adhesives which are less dependent on
very low cohesive strength and are generally surface cleanliness. Acrylic adhesives
used in areas which will not be painted. They which have been used in nonautomotive
are used extensively to seal firewall openings, applications for several years typify this
where their ability to adjust to temperature approach.
changes without cracking and to reduce mois- 2. Quicker curing structural products.
ture are important. Structural hot melts may not be too far
Polyvinyl sealing compounds are used as a away. The savings in time, space, and
replacement for lead body solder for joints tooling would be significant.
which will be subsequently covered by vinyl 3. The use of acrylic adhesive for metal-to-
roofs. metal bonding.
Formed-in-place gaskets are a final example 4. Lower cure temperatures. Such a devel-
of adhesive sealants. These products reduce the opment would mean tremendous savings
need to stock assorted gaskets and thus enhance in fuel and fixtures. A new approach to
assembly efficiency. They are extruded man- the shelf life-cure temperature dilemma
ually or automatically on one of the surfaces is needed here. Perhaps electromagnetic
involved just prior to assembly. Alternatively, or friction-induced activation is possible.
formed-in-place gaskets may be silk screened. S. The real possibility of totally bonded
Silicones and polyesters are generally the res- metal or plastic body components, per-
ins of choice because of their adhesion, hot haps starting with doors or decklids in or-
strength, low temperature flexibility, and good der to take advantage of the stiffening
resistance to nearly all chemicals. propertif"" of adhesives.
 46
Meter, Mix and Dispensing
Equipment: Basic Designs
HAROLD W. KOEHLER
Hardman Incorporated
Belleville, New Jersey

Many fonnulations of reactive adhesives re-

A
quire mixing of the resin and hardener in a crit-
ical ratio. This chapter deals with the basic
designs of equipment for this purpose.
The most popular meter, mix and dispensing
machines have been designed around gear
pumps and pistons, or a combination of both.
This chapter will explain how both systems
function, their strengths and weaknesses.
In order to select a machine, several ques-
tions must be answered:
1. What material is to be dispensed: epoxy,
polyurethane, silicone, etc.? Fig. 1. Gear pump metering circuit. PA-resin metering
pump; PB-hardener metering pump; V-three-way valve;
2. What are the characteristics of that ma- M-drive motor; C-mixer. A-resin tank, B-Hardener
terial which will affect metering: viscos- tank.
ity (rheology), component ratio, filled or
unfilled, abrasive or nonabrasive, pot
ply and Tank B the hardener supply. These
life?
3. Application, production rate, volume re- tanks can vary in size from one quart up to 55
quired, continuous or intermittent dispen- gallons. T~ey may be ASME tanks which are
sing? capable of handling pressures to 75-80 psi. The
tanks may be heated or cooled and may incor-
porate agitators, driven by electric or air mo-
THE GEAR PUMP SYSTEM
tors.
The circuit diagram in Fig. 1 shows the com- The tanks may be equipped with liquid level
mon gear pump metering system. The degree controls which sense the amount of material in
of sophistication governing the driving and a tank. These sensors will send a signal, caus-
monitoring of these devices varies from man- ing a pumping device to start filling the tank.
ufacturer to manufacturer, as does the cost. Upon reaching a predetennined liquid level, a
In Fig. 1, the letters A and B represent the sensor will signal the filling device to stop. A
supply tanks. Tank A is usually the resin sup- system such as this makes the machine com-

736
 METER, MIX AND DISPENSING EQUIPMENT; BASIC DESIGNS 737

pletely self-sufficient so long as the main ma- the tip of the blades and the inside diameter of
terial supply is maintained. the mixing chamber is very small. Usually, part
The letters PA and PB represent the metering A (resin) will enter the chamber behind the part
pumps. These pumps are fixed displacement B (hardener) entry port. In some cases, a check
type, using either gears, diaphragm, or piston valve is used to prevent the intrusion of resin
to displace the material being pumped. Only into the B side of the machine as the result of
gear pumps and piston pumps will be covered, a drop in B side system pressure. If this occurs,
as diaphragm pumps are not popular. the valve closes, preventing part A from enter-
Gear pumps vary in the precision with which ing.
they pump material against a resistance. The The mixer is driven by either electric or air
machine designer selects a specific pump ac- motor; mixer speeds vary from 1700 up to
cording to the characteristics of the material 20,000 rpm.
being processed and the production require- Mixer shaft seals range from V-ring packings
ments. Materials having viscosities, 500 cps to mechanical rotary seals. The degree of back
and up, do not require the precision of pumps pressure and speed a mixer can tolerate is a
that pump materials with viscosities in the 50- function of mixer shaft seal type.
500 cps range. Pump speeds (rpm) must be such V-ring packings would require lubrication to
that pump cavitation will not occur. extend the life of the seal, especially at high
Gear pumps are very accurate metering de- speeds and pressures. Mechanical (rotary) seals
vices and when used properly can do an excel- do not require lubrication, but have speed and
lent job. They cannot, however, be used with pressure limitations, red lined by the manufac-
materials containing abrasive fillers, or highly turer of the seal. Maximum speed for seals in
filled materials which will prevent lubrication the 0.500-0.625 in. shaft diameter range is
of moving parts. The filler material will cake about 4500 rpm at 100 psig system pressure.
up in the pump, causing the pump to jam. On The dynamic mixer can mix a variety of for-
the other hand, materials which have relatively mulations since mixer speed, size, and resident
high viscosity, but are still pumpable, cause the time (the time the mixture spends in the mixing
pump to run at near 100% efficiency since slip chamber) can be varied.
is at a minimum. The disadvantages are that it does require
The advantage of the gear pump system (Fig. maintenance, primarily cleaning and seal re-
1) is its simplicity. The system contains no placement. It cannot take high back pressure
check valves. It may contain a three way valve without premature shaft seal failure. In addi-
(V) to divert hardener from the mixer to the tion, being a mechanical device, it takes energy
tank for the purpose of ratio checking or purg- to drive; seals create frictional heat in addition
ing the mixer with resin. to the heat generated by the shear action of the
The letter M denotes the drive of the pumps. blades through the mixture. Mixing tempera-
This could be a simple gear head motor linked tures can exceed 120°F but this depends upon
to the pumps via gears or chain and sprocket. the rate of the material through the mixer and
It could also use a SERVO motor drive system. the temperature of the components being
With this setup, ratio may be changed at will. mixed. It should be noted that the gel time of
With gears or sprockets, these must be physi- the material being processed is no longer the
cally changed in order to effect a change in ra- published time and in all probability will be
tio. shorter due to the heat generated by the mixer.
The letter e denotes the mixer of the ma- A good rule of thumb is: for every lOoe rise
chine. The two most popular types are the dy- in temperature the pot life is reduced by one-
namic and the motionless mixer. half.

The Dynamic Mixer The Motionless Mixer

This mixer is simply a rotating (usually bladed) This mixer does not require mechanical energy
agitator within a chamber. The space between to achieve the mixing of the two streams. Mix-
738 HANDBOOK OF ADHESIVES

ing is accomplished by geometric shapes pre- this aids in verifying proper mixing and ade-
sented to the stream of material. The motionless quate purge of the mixing chamber.
mixer has no moving parts, and with the advent In conclusion, both mixer types are excellent
of the inexpensive throwaway mixer and mix- tools if used with suitable formulations.
ers which can be disassembled and cleaned, it
must be considered as a mixing alternative in THE METERING CYLINDER SYSTEM
the design of a machine.
The basic circuit diagram for this type of me-
The motionless mixer, unlike the dynamic
tering system is shown in Fig. 2. The resin (A)
mixer, cannot be relied upon to mix any and all
and hardener (B) tanks can incorporate the same
formulations. Mixing is aided by increasing the
features as described previously for the gear
back pressure by restricting the flow at the exit
pump metering system, in addition to mixing
end of the mixer or increasing the throughput
methods.
(the speed at which the materials pass through
The valves identified as E and F are called
the mixer). The next step to obtain a good mix
charge valves. The function of these valves is
would be to add another mixing element which
to prevent any back flow of material to tank
will increase back pressure. What must be re-
when the metering pistons (cylinders) PA and
alized is that a motionless mixer may do an ex-
PB move forward to dispense material through
cellent job mixing one formulation, but may fail
the discharge valves.
to mix another.
Valves C and D are called discharge valves.
The factors which influence the success or
Their function is to prevent any suckback of
failure of a motionless mixer are: material vis-
material into the metering cylinders, which
cosity (rheology), ratio, flow rate, and com-
could occur during the charging cycle.
patibility of the materials. If resin (A) and
The letters PB and PA denote the metering
hardener (B) have widely differing viscosities,
pistons. These could be pistons with V-ring
e.g., 50,000 cps (A) and 50 cps (B), the ma-
seals as shown in Fig. 3(a), cup type piston
terial having the lower viscosity may just' 'rat-
[Fig. 3(b)], or blind rod cylinders [Fig. 3(c)].
hole" through the mixer, resulting in a poor
mix. If a formulation calls for a ratio range of
3-5 parts per hundred, it may be difficult to
mix.
B A
The mixer also creates a great deal of back
pressure (depending upon viscosity), approxi-
mately 5-10 times the pressure created by a dy-
namic mixer. In addition, the passageways
slowly close (due to the curing of the stagnant (+)-(-)
F
layer of material), restricting the flow, which Ratio Adj.

subtly places added burden on the pumping de-

vice of the machine in the form of back pres-
sure.
At this point it must be apparent that the ma-
terial intended for use should be selected with
care that it be machine compatible. The sup-
D
plier should be able to confirm this. If possible,
one should insist on nonabrasive fillers or no
fillers at all, and reasonable, easy-to-obtain ra-
tios. If possible, ratios such as 1-2 parts per H
hundred should be avoided, as they are very
difficult to hold without constant attention to
Fig. 2. Single-acting metering system. A. B-material
the metering equipment and the condition of the tanks; C. D-discharge check valves; E. F-charge check
materials being processed. One should insist on valves; G-drive cylinder; H-mixer; PA-resin cylinder;
color changes when mixing resin and hardener; PB-hardener cylinder; V-hardener bypass valve.
 METER. MIX AND DISPENSING EQUIPMENT; BASIC DESIGNS 739

spool, poppet or rotary designs. The selection

of a valve type is based upon the material being
processed.

(a) Spring-Loaded Check Valve.

This valve (Fig. 4) is relatively inexpensive and
will perform well with low viscosity liquids. It
is used extensively in oil and pneumatic cir-
cuits, but has some limitations when used to
control very viscous materials. It can momen-
tarily open when subjected to abrupt pressure
(b)
changes.
Spring-loaded valves appear to be great
strainers, especially on low ratio systems,
where the fluid flow velocity is low. In this
case, the valve would only crack open, pre-
senting a very small opening through which the
liquid flows, . as a result, any contaminants
(e)
could be trapped between the ball and seat. In
Fig. 3. Piston seals. (a) Chevron V-ring seal; (b) piston some cases, crystals formed by moisture can
cup-type seal; (c) blind rod (no piston) cylinder. cause valve problems.
When operating from pressurized material
tanks or from transfer pumps, the closing spring
The designs shown in Figs. 3(a) and 3(b) are
pressure required for the discharge check valves
useful when nonabrasive materials are being
must be greater than the highest pressure de-
used, although some degree of success has been
veloped by the transfer pump during the charg-
achieved with abrasive materials using polyu-
ing cycle. Otherwise it is possible to open the
rethane seals in conjunction with a hard chrome
discharge check, allowing unmetered material
plated cylinder wall. The cylinders in Figs. 3(a)
to enter the mixing chamber. This can easily be
and 3(b) each incorporate a tank which supplies
checked by observing if a steady drip of ma-
the bearing side of the cylinder with lubrication
terial is present at the dispensing nozzle.

-t
in addition to excluding air from the metering
cylinders. This is essential when moisture-sen-
sitive materials such as isocyanates or polyu-
rethanes are used. The lubricant is usually an
inert plasticizer. Flow
From a design standpoint, Fig. 3A is supe-
rior since it contains a piston assembly which
is supported at two points (1 and 2). This piston
rod assembly is capable of taking more side

FlOW~
load than the cylinders shown in Fig. 3(b) or
3(c). The cylinder shown in Fig. 3(c) is a blind
rod cylinder, and when equipped with the
proper shaft scrapers and seals will do a good
job with abrasive materials.
The check valves, C, D, E, and F, are the
heart of the system. If they foul up, the best
metering pistons or mixer cannot remedy an off- Flow
ratio condition. These valves range in com-
plexity and cost from a simple spring-loaded
check to expensive powered valves of either Fig. 4. Check valve arrangements.
740 HANDBOOK OF ADHESIVES

Powered Check Valves. The machine described in Fig. 2 may be clas-

sified as a single-acting metering device. This
These valves are usually driven by a solenoid, device requires time to recharge, once cylin-
a pneumatic cylinder, or a mechanical linkage. ders PA and PB have discharged. If the mate-
If properly designed, they will not function as rials are low in viscosity, this time may be as
displacement devices and will be held closed short as 2-5 seconds. If viscosities are high,
by system pressure. the recharge time can be 15-30 seconds or
The seats of these valves are usually soft, longer.
made of plastic such as Teflon, polyethylene, An important factor: in many applications,
or nylon. The valves tend to form their own tanks A (resin) and B (hardener) must be pres-
seat configuration when cycled several times. surized to achieve meter cylinder recharge
The weak point in this valve is the actuating within a reasonable time period. In addition,
shaft, which contains a seal. This shaft con- heating of the materials will reduce recharge
nects the poppet spool with the actuator. If this time. If the proper recharge of the cylinders is
seal fails, no matter how good the internal not achieved, an off-ratio condition will exist.
seals, the valve must be repaired. The circuit diagram in Fig. 5 shows a dou-
In terms of cost, the powered check valve is ble-acting metering system. The principles of
more expensive than the spring loaded ball operation are the same as those used in Fig. 2.
check valve, not only because of design differ- In this device, the machine is driven by transfer
ences but also because of the control devices pumps A and B which charge (fill) the metering
required for operation. Regardless of the pow- cylinders with material. The charge and dis-
ered valve's cost, it is a comfort to know that charge valves allow the metering cylinders to
the valve is going to operate regardless of the be filled with material during the dispensing
material or operating conditions. cycle. No recharge time is required. An expla-
Powered valves, being operated by one of nation as to how this system works follows,
several types of actuators (solenoids, air cyl- using Fig. 5 as a guide.
inders, and rotary actuators), lend themselves At a given signal, transfer pumps A and B
well to microprocessor-controlled machines. will start pumping. At that same instant all

5
f-'--.::;o~""" PA

-G

Fig. 5. DoUble-acting cylinder-type metering system. eVA, eVB-charge (suction) valves; DVA, DVB-discharge
valves; PA, PB-metering cylinders; V-hardener bypass; TA-resin transfer pump; TB-hardener
transfer pump; G-mixer.
 METER. MIX AND DISPENSING EQUIPMENT; BASIC DESIGNS 741

charge and discharge valves will shift to the po- ing in a vacuum within the metering chamber.
sition indicated. On the resin side, valve CVA If strong enough, this vacuum will collapse the
has isolated line 5, allowing pressurized mate- piston seal and allow material to enter the
rial to flow through line 4 to metering cylinder chamber. This is of no concern so long as the
PA. Cylinder PA moves, pushing material piston seal recovers to seal during the metering
through valve DVA which isolated line 8, al- cycle, as the piston pulls out of the metering
lowing material to flow through line 7 to mixer zone, if the recharge is not controlled, the sud-
G. The sequence is the same for the hardener den surge of material caused by the vacuum
(B) side, and both sides act simultaneously. break can momentarily open the discharge
Cylinders PA and PB, upon reaching the end check, allowing unmetered material to enter the
of their stroke (length of travel), actuate a limit mixing chamber. The rod check valve shown
switch which signals all charge and discharge in Fig. 6 helps eliminate this problem.
valves to switch, reversing the flow of the ma-
terial and the travel direction of cylinders PA
RECOMMENDED ACCESSORIES
and PB.
In Figs. 2 and 5 the discharge checks are Positive Cutoff
shown individually, but in actuality all the
This device is usually located at the dispense
check valves may be combined into one or two
nozzle. Its function is to prevent dripping. It is
single units, depending upon the metering sys-
used where precise shot sizes are required with-
tem. In other designs the charge check may be
out tailings.
the piston itself (Fig. 6). As the piston in Fig.
The positive cutoff must be timed with the
6 is driven forward, material is pushed back to
cycle of the machine. It must open at the in-
tank until the metering stage is started. That
stant the dispense button is depressed and is set
happens when the leading edge of the piston
to close a few milliseconds after the dispense
seal passes the tank port and makes contact with
button is released. The designs range from a
the cylinder walls. Visualize two such devices
simple scissor arrangement to the manipulation
hooked to a single drive; this produces a rela-
of valves: pinch valves, collapsible tubes and
tively simple two-component metering device.
duck bill valves. The best are those which op-
Some cautions: The entry of both resin (A) and
erate without contacting the mixed materials.
hardener (B) pistons into the metering stage
must be exact; any lead or lag between pistons
Pot-Life Guard
constitutes an off-ratio condition (how much off
ratio depends upon the lead or lag). On the re- This device prevents the accidental curing of
charge, the piston is being pulled back, result- mixed material in the mixing chamber. The de-

Thrust -~

Thrust - "--.....,.,.,,.,.,.-_-"1 - Metered Flow

Fig. 6. Piston charge check.

742 HANDBOOK OF ADHESIVES

Table 1. Meter. Mix and Dispensing Equipment.

Accumetrics Hardman Industries, Inc.
Box 843 600 Cortlandt Street
Elizabethtown, Kentucky Belleville, New Jersey 07109
Amplan, Inc. Liquid Controls
200 Egel Avenue 7576 Freedom Avenue N.W.
Middlesex, New Jersey 08846 Box 2747
North Canton, Ohio
APe INC. Maguire Products, Inc.
1123 Morris Avenue 6 Miller Road
Union, New Jersey 07083 Edgemont, Pennsylvania 19028
Ashby Cross Company, Inc. Otto Engineering Corp.
20 Riverside Avenue 2 Main Street
Danvers, Massachusetts 01923 Carpenterville, Illinois 60110
Fluidyne Instrumentation Pyles Industries, Inc.
2930 Lakeshore Avenue 28990 Wixom Road
Oakland, California Wixom, Michigan 48096
Glenmarc Manufacturing, Inc. Resi-Mix
300 South Harbor 26 Ashmont Avenue
Suite 600 Whitinsville, Massachusetts 07588
Anaheim, California 92805
or
330 Melvin Drive Sealant Equipment & Engineering Co.
Northbrook, Illinois 60062 2100 Hubbell
Oak Park, Michigan 48237

Spray Equipment
Binks Manufacturing Company Zicon
Franklin Park, Illinois Mt. Vernon, New York

vice is simply a flip-flop timer circuit. The first two- and three-axis indexing tables and robots
timer monitors the off time (the time from the having both point-to-point and continuous-path
end of the dispense cycle to the preset time pro- capabilities.
grammed into the first timer). This time is based With the increased use of adhesives in the
upon the pot life (gel time) of the mixture. construction of structural assemblies, the need
When this timer times out, it starts the second for dispensing equipment should expand. In-
timer going. At this time the dispenser starts. deed, control of the machines will become more
This continues until the timer runs out, at which complex as they find their way into the world
time dispensing stops. This is called purge of robotics and automation.
time, and is a function of mixer volume.
In conclusion, the methods of dispensing re-
EQUIPMENT SUPPLIERS
active materials are varied. We are seeing the
meter, mix, and dispense machine being inte- Table 1 shows suppliers of equipment for me-
grated into computer controlled production tering, mixing and dispensing, as well as spray
lines. Dispensers are working successfully with . equipment.
 47
Robotic Dispensing of Sealants and
Adhesives
HERB TURNER
Engineering Manager
Automotive Business Group
Nordson Corporation
Amherst, Ohio

INTRODUCTION Robots are used to dispense adhesives and

sealants throughout the automotive industry to-
The dispensing of adhesives and sealants (hot,
day. Automation requirements will be exam-
wann, or cold) has been established as a proven
ined for windshield bonding to the vehicle, door
market for the application of robotics. Robots
manufacturing, passenger compartment inte-
are being used across industries for applying
rior seam sealing, and the application of seal-
adhesive and sealants to increase quality and to
ants during the buildup of the vehicle body.
reduce labor and material costs. The automo-
These account for the vast majority of robotic
tive segment has led the way for the application
sealant and adhesive dispensing applications in
of robotics. This chapter will deal with that
the automotive industry.
segment and some of the criteria associated
with automating particular applications, em-
DISPENSING EQUIPMENT FOR
phasizing the relationships between the appli-
ROBOTIC APPLICATIONS
cation objectives and the adhesive/sealant
dispensing equipment. Successful applications The three elements of a dispensing system are
take into consideration the capabilities and lim- the pumping system, the delivery or header
itations of the adhesive/sealant materials, the system and the dispensing gun or valve. Care-
dispensing equipment, the tooling and fixtures ful selection of each element is required to de-
and the robot. liver the desired bead at the required flow rate.
Selection of the robot and the dispensing Lack of perfonnance in anyone of the three
equipment are of primary importance when au- elements will limit the benefits of the auto-
tomating sealant and adhesive application pro- mated dispense system.
cesses. Those installations that have taken into
account all aspects of the application require- Pumping System
ments have been successful.
The pumping system is typically made up of
two bulk unloaders, two feed hoses delivering
Text excerpted from "Robotic Dispensing of Cold Seal- the pumped material to a common changeover
ants and Adhesives-New Advancements," presented at
the 1987 Fall Seminar of The Adhesive and Sealant Coun- manifold and a system controller. Two bulk
cil, Inc. unloaders (A and B) are nonnally selected in a

743
744 HANDBOOK OF ADHESIVES

robotic system to provide a continuous flow of unloader B waits in a standby (reduced

material. The bulk unloaders could be provided temperature) mode until needed.
with either piston or gear pumps, depending on • When bulk unloader A reaches a predeter-
application and material requirements. mined level known as Low drum, a limit
A heated dispensing system is used here for switch sends a signal to the system con-
illustration, however, many of the system var- troller, which in tum increases the set-
iables are equally relevant for cold dispense point temperature of bulk unloader B from
systems. In a typical heated sealer application the setback temperature to the required ap-
(Fig. 1), bulk unloader A would be the on-line plication temperature (usually the same as
unloader. The on-line unloader is the unit cur- A).
rently heating the material to application tem- • When bulk unloader A reaches empty
perature and pumping the material to the drum, another limit switch sends a signal
changeover manifold at the required tempera- to the system controller indicating that
ture, pressure, and flow. Bulk unloader B is the bulk unloader A is out of material. The
standby unloader and will usually be at a set- system controller automatically then
back (reduced) temperature to minimize the switches bulk unloader B to on-line status
amount of time the sealer is at application tem- and signals manufacturing personnel that
perature while ensuring that minimum time is a changeover has occurred and that a new
allotted to come up to full application temper- drum of material is required. Bulk un-
ature when commanded from the system con- loader A will remain at application tem-
troller. perature to facilitate easy removal of the
The control logic for the two bulk unloaders drum follower plate. After the follower
is as follows: plate has been raised and the empty drum
removed and replaced by a new drum, the
• Bulk unloader A provides material as follower plate is then reinserted followed
needed by the dispensing guns while bulk by purging of air from beneath the fol-

, .....
" ' ....
" .... , ....
;,' ........
" ' .....
DELIVERY OR " HEATED HOSE ..
HEADER SYSTEM ,,"
- - ,, , '
,
, ",
, ",
<..
............
CHANGEOVER
MANIFOLD

_~
lllJ
SYSTEM
CONTROLLER

BULK UNLOADER /
"A"

Fig. 1. Typical dispensing system configuration with robotic and manual application points.
 ROBOTIC DISPENSING OF SEALANTS AND ADHESIVES 745

lower plate (total time takes about 3-8 providing immediate feedback, has advantages
minutes depending on training and skill). relative to inferred sensing controls. An ex-
A ready button on unloader A is then ac- ample of inferred sensing would be a controller
tivated by the operator to place drum A that was designed to monitor the minimum set-
into the standby mode by the system con- point temperature. For inferred sensing, an
troller. alarm will sound when the actual running tem-
perature reaches the minjmum setpoint temper-
Bulk unloaders come in three common sizes: ature. Due to the inferred temperature sensing
5, 55, and 300 gallons. Selection of the appro- mechanism a time delay of 20 minutes may
priate size is application dependent and re- elapse before a system failure is detected. A
quires several considerations. First, acceptable control system that pinpoints heater loss and lo-
time intervals between drum changes should be cation within the system immediately prevents
determined. The volume of the bead deposition lost production and simplifies system trouble-
per application and the number of applications shooting. Immediate feedback also signals
per hour will dictate the amount of time be- maintenance before critical downtime occurs.
tween drum changes. Some materials have a Another system control feature often re-
very long shelf life and therefore provide more quired for robotic systems is an automation in-
flexibility in container size. Other considera- terface card that allows signals to be sent back
tions are economies of larger drums and ac- and forth between the robot, the cell controller,
cepted plant practice for material handling. For and the system controller. Signals such as SYS-
materials having shorter shelf life or where TEM READY indicate that there are no major
there is low daily material usage, a smaller malfunctions and that the system has reached
drum size is optimal. For example, in the pro- application temperature. Another valuable sys-
cess of building vehicle doors, approximately tem control feature in a robotic dispense system
2. I cubic inches of material are required in the is simplified gun purge capability. In the event
assembly process. If 120 doors per hour are that skilled personnel that know how to facili-
manufactured to meet production require- tate a purge signal from the robot cannot be
ments, then 252 cubic inches (1.09 gallons) per located, an easily located button on the system
hour will be needed from the pumping system. controller for this purpose is important. All of
In this case the proper bulk unloader/material these features are needed to minimize down-
container size would be 55 gallons and not 5 or time, which is often the yardstick by which ro-
300 gallons. A 55 gallon drum of material al- botic systems are measured.
lows for 6.3 days per bulk unloader of produc-
tion, as compared to 4.6 hours for a 5 gallon
Header System
drum or 34.4 days for a 300 gallon container.
Sized correctly and with tandem bulk unload- The delivery or header system usually consists
ers, scheduled drum changes can be made in- of flexible hoses and rigid pipes. The design of
stead of emergency/reactionary drum changes. this system must be coordinated with the plant
The tandem unloaders also provide backup for layout, the material to be dispensed, and the
each other in the event of failure, or during sys- instantaneous material delivery rate required.
tem maintenance, and they output a continuous The two primary factors are material and deliv-
bead even during the automatic changeover se- ery rate. Each material to be dispensed (adhe-
quence. sive or sealant) requires a unique and specific
System design and controls monitor material pumping pressure based on header size (hose
usage and other system conditions to ensure and pipe inner diameter) and delivery rate. Cal-
continuous production. Another feature of a culations should be made to estimate system
well designed automatic control system is di- pressure drop for a proposed system configu-
agnostics, particularly in the area of pinpoint- ration to determine if sufficient system pressure
ing the location of failed heaters or temperature availability exists. Tests should also be con-
sensors. A system that monitors all temperature ducted to verify system design. These calcula-
fluctuations throughout the distribution path, tions and tests should take into account
746 HANDBOOK OF ADHESIVES

maximum robot velocity and bead size to be

dispensed to detennine instantaneous delivery
rate. Available cycle time is not sufficient in-
fonnation for calculating instantaneous deliv-
ery rate requirements. Available dispense time
and maximum robot velocity are also critical
considerations for proper selection of delivery
system components.
Other considerations for both heated and un-
heated delivery/header systems include modu-
larity for system configuration or redesign,
backup temperature sensors, hose and pipe siz-
ing, ease of maintenance, and routing of hoses
on the robot with regard to its movements dur-
ing robot cycles and for robot maintenance.

Dispensing Gun
Over the years many attempts have been made
at designing a robotic dispensing valve. The
Fig. 2. Robotic application of hem flange adhesive at
progression from each design has been evolu-
BOC-Lansing's Reatta Craft Centre featuring a Nordsonil>
tionary rather than revolutionary in the attempt Pro-Flck) System.
to design dispensing equipment that has the
same level of perfonnance as the robot. Many
of the dispense valve designs have fallen short negatively impact part quality as well as ma-
of meeting the same perfonnance criteria that terial usage.
robots have met in the area of speed of re- The key to unifonn material deposition using
sponse. Recently Nordson Corporation re- robotics is the interface between the equipment
leased a variable orifice dispensing gun known and robot. The robot sends and receives elec-
as the Pro-FloTlf System (patent pending) that trical signals from the dispensing gun in a con-
has met the design criteria that all systems have tinual feedback system. The signals sent from
tried to obtain-speed of response equal to or the robot to the dispensing system cover basic
greater than the robot. The Nordson Pro-Flo™ functions, such as gun on/off, while the dis-
System (Fig. 2) has the ability to adjust mate- pensing system offers diagnostic signals that
rial flow rate as the robot adjusts velocity to indicate fault conditions and provide trouble-
achieve unifonn bead deposition. shooting assistance. These signals are impor-
Bead control, or management of bead depo- tant because they aid in minimizing manpower
sition, is driven by both the manufacturing pro- for checking quality (i.e., verifying bead dep-
cess and the rheology of the materials to be osition), system maintenance and downtime.
dispensed. Process requirements may dictate a
short cycle time to dispense the material, hence
Typical Methods of Bead Management
varying velocities and accelerations are re-
quired to meet path accuracy and cycle time Alternative methods of bead management in-
constraints. As the robot varies its velocity to clude the pump and gun combination, the shot
meet these sometimes opposing constraints, metering system, and the electropneumatic
management of the deposition becomes more control of gun orifice size relative to changing
important in dispensing unifonn beads. As ma- robot velocity and to hydraulic and pneumatic
terials develop, the amount dispensed, as well pressure variations. The relative merits of each
as the cost, play an important role in the dis- method will be discussed.
pensing equipment selection. A material dis- The simplest method for robotic dispensing
pensed in too small or large a quantity may is the pump and gun combination. The pump is
 ROBOTIC DISPENSING OF SEALANTS AND ADHESIVES 747

used to unload material from bulk containers The shot pump may be air, hydraulic, or
and create hydraulic pressure in a distribution electrically controlled. The shot pump control-
system. The gun is used to tum the flow on and ler accomplishes bead management by process-
off while at the same time providing a fixed ing an output control signal from the robot and
flow resistance to the material. The greater the varying the shot pump output proportional to
flow resistance, and consequent pressure drop, the robot signal. This robot output control sig-
the greater pump pressure required to increase nal is either a constant DC voltage or a variable
flow or bead size. There are many drawbacks DC voltage that is proportional to robot tool
in this type of system. Variations in pump pres- center point (TCP) velocity. This technique
sure output during the robot cycle result in vari- provides greater control over the preceding
ations in flow (bead size) which can result in method of constant pressure and fixed orifice.
bead deposition which does not meet process However, there are several constraints affect-
specification. Variations in robot velocity com- ing the application of shot pump dispense sys-
bined with no bead control other than gun on/ tems.
off can also result in inconsistent bead size. As The first constraint is floor space require-
a result of changes in robot velocity, excess ments for the shot pump and shot pump con-
material is often applied to ensure that the min- troller. The second constraint is the distance
imum bead size is always applied. between the shot pump and the gun tip. Typi-
Simple pump and gun dispensing equipment cally, the shot pump is one hose length away
of this type requires constant robot velocity to from the dispensing gun tip, causing response
provide a constant and consistent bead. How- delays in the required fluid output variance. To
ever, to achieve the objectives for cycle times, compensate for the delayed change in material
productivity goals, and quality needed to meet flow at the gun tip, robot manufacturers have
today's standards, robot velocities are varied to tried both prepressurizing the system and pro-
maintain path accuracy, especially in corner- gramming the robot in anticipation of material
ing. The equipment configurations and limita- output. The resulting system hysteresis from
tions discussed are often frustrating to the pressurizing and uncontrolled pressure decay
manufacturing/process engineer who is respon- often provides poor overall bead management.
sible for product quality and productivity. As mentioned earlier, it is possible to model
Programmable transfer pumps, better known the dispensing systems performance character-
as shot pumps, are another equipment variation istics and to compensate for them in robot pro-
available for robotic dispensing of adhesives gramming. However, due to the complexity of
and sealants (Fig. 3). In shot pump systems, the dispensing configuration, overall bead
the dispensing gun has a fixed needle-and-seat management is typically not optimized. Re-
arrangement, providing a constant orifice di- ported system response time to changes in the
ameter. robot signal varies from 200 milliseconds to

VISION & SHOT PUMP SHOT PUMP

ROBOT CONTROLLER
CONTROLLER DISPENSING
\ GUN)

I
SEALING
CABLE

J""'c:-r---LJ'Il..--ROBOT
HEADER
SYSTEM
PUMPING
SYSTEM

Fig. 3. Typical system configuration for a shot meter installation.

748 HANDBOOK OF ADHESIVES

over 1 second. Today's robots are known to with gear metering systems since tolerances
update and respond in as little as 30 milli- must be held tight to minimize pump leakage
seconds. With a robot velocity of 20 inches per across the side plates from high upstream pres-
second a 200 millisecond response would result sure. In addition, many of the materials dis-
in an incorrect bead size for up to four inches pensed have a high content of abrasive fillers,
while the metered output lags behind the robot further contributing to excessive pump wear.
signal.
The remaining two issues associated with ADVANCEMENTS IN DISPENSING
shot pumps, limited dispense output volume TECHNOLOGY
and a condition known as "packing out," per-
To meet the challenge oftoday's robotic appli-
tain directly to the pump itself. These two is-
cations, a new approach to automated dispen-
sues are interrelated. A properly sized shot
sing has been developed involving electro-
pump will evacuate all material in the cylinder
pneumatic control of the gun orifice size as a
during the dispense cycle. As a result, the sys-
function of robot velocity. The system is able
tem is iriflexible to meet increases in dispensing
to respond with equal or greater speed than the
requirements. Between the time the dispensing
robot-to-input command signals. The system is
equipment was first specified and the actual in-
also designed to handle a wide range of mate-
stallation date, the material dispensing require-
rials and features a linear relationship between
ments are likely to have changed due to
robot input command voltage and flow (Fig. 4)
automobile design changes or to meet the man-
for accurate bead proportioning. Additional
ufacturing/tooling capabilities. If the shot cyl-
product features include near-zero floor space,
inder is oversized relative to the specification,
ease of maintenance, repairability, and modu-
then a given amount of material will not be
lar components for compatibility of parts across
evacuated for each application. The material
many models of guns. Finally, the gun design
remaining in the cylinder is then subjected to
incorporates dowel pins and piloted fits to en-
repeated high pressure applications, potentially
sure accuracy and repeatability from gun to gun
causing fillers to be compacted due to squeeze-
for successful automation.
out of the carrier (e.g., plastisol). This com-
For accurate metering and flow adjustment,
pacting, also known as packing out, results in
and to ensure fast response time, adjustment of
a solid plug in the cylinder that cycles back and
flow occurs close to the gun nozzle. To accom-
forth for each application. Problems occur
plish this, pressurized material flows into the
when bits and pieces of this solid plug break
gun and across a variable orifice. The variable
off and cause nozzle clogs during dispense. orifice is comprised of a solid carbide needle
Once a nozzle clog occurs, the shot pump will and seat for maximum wear resistance. Down-
usually continue to pressurize the system until stream of the needle and seat, but before the
the weakest system component ruptures to re-
nozzle, a pressure transducer provides pressure
lieve the overpressure condition.
Another variation of the programmable
transfer pump involves the use of an electric
servomotor-driven gear pump. These pumps
have the same deficiencies associated with shot
pumps. Response lags caused by gear pump in-
ertia as well as the distance between the pump
and the dispensing gun contribute to limited
control and poor response over the length of the
bead. In addition, floor space is consumed by
the control panel required for receiving signals
from the robot and sending control signals to
the servomotor controller and ensuing servo- ROBOT VELOCITY SIGNAL
motor/gear pump combination. (VOLtS)

Pump wear is another problem associated Fig. 4.

 ROBOTIC DISPENSING OF SEALANTS AND ADHESIYES 749

ELECTRICAL CONTROL ity. The first control is a purge function. With

SIGNAL INPUT
a simple switch closure from the robot, the sys-
.-,sEA~~~:~~t~~~R tem is placed into a purge mode that is fully
controllable via the system control settings. In-
creasing the purge value causes an increase in
VALVE STEM SEAL
VALVE STEM
the flow, while decreasing the purge setting de-
ADHESIVE INPUT
creases the flow. During the purge cycle the
FEEDBACK
TRANSDUCER
robot controls the duration of gun on time by a
timed switch closure. The second control set-
~DISPENSING NOZZLE
ting controls bead size during the dispense
cycle. The bead size control function and in-
Fig. 5. Variable orifice dispensing gun. (Courtesy Norcl- coming robot signal are multiplied together to
son Corporation, Amherst, Ohio.)
form a proportional control. To ensure the lin-
ear relationship between input signal and flow,
feedback to the dispenser's closed loop control two additional controls are used. The two ad-
(Fig. 5). A nozzle pressure control is used to ditional controls, referred to as high speed and
compensate for variations in both hydraulic and low speed, compensate for material properties
pneumatic system pressures. such as shear thinning. These controls trans-
Figure 6 is a graphical presentation of the form material nonlinearities into a linear func-
control loop illustrating the operating se- tion over a wide range of flow.
quence. The diagram shows the relationship Figures 7 and 8 display the speed of response
between the robot signal, pneumatic servo, hy- by the system duri!1g the course of the sample
draulic/pneumatic pressure supplies, pressure path. The path (Fig. 7) has speed variations
feedback, and nozzle orifice. As the diagram ranging from 4 in.lsec to 16 in.lsec. The in-
illustrates, a change in the incoming robot sig- verted pressure transducer signal and the ac-
nal causes a change in the controlled nozzle companying robot command signal are
pressure and subsequently adjusts gun orifice illustrated in the response curve in Fig. 8,
size to provide accurately controlled material which also shows how the system compensates
flow. for pump wink. Pump wink occurs when the
Four operator-adjustable controls are used to piston changes direction and causes a dip in the
ensure ease of use and maximum controllabil- system supply pressure. Variations in pump

FILTERED
_ [ SEE VIEW "A" SHOP AIR FLUID PRESSURE

/
".. . - ,a:.~
IROBOT+ ffi
ISIGNAL

\
" CRITICAL DAMPING

Fig. 6. Analog control loop for variable orifice dispensing gun. (Courtesy Nordson
Corporation, Amherst, Ohio.)
750 HANDBOOK OF ADHESIVES

TEST PATH these quality defects resulting from improper

START/FINISH
2 1115 14
seam sealing can lead to costly warranty repairs
3 13
for the automotive manufacturer. For interior
4 Slnlsec 161nlsec Slnlsec 12 seam sealing the bead applied has a ribbonlike
appearance that is generally 0.75-1.50 in. wide
and 0.050-0.125 in. thick. In order to achieve
121nlsec
121nlsec this ribbonlike deposition, an air mix airless
paint tip is used. The air mix, which uses var-
5 41nlsec 11
ious combinations of hom and face air, pro-
41nlsec 161nlsec
duces fan or conical spray patterns. The conical
6 7 S 9 10 spray pattern is predominantly used because lit-
Fig. 7. Test path with varying velocities. (Courtesy tle or no orientation of the spray pattern is re-
Nordson Corporation, Amherst, Ohio.) quired relative to the substrate. The net result
is more time to dispense with less time used to
supply pressure such as pump wink are mini- orient the robot wrist to achieve a directional
mized by the electropneumatically controlled spray pattern. Inadequate management of the
dispense gun to provide uniform material flow. bead as the robot varies its velocity results in
nonuniform material deposition.
Figure 9 shows the typical seams to be sealed
APPLICATIONS on an automotive chassis. This sealing process
Dispensing of adhesives and sealants is accom- is normally found in an area in the plant known
plished robotically in many industries. The fol- as the paint shop. The sealant material is ap-
lowing robotic dispensing applications of plied immediately, prior to topcoat paint pro-
adhesive and sealant, are taken from the auto- cesses. The ensuing paint ovens then cure both
motive industry where the majority of robotic the paint and sealant.
Typical equipment configuration for robotic
dispensing applications are used.
seam sealing includes high response variable
Interior Seam Sealing
This application involves the sealing of body
joints necessary for the unibody construction of
automobiles. These seals are critical because
they seal the passenger compartment from
moisture, dust, and wind noise. Anyone of

NOTE ' ASTERISK DENOTES PUMP WINK

,
TRA.NSOUC ER
SIGNAL

r
0 10 ·2VOC GU ! TRAiNSD J CER iSIGNL SPRA YEO SEALANT

..... - - '
rI r ..... --' -
~
I L
* -
SPRA YEO SEALANT
ROBOT COMMAND SIGNAL
;--0 - r-

r -,
l
ROBOT OUTPUT
COMMAND SIGNAL
0 10 SVOC TIME

Fig. 8. Variable orifice gun response to input command

signal from robot. (Courtesy Nordson Corporation, Am- Fig. 9. Typical seams to be robotically sealed on an au-
herst, Ohio.) tomobile chassis.
 ROBOTIC DISPENSING OF SEALANTS AND ADHESIVES 751

orifice guns, recirculating pumping systems and tioning uses heaters and sensors across the dis-
material temperature conditioning elements. tribution path. This system temperature
The materials applied for interior seam seal- conditions the material by applying heat in the
ing are predominantly plastisol sealants. These header system equivalent to the maximum am-
plastisol materials may be complex rheological bient temperature. The system utilizes a mod-
systems designed to promote interactions be- ular piping network outfitted with zoned
tween the suspended component particles, temperature controls (similar to Fig. 1) that al-
yielding unique pumping characteristics. These low the materials temperature to be gradually
interactions form a network which raises the raised to the desired application temperature.
material's inherent viscosity. However, when The two basic pieces of information required to
the material is sheared by pumps, fittings, correctly apply this system is the temperature-
hoses, and pipes, the network is broken down viscosity curve for the material and the maxi-
and the viscosity returns to a lower stabilized mum recommended material application tem-
value. The material is said to be thixotropic perature. Since the material temperature is
when it displays this type of shear-thinning equal to ambient temperature while in the bulk
rheological behavior. Shear-thinning material drum, during storage and shipping, raising the
behavior is desirable, as it allows the material material temperature so it is slightly below the
to be sprayed without regard to orientation of maximum am~ient temperature minimizes vis-
the vehicle body without running, dripping, or cosity variations. Stabilized material viscosity
sagging. Material recirculation throughout the provides uniform spray depositions on the au-
dispense system prior to daily startup of pro- tomobile seam. Material temperature condi-
duction allows stabilization of material viscos- tioning equipment of this type should include a
ity to ensure consistent spray patterns and header system with machine wound heater tape
ribbon depositions, critical to the success of the on the pipes for uniform heating and tempera-
robotic installation. ture control. A control system is required to ac-
Another material property that can influence curately measure and control the temperature to
spray pattern and ribbon deposition is temper- ± 1°F. Maximum uptime is achieved with
ature-induced viscosity variation. In general, as modular/zoned temperature controls. Should
the material temperature is raised (usually due one of the zones deviate from the temperature
to changes in ambient air temperature), the ma- set point, the controller can automatically tum
terial viscosity will also decrease. To minimize that zone off while continuing to run the re-
the impact of temperature changes on the ma- mainder of the system with adequate tempera-
terial viscosity, the material can be temperature ture conditioning. Fig. 10 shows a robotic spray
conditioned. There are two strategies for ma- sealer application gun reaching across the in-
terial temperature conditioning. The first tech- side of a vehicle applying a ribbon of material
nique is to water jacket the header system to to the automobile seams.
provide heating and cooling for viscosity sta-
bilization. Traditionally the temperature has
Adhesive Bonding of Automotive Doors
been set at 70°F to stabilize material viscosity.
The major drawbacks for this type of system As competition for automotive market share
are cost, reliability, and .maintenance. Because continues to intensify and manufacturers ex-
of the water lines, heat exchangers, pumps, and tend warranties for corrosion protection, ad-
installation complexity, the cost for such a sys- hesive bonding of components rather than spot
tem is often high. Reliability and maintenance welding has become the required assembly
of the system also play an important role, es- technique. Many of today's automobiles are
pecially if the pumps or heat exchangers fail, constructed with two-sided galvanized sheet
allowing inconsistent material temperature. metal. When the galvanized metal is spot
Since the material is no longer temperature welded, the galvanization is burned through,
conditioned, variations in spray pattern or rib- leaving an area vulnerable to corrosion. In ad-
bon deposition result. dition, spot welding in certain areas of the au-
The second method of temperature condi- tomobile is labor intensive and may require
752 HANDBOOK OF ADHESIVES

Fig. 10. Robotic seam sealing; arrows point to seam.

time to repair and touch up for customer ac- heating that causes the material to cure to a
ceptance. green strength sufficient to hold the door in po-
This applicatIon covers adhesive bonding of sition during shipping and handling until the fi-
the hem flange for automotive doors. For hem nal cure in the assembly plant paint ovens.
flange bonding the door is made up of an inner Figure 12 depicts the process of joining inner
skin and an outer skin. The inner skin mounts and outer panels. When the hem is formed by
the lock and window mechanisms as well as the the dies, the bead of material is pressed out to
various trim pieces, hinges and crash bar while form a thin film of adhesive between the two
the outer skin provides design contour and ac- door panels. If too little material is applied, a
cepts the color coat of paint. film bond of inadequate strength is formed be-
The process of building door assemblies re- tween the two panels. On the reverse side, if
quires the application of a structural adhesive too much material is applied to the outer panel,
to the outer door panel. The next step in the excess adhesive will be forced out of the
assembly of doors is the joining of the inner hemmed joint (known as squeeze-out) during
and outer panels. Finally, a hemming die is the hemming operation, causing contamination
used to turn a small section of the outer panel of the die tooling. As this adhesive begins to
over the inner panel to form a hem. Accurate build up on the die, it often transfers to the door
bead placement and uniform material deposi- assembly and results in expensive rework after
tion are critical to achieve a structural bond. final paint has been applied. The other draw-
These requirements, combined with high pro- back to squeeze out is in the area of increased
duction speeds, make hem flange bonding well maintenance for the hemming dies. Over time,
suited for robotic automation. Fig. 11 depicts the material builds up on the die and hardens,
the entire door assembly line process complete ultimately requiring a rework to maintain die
with hemming die and induction cure fixture. specification.
The induction cure fixture applies localized The best solution to meet hem flange appli-
 OlE FOR HEMMING
OUTER DOOR SKIN TO
INNER DOOR SKIN

::u
oIII
o-t
o
C
en
"ll
m
Z
C/I
Z
Cl
o"TI
C/I
m
>
>
Z
-t
C/I
,
OUTEROOOR
SKIN FLOW >
Z
INNER DOOR C
SKIN FLOW

Fig. II. Typical door assembly line at a stamping plant or in the body shop of a final assembly plant.
>
C
X
m
C/I
<:m
C/I

...
UI
W
754 HANDBOOK OF ADHESIVES

DISPENSED
would run in a mode known as degrade and

~
execute both robot programs in an effort to
maintain production. The upper robot velocity
~~~EE~-<( limit for dispensing material has traditionally
been 30 in.lsec, with 20 in.lsec being the av-
Section A
PRIOR TO ASSEMBLY
erage velocity for dispensing material. Material
temperature conditioning is also appropriate for
~MMED hem flange bonding. For this application, the
~~ material is heated to about 82 OF to stabilize the
viscosity as well as to ensure that the material
has enough heat to wet out the oily metal and
Section A
ASSEMBLED provide good adhesion to avoid movement of
Fig. 12. Adhesive bonding of an automobile door hem the bead until it has been hemmed in the man-
flange. ufacturing process.

Windshield Bonding and Body Shop

cation requirements is to use a robot to position
Robotic Sealing
the dispensing gun around the programmed path
and to utilize a dispensing system with suffi- Figures 13 and 14 depict possible robot system
cient response to adequately control the size of configurations for windshield bonding and body
the bead regardless of velocity changes. It is shop sealing. All of the applications mentioned
not uncommon for doors to have a 0.120 in. have similar considerations. for evaluation of
bead that is 100 in. long robotically dispensed robotic applications. The common considera-
in 4 sec. Generally, two robots are used, with tions for robotizing these and other adhesive
one robot applying adhesive around the win- and sealant applications include required bead
dow frame area while the second robot applies profile (round, flat, or triangular); instanta-
adhesive around the perimeter of the lower half neous flow or delivery rate; robot speed, ac-
of the door. Systems are often set up to ensure curacy and repeatability; and workspace of the
maximum production by having the two robots robot.
back each other up. Should one of the robots Windshield bonding often requires the dis-
have a failure of some type, the second robot pensing of a triangular bead at 10-18 in.lsec.

STATIONC
• ROBOT APPLIES BLACK PRIMER

STATIOND
• IDLE STATION

STATIONE
STATIONB • ROBOT APPLIES URETHANE
• ROBOT APPLIES
CLEAR PRIMER &
WIPES EXCESS

STATION A
• OPERATOR LOADS GLASS
TO WCATING FIXTURE
• OPERATOR RELEASES GLASS
FROM FIXTURE & INSTALLS

----::;::::::----
IN BODY OPENING

Fig. 13. Trimline windshield primer and urethane robotic application.

 ROBOTIC DISPENSING OF SEALANTS AND ADHESIVES 755

SEALER
PUMP

Fig. 14. Robotic sealing in the body shop.

The dispensing of a triangular bead that has a problems affecting the paint finish or phosphate
base dimension of 0.400 in. and a height of washer, the best solution has been to dispense
0.470 in. requires that the gun nozzle be con- a warm or hot applied weldable sealant. These
stantly oriented about the glass to obtain the materials are able to bite through the oils on the
desired bead profile. sheet metal to ensure good adhesion.
The material traditionally used in windshield
bonding has been a single-component mois- DEVELOPING A ROBOTIC SYSTEM*
ture-cure urethane. These urethanes are often
When developing a robotic system for product
high in viscosity resulting in high application
assembly using adhesives, sealants, or gaskets,
pressures to meet the robotic dispense rate.
the following procedures may be useful:
Robotic sealing in the body shop, like seam
sealing and door assembly, is performed to seal
Set Up a Team
out dust and moisture while protecting weld lo-
cations from corrosion due to the galvanization • Establish a project team with representa-
being burned off. The bead dispensed is nom- tives who have strong managerial, orga-
inally a 0.160-0.200 in. diameter, at velocities nizational, and technical skills. It is
that approach 20 in.lsecond. The robotic sys- important to establish a competent team
tems used in this system are similar to Fig. 1. because the equipment includes sophisti-
The materials used in body shop sealing vary cated electronics, mechanics, application,
in application temperature. Traditionally, cold and interface equipment.
(or ambient) materials are applied during sheet • If a consultant is considered, choose one
metal body construction. In some instances, who has experience with robotics and is
cold body shop sealers have caused manufac- familiar with your manufacturing process.
turing difficulties in ensuing production opera-
tions, for example, during the phosphate
*Reprinted with permission from Adhesives Age, April
process. In those assembly areas where mate- 1983, Publication of Communication Channels Inc., At-
rial washout has caused quality or process lanta, GA, USA.
756 HANDBOOK OF ADHESIVES

Select Proper Tasks Cost Savings.

• Start simple. Do not become involved in • Calculate material and labor savings.
something overly complex, particularly if • Identify expenses for the equipment, man-
this is your first experience with robots. ufacturing analysis, and relocation of
• To begin, identify tasks that will not re- equipment.
quire major changes in the manufacturing • Investigate tax credits.
process.
• Define a task that which requires only one Safety.
type of application equipment. • Define systems and precautions that are
• Define material requirements for the task. necessary.
• If the application requires only one or two
axes of movement, then some other form Training.
of automation may be better. However,
batches of simple operations can be com- • Consider impact to workforce and what
bined at some centralized location where retraining will be involved.
robots can provide the flexibility to handle • Identify who will need training and on
a variety of operations which would oth- which parts of the system.
erwise each require its own equipment de- • Determine how and where the training will
sign. be given.
• Product variety for one robot is limited by • Recognize the benefits of the exposure to
its memory size. Check for both the num- automation for other manufacturing oper-
ber of positions and programs that the ro- ations.
bot can store.
Future Requirements.
• Be sure that the part can be accurately po-
sitioned in the robots workspace. It is gen- • Discuss how needs and processes may
erally less expensive to design new fixtures change in the future and how the flexibil-
than to modify existing fixtures. ity of the robotic system can contribute to
• Construct a work flow chart. those changes.

Design the System

Define Objectives
• Involve materials, application equipment,
Quality.
and robot vendors early in the design pro-
• Define requirements for the accuracy, uni- cess.
formity, and consistency of the bead of the • Understand the interrelationship of each
hot melt (adhesive or sealant). piece of equipment and identify one ven-
• Discuss the equipment quality record. dor who will coordinate these interrela-
Identify the expected time interval during tionships.
which the system will operate reliably and • Ask for trials with your product and ma-
the service requirements. terials.
• Identify who will have responsibility for • Identify how part positioning and part
installation and service of the system. identification requirements will be de-
• Identify which standards are applicable to signed and controlled.
the system. • Determine how much the present facility
will have to be redesigned.
Productivity.
ACKNOWLEDGMENT
• Establish cycle time goals for each appli-
cation. Special thanks to Sharon Dodson, Market An-
• Define the minimum amount and fre- alyst, Automotive Business Group, Nordson
quency of downtime for the system. Corporation, for taking the time to help edit and
• Develop backup procedures. critique this chapter.
 Index

(page numbers in italics are main headings)

A-I72,547 carpet tile, 445

A-174, 538, 545, 547 catalysts, crosslinkers, 441
A-186, 538, 542 ceramic tile, 446
A-IS7, 538, 542, 543 chemistry, 437
A-lloo, 538, 541, 543, 547 chloroprene, 290
A-B-A block copolymers, 239 contact bonding, 443
A-line products, 188 emulsion sealant, 622
AASHTO specification, 638 engineering adhesives, 447
Abalyn, 563 filled,445
Abbreviations, 38 floor tile, 446
Abhesive silicone, 531 formulation, 441
Abietic acid, 562 glass transition temperature, 439, 440
Abitol,563 heat and pressure bonding, 443
Abrading, 576 impact resistant, 447
Abrasion, 79 modified,447
Abrasive, 37, 130 pressure-sensitive, 648, 659
bonded,664 properties, testing, 442
coated, 671 radiation curing, 448
grit, 671, 673 sealant, 616
wheel, organic bonded, 666 solution caulk, 621
ABS, 86, 444, 538, 732 suppliers of raw materials, 449
AC-8 polyethylene wax, 417 vacuum bonding, 444
Accelerated aging, 116 wet laminating, 444
Accelerator, 18, 177, 212 Acrylic acid, 17,271,438,441,651
Acetal,538 Acrylic acid-modified polypropylene, 553
Acetate film backing, 659 Acrylonitrile %,207
Acetoxy curing, 524 Acrylonitrile-butadiene-carboxyl, 276
Acetoxy sealant, 522 Acryloxypropionic acid, 448
Acetylene, 285 Additives for block copolymers, 242
Acetylene-terminated phenylquinoxaline oligomers, 507 Adherend preparation, 74,97
Acid acceptor, 285, 292 Adhesion, 39
Acid etching, 52 contact, 65
Acid number, in EVA, 410 contact angles, 45
Acoustical material, 98, 116 measurement, 54
Acrylamide, 438, 441 mechanical interlocking, 574
Acrylate, 15 metal,48
Acrylate-terminated nitrile, 210 molecular diffusion, interpenetration, 574
Acrylated epoxy, 672 physical adsorption/wetting, 574
Acrylated urethane, 672 pressure-sensitive, 66
Acrylic, 24, 457, 5, 7, 22, 23, 158,593,693,700,702, promoter, 596
703,707,732,733, 735 setting, 40
application processes, 448 static, 584
brick mastic, 445 strength of, 61

757
758 INDEX

Adhesion (Continued) Amino silane, 190, 538, 541

thermodynamics, 45 Aminoethyl piperazine, 354
work of, 47 Aminoplast, 441
Adhesive primer, 719 Aminopropyltriethoxysilane, 538
Adhesive selection, 94 Amioca starch, 156
Adhesives in the economy, 21 Ammonia, 53
Adtac, 266, 267 Ammonium caseinate, 142
Advanced composite, 10 Ammonium thiocyanate, 128
AEP. See also Aminoethyl piperazine, 354 Amoco, 413
Aero Research Ltd., 714 Amphoteric, 137
Aerospace, 713. See also Aircraft starch, 157
bonding procedures, 727 AMS, 563
film adhesives, 720 AMS/vinyl toluene, 564
silicone, 530 Amylaceous matter, 119
AES, 43 Amylopectin, 153
Agerite, 292 Amylose, 153
Air pollution, 191 starch, 161
Air Products, 381, 401, 354, 406, 651 Anaerobic, 25, 451, 7, 22, 23, 731, 732, 734
Aircraft,32, 713,28,359. See also Aerospace chemistry, 452
metal bonding-nitrile phenolic, 217 microencapsulation of curatives, 453
schematic, 717 polyurethane adhesive, 367
sealant, 307, 631 ultraviolet light priming, 473
Airfield sealant, 631 Ancamine, 354
Alclad aluminum, 719 Anchor coat for tufted carpet, 176
Aliphatic amines, 351 Anhydride, 353
Aliphatic resin, 562 Animal blood, 135
glue, 692 Animal glue, 123
Alkoxyalkyl cyanoacrylate, 476 amino acids, 124
Alkyd,668 bone, 126
Allied Chemical, 342, 354, 417 composition, 125
Alloprene, 365 flexible, 129
Allyl ureide, 17 for coated abrasive, 673
Alpha Techno, 463 hide, 126
Alpha-methylstyrene, 413, 563 lay flat, 129
Alumina, 708 liquid, 128
trihydrate, 544 non-warp, 129
Alumina-zirconia abrasive, 671 properties, 127
Aluminum, 50, 48,81,97,274,313,542,618,714, test grades, 127
726 Animal hair, 183
alloy, 719 Anodizing, 97, 719
oxide, 542 ANSI,114
oxide abrasive, 671 specification, 638
to mylar, 278 Antifoam, 142
zirconium, 552 Antimony oxide, 189
Ambient temperature bonding, 605 Antioxidant, 176, 179, 190,212,292, 557
American Cyanamid, 713,292,346, 372,719 2246,292
American National Standards Institute, 114, 638 for neoprene latex, 303
American Plywood Association, 683, 686 for thermoplastic rubbers, 256
American Sealants Company, 451 APA,683
Amicure, 354 glued floor system, 686
Amidoamine, 352 APP,409,411,414,416
Amine, 15 Appendix 2, 116
antioxidant, 212 Appliance, 33, 31
curing agents, 350 silicone, 530
reactivity, 537 Application, 98
terminated nitrile, 210, 221 Araldite, 347
Aminimide, 369, 370 MY720, 348
AL-X-300, 378 Aramid, 327, 714
Amino acid, 479 tire cord, 592
in animal glue, 124 Architectural caulk, 617
Amino resin, 341, 601, 605 Ardel,88
 INDEX 759

Arizona Chemical, 413, 419, 564 BOA, 311

Annak,418 BOMA, 353, 354
Armid C amide, 418 Be Square 175 microwax, 417
Aromatic amine, 352 Bead management, 746
Aromatic monomer resins, 412 Bending, 104
Aromatic resin, 562 Bentonite, 158, 624
Arylene ether polymers, 515 Benzenoid resorcinol nucleus, 587
Asahi,241 Benzimidazole po!ymers, 500
Asaprene,241 Benzophenone, 53
Asbestos, 327 Benzothiazole sulfenamide, 595
Ashland, 337, 369, 370 Benzyl dimethylamine, 353, 354
Asphalt, 184, 252, 615 Beryllium, 81
cutback, 687 Beryllium oxide, 708
Asphaltic, 180 Beta ray, 111
ASTM, 116, 114,638,656 BF 3 oMEA, 353, 711
Committee 0-14, 96 Bikerman, 537
sealant test methods, 636 Bimodal distribution of particles, 276
Astrel,88 Biocide, 398
360, 516 Bismaleimide, 720, 725
Atactic polypropylene, 409, 411, 414, 416 Bisphenol A, 276, 347
ATBN,21O Bitumen, 181
Athletic tape, 659 Bituminous, 615, 735
Atmospheric pollutant, 593 Black adhesive, 180, 183
ATPQ,507 Bleach, 158
ATR,42 Blister test, 59
Attenuated total reflectance spectroscopy, 42 Block compression shear, 102
Auger electron spectroscopy, 43 Block copolymer, 239, 17,421,568,645
Auger spectrum, 48 Block shear, 99
Automotive sealant, 631 Blocked di- or poly isocyanate, 369
Auto aftermarket, 22 Blocked isocyanate, 592
Autohesion, 67 Blocking point, 119
Automotive, 32, 729,28, 182,284,300, 301, 308, 359, Blood, 135, 145
470,497 Blow line blending, 608
aftermarket, 529 BMC,550
door, 751 BMI,725
glazing, 189 Body shop robotic sealing, 754
holding adhesive, 731 Boehmite, 50
hot melt, 417 Boeing, 717
internal trim, 177 Boil test, 112
robotic dispensing, 750 Bonded abrasive, 664, 323
sealer gasket, 734, 735 epoxy, 667
silicone, 529 phenolic, 667
structural adhesive, 730 rubber, 667
tape, 660 shellac, 667
Avery, 207 Bonding technology, 571
Azamine, 354 Bonding, anaerobic, 457
Azido-formyloxyethylisophthalate, 592 Bone glue, 126
Aziridinyl ester, carboxylic, 281 Bookbinding, 35, 34, 165
hot melt,415
Backing for coated abrasive, 672 Borated dextrin, 159
Backing for pressure sensitive, 643 Borax, 158, 405
Backup, 632 Borax fluidity method, 157
Bacteria, 112 Borden, 337, 346
Bag adhesive, 162 Boric acid, 405
Bakelite, 423 Boron trifluoride amine, 354
Bandage tape, 659 Boron trifluoride monoethylamine, 353
Bareco, 417, 418 Boscodur, 368
BASF,186 Bostik, 478, 368,483,484,485,487,493
Wyandotte, 371 Bottle labeling, 159
Bathtub caulk, 531 Bottom paste adhesive, 162
Bayer, 295, 372, 374 Box tape, 164
760 INDEX

BP performance polymers, 554 Carbon black, 179, 524

BPDA,295 loading, 595
Brake, 730 Carbon fiber, 714
lining, 327 Carbonless paper, 331
Branched polymer, 155 Carbopol, 213
Brass, 82, 274 Carborundum Co., 324
composition, 595 Carbowax, 164
Brass-coated steel wire, 593 Carboxyl, 270, 15
Brick, 92 functional vinyl copolymer resin, 280
British gum, 157, 159 functionality, 392
Brominated butyl rubber, 187, 188 reactive liquid polymer, 275
Brominated phenolic resin, 191 terminated liquid polymer, 272
Bromobutyl, 186 terminated nitrile, 210, 221
Bronze, 82 Carboxylated acrylonitrile butadiene latex, 214
BRS Information Technologies, 114 Carboxylated butadiene-styrene, 271
BTL, 337 Carboxylated natural rubber, 271
Building. See Construction, 678 Carboxylated neoprene latex, 281
Bulk unloader, 743 Carboxylated olefin copolymer, 279
Bureau of Standards, 114 Carboxylated SBR latex, 230
Burke-Palmason, 188 Carboxylated vinyl acetate-ethylene polymer, 393
Butacite, 423 Carboxylic polyacrylate, 278
Butadiene, 207, 285 Carboxylic polymer, 270, 441
Butadiene-styrene-methyl methacrylate, 448 Carboxylic vinyl polymer, 213
Butadiene-styrene-vinyl pyridine, 15 Carboxymethyl cellulose, 164
Butvar, 423 Carboxymethyl starch, 158
Butyl acrylate, 438, 441 Carcinogen, 712
Butyl glycidyl ether, 355 Cardipol wax, 418
Butyl phenol dialcohol, 295 Cariftex, 241
Butyl phenolic, 293 Carpet backing, SBR, 232
resin reactant, 292 Carpet seam hot melt tape, 418
Butyl rubber, 185, 185, 538, 647 Carton sealing, 159
additives, 190 Cartridge, 613
applications, formulations, 194 Case sealing, 159, 162
commercial grades, 186 Casein, 135,4,99, 116, 175, 176,714
curing systems, 190 and blend formulas, 147
formulation, processing, 188 glue, 135
pigments, fillers, 189 lime, 145
sealant, 618,201,616,731 SBR latex, 143
solvents, 191 Cashew nut shell liquid, 328
tape, 731 Catalytic curing agent, 353
Cationic starch, 157
C-4 olefin, 617 Caulk,611
C-5 aliphatic resins, 411 Cavedon, 552
C-5 oligomer, 645 Cellolyn, 563
C-5 resin, 562 Cellophane tape, 659
C-9 aromatic resin, 412 Cellular elastomer, 615
C-9 oligomer, 645 Cellulose plastic, 86
C-9 resin, 562 Cement, 196, 558
Cab-O-Sil, 448 high tack, 215
Cadmium, 81 Centrifuged latex, 168
Calcium carbonate, 189, 624 Ceramic dual inline package, 712
Calendering, 643 Ceramic frit, 700
Calixarene, 475 Ceramic tile, 175, 182,689
Can sealant, 182 Ceramics, 91
Canadian Specifications, Casein, 149 CERDIP,712
Canary dextrin, 157, 159 Chang Chun, 406
Canvas shoe sole, 182 Chang test, 657
Caprolactam-blocked, 369 Channel black, 212
Carbodiimide, 374 Check valve, 739
Carbon, 90 Chelate titanate, 550
 INDEX 761

Chelating agent, 453 Colloid stabilizer, 158

Chembond, 337, 346 SBR,232
Chemical pretreatment, 97 Composition board, 335
Chemical reagent, III Composition vs. properties, polyvinyl acetal, 427
Chemical surface treatment, 576 Compounding ingredients-nitrile rubber, 212
Chemical treatment, 80 Compression loading, 98
Chemically cured sealant, 614 Compression seal, 615
Chemigum, 207 Compression shear, 101
Chloride impurity, 712 Computer searchable database, 114
Chlorinated alkyl carbonate, 212 Concrete, 92, 182, 312, 686
Chlorinated diphenyl, 310 adhesive, 356
Chlorinated paraffin, 623 wall, 691
Chlorinated rubber, 179,212,295,310 Conductive, 705
Chlorinated solvent system, 688 adhesive, 119
Chlorinated terphenyl, 623 die attach, 710
Chlorobutyl, 186 high purity adhesive, 710
Chlorobutyl rubber, 187,618 low cost, 707
Chlorophenol, 591 polymer, 18
Chloroprene, 284 tape, 712
Chlorosulfonated polyethylene, 447 thermal conductivity, 708
Chroman, 587 vs. solder, 708
Chromatography, 60 1 Construction, 29,98,678,22,28, 116,284,300,301,
Chrome complex, 553 359
Chrome glue, 126 adhesives performance, 680
Chrome-sulfuric acid etching, 719 adhesive selection by substrate, 684
Chromic acid, 576 adhesive types, 685
anodize, 719 APA glued floor system, 686
surface treatment, 78 ceiling tile, 693
Chromium, 177 ceramic tile, 689, 692
Ciba-Geigy, 277, 347 concrete, masonry, 691
Clay, 158, 189,624 coverage, 681
Cleaning, 576 duct tape, 660
Cleavage, 58, 109 freeze-thaw stability, 695
Cleavage strength, 107 floor, 687
Climbing drum, 105 flooring, 683
Cloth filling adhesive, 672 marble, 680
Cloud point, 567 panel, 692
Coalescence, 96 plaster, gypsum wallboard, 691, 692
Coated abrasive, 671, 130, 324 plastic foam, 691, 692
flexing, 676 plywood, 607
glue binder, 673 poured concrete, 686
machine methods, 677 quarry tile, 689
markets, 677 resilient flooring, 688
phenolic resin in, 674 SBR latex, 233
pressure sensitive, 676 sealant, 612
radiation curable resin in, 674 sealant selection, 631
splicing, 676 slate, 689
urea-formaldehyde in, 674 specialty adhesives, 693
varnish in, 674 subfloor, 686
Coating, glue, 131 tileboard, 692
Coating, phenolic, 325 trowel coverage, 682
Cobalt salts, 596 wall, ceiling elements, 690
Coefficient of linear expansion, 613 wood glue, 692
Cohesive strength, 655 wood subfloor, 687
Cohesive-energy density, 13 Consumer, 37, 36, 359
Coir, 183 sealant, silicone, 531
Cold corrugating, 161 Contact adhesive, 280, 287. 336
Cold pour sealant, 614 Contact angle, 45, 75
Cold-box process, 326 Contact cement, 693
Collagen, 123, 124 Contact wheel, 675
762 INDEX

Control loop, 749 Cyanoacrylate, 463, 24, 9, 22, 23, 694

Convolute tube winding, 162 acid stabilizers, 465
Coordinate titanate, 550 adherend combination, 471
Copolymerization, 17 alkoxyalkyl, 468, 476
Copper, 51, 82 allyl,468
foil,700 ethyl,463
Copper sulfide, 594 toughened, 473
Cork,177 Cyanoethyl, 523
Corn starch, 156 Cyanurate, 591, 592
Corona discharge, 52 Cycle, 113
Corrosion, 94 Cyclic aging, III
Corrosion protection tape, 660 Cycloaliphatic, 564
Corrosivity, 119 Cycloaliphatic amine, 352, 354
Corrugated box, 162 Cycloheteroatom titanate, 550
Corrugating, 160, 159
Cosmetic item, 472 D-417 aqueous dip, 590
Cotton lamination, 274 D.E.H., 354
Coumarone indene, 645 D.E.R., 347
Coumarone resin, 175 DAD!, 365, 376
Coupling agent, 63, 9, 62 Dainippon ink, 371, 374
non-silane, 549 Dajac Labs., 346
silane, 536 Daltoftex A-IO, 376
CR,538 Daltrol PRl, 376
Crack propagation, 724 Database, 114
Creep, 94, 108, 196 De Bruyne, 714
Crepe, 168 Decal, 660, 733
Cresol-blocked, 369 Decorative laminate, 333
Cresylic acid, 328 Decorative plywood, 607
Critical surface tension, 12, 13, 76 Defoamer, 142, 158
CRLP, 275 Degradation, S-B-S vs. S-I-S, 646
Cross paste, 162 Degradation, thermoplastic rubber, 255
Crosslinking, 8, 18 Degrade mode, 754
Crosslinking degradation, 255 Degreasing, 49, 79
Crosslinking silicone, 523 Delamination test, 113
Crown cork adhesive, 182 Den, 221
Crown cork closure, 177 Denaturation, 137
Crown ether, 475 Denka,406
Crystal display, 702 Density, 119
Crystallinity, 285 Dental devices, 472
CTBN,210 Depolymerized rubber, 171
CTBN-epoxy adduct, 222 Desmocoll, 367, 368
CTLP,272 Desmodur, 359
Cumar,259,262,564 HH,376
Cumene hydroperoxide, 451 L,376
Cure, 8 R,359, 360, 363, 375
rate,601 RF, 295, 376
temperature, 735 TH,375
with sulfur, 190 Desmophen, 360, 375
Cure, phenol-formaldehyde, 321 DET,311
Curing, 190 DETA. See Diethylene triamine, 354
Curing agent, 212, 292, 349, 557 Dexter Hysol, 482
SBR,231 Dextrin types, 157
neoprene, 296 Dextrin/silicate, 159
Curithane, 354 Dextrinization, 156
Curtainwall silicone, 531 Diallylphthalate, 86
Cutback, 618 Dialog Information Retrieval Service, 114
Cutoff, 741 Diamine, 479
Cutting, 558 Diaminodiphenyl sulfone, 354
CV latex, 168 Diamond Alkali, 313
Cyanabond, 372 Diamond in grinding wheel, 665, 668
Cyanoacid initiator, 272 Dianisidine, 365
 INDEX 763

Dianisidine diisocyanate. See DADI Edge effect, 101

Diaper, 416, 659 EDTA, 177,232
Dibasic acid, 479 EEA,419
Dichloro-l,3-butadiene, 302 Elastic glazing compound, 617
Dicy, 711 Elastomer, 22, 546
Dicy. See Dicyandiamide, 352 Elastomer blends, thermoplastic rubber, 251
Dicyanatobenzene, 518 Elastomeric modifier, 355
Dicyandiamide, 352, 354 Electrical, 698, 484
Die attach, 710 bonded mica, 702
Die bonding, 698, 700 chloride impurity, 712
Dielectric spectroscopy, 19 conductivity, 705
Diels-Alder adduct, 562 display, 702
Diels-Alder reverse reaction, 514 glass/ceramic sealing, 701
Diethylene triamine, 354 gold filled, 706
Diethylhydroxylamine crosslinker, 627 insulation, 116, 119
Dihydric phenolic, 276 laminate, 332
Diisocyanate, 605 pressure sensitive, 701
Diluent, 354 printed wiring board, 700
Dimer acid, 480 properties, 548
Dimer-5 cycloaliphatic resins, 412 silver filled, 706
Dimethacrylate, 451 tape, 189,200,660
Dimethyl silicone polymer, 523 Electrical/electronic, 32, 28
Dimethyldichlorosilane, 523 Electrolytic corrosion, copper, 119
Dimethylsiloxane, 592 Electromagnetic welding, 575
Dioctyl maleate, 651 Electron, III
Diphenylmethane-4,4'-diisocyanate. See MDI Electron beam crosslink, 266, 267
Dispensing equipment, 736 Electron microprobe, 43
Dispensing gun, 746 Electron spectroscopy, 19
Dispersion, 320 for chemical analysis, 43
Disposable, 37, 36 Electronic component, 472
Dissolving neoprene, 299 Electronic encapsulation, 325
Dithiocarbamate, 177 Electronic silicone, 530
Divinylbenzene, 188 Electropneumatic control, 748
DMP-30, 311, 312 Electrostatic coating, 673
Do-it-yourself, 180 Electrostatic shielding, 660
Domain, 240 Elvax, 408, 414, 417
Door assembly, 753 Elvax 170,418
Double lap, 101 Elvax II ethylene acid copolymer, 421
Double-faced tape, 660 Emerez, 481
Dow, 347, 421 Emery Industries, 480
Dow Coming, 538, 649 Emhart, 478
Dry bonding, 173 Empty drum, 744
Dry use, 99 Emser Werke, 485, 487, 495
Drying, 96 Emulsion, thermoplastic rubber, 254
Du Pont, 284,408,277,327,337,364,369,406,417, Encapsulated locking compound, 734
423,485,491,553,555,583,590,700 End joint, 336
Duplex nitrile-epoxy film, 720, 723 Endblock-compatible resin, 568
Dupre, 47, 75 Endex, 564
Duprene, 284 Ending, 164
Durability, 109,69,97,117,118,119 Endblock compatible resins, 248
aluminum, 97 Engine nacelle, 713, 718
Durez, 219, 220, 221, 310 Engineered plastics, 329
Durez 12603, 295 Engineering adhesive, 447
DVB,188 Enichem, 241
Dymerex, 563, 564 Envelope, 164
Dynamic mixer, 737 adhesive, reseal, 176
self-adhesive, 174
Eastman, 414, 416, 419, 463, 493 EPDM, 181,538,547,548
Eastman 910, 463 Epi-Rez, 347
Eastobond,419 Epichlorohydrin, 347
ECN,277 Epikote, 219, 221
764 INDEX

EPM,538 Estane, 367

Epo-Tuf, 354 Etching, 50, 80
Epolene, 414 solution, 576
Epon, 277, 347 Ethacrylonitrile, 207
Epon 1031, 348 Ethyl acrylate, 438
Epotuf,347 Ethyl acrylate-ethylene copolymer, 418
Epoxide equivalent weight, 347 Ethy I orthosilicate, 524
Epoxy, 347, 713,9,53,89,219,271,276,277,311, Ethylene copolymer, 408
312,313,427,441,537,540,541,542,550,603, Ethylene dichloride, 213
688,694,703,707,710,711,719,730,731,732, Ethylene glycol dimethyacrylate, 447
735 Ethylene-acrylic acid, 271
acrylated, 672 Ethylene-ethyl acrylate, 418, 419, 421
adhesive formulations, 355 Ethylene-methacrylic acid, 421
aliphatic amines, 351 Ethylene-vinyl acetate, 27, 22, 25, 251, 408. See also
aluminum, 50 EVA
amidoamines, 351 Ethylenebisstearamide, 593
amine curing agents, 350 Ethylhexyl acrylate, 441, 648
anhydrides, 353 Ethynyl, 15
aromatic amines, 352 Ethynyl-terminated imide oligomer, 514
carbon fiber, 90 Europrene, 241
carboxylated elastomer powder, 273 EVA, 408, 5, 9, 251, 289, 301, 414, 416, 418
carboxylated VAE, 393 adhesive formulation, 409
catalytic curing agents, 353 polymers, 409
concrete adhesive, 356 pressure sensitive, 648
conductive, 705 vinyl acetate content, 412
CTBN,222 Expandable foam, 716, 717
curing agents, 351, 354, 349 Expandable monomer, 17
cycloaliphatic amines, 352 Expansion, 613
dicyandiamide, 352 . Experimental E-320 blocked isocyanate, 377
die-attach, 700 Extender, 608
diluents, 354 Exterior, 116
duplex film, 723 wet use, 112
elastomer, 726 land and air, 111
elastomeric modifiers, 355 marine, 111
electrical, 698 Extruded tape, 613, 617
fillers, 355, 356 Exxon, 185, 186,417,564
film adhesive, 720 Exxon Butyl, 186
flexible, 349
from glycerine, 592 Fabric bonding, 485
high functionality, 724 Factice, 190
high performance, 348 Fairing compound, 718
high temperature, 725 Fatigue, 95
IC,699 Fatigue strength, 108
in bonded abrasive, 667 FDA, 143, 165
in adhesives, 350 PVOH,407
nitrile, 9 Fiber fragmentation, 60
novolac, 347 Fiber Industries, Inc., 591
nylon, 720, 723 Fiberboard, 99, 605
phenolic, 325, 714, 721, 720 shipping case, 116
polyamides, 352 Fiberglass, 536, 543
polyethylene, 78 Fiberite, 337
poly sulfide curing agents, 349 Filler, 158, 179, 189,252,305,310,355,557,608
silane, 538, 190 bonded abrasive, 664
surface mount, 702 content, 119
two-phase toughened, 725 for neoprene, 296
vinyl, 720, 722 for phenolic, 327
water-soluble, 590 for SBR, 231
ESCA,43 Fillet formation, 717
Escore, 267 Film adhesive, 720, 10, 96, 714, 716
Escorez, 417,564 Filter, 334
 INDEX 765

Fina, 241 Gap filling, 98, 116,472,695, 717

Finaprene, 241 Gasket, 735
Finger joint, 101, 336 glue in, 132
test, 99 Gear pump, 736
Fire door, 148, 149 Gel depressant, 128
Firestone, 241 Gel polymer, 286
Flame retardance, 10 Gel time, 601
Flame retardant, 189 Gelatin, 123
Flame treatment, 53, 576 Gelatinization temperature, 155
Floating roller metal peel, 722 General Electric, 522, 310, 337, 451, 649
Floating roller peel resistance, 105 General Mills, 480
Flocking adhesive, 178, 183 Geon, 365
Floor, 687, 98 Georgia-Pacific, 598, 337
Flooring, 683 Gibbs free energy, 44
Flow properties, 119 Glass, 91, 114, 714
Fluidity starch, 156 bonding, 118
Fluorescent probe, 19 chipping, 131
Fluorocarbon, 53, 46, 86 fiber, 536
Fluoropolymer sealant, 628 microsphere, 718
Fluorosilicone, 530 reinforced laminate, 90
Fluorosurfactant, 555 tire cord, 592
Flush door, 148 Glass transition temperature, 241, 244, 322, 391
FM film adhesive, 720 Glass-to-metal assembly, 103, 731
Foam, 336 Glazing design, 633
Foam control agent, 398 Glazing silicone, 530
Foil-to-paper, 143, 159 Globular protein, 137
Foral, 261, 417, 563, 564 Glove, 178
Forest products, 31, 598, 28 Glue binder, 673
Forest Products Laboratory, 50 Glycerol, 158
Formaldehyde, 317, 337, 342 Glycidoxy silane, 538
emission, 610 Glycidyl methacrylate, 17,441
release, 605 Glyoxal, 405, 426
scavenger, 344 Gold,82
toxicity, 346 Gold-filled adhesive, 706
Formaldehyde-to-resorcinol ratio, 585 Goodrich, BF,206, 270, 365, 373,463
Formvar, 423 Goodyear, 207, 292, 412, 494, 564
Foundry, 22, 326 GR-S, 227
sand, 541 Grace, W.R., 381
sand binder, 38, 37 Grafted copolymer, 181
FPL,50 Grafted starch, 158
Fracture strength, 109 Grafting, 15, 287
Framing, 98 Grain coat, 671
Franklin International, 678 Graphite, 90
Free energy, 45 fiber, 10
Freeze-thaw stability, 695 GRAS, 143
Friction, 38, 37 Gravity coating, 673
Friction composite, 327 Greaseless buffing compound, 131
Fuller, H.B., 381 Griltex, 487, 495
Fumaric ester, 271 Grinding, 664
Fumed silica, 524 Grit blasting, 49
Functionality, 10 Gum adhesive, 178
Functionally terminated polymer, 209 Gum rosin, 412, 562
Furan resin, 541 Gummed tape, 131, 164
Furane resin, 89 Gun caulking, 613
Furfuryl alcohol, 148 Gun orifice size, 748
Furniture, 31, 28, 284, 359 Gypsum, 98
hot melt, 416 wallboard, 116, 690

GAF,651 H-7 single-step adhesive dip, 591

Gamma ray, 111 Halogenated butyl rubber, 187
766 INDEX

Hammond, 656 application equipment, 419

Hardboard, 605, 608 applications, 414
Hardener, 142 aromaticity of hydrocarbon resin, 412, 413
Hardening, 95 bookbinding, 415
Hardman, 187, 188 butyl sealant, 619
Header system, 745 by polymer type, 411
Heat resistance, 18, 113 cases, cartons, trays, 414
Heat sink, 709 coating, 642
Heat welding, 575, 579 comonomers, 410
Helicopter blade, 718 dimer acid polyamide, 480
Henkel, 342, 346, 354, 463, 480, 482 ethylene acid copolymer, 417
Hercolyn, 563 furniture, 416
Hercotac, 564 hydrocarbon resins, 411
Hercules, 556, 564, 413, 414, 417, 418 labels, 417
Hershey drop, 730 melt index, 410
Heterocyclic diamine, 482 nonwovens, 416
Heveaplus MG, 170, 181, 184 nylon, 484
HEW, 165 polyamide, 417
Hexa, 596 polymer suppliers, 412
Hexamethylene diisocyanate, 375 polymers, 409
Hexamethylenetetramine, 321 pressure sensitive, 418
Hide glue, 126,692 pressure sensitive S-I-S, 259
High modulus composite, 716 rosin-based tackifiers, 412
High movement elastomeric sealant, 631 sealant, 203
High temperature adhesives, 499 structural, 735
addition polyimide, 514 tackifiers, 411
arylene ether polymers, 515 terpolymer, 421
chronology, 501 waxes, 413
needs, 519 Hot pour sealant, 613
other polymers, 518 Hot-box process, 327
PI,509 HRH System, 596
PPQ,504 Huels, 485
PPQ, crosslinked, 507 Humectant, 158, 398
PQ,502 PVOH,404
High temperature resistance, 10 Humidity, 97, 111
High temperature titanate, 550 Hybrid, 9, 15
High-energy radiation, III Hycar, 207, 210
High-pressure decorative laminate, 345 1072, 277, 278
High-tack cement, 215 1300 X 8, 277
Highway sealant, 631 CTBN,276
Hildebrand, 13 Hydrated calcium silicate, 285
Hindered bisphenol, 292 Hydrated silica, 212
Hisil, 233, 296 Hydrazide accelerator, 452
Hitachi, 217, 295 Hydrocarbon, 190
HMPSA,642 Hydrocarbon resin, 564, 411, 561, 562
HMTA,321 Hydrochloric acid, 285
Hobby glue, 531 Hydrogen bond, 12
Hoechst, 406 Hydrogen bonding, 14, 296, 297
Hold, 196 Hydrogen ion concentration, 119
Home, 98 Hydroperoxide, 452
Honeycomb, 713, 105, 714, 723 Hydroxy silane, 538
climbing drum test, 723 Hydroxyethyl cellulose, 165
sandwich construction, 715 Hydroxyethyl methacrylate, 367,438,441
Hooker Chemical, 313 Hydroxyethylation, 157
Hospital tape, 659 Hydroxyl, 15
Hostile environment, 109, 112 Hydroxypropyl methacrylate, 448
Hot melt, 408,478,497,5,96, 197, 199,279,560, Hydroxypropylated starch, 158
694,731,732,735,756 Hylene, 364
alpha-pinene, 413 Hylene M, 375
 INDEX 767

Hylene MP, 377 handling of, 375

Hypalon, 620 prepolymer,9
sealant, 616 primer, 190,363
Isocyanate-based adhesives, 359
IC,698 Isocyanatoethy I methacrylate, 17
adhesive, 699 Isoelectric point, 137
packaging, 710 Isoionic point, 125
Ice water label paste, 144 Isonate, 369
ICI,591 Isonate 123P, 377
IISRP, 234 Isooctyl acrylate, 648
Imidazole, 221 Isoprene, 185
Imide oligomer, ethynyl, 514 ISS, 44
Imide oligomer, Nadic, 514 Itaconic ester, 271
Imide oligomer, norbornene, 514
Imide polymers. See also PI, 509 Jelly gum, 159
Impact, 94 Joining process, 574
Impact resistant acrylic, 447 Joint, 96
Impact strength, 107 assembly, 98
Imperial Chemical Industries, 365 design, 578
Impranil, 372 strength, 41
In situ resin fabric dip, 584 stressed in shear, 112
Induction curing, 357
Industrial laminate, 332 Kadel-II, 515
Information Handling Services, 114 Kalar, 188
Information sources, 5 Kalene, 187
Inhibited starch, 158 Karathane,372
Insulated window sealant, 203 Kenrich, 550
Insulating glass, 307 Ketoxime-blocked, 369
sealant, 631 Kevlar, 327
Insulation, 336 Kitchen cabinet, 301
Integrated circuit. See also IC, 698 Knife application, 613
Interdiffusion, 67 Knoevenagel reaction, 464
Interez, 347 Kraton, 241, 263, 415, 416
Interfacial tension, 46 Kraton 1l01, 261, 262, 264
Interior, III Kraton 1102,262
Interior exposure, 99 Kraton 1107,258,259,260
Interior seam sealing, 750 Kraton D1320X rubber, 265, 266
Internal pressure, 13 Kristalex, 564
Internal reflection, 42 Kuraray, 172, 406
Internal trim, 182
International Institute of Synthetic Rubber Producers, 234 Label, 641, 164, 660
Interpenetrating Polymer Network, 18 hot melt, 417
Invert emulsification, 304 paste, 144
Inverted emulsion, 165 Labeling, 99, 116, 159
Inverted probe machine, 119 Lactam, 479
lon-scattering spectroscopy, 44 Laminate, high-pressure decorative, 345
IPN,18 Laminated assembly, 10 1
Irgacure, 265 Laminated beam, 335
Irganox, 261, 374 Laminated veneer lumber, 607
Iron, 82 Laminated wood, 99, 113
alloy, 83 Laminating, 162,213
oxide, 212, 530 phenolic, 331
substrate, anaerobics, 452 Lap shear, 56
ISO, 114 specimen, 721
Isobutylene, 185 LARC, 514, 515
Isocyanate, 15, 179 Latex, 559
crosslink, 289 adhesive, 559
cure, 296 for casein and protein blends, 148
fiber treatment, 589 natural rubber, 167
768 INDEX

Latex (Continued) MDA. See also methylene dianiline, 354

nitrile, 214 MDI, 359, 363, 364
preservation, 168 phenol-blocked, 590
pressure-sensitive, 174 MDI-50, 375
SBR,229 Meat packaging hot melt, 418
sealant, 616 Mechanical fastener, 715
Lauryl pentachlorphenate, 178 Medical device, 472
Lawter, 413 Medical tape, 647
LDPE, 411, 414 Medium density fiberboard, 608
Lead,82 Medium movement caulk and sealant, 616
body solder, 735 MEK cement, 367
Leather, 177, 182,220 Melamine, 343, 540, 609
adhesive, nitrile, 216 Melamine-formaldehyde, 341, 89, 405, 426, 538, 540
LED,712 Melamine-urea-formaldehyde, 605
LEED,42 Memory, 415
Leukonat, 376 Mercaptan, 208, 308, 349
Lewis acid salt, 711 Mercaptan-terminated polymer, 313
Lewisol, 563 Mercapto silane, 538
Library paste, 159 Metal,48
Lignocellulose structure, 602 bonded cutoff wheel, 665
Limonene, 413 bonded wheel, 669
Linear polymer, 154 bonding, 116
Linseed oil, 328 bonding with nitrile-phenolic, 217
putty, 617 complexing agent, 177
Liquid adhesives, specifications, 116 oxide, 289, 292, 303
Liquids, surface tension, 44 refining, glue in, 133
LMWPE, 412, 414, 416, 419 solder, 700
Loctite, 451, 463 surface treatment, 81
Loose wrapping, 164 Metal-to-metal, 101,273,274
Low density polyethylene. See also LDPE Metallic sodium, 576
Low drum, 744 Meter, mix and dispensing, 736
Low energy electron diffraction, 42 Metering cylinder, 738
Low molecular weight polyethylene. See LMWPE Methacryl silane, 538
Low molecular weight resin, 556 Methacrylate, 15
Lower movement caulk, 616 graft, 181
LP-3,311 Methacrylato chromic chloride hydroxide, 553
Lubricant, 158 Methacrylic acid, 207, 441, 447
Lumber, 99 copolymer, 302
laminate, 605, 607 Methacrylic acid-butadiene copolymer, 273
Methacrylic acid-chloroprene, 289
Macromer, 15 Methacrylonitrile, 207
Magnesia, 285 Methacryloxy silane, 190
Magnesium, 82 Methanolysis, 404
Magnesium oxide, 281, 292 Methoxy curing, 524
Make coat, 671 Methyl acetate, 404
Malaysian Rubber Producers' Research Assoc., 167, 181 Methyl ethyl ketone, 213
Maleic anhydride, 271, 280 Methyl methacrylate, 447
Maltose, 155 graft on neoprene, 301
Mandrel bend test, 119 graft on rubber, 170
Manufactured board, 608 graft onto nitrile, 214
Marble, 690 Methyl styrene, 645
Marine, 111 Methyl tris(methylethylketoximino)silane, 524
sealant, 631 Methylene dianiline, 354
Marsden, 537 Methylene quinone intermediate, 587
Masking tape, 645, 659 Methylimidazole, 353
Mastic, 180, 559 Methylolacrylamide, 392
Mastic strip, 614 Methylon, 310
Match glue, 133 Methyltriacetoxysilane, 524
Matrix resin, 536 Methyltrimethoxysilane, 524
MDA/MPDA eutectic, 354 MI,353
 INDEX 769

Mica board, 702 NEMA,332

Microcrystalline wax, 419 laminate grades, 333
Microelectronics, 698 Neoalkoxy titanate, 550
Microscopy, 42 Neoprene rubber, 284, 693, 732
Midblock tackifier, 568 AC, 285, 287, 289, 299, 301
Midblock-compatible resins, 248 AD, 285, 287, 289, 290, 293, 299, 300, 301
Mildewicide, 531 AD-G, for methyl methacrylate graft, 287, 289, 301
Military applications, polysulfide, 307 AF,289,290,294,296,299
Military specification, 114 AG, 286, 289, 290, 291, 296, 301
Milligan & Higgins, 123 AH, acrylic copolymer, 290, 291, 294
Milling vs. viscosity, 211 application methods, 30 I
Milling, neoprene, 298 carboxyl function, AF, Al, 280
Millmaster Onxy, 372 CG,285
Mirror, 734 contact bond adhesive, 287
Mitsubishi, 220 end uses, solvent cement, 300
Mix equipment, 736 FB,292
Mixing, 97 GN, 285, 292
Mobay, 369 latex, 286
Modified rosin, 564 latex anionic types, 303, 305
Modified-rail test, 104 latex nonionic type, 303
Modifying resin, 566 latex 671A, 303, 304
Modulus, 104, 715 latex-based adhesives, 301, 302
Moisture, Ill, 609 mastic, 291
resistance, 113 methacrylic acid copolymer, 289
Moisture-curable, 8 nonionic "latex-1I5", 301, 303, 305
Mold, 112 phenolic, 9, 337
resistance, 99 sealant, 616, 620
Molding compound, phenolic, 328 solvent adhesive, 287
Molecular weight, 68, 568 solvent properties, 298
modifiers, 208 types, solvent adhesive, 288
Mondur, 366 WHV-A, 289, 291, 301
Mondur CB-75, 378 Nevchem, 564
Mondur S, 377 Neville, 564
Mondur SH, 377 Nicamol,219
Mondur TM, 376 Nickel,83
Monoalkoxy titanate, 550 Nicolmelt, 422
Monomer-Polymer, 346 Nieuwland, 284
Monsanto, 219, 292, 337, 346,497 Nippon Goshei, 406
Montac, 497 Nirez, 564
Monuron, 277 Nitrile rubber, 206, 538, 621, 694
Motionless mixer, 737 anaerobics, 453
MPDA: See also m-phenylene diamine, 354 applications, 213
Multicomponent sealant, 614 carboxyl terminated, 210
Multron, 366 cold polymerization, 208
Mylar to aluminum, 278 compounding, 210, 212
epoxy, 220
Nadic, 15 epoxy duplex film, 720, 723
end-capped imide oligomer, 514 hot, % acrylonitrile, 207
imide end group, 726 isocyanate, poly isocyanate, 214
Naphthalene, 53 latex, 214
Napkin ring, 104 phenolic, 217, 9, 714, 720, 730
NASA, 499, 332 phenolic, epoxy, 221
National Casein, 135 preparations, 206
National Electrical Manufacturers Assoc., 332 PVC latex, 215
National Standards Assoc., 114 solvents,211
National Starch, 381, 416, 463 styrene-butadiene latex, 215
National Wood Window and Door Assoc., 149 Vinsol,215
Natural adhesive, 22 Nitrocellulose, 714
Natural rubber, 167, 645 No-bake process, 326
Naval stores, 644 No-carrier system, 161
770 INDEX

Nomex paper, nitrile-phenolic-epoxy, 220 Paper coating, 160

Non-block, 164 carboxylated SBR, 232
Non-reactive diluents for epoxy adhesives, 355 casein in, 142
Non-silane coupling agent, 549 Papermaking, 160
Nondestructive test, 69 PAPI, 359, 376
Nondrying mastic sealer, 617 Para-tertiary butyl phenolic, 293
Nonhygroscopic plasticizer, 164 Paracril, 207, 219
Nonsag sealant, 614 Paraffin wax, 252
Nonvolatile content, 119 Paraformaldehyde, 343
Nonvulcanizing latex adhesive, 176 Paraplex, 251
Nonvulcanizing solution adhesive, 179 Particleboard, 344, 605, 609
Nonwoven, 178,416 Particulate structural adhesive, 277
carboxylated SBR, 232 Paste, 159,718
Nopco Chemical, 373 adhesive, 716
Nordson, 743 Patrick, 308
foam melter, 484 PBI,501
Novolak, 318, 583 PBT, 544,545
Novolak RFL dip, 584 PEEK, 88,90,515
NR,645 Peel, 112
Nutshell flour, 608 Peel adhesion, 654,442
NWWDA,149 testing, 657
Nylon, 538, 544 Peel back, \05
epoxy, 720 Peel resistance, 105
fabric bonding, nitrile-epoxy, 221 Peeling, 55
hot melt, 484 Penacolite resin, 596
Penetration, 119
Occidental Chemical, 295, 3\0, 337
Pentalyn, 190, 262, 263, 563, 564
Octylated diphenylamine antioxidant, 292
Perfect binding, 415
Odor, 119
Permafil,452
Oil filter, 484
PET, 87,489
Oil for SBR, 230
Petroleum chemicals, 609
Oil-based caulk, 617
Petroleum resin, 179
Oil/resin-based caulk, 616
Petrothene, 414
Oleoresinous, 617
Pewter, 82
Oligomer, 15
Pexite, 564
Oppanol, 187
Pexul single-step adhesive dip, 591
Optical adhesive, 98
Phase inversion temperature, 304
Organofunctional silane, 536
Phase ratio, 243
Oriented strand board, 605, 609
Phasing, 294
OSB,609
Phenol,337
Over-bake process, 327
Phenol-blocked, 369
Oxazolene, 422
isocyanate, 590
Oxidation, 49
Phenol formaldehyde, 316, 598, 603, 89, 190, 280,425,
Oxidized starch, 156
538, 540, 541, 542, 592, 593, 601, 703, 714
Oxime curing, 524
baking primer coating, 325
Oxychloride bond, 668
carboxylated VAE, 393
Oxygen agent, 255
consumption, 317
Oxygen bomb aging, 98
contact adhesive, 336
Oxygen-pressure method, 116
crosslink pressure sensitive S-I-S, 264
Ozone, 593
cure, 321
Ozone attack, 255
dispersion resole, 321
Pacific Anchor, 354 epoxy, 325, 720, 721
Packaging, 163,33,22,31, 199,359 foundry resin, 326
hot melt, 414 in bonded abrasive, 323, 665, 667
tape, 659 in coated abrasive, 324, 674
Pandel,374 in coating, 325
Paper bonding, 119, 99, 114, 116 in friction composite, 327
glue in, 132 in insulation, 336
Paper box, 164 in wood bonding, 334
 INDEX 771

laminating, 331 Plywood, 98, 101, 116, 334, 345, 605

manufacture, 323 PMDI,606
molding compound, 328 PMF,327
neoprene blend, 337 PMR,515
nitrile, 217, 212, 720, 721 Poly BD glycol, 360, 366, 377
novolak, 318 Poly-pale resin, 564
poly sulfide, 311 Polyacetal, 576
reactions, 604 Polyacrylamide, anionic, 165
resin analysis, 322 Polyalkylene ether, 475
resole, 319 Polyalphamethyl styrene, 295
structural adhesive, 337 Polyamide, 478, 5, 10,352,354,417,478,732
toxicity, 337 antioxidant, 482
vinyl, 720, 721 application, 484
Phenol-resorcinol-fonnaldehyde, 604 aromatic, 592, 714
Phenolic resin, 316, 212. See also Phenol-fonnaldehyde dimer acid-based, 480
Phenylenediamine antioxidant, 176 heterocyclic diamine, 482
Phenylquinoxaline polymers: See also PPQ, 504 hot melt, 480
Phillips, 241 melt point, 485
Phosphite functionality, 550 monofilament, 483, 484
Phosphoric acid anodizing, 97, 719 monomers, 479, 484
Phosphorylated starch, 158 nylon terpolymer powder, 486
Photoresist, 330 nylon, effect of moisture, 486
Phthalate plasticizer, 623 nylon-type hot melt, 484
Physical properties, 114 plasticizers, 482
PI, 509, 500. See also Polyimide shoe bonding, 484
glass transition temperatures, 511 tackifying resins, 482
properties, 513 Polyamideimide, 10, 668
PlB,618 Polyaryl sulfone, 88
Picco, 262, 263, 564 Polyarylate, 88
Piccodiene, 564 Polyarylene ether properties, 517
Piccolastic, 564 Polybenzimidazole, 10. See also PBI
Piccolyte, 190,413, 564 Polybenzimidazoquinazoline, 502
Piccotac, 414, 564 Polybutadiene glycol, 360, 377
Piccotex, 262, 564 Polybutadiene segment, 453
Piccovar, 262, 564 Polybutadiene, thiol-terminated, 314
Pigment, 189,212 Polybutene, 190,413,617
Pin and collar compression shear, 103 Polybutene/polyisobutylene caulk, 616
Pinene, 563 Polycaprolactone glycol, 360, 377
Pipewrap, 660 Polycarbonate, 87, 538
Pipewrap adhesive, 647 Polychloroprene, 284
tape, 200 Polyester, 478, 488, 5, 9,87,181,540,550,668,702,
Plaslok, 338 703,735. See also PET
Plasma treatment, 52, 576 amide, 497
Plasticizer, 158 copolymers, 491
Plastic, 114 fiber activation, 591
Plastic laminate, 300, 301 film backing, 650
Plasticity retention index, 169 flame treatment, 576
Plasticizer, 142, 190,212, 310, 393, 482, 557 hot melt gravure printing, 496
forthermoplastic rubber, 249 hydroxyl-terminated, 360
for SBR, 230 melt point, 492
Plasticizing oil, 250 monomers, 490
Plastics, 118,573 silane, 538
Plastics bonding selection chart, 580 substrate, 77
Plastics Engineering Co., 338 synthesis, 490
Plastisol, 730, 751 thiol-terminated, 314
See also PVC tire cord, 589
Platamid,487 unsaturated, 537
Platinum, 83 Polyether, chlorinated, 87
Plueddemann, 537, 539, 542 Polyether, thiol-terminated, 314
772 INDEX

Polyether-ether-ketone, 88,90, 515 anaerobic, 453

Polyether-polyester poly mercaptan, 314 aqueous dispersion, 371
Polyethersulfone, 515 blocked di- or polyisocyanate, 369
Polyethylene, 14,78,87,538,546,576 blocked MOl-epoxy, 590
liner, 716 crystallizing, 367
Polyethylene glycol, 164 elastomer, 367
Polyethylene glycol dimethacrylate, 453 film and tape, 373
Polyethylene-vinyl acetate graft, 53 foam, 691
Polyethyleneterephthalate, 87, 489 handling isocyanate, 375
Polyformaldehyde, 87 identification of components, 375
Polyimide, 500, 509, 10, 89, 668, 700, 703, 710, 712, in situ polymerization, 366
720, 725. See also PI MOl adhesive for fibers, 364
Polyimide, nadic end group, 726 MOl adhesive for rubbers, 363
Polyimides, addition, 514 powder, 373
Polyisobutylene, 185,618,619, 647 sealant, 625, 616
blending, 194 stabilization, 374
Polyisocyanate, 179 thermoplastic, 360, 367
curing agent, 295 thiol-terminated, 314
Polyisoprene, synthetic, 172 Polyvinyl acetal, 423
Poly ken probe, 443 health, toxicology, and safety, 424
tack tester, 656 reaction with dialdehydes, 426
Polyketone, 515 reaction with isocyanates, 425
Polymaleimide, 668 solvents, 428
Polymer, 360, 516 viscosity, 430
Polymercaptan sealant, 625 Polyvinyl acetate, 26, 381, 22, 23, 99, 116, 158, 162,
Polymeric MOl, 606 163, 175, 603, 688, 692
Polymethylene polyphenyl isocyanate. See PAPI biocide, 398
Polymethylmethacrylate, 87 branching, 391
Polyolefin, 408, 46, 538, 550, 735 carboxyl functionality, 392
polymer suppliers, 412 comonomers, 382
Polypale, 563 compounding, 393
Polyphenylene sulfide, 88, 576 copolymers, 384
Polyphenylsulfone, 515 effect of accelerated aging on copolymers, 386
Polypropylene, 87, 190,409,538,546,576 effect of plasticizer on copolymers, 386
Polypropylene carpet laminate with nitrile, 215 emulsions, 383
Polypropylene clay composite, 554 ethylene versus ester comonomers, 385
Polyquinoxalines, 502 fillers, 397
Polysar, 227, 186, 187, 188 functional groups, 392
Polystal, 360, 366 foam control agents, 398
Polystyrene, 87, 538 glass transition temperature, 391
foam, 691 heat sealing temperature, 390
Polystyrene-polybutadiene-polystyrene, 240 homopolymers, 384
Polystyrene-polyethylene/butylene-polystyrene, humectants, 398
240 modifiers, suppliers, 399
Polystyrene-polyethylene/propylene, 240 monomer, 382
Polystyrene-polyisoprene-polystyrene, 240 nonionic surfactant protection, 389
Poly sulfide, 307, 9, 349, 631, 694, 703 N-methylolacrylamide, 392
compounding, 309 plasticizers, 393, 395
curing agents, 309 polymerization, 382
glass, 307, 731 pressure-sensitive, 650
military applications, 307 protection by colloids, surfactants, 388
phenolic, 310 sealant, 622
sealant, 307, 616, 623 self-crosslinking, 392
specifications, 310 solvent reactivation, 390
Polysulfone, 88,515, 538 solvents, 396, 397
Polyterpene , 190,416,563 surfactant and cellulosic protection, 389
Polytetrafluoroethylene, 86, 576 tackifiers/ extenders, 395, 396
Polyurethane, 28, 359, 22, 27,89,307,308,425,550, thickening response to plasticizer, 390
603,605,610,631,668,703,731,754 viscosity/rheology modifiers, 394, 395
acrylated,672 wetting agents, 398
 INDEX 773

Polyvinyl alcohol, 401, 158, 162,302,423,668 construction, 642

borax, 405 EVA,648
boric acid, 405 hot melt, 418, 642
crosslinking, 405 hot melt S-I-S, 259
degree of hydrolysis, 404, 406 latex, 174, 568
FDA regulations, 407 manufacture, 642
film, 405 nitrile-epoxy, 222
gelation, 405 polyisobutylene, butyl rubber, 647
in PVAC emulsions, 404 PVC tape, 621
manufacture, 404 reclaim rubber, 648
molecular weight, 406 rubber-based adhesive, 645
physical properties, 401 SBR,234
production, 406 S-B-S, 261
solubility, 402 silicone, 649
solution viscosity, 403 S-I-S, electron beam, 266
specifications, 406 S-I-S, phenolic crosslink, 264
Polyvinyl butyral, 6, 10,423,426,429, 703 S-I-S/triacrylate, UV, 265
Polyvinyl chloride, 6, 10,87, 181, 184,220,289,301, tackifier, 644
308,359,365,367,444,470,472,484,538,578, test methods, 655
661, 732, 733, 735 theory, 651
bonding, carboxylated polymer/phenol-formaldehyde, vinyl acetate copolymer, 650
280 Pressure-Sensitive Tape Council, 259, 570, 656
bonding, nitrile-phenolic, 218 PRF,604
floor tile, 647 PRI, 169
plastisol, 730, 748, 751 Primary backing, 176
pressure-sensitive tape, 621 Primer, 49, 310, 716, 719
Polyvinyl fluoride, 86 Primicor, 421
Polyvinyl formal, 423, 428, 429 Printed circuit, 472
Post-It Note, 661 Printed wiring board, 700
Pot life, 608 Probe tack tester, 656
guard, 741 Products research, 313
Potato starch, 156 Professional glaze, 617
Powder adhesive, 277 Proportioning, 97
carboxylic elastomer/epoxy, 273 Protective colloid, casein, 142
Powdered thermoplastic rubber, 255 Protein, 99
Powdered check valve, 740 adhesive, 135
PPG Industries, 296 blend glue, 145
PPQ,504 Pseudoplasticity, 212
crosslinked, 507 PSTC, 656
glass transition temperatures, 505 PTFE, 53, 86, 576
PQ,502 Pull-off test, 58
PRC, 313 Pull-out, 59
Preformed strip, 614 Pumping system, 743
Preformed tape, 618 Purge time, 742
Pregelatinized starch, 159 Putty, 617
Preparation, 74, 97, 117 PVC latex-nitrile latex, 215
Prepreg, 714 PVOH, 401. See also Polyvinyl alcohol
Preservative, 158, 178 Pyrrone, 10
for casein, 141
Pressure-sensitive, 35,641,7,22,116,119,179,183, Quarry tile, 689
195, 199,560,701,732 Quartz, 91
acrylic, 648, 440, 732 Quat titanate, 550
adhesion, 66 Quick grab, 286
adhesive systems, 644 adhesive, 173
adhesive thicknesses, 662 Quick stick, 442, 565, 657
backing, 643 Quinoid cure, 190
block copolymer adhesive, 645 Quinoxaline polymers, 502
carboxylic polyacrylate, 278
coated abrasive, 676 Radel, 515
coated sheet, 661 Radiation curing, Ill, 448
 774 INDEX

Radiation-curable, 672 pumping system, 743

coating silicone, 534 seam sealing, 752
resin in coated abrasive, 674 Robotics, 357, 422
Rail test, 104 Rogers, 338
Rate of development of shear strength, 104 Rogue Valley Polymer, 338
Rate process assessment, 113 Rohm and Haas, 437, 251, 381
Rats, 119 Rolling ball, 119
RDGE,711 tack, 261
Reactive diluents for epoxy adhesives, 355 Roofing silicone, 531
Reactive liquid polymer, 210 Room temperature vulcanizing, 522
Reactive oligomer, 15 Rope caulk, 617
Reclaimed rubber, 180, 183, 184 Rosin, 564, 561, 562, 644
pressure-sensitive, 648 Rosin derivatization, 563
Redux,714 Rosin ester, 564, 175,412
Regalite, 564 RTV, 522
Regalrez, 267, 564 molding compound, 531
Reichhold, 347, 381, 564 sealant, 627
Reinforcing agent, 179 Rubber, 167,91, 538
Reinforcing black, 190 bonding, 220
Reinforcing resin, 564 cement, 119
Reinforcing tape, 660 compounding with glue, 132
Release coating, 532 phenolic, 703
Release paper, 716 research elastomerics, 188
Remoistenable, 164 to brass, 594
Reseal adhesive, 176, 182 to metal, 273
Resilient flooring, 688 to textile, 583
Resin based mastic, 693 Ryton, 88
Resin cloud point, 567
Resin for elastomer adhesive, 556
Resin for neoprene, 293
latex, 304 S-B-S polymer, 239, 646
Resinoid, 338 S-EB-S polymer, 240
wheel,665 S-EP polymer, 240
Resole, 319, 584 S-I-S polymer, 646
Resorcinol dicyanate, 518 S-I-S pressure-sensitive, 257
Resorcinol diglycidyl ether, 711 Saccharin, 452
Resorcinol-formaldehyde, 15, 158,214, 596, 604 SAE, 114
latex, 583 Saflex, 423
Resorcinol-phenol-formaldehyde, 694 Sago starch, 156
Resotropin, 596 SAN, 538
Retrogradation, 157 Sanding, 97
RF,604 Sandwich panel, 105
resin-to-Iatex ratio, 585 Sanitary napkin, 659
RFL, 583, 9, 15 Santowhite, 292
adhesion theory, 586 Sartomer, 265, 554
dip pickup, 586 SBR,227, 301, 538, 547,688, 689
pH,586 cold latex, 229
Rheology, 64, 94, 119 hot latex, 229
silicone, 525 latex, 233
Ribbed smoked sheet, 168 latex, carboxylated, 230
Rilsan, 485, 487 pressure-sensitive, 234
Roaches, 119 sealant, 621
Robotic dispensing, 743, 529 tufted carpet backing, 232
advances, 748 SBR-casein, 143
applications, 750 Scanning electron microscopy, 42
automotive, 750 Schenectady, 190, 191,263,295,338
bead management, 746 Scission degradation, 255
gun, 746 Scorch retarder, 292
header system, 745 Screening, 94, 98
 INDEX 775

Sealant, 611, 181 Silicon carbide, 672

and caulk properties, 615 Silicone, 522, 9, 307, 632, 660, 694, 703, 709, 732,
butyl, 201 734,735
characteristics, 616 abhesive, 531
latex, 177 adhesive, 529
selection, joint design, 629 applications, 528
silicone, 522 crosslinking, 523
specification, 634, 632 cure characteristics, 525
Sealing, 99, 116 electrical properties, 528
Sealing tape, 189, 202 in aerospace, 530
Secondary ion mass spectroscopy, 44 in appliances, 530
Selecting adhesives, 16 in automotive, 529
Self-adhesive envelope, 174, 182 in circuit board, 530
SEM, 42, 50 in construction, 530
Semi-interpenetrating polymer network, 513 in consumer sealant, 531
Sensitizer, 53 in electronic assembly, 530
Separator, 334 molding compound, 531
Sequestrant, 232 polyisobutylene, 308
Set-up wheel, 131 pressure sensitive, 649
Setback, 144 radiation-curable coating, 534
Setting, 40 release agent, 531
Shall, 415 release coating, 532
Shear, 100 rheology, 525
Shear adhesion, 442 sealant, 627, 529, 616
Shear load at rupture, 10 I shock-absorbent, 529
Shear modulus, 104 strength, elongation, 527
Shear properties, 100 thermal properties, 528
Shear resistance testing, 658 weathering, 527
Shear-rate-dependent flow, 119 Siloxane, 522
Shell Chemical, 239, 277, 347, 415, 416, 421,645 Silver, 83
Shell molding process, 327 migration, 707
Shellac bond for abrasive, 667 Silver-filled adhesive, 706
Shellflex, 251, 259, 262, 263, 264, 417 Silyl hydride group, 533
Shellwax, 263 SIMS, 44
Sherex,354 Single lap tensile shear, 10 1
Shoe,3~ 36,176,300,359,484 SIPN,513
sole, 284, 289 Size coat, 671
sole-attaching adhesive, 119 Sizing, glue, 131
Shot pump, 747 Slate, 689
Shrinkage, II, 94 SMA resin, 554
Side seam adhesive, 162 SMC, 550, 731
Silane, 536, 190, 592 SMR,168
amino, 538 Sodium, 53, 576
coupling agent, 536, 538 Sodium acetate, 404
epoxy, 538 Sodium alginate, 165
for elastomer, 546 Sodium polyacrylate thickener, 214
for thermoplastic resin, 540 Softener, 179
for thermosetting resin, 539 Sol polymer, 286
glycidoxy, 538 Solar radiation control film, 662
hydroxy, 538 Solder, 735
mercapto, 538 Solder versus conductive, 708
methacryl, 538 Solprene, 241, 263
monomer, 310 Solubility, 8
primer, 310 Solubility parameter, 12,266, 13,75, 242, 245, 296,
vinyl, 538 297,428,577,592,645
Silanol-terminated poly(dimethylsiloxane), 522 Soluble blood, 138
Silica, 624 Soluble soap, 158
Silica, fumed, 524 Solution, natural rubber, 179
Silicate bonded wheel, 668 Solution-polymerized, 210
776 INDEX

Solvent, 158, 191 hot melt, 735

cement, 558 laminated wood, 113
for carboxylic elastomers, 272 aerospace, 713
for neoprene, 296 Styrene, 563, 564
for polyvinyl acetal, 428 Styrene-butadiene. See also SBR, 227
mixtures for hycar rubber, 211 block copolymer, 415
reactivation, 390 latex-nitrile latex, 215
release sealing compound, 201 rubber, 227
SBR,231 Styrene-isobutylene resin, 413
thermoplastic rubber, 244 Styrene-maleic anhydride copolymer, 554
welding, 579 Styrenic block copolymer, 27, 22, 25
wiping, 97 Subfloor, 686
Solventless release coating, 533 Sugar, 602
Soy, 135 Sulfated alcohol, 158
bean oil, 328 Sulfenamide accelerator, 595
casein glue, 150 Sulfimide/amine salt, 452
flour, 145 Sulfochromate, 97
protein, 135, 137 Sulfochromate etch, 97
Soybean, 136 Sulfonated caster oil, 158
flour, 136 Sulfur cure, 191
SP-560,295 Super glue, 694
Specification sealant, 632 Super nirez, 564
Spectroscopy, 42, 601 Super sta-tac, 263, 564
Spiral tube winding, 162 Suprasec GA, 376
Spiro monomer, 17 Surface, 41
Sporting goods, 472 abrasion, 79
Spring loaded valve, 739 cleanliness, 735
SST, 504 oxidation, 51
Stabilizer, 158, 255 preparation, 74
SBR,231 Surface tension, 12, 46
Stainless steel, 84 Surface treatment, 48, 74, 118, 576, 726
Standard Malaysian Rubber, 168 aluminum, 719
Starch, 153 carbon fiber, glass fiber composite, 90
cook characteristics, 155 ceramics, glass, 91
succinate, 158 construction material, 92
varieties, 156 metals, 81
Static electricity, 253 rubber, 91
Staybelite, 190,418, 563, 564 thermoplastics, 86
Staybelite ester, 563, 564 Surfactant resins, 473
Stearic acid, 550, 596 Surgical tape, 179, 645
functionality, 550 Swift adhesives, 123
Steel, 51, 83 Sylvachem, 354
belted tire, 593 Syntactic foam, 716, 718
Stein Hall System, 160 Synthetic poly isoprene, 172
Stenciling tape, 660
Stereon, 241 T -Peel test, 105
Sterman and Bradley, 537 T. R. America chemicals, 346
Sterman and Marsden, 542 Tack, 652, 172, 189, 196,442,563
Stiffness, 715 rolling ball test, 443
Stonework, 92 tasting, 656
Storage hardening, 169 Tackifier, 565, 64, 65, 190
Storage life, 119 for pressure-sensitive, 644
Storage temperature, 97 SBR,230
Strength in bending, 104 selection, 566
Stress concentration, 715 Tackifying agent, 212
Strip sealant, 614 Tackifying resin, 556, 175, 179,482,641
Stripping, 164 Tactix 742, 348
Stripping tape, 659 Talc, 189
Structural adhesive, 713 Tall oil resin, 412, 562, 645
automotive, 730 Tannin, 602
 INDEX 777

Tape, 641, 613 Titanium bonding, 85

automotive, 189 PI,513
butyl,200 polyarylene ethers, 518
gummed, 131 PPG,507
pressure-sensitive, 659 PPQ, 505, 508, 510
Tapioca starch, 156 Titanium dioxide, 212, 624
TAPPI, 99, 114, 143 TMPTA,265
TDI, 359, 366, 375 Toa Gosei, 463
Tefton, 700 Toluene diisocyanate, 375. See also TDI
Telechelic liquid polymer, 209 Torque strength, 103
Temperatures, 97, Ill, 112 Torsional braid analysis, 19
Tennis ball, 178, 183 Torsional fracture, 57
Tensile detachment, 56 Toshiba, 217
Tensile properties, 99 Toughening with CRLP, 275
Tensile shear, 101 Toxicity, 18
Terephthalate, 489 formaldehyde, 345
Terlan,483 Toys, 472
Terminology of adhesives, 116 Trailing edge ftap, 718
Terpene, 564 Transformer, 165
Terpene phenolic, 285, 295, 304 Triethylene glycol-bis(2-ethyl butyrate), 426
Terpene resin, 413 Triethylene tetramine, 354
Terpene tackifier, 644 Triftuoropropyl, 523
Terrell,483 Trifunctional silane, 524
Tertiary amine, 353 Trimethylolmelamine, 405
Testing, 94, 99, 54, 581 Trimethylolphenol, 592
TETA,354 Trimethylolpropane triacrylate, 265
Tetraethoxysilane, 524 Trioxane, 343
Tetraethyl thiuram disulfide, 290 Triphenylmethane triisocyanate. See Desmodur R
Tetrafunctional silane, 524 Tube,613
Tetrahydrofuran, 53 TufHo, 251
Tetramethyl thiuram disulfide, 595 Tufprene, 241
Textile, 36, 164, 359 Tufted carpet, 176
Textiles to rubber, 583 anchor coat, 182
Thermal conductivity, 708 backing, SBR, 232
Thermal greases, 709 Tung oil, 328
Thermid,514 Tungsten, 84
Thermodynamics of adhesion, 45 Two-component RTV, 529
Thermoplastic, 5, 22, 550 Two-phase structure, 240
blends, thermoplastic rubber, 251 Tyrite, 366
elastomer, 621
polyurethane, 367 USA
rubber, 239, 289, 301 US Bureau of Standards, 114
Thermosetting, 22 US Consumer Products Safety Commission, 693
Thiazole, 177 US Department of Agriculture, 480
Thickener, 212 US Department of Health, Education and Welfare, 165
PVOH,404 US Food and Drug Administration, 143, 165
SBR,232 US Government regulations, 165,610
Thioglycollic acid, 271 US Military specifications, 713
Thiol-terminated polymer, 313 US Occupational Safety and Health Administration, 80
Thiourea, 128 US Specification, 114
Thixotropic, 614 US Specification sources, 638
Thixotropic gel, 476 US Supersonic transport, 504
Tight wrap, 164 US Wright Air Development Center, 217
Tile, 175 UCAR,220
Tileboard adhesive, 690 UDEL, 88, 515
Tinuvin, 374 UF concentrate, 85, 342
Tire cord, 9 UF reactions, 606
dip,233,274 Ultraftex wax, 418
Titanate, 549 Ultramoll, 374
coupling agent, 10 Ultrasonic cleaning, 49
778 INDEX

Ultrasonic welding, 575, 579 Vinyl tile, 176, 182

Ultraviolet light, 53 Vinyl toluene, 563, 645
priming, 473 Vinyl. See also Polyvinyl acetate, PVC
Uni-Rez, 482, 483 Vinylite VMCH, 280
Union Camp, 416, 482, 483, 564 Viscosity, 119, 192,430
Union Carbide, 536, 538, 338, 381,419,421,423,651 Viscosity of S-B-S thermoplastic rubber, 246
Union Oil, 381 Viscosity reducer, 142
Uniroyal, 207 Vistanex, 186
Unitiken, 406 Vitrified bond, 668
Upjohn, 369 bonded wheel, 665
Urea, 128, 158, 343 Vituff,494
Urea viscosity reducer, 144 Volan, 553
Urea-formaldehyde, 341, 598, 99, 116, 119, 158,405, VTBN,21O
605,714 Vulcabond, 365
in coated abrasive, 674 TX,376
carboxylated vae, 393 Vulcanizing, 177
USl, 414, 420 adhesive, 180
UV, 103 latex, 177
crosslink, 265 Vynathene, 420
cured, 103
inhibitors for thermoplastic rubber, 256
curing methacrylate, 702 Waferboard, 605, 609
Wall covering, 164
Wall materials, 690
Vacuum bonding, 444 Wall paper printing, 159
VAE,386 Walters (Jim) Resources, 327
Valve, 739 Warp sizing, 132, 164
Vanax, 290, 296, 552 Washable rug anchor backing, 182
Vanderbilt, 290, 292, 296 Water immersion, 111, 112
Vapor degreasing, 49 Water in wood, 603
Varnish in coated abrasive, 674 Water on the surface, 537
Velcro, 662 Water soak, 112
Veneer, 101,607 Waterproofing, 530
Verona, 372 Wax, 5, 413, 593
Versa1on, 482 Wax blend, 198
Versamid,480 Waxy starch dextrin, 159
Versamine, 354 Weathering test, 111
Vespel,89 Wedge test, 97
Victrex, 515 Welding, 579
Vinsol ester gum, 213 Westinghouse Electric, 338
Vinsol resin, 215 Wet bonding, 173
Vinyl acetate, 382 Wet grab, 214
in EVA, 409 Wet test, 112
-acrylate, 386 Wetting, 94
-dibutyl maleate, 385, 386 Wetting agent, 398
-ethylene, 385, 386 Wheat flour, 608
Vinyl chloride-vinyl acetate-maleic anhydride, 280 Wheat starch, 156
Vinyl cyc1ohexene, 314 White dextrin, 157, 159
Vinyl epoxy, 720, 722 White glue, 381,692
Vinyl ester, 538 Whittaker, 494
Vinyl ether polymer, 651 Williams, Landel, Ferry, 64
Vinyl flooring, SBR, 233 Windshield bonding, 754
Vinyl phenolic, 714, 720, 721 Wingstay, 292
Vinyl pyridine, 15 Wingtack, 259, 260, 262, 265, 267, 412, 413,564
latex, 583 Witco, 373
terpolymer, 584 WLF,64
Vinyl resin, 714 Wood, 99, 112, 117,598,22,92,98, 101, 145
Vinyl silane, 538 framing, 116
Vinyl siloxane, 529, 532 phenolic resin bonding, 334
 INDEX 779

rosin, 412, 561, 562, 563, 644 Zinc, 85

turpentine, 644 Zinc acetate, 144
Working properties, 114 Zinc dibutyldithiocarbamate, 259
Zinc diethyldithiocarbamate, 177
X-ray, III Zinc mercaptobenzthiazole, 177
photoelectron spectroscopy, 43 Zinc oxide, 144, 179, 180, 189,212,285,292,303,596
Xanthogen disulfide, 208 cure, 190, 191
XPS, 43, 53 Zircoaluminate, 552
Zirconate, 549
Yellow dextrin, 157 Zisman, 12, 46, 76, 537
Young equation, 46, 75 2MBT,I77
Zonatac, 564
Z-6020,538 Zonester, 419
ZBUD,I77 Zonyl,555