©Operative Dentistry Supplement 6, 2001, 119-144

Theme 3

Adhesives and Cements

to Promote
Preservation Dentistry
B Van Meerbeek • M Vargas • S Inoue • Y Yoshida
M Peumans • P Lambrechts • G Vanherle
Bart Van Meerbeek

Introduction

D
uring the last three decades clinicians have been confronted with a continuous
and fairly rapid turnover in adhesive materials. It started in the mid-’60s with
the advent of the first commercialized restorative resin composites, followed in
the early ’70s with the introduction of the acid-etch technique in clinical practice. Since
then, there has been ongoing progress in developing more refined and diversified
restorative composites along with the production of steadily improved bonding agents.
Effective adhesion to enamel has been achieved with relative ease and has repeatedly
proven to be a durable and reliable clinical procedure for routine applications in mod-
ern adhesive restorative dentistry. Although adhesion to dentin is not as reliable as
adhesion to enamel, today’s adhesives produce superior results in laboratories
(Perdigão & Lopes, 1999; Inoue & others, 2000a,b; Tanumiharja, Burrow & Tyas, 2000),
along with improved clinical effectiveness (Van Meerbeek & others, 1994b, 1996, 1998a;
Brunton & others, 1999; Folwaczny & others, 2000; Tyas, 2000; Van Dijken, 2000),
thereby, approaching enamel-bonding performance.
Early one-step dentin bonding agents became multi-step systems with more complicated,
time-consuming and technique-sensitive application procedures. In the early ’90s, the
selective enamel-etching technique was replaced by a total-etch concept. Since then,
universal enamel-dentin conditioners have been simultaneously applied to enamel and
dentin. Now that today’s total-etch adhesives have reached a clinically acceptable bonding
effectiveness, most recent research and development efforts have focused on simplifying
the multi-step bonding process and reducing its sensitivity to errors of inaccurate or
incorrect clinical handling (Sano & others, 1998; Finger & Balkenhol, 1999; Inoue &
others, 2000b).
In addition to interposition of a resin-based adhesive system between the restorative
material and the remaining tooth structure, bonding to tooth tissue can also be clini-
cally achieved directly using glass ionomer cements (Davidson & Mjör, 1999). Glass
ionomer-based materials have an auto-adhesive capacity thanks to their specific chem-
ical formula and structural nature (Wilson, Prosser & Powis, 1983; Van Meerbeek &
others, 1998b; Yoshida & others, 2000). Parallel with the progress made in resin-based
adhesives, glass ionomer technology has undergone many improvements and modifica-
tions of its original chemistry since being developed in the early ’70s by Wilson & Kent
(1971). A thorough discussion of self-adhering glass ionomer materials is beyond the
120 Operative Dentistry Supplement 6

scope of this paper. Nevertheless, some reference will be made to one of the latest trends
in adhesive material development that converges both glass ionomer and composite
technology into new adhesive systems and restorative materials with mixed character-
istics.
This paper critically reflects on the current status of adhesives. An overview is provided
with today’s commercial adhesives classified according to their adhesive approach
towards enamel and dentin. Some critical steps in the rather technique-sensitive bond-
ing procedure are discussed in detail. Finally, bonding effectiveness of a selected group
of adhesives is presented in terms of micro-tensile bond strength to enamel and dentin
and by clinical retention rates in Class V non-carious cervical lesions.

Classification of The most commonly used classification of adhesives is chronologically based, more or
Modern Adhesives less on the time of their release into the dental market (Kugel & Ferrari, 2000; Van
Meerbeek & others, 2000b). Typically, five or even six generations are considered.
However, this classification in generations lacks scientific background and thus does not
allow the adhesives to be categorized on objective criteria. Therefore, classification of
adhesives is presented on the basis of the number of clinical application steps, and more
importantly, how they interact with the tooth substrate (Figure 1 and Table 1).
The basic mechanism of bonding to enamel and dentin is essentially an exchange
process involving replacement of minerals removed from the hard dental tissue by resin
monomers that upon in situ setting become micro-mechanically interlocked in the cre-
ated porosities (Figure 2). Depending on the clinical approach, three mechanisms of
adhesion are currently in use with modern adhesive systems (Van Meerbeek & others,
1998a, 2000b; Inoue & others, 2000b).

Figure 1. Classification of
current adhesives according
to their adhesion strategy
towards enamel and dentin.

Figure 2. Schematic
presentation explaining
the basic mechanism of
adhesion to
tooth substrate.
Van Meerbeek & Others: Adhesives & Cements 121

Total-Etch Total-etch adhesives involve a separate etch-and-rinse phase. In their initial configura-
Adhesives tion, the conditioning step is followed by a priming step and application of the adhesive
resin, resulting in three-step total-etch adhesives (Figure 1 and Table 1). Two-step total-
etch adhesives combine the primer and adhesive resin into one application (Figure 1
and Table 1).

Figure 3Aand B. Fe-SEM

photomicrographs illustrating
the enamel-resin interface
produced by an experimental
two-step total-etch adhesive
(Ivoclar-Vivadent) that
involved acid-etching of
enamel with a 37% phosphoric-
acid etchant. Etch-pits have
been exposed at the enamel
prisms up to a depth of about
5 µm. Macro- as well as
micro-tags are formed at
respectively the enamel prism
peripheries and cores.

Bonding to acid-etched enamel theoretically requires an air-dried surface to allow the

photo-polymerizable hydrophobic bonding agent to be drawn by capillary attraction into
the pits created by acid-etching. As a result, two kinds of tag-like resin extensions are
formed (Peumans & others, 1999; Van Meerbeek & others, 2000b). Macro-tags are cir-
cularly formed between enamel prism peripheries. Microtags are formed at the cores of
enamel prisms where the resin cures into a multitude of distinct crypts of dissolved
hydroxyapatite crystals (Figure 3). Although most research dealing with adhesive tech-
niques lately has focused mainly on bonding to dentin, the importance of enamel bonding
effectiveness may not be neglected with the development of new adhesive systems. The
bond to enamel remains the best that can be clinically achieved. Preserving adjacent
enamel as much as possible, therefore, remains one of the most important guidelines
when preparing cavities for adhesive restorations.
The underlying mechanism of adhesion to dentin is alike for the three- and two-step
total-etch adhesives. The dentin smear layer produced during cavity preparation is
removed by the etch-and-rinse phase, which concurrently results in a 3-5 µm deep dem-
ineralization of the dentin surface (Perdigão, 1995; Perdigão & others, 1996a). Collagen
fibrils are nearly completely uncovered from hydroxyapatite (Figures 4-6), and form a
micro-retentive network for micro-mechanical interlocking of monomers (applied suc-
cessively with the primer and adhesive resin for three-step total-etch systems, or com-
Figure 4. (left) Fe-SEM of dentin bined in one application for two-step total-etch systems). This interlock was first
etched for 15 seconds with
35% phosphoric acid (Ultra-
Etch, Ultradent). C =Exposed
dentinal collagen; U =
Unaffected dentin; Bar = 2 µm.

Figure 5. (right) TEM photo-

micrograph of an unstained,
non-demineralized section
through the dentin-resin interface
produced by the three-step
total-etch adhesive OptiBond
FL (Kerr). Note that a 2-3 µm
hybrid layer (H) was formed
that did not contain any residual
hydroxyapatite crystals. A=
Adhesive resin; F= Glass filler;
U = Unaffected intertubular
dentin; Bar = 1 µm.
122 Operative Dentistry Supplement 6

Table 1. Classification of
Modern Adhesive Systems Brand Name Manufacturer
According to Their Clinical One-Step Compomer Adhesives
Application Mode and the [Ariston Liner (Ariston)] 1 Vivadent, Schaan, Liechtenstein
Resultant Mechanism of Compoglass SCA(Compoglass) Vivadent
Adhesion to Tooth Substrate F2000 Adhesive (F2000) 3M, St Paul, MN, USA
Hytac OSB (Hytac) ESPE, Seefeld, Germany
Prime&Bond 2.1 (Dyract AP) Dentsply, Konstanz, Germany
Prime&Bond NT2 (Dyract AP) Dentsply
Prompt L-Pop for compomers ESPE
Solist (Luxat) DMG, Hamburg, Germany
One-Step Self-Etch Adhesives
AQ Bond - Touch&Bond Sun Medical, Kyoto, Japan
Etch&Prime 3.0 Degussa, Hanau, Germany
One-up Bond F Tokuyama, Tokyo, Japan
Prompt L-Pop for composites ESPE
Prompt L-Pop 3 (exp) ESPE
Syntac 3 (self-etch; exp) 2 Vivadent
Xeno CF Bond Sankin, Otahara, Japan
One-Step Glass Ionomer Adhesives
FujiBond LC Liq-Liq (exp.) 2 GC, Tokyo, Japan
Reactmer 2 Shofu, Kyoto, Japan
Two-Step Glass Ionomer Adhesives
FujiBond LC2 GC
FujiBond LC Liq-Liq (exp) 2 GC
Photac Seal (exp.) 2 ESPE
Two-Step Self-Etch Adhesives
ABF2 (exp) Kuraray, Osaka, Japan
Clearfil Liner Bond 2 2 Kuraray
Clearfil Liner Bond 2V 2 Kuraray
Clearfil SE2 Kuraray
Imperva FL-Bond2 (Fluorobond) Shofu
NRC & Prime&Bond NT 2 Dentsply
OptiBond (no-etch)2 Kerr, Orange, CA, USA
OptiBond FL (no-etch)2 Kerr
Sustel (F2000) 3M
Unifil BOND GC
Coltène ART Bond 3 Coltène, Altstätten, Switserland
Denthesive II3 Hereaus-Kulzer, Wehrheim, Germany
Ecusit Primer-Mono3 DMG
Imperva Bond (no etch) 3 Shofu
Scotchbond 23 3M
Solid Bond 3 Hereaus-Kulzer
Superlux Universalbond 2 3 DMG
Syntac3 Vivadent
XR-Bond3 Kerr

described by Nakabayashi, Kojima & Masuhara in 1982 and is commonly referred to as

hybrid layer (Van Meerbeek & others, 1992, 1993a; Nakabayashi & Pashley, 1998).
Concurrent with hybridization, resin tags seal the unplugged dentin tubules and offer
additional retention through hybridization of the tubule orifice wall (Figure 7).
Three specific ultra-morphologic features have been described as resulting from this
hybridization process. A shag-carpet appearance stands for the loose organization of col-
lagen fibrils that are directed towards the adhesive resin and often unraveled into their
micro-fibrils (Figure 8). This feature typically appears when the dentin surface, after
being acid-etched, has been actively scrubbed with an acidic primer solution. A similar
pattern of deeply tufted collagen fibrils has been observed to result from citric-acid bur-
nishing of root surfaces as part of a tissue-regenerative periodontal treatment (Sterrett
& Murphy, 1989). The physical rubbing action combined with the chemical action of the
citric acid was found to enhance the removal of acidically-dissolved inorganic dentin
Van Meerbeek & Others: Adhesives & Cements 123

Table 1. (continued)
Brand Name Manufacturer
Two-Step Total-Etch Adhesives – ‘One-Bottle’Adhesives
Bond 1 Jeneric/Pentron, Wallingford, CT, USA
Dentastic Uno Pulpdent, Watertown, MA, USA
Dentastic Duo Pulpdent
EasyBond Parkell, Farmingdale, NY, USA
Everbond (exp)2 ESPE
Excite2 Vivadent
Gluma 2000 Bayer, Leverkusen, Germany
Gluma One Bond Heraeus-Kulzer
Gluma Comfort Bond Heraeus-Kulzer
One Coat Bond Coltène
One Step BISCO, Schaumburg, IL, USA
Optibond SOLO2 Kerr
Optibond Solo Plus 2 Kerr
Prime&Bond 2.1 Dentsply
Prime&Bond 2.1 Dual Cure Dentsply
Prime&Bond NT2 Dentsply
Prime&Bond NT Dual Cure2 Dentsply
PQ12 Ultradent, South Jordan, UT, USA
Scotchbond 1 (Single Bond) 3M
Snapbond Cooley & Cooley, Houston, TX, USA
Solist DMG
Solobond M Voco, Cuxhaven, Germany
Stae Southern Dental Industries, Victoria, Australia
Syntac Single-Component Vivadent
Syntac Sprint Vivadent
Syntac 3 (total-etch; exp) Vivadent
Tenure Quik with Fluoride Den-Mat, Santa Maria, CA, USA
Three-Step Total-Etch Adhesives
ABC Enhanced Chameleon, Kansas City, KA, USA
Ælitebond BISCO
All-Bond 2 BISCO
Amalgambond Plus Parkell
Clearfil Liner Bond 2, 4 Kuraray
Dentastic Pulpdent
Denthesive Hereaus-Kulzer
EBS ESPE
EBS Multi ESPE
Gluma Bonding System Bayer
Gluma CPS Bayer
Imperva Bond (total-etch) Shofu
Mirage Bond Chameleon
OptiBond (total-etch)2 Kerr
OptiBond FL (total-etch)2 Kerr
PAAMA 2 Southern Dental Industries
Permagen Ultradent
Permaquik2 Ultradent
Quadrant UniBond Cavex Holland, Haarlem, Netherlands
Restobond 3 Lee Pharmaceuticals, South El Monte, CA, VS
Scotchbond Multi-Purpose 3M
Scotchbond Multi-Purpose Plus 3M
Solid Bond Heraeus-Kulzer
Super-Bond D Liner Sun Medical
Tenure S Den-Mat
1 One-step adhesive used in combination with an ion-releasing restorative material; 2Adhesives providing filled adhesives; 3Early self-etch adhe-
sives developed to be applied on dentin only, whereas enamel is etched separately with a phosphoric acid (>30%) conditioner; 4Because of the
application of a silica-filled low-viscosity resin (Protect Liner) in addition to the application of the adhesive resin, Clearfil Liner Bond is applied in
four steps.

material and surface debris. This resulted in a deeply tufted collagen fibril surface
topography, similar to the appearance of a shag carpet. In this way, the dentinal root
surface became more receptive to the attachment of cells from new connective tissue-
formation. Likewise, the combined mechanical/chemical action of rubbing the acid-
etched dentin with an acidic primer (or primer/adhesive combination) probably
124 Operative Dentistry Supplement 6

Figure 6. Schematic drawing

presenting a mineralized
collagen fibril with its micro-
fibrils before and after being
etched with a conventional
phosphoric acid etchant.

Figure 7. (A) (left) Fe-SEM

photomicrograph illustrating the
dentin-resin interface produced
by the three-step total-etch
adhesive OptiBond FL (Kerr)
after removal of the adjacent
unaffected dentin. An acid-
resistant hybrid layer of 3-5 µm
was formed along with particle-
reinforced resin tags. The hybrid
layer triangularly extends within
the tubule orifice walls, repre -
senting “tubule wall hybridization”
(arrows). Micro-tags (asterisks)
are formed within the tubule lat -
eral branches and branch off
dissolves additional mineral while fluffing and separating the entangled collagen at the
the main resin tags. Bar = 5 µm.
surface (Figure 9). This active rubbing application is thought to promote infiltration of
Figure 7 (B) (right) Fe-SEM monomers into the loosened collagen scaffold by a kind of “massaging” effect.
photomicrograph of a diamond- Asecond typical hybridization characteristic has been termed as tubule-wall hybridiza -
knife sectioned dentin-resin
tion and represents the extension of the hybrid layer into the tubule wall area (Figure
interface produced by Optibond
Dual Cure (Kerr). Aclear loosely 10). Resin-tag formation in the opened tubules is circularly surrounded by a hybridized
organized collagen fibril network tubule-orifice wall that is thought to be favorable in hermetically sealing the pulpo-
can be observed within the 4-5 dentinal complex against microleakage and the potential subsequent ingress of micro-
µm hybrid layer (H). A= organisms. This effect may be especially protective when the bond fails either at the
Adhesive resin (particle-filled); bottom or top of the hybrid layer, which are considered the two weak links in the micro-
U = Unaffected intertubular mechanical attachment. Then, the resin tags usually break off at the hybrid layer sur-
dentin; Arrow = Tubule wall
hybridization; Bar = 5 µm.
face keeping the dentin tubules and thus the direct connection to the pulp sealed
(Figure 11). In particular, the resin-tag necks at
Figure 8. TEM photomicrograph the top 5-10 µm of the tubule orifices are thought
illustrating the typical shag-carpet to contribute most to retention and sealing effec-
appearance at the transition of tiveness (Figure 10). The actual length of the
the hybrid layer (H) to the
resin tags must probably be regarded as being of
adhesive resin (A) when the
three-step total-etch adhesive secondary importance.
Optibond Dual Cure (Kerr) was Thirdly, lateral tubule hybridization has been
used. The collagen fibrils are described as the formation of a tiny hybrid layer
directed towards the adhesive
into the walls of lateral tubule branches (Figure
resin and are frayed at their
ends into their micro-fibrils 12). This micro-version of a hybrid layer typically
(arrows). This ultra-morphologic surrounds a central core of resin, called a micro-
feature is ascribed to result resin tag.
from actively rubbing the
A plus-minus balance featuring three-step total-
etched dentin surface using an
acidic primer solution. F= etch systems is given in Table 2. Although the
Glass filler incorporated within clinical application procedure of the newest gen-
the adhesive resin; Arrow eration of “one-bottle” or two-step total-etch adhe-
heads = 10-20 nm resin-filled sives might be simpler due to the reduction by one
interfibrillar spaces; Bar = 0.2 µm. step, the eventual application time may not have
(Reprinted from Van Meerbeek been substantially reduced as compared to con-
& others, 1998c).
Van Meerbeek & Others: Adhesives & Cements 125

Figure 9. Fe-SEM photo ventional three-step systems (Table 3). In

micrograph demonstrating the
conventional three-step systems, the
effect of Non-Rinse Conditioner
(Dentsply) on dentin (top view)
primer should assure efficient wetting of
that resulted in a typical “shag- the exposed collagen fibrils, displace any
carpet” appearance. Note that residual surface moisture, transform a
due to smear layer preparation, hydrophilic into a hydrophobic tissue state
a bundle of intratubular collagen and sufficiently carry monomers into the
was pulled out of the dentin interfibrillar channels. The adhesive resin
tubule and smeared over the
should fill up the remaining pores
exposed intertubular collagen
fibril network. Bar = 5 µm. between the collagen fibrils, form resin
tags that seal the opened dentinal tubules,
initiate and advance the polymerization
Figure 10. TEM photomicro -
graph of a demineralized section reaction, stabilize the formed hybrid layer and resin
through the dentin-resin inter - tags and provide sufficient methacrylate double bonds
face produced by Optibond for co-polymerization with the successively applied
Dual Cure (Kerr). The loosely restorative resin. In simplified one-bottle systems, the
organized hybrid layer (H) typi - functions of the primer and the adhesive resin should
cally contains collagen fibrils be perfectly combined. As a consequence, higher tech-
separated by resin-filled interfib -
rillar spaces and extends trian -
nique sensitivity has often been ascribed to the use of
gularly into the tubule wall area these one-bottle systems (Finger & Balkenhol, 1999;
(open black arrows). This Perdigão, Swift & Lopes, 1999; Inoue & others,
“tubule wall hybridization” firmly 2000a,b; Blunck, 2000). As these combined primer/
attached the resin tag (R) to the adhesive resin solutions have a higher solvent-to-
tubule orifice wall and most monomer ratio, a realistic risk exists that such adhe-
importantly contributed to a her -
sives are applied in a too thin layer (Table 3). To achieve
metic seal of the tubule. A=
Adhesive resin; I = Lab-dem -
adequate bonding, it is of major importance, however,
ineralized intertubular dentin (I). that the one-bottle solution is abundantly applied.
Bar = 500 nm. Monomers should be sufficiently supplied
Figure 11. Fe-SEM photomicro - not only to saturate the exposed collagen
graph of a dentin-resin interface fibril network, but also to establish a sat-
that was produced by the three- isfactorily thick resin layer on top of the
step total-etch adhesive hybrid layer. Such a distinct resin layer
Permagen (Ultradent). The (that definitely must be pre-cured prior to
interface was separated applying the restorative composite) must
between the adhesive resin (A)
be regarded as a flexible, intermediate
and the hybrid layer (H), while
the resin tags (arrows) kept the shock-absorber (see below). In light of an
tubules sealed as they broke off elastic bonding concept, it is expected that
at the level of the hybrid layer. this shock-absorber may help to protect
This must be attributed to the the adhesive joint against early failure
tubule wall hybridization that caused by the shrinking composite cured
ensures a leakage-free seal of on top. Therefore, when using one-bottle
the tubules and strong bond to
the tubule orifice walls. I =
adhesives, it is recommended to apply
Intertubular dentin; Bar = 4 µm. multiple layers to ensure a sufficiently
thick resin film on top of the hybrid layer.
Figure 12. TEM photomicrograph They are particularly necessary when
of a non-demineralized section using primer/adhesive resin combina-
demonstrating the resin-dentin tions with high acetone content. The so-
interface produced by the three- called nanofiller added to certain one-bot -
step total-etch adhesive Opti- tle adhesives (Prime&Bond NT, Dentsply;
bond Dual Cure (Kerr). Note the
Excite, Vivadent) may also help to estab-
formation of a micro-resin tag
(arrows) into a lateral tubule lish a uniform resin film that stabilizes
branch. Acore of resin is the hybrid layer. After priming, the sur-
surrounded by a hybridized wall face should appear glossy without so-
(lateral tubule hybridization) called dry spots, the clinical indication
A= Adhesive resin; H = Hybrid that resin was adequately and sufficiently
layer; I = Intertubular dentin; applied. Especially in the latter respect,
R = Resin tag; Bar = 1 µm.
(Reprinted from Van
Meerbeek & others, 1998a).
126 Operative Dentistry Supplement 6

Table 2. Plus-Minus Balance Plus Minus

of Three-Step “Total-Etch”
Adhesives • Separate application of conditioner, primer and • Risk of “over”-etching dentin (highly concen-
adhesive resin trated phosphoric-acid etchants)
• “Lowest” technique-sensitivity • Time-consuming three-step application pro-
cedure
• In-vitro and in-vivo proven effectiveness of • Post-conditioning rinse phase required (time-
adhesion to enamel and dentin consuming and risk on surface contamina-
tion when not using rubber dam)
• Best bond to enamel • Sensitive to “overwet” or “overdry” dentin
surface conditions
• Most effective and consistent results • Weak monomer-collagen interaction (which
may lead to nano-leakage and early bond
degradation; Figure 6)
• Possibility for particle-filled adhesive
(“shock-absorber”)

Table 3. Plus-Minus Plus Minus

Balance of Two-Step
“Total-Etch” Adhesive • Basic features of three-step systems (Table 2) • Not substantially “faster” application (multiple
layers)
• “Simpler” application procedure by reduction with 1 step • More technique-sensitive (multiple layers)
• Possibility for “single-dose” packaging • Risk of a too thin bonding layer (no glossy
• Consistent and stable composition film, no “shock” absorber, insufficiently poly-
• Controlled solvent evaporation merizable due to oxygen inhibition)
• Hygienic application (>< cross-infection)
• Possibility for particle-filled adhesive (“shock-absorber”) • Effects of total-etch technique (Table 2)
• Risk of “over”-etching dentin
• Post-conditioning rinse phase required
• Sensitive to degree of dentin wetness
• Weak monomer-collagen interaction
• Insufficient long-term clinical results

the addition of nanofiller must be regarded as beneficial, rather than perceived that the
nanofiller would infiltrate the exposed collagen fibril network and thus reinforce the
hybrid layer, as has been hypothetically claimed. TEM (Transmission Electron
Microscopy) of unstained sections has clearly demonstrated that the collagen fibril net-
work mostly filters out the nanofiller, holding them at the hybrid layer surface (Tay,
Moulding & Pashley, 1999; Inoue & others, 2000b). Besides, it is not obvious that pen-
etration of the nanofiller in the hybrid layer would strengthen the bond or improve the
bond stability. Even simply providing evidence that this effect may occur must be
extremely difficult, if not impossible.

Self-Etch The alternative approach is based on the use of non-rinse acidic monomers that simul-
Adhesives taneously condition and prime dentin and enamel. The concept of self-etch primers was
first introduced with Scotchbond 2 (3M) in the early ’90s (Table 1). However, this system
was advocated only to be applied on dentin alone, and therefore required clinically
selective-enamel etching in a separate step. The current self-etch adhesives provide
monomer formulations for simultaneous conditioning and priming of both enamel and
dentin. Most common self-etch adhesives involve two application steps with the self-
etch primer followed by an adhesive resin, resulting in two-step self-etch adhesives
(Figure 1 and Table 1). Most recently, one-step self-etch or so-called all-in-one adhesives
combining the conditioning, priming and the application of an adhesive resin into a sin-
gle application have been marketed (Figure 1 and Table 1). Besides, on the basis of the
number of application steps, self-etch adhesives should also be subdivided into mild and
strong self-etch adhesives, depending on their pH and thus etching potential (Table 4).
Van Meerbeek & Others: Adhesives & Cements 127

Table 4. Classification of “Self-

Mild (pH = ± 2) Strong (pH 1)
Etch” Adhesives Following
Their Etch Potential* Clearfil Liner Bond 2V (Kuraray) Non-Rinse Conditioner & Prime&Bond NT
(Dentsply)
Clearfil SE Bond (Kuraray) Prompt L-Pop 1,2 (ESPE)
F2000 Primer/adhesive (3M) Vivadent experimental self-etch adhesive
Imperva FL-Bond (Shofu)
Mac-Bond II (Tokuyama)
One-up Bond F (Tokuyama)
Experimental PQ/Universal (Ultradent)
Unifil Bond (GC)
* Some of the self-etch adhesives mentioned in Table 1 were not included in this table, as their interfacial interaction with dentin has not yet
been studied.

Figure 13. TEM photomicrograph The bonding mechanism of “mild” self-

of an unstained, non-deminer - etch adhesives to dentin is also based on
alized section illustrating the hybridization, with the difference that
interface between dentin and only submicron hybrid layers are
the “mild” self-etching adhesive
Clearfil Liner Bond 2V (Kuraray).
formed and resin-tag formation is less
Ahybrid layer (H) with the depth pronounced (Figure 13). Within such
of on average 600 nm was submicron hybrid layers, collagen fibrils
formed with only partial dem - are not completely deprived from
ineralization and exposure of hydroxyapatite (in contrast to total-etch
collagen fibrils (not visible adhesives, Figure 6). This residual
because this section was not
hydroxyapatite may serve as a receptor
stained). Hydroxyapatite crystals
are clearly scattered within the for additional intermolecular interac-
hybrid layer. A= Adhesive tion with specific carboxyl or phosphate
resin (particle-filled); U = groups of the functional monomers. For
Unaffected intertubular dentin; instance, the primary ionic bonding
Bar=500 nm. potential of the two carboxyl groups of a
4-MET (4-methacryloxyethyl trimellitic
acid) based two-step self-etch adhesive
Figure 14. XPS narrow-scan (Unifil Bond, GC) with hydroxyapatite
spectrum of the C 1s peak
has been confirmed in a correlative XPS
when 4-MET was applied on
synthetic hydroxyapatite (X-Ray Photo-electron Spectrosopy) and
suggesting the formation of an TEM study (Van Meerbeek & others,
ionic bond between the 2000a) (Figure 14). If not through pri-
–COO- of 4-MET with Ca2+ of mary chemical bonding, we speculate
hydroxyapatite. that such monomers will at least be able
to more intimately interact with hydrox-
yapatite-coated collagen than with colla-
gen that due to the rather aggressive
total-etch technique, almost completely
lost its hydroxyapatite coating (Figure
6). Moreover, this two-fold bonding
mechanism may be advantageous in
terms of restoration longevity. It comprises a micro-mechanical bonding component that
may, in particular, provide resistance to “acute” de-bonding stress (for instance, imposed
during laboratory bond testing experiments which, however clinically, may be less rel-
evant). The additional monomer/hydroxyapatite-around-collagen interaction on a
molecular level may result in bonds that better resist hydrolytic degradation processes
(through, for instance, nanoleakage as suggested by Sano & others, 1995a,b), and thus
may help keep the restoration margins sealed for longer periods. It is also noteworthy
that although these mild self-etch adhesives typically present with submicron hybrid
layers, nevertheless, they are most often documented with bond strength and margin-
al sealing data equal to those obtained with total-etch adhesives (Blunck, 2000; Inoue
128 Operative Dentistry Supplement 6

Table 5. Plus-Minus Balance of

“Self-Etch” Adhesives Plus Minus
• Simultaneous demineralization and resin-infiltration • Insufficient long-term clinical research
• No post-conditioning rinsing • Adhesion potential to enamel needs yet to be
clinically proven
• Not sensitive to diverse dentin-wetness conditions
• Time-saving application procedure
• Low technique-sensitivity
• Possibility for “single-dose” packaging
• Consistent and stable composition
• Controlled solvent evaporation
• Hygienic application (>< cross-infection)
• Possibility for particle-filled adhesive (‘shock-absorber’)
• Adequate monomer-collagen interaction
• Effective dentin desensitizer

Figure 15. TEM photomicro - & others, 2000a,b). This suggests

graph of a lab-demineralized that such hydroxyapatite-containing
and UA/LC positively stained hybrid layers apparently provide
section illustrating the acid- adequate bonding performance and
resistant hybrid layer (H) pro -
duced by the “strong” “one-step
that the thickness of the hybrid
self-etching” adhesive Prompt layer, itself, (or the amount of micro-
L-Pop (ESPE). Note the “shag- mechanical interlocking) is probably
carpet” appearance at the tran - of minor importance. However, little
sition of the adhesive resin (A) has been described regarding the dis-
to the hybrid layer (H), the tribution of minerals and/or the
“tubule wall hybridization” (thin
resins within such submicron hybrid
arrows) and the formation of a
micro-resin tag surrounded by layers of mild self-etch adhesives.
“lateral tubule hybridization” Self-etch monomers should, while
thick arrows). L= Low-viscosity dissolving the smear layer, engage
resin; R = Resin tag; U = intact dentin. How far the resin must
Unaffected dentin (lab- penetrate to obtain this goal remains
demineralized); Bar = 1 µm. unknown.
“Strong” self-etch adhesives have been documented with an interfacial ultra-morpholo-
gy at dentin resembling that produced typically by total-etch adhesives (Figure 15).
Consequently, the mechanism of bonding strong self-etch adhesives to dentin is more
alike that of total-etch adhesives. This means that nearly all hydroxyapatite is removed
from collagen and thus any chemical interaction between hydroxyapatite and functional
monomers is excluded (Figure 6). These strong self-etch adhesives present with all typ-
ical hybridization features of total-etch adhesives (see above) along with the formation
of abundant resin tags.
Clinically, self-etch systems not only simplify the bonding process by eliminating steps,
but also eliminate some of the technique-sensitivity of total-etch systems (Gordan &
others, 1998; Inoue & others, 2000b) (Table 5). Furthermore, the clinician is not preoc-
cupied regarding the degree of moisture at the dentinal surface after etching, so the
issue of “wet-bonding” is of no relevance for these kinds of adhesives. Finally, the risk
on incomplete resin infiltration is eliminated by simultaneous infiltration of the
exposed collagen fibril scaffold with resin up to the same depth of demineralization. The
questionable self-etch potential on enamel is discussed below.

Glass Ionomer A third adhesion strategy differs from the former approaches (pursued by resin-based
Adhesives systems), as it involves a glass ionomer based interaction with the tooth substrate
(Table 1 and Figure 1). Dilution of restorative materials by adding more resin has
Van Meerbeek & Others: Adhesives & Cements 129

Figure 16. Fe-SEM photo- resulted in the development of resin-modified

micrograph illustrating the
glass ionomer adhesives that can bond resin
effect of a 10-second applica -
tion of 20% polyalkenoic acid composites to tooth tissue. From its origin, a
(Cavity Conditioner, GC) to two-fold mechanism of adhesion can be predict-
dentin. Note that although ed. A short polyalkenoic acid pre-treatment
intertubular collagen was cleans the tooth surface (Figure 16); it removes
exposed, the fibrils were not the smear layer and exposes surface collagen
completely denuded from fibrils only up to about 0.5-1 µm depth; herein,
hydroxyapatite. O =
resin interdiffuses with the establishment of a
Odontoblast process; P=
Peritubular dentin; Bar = 1 µm. micro-mechanical bond following the principle

Figure 17. TEM Photomicro-

graph of an unstained, non-
demineralized section demon -
strating the interface formed at
dentin by a glass-ionomer
adhesive (Fuji Bond LC, GC).
The shallow hybrid layer (H) of
about 0.5 µm results from the
short (10 seconds) application
of a 20% polyalkenoic acid, by
which collagen fibrils are
exposed, butnot completely
denuded from hydroxyapatite
(collagen is invisible on this
image as the section was not
positively stained). The
hydroxyapatite crystals
remaining around the collagen
fibrils served as receptors for
chemical bonding with the
carboxyl groups of the
polyalkenoic acid. On top of
the hybrid layer, a 0.5-µm gray
zone (asterisks) typically contains
small black globules of yet
unknown origin and is clearly
demarcated from the glass
ionomer matrix (M). This phase
represents the morphological
manifestation of a gelation of hybridization (Figure 17). The polyalkenoic acid pre-treatment is much less invasive
reaction of the polyalkenoic acid
with calcium that was extracted
than a traditional phosphoric-acid treatment in the way that the exposed collagen fib-
from the underlying dentin rils are not completely denuded from hydroxyapatite (Figure 16). Chemical bonding is
surface. G = fluoro-alumino- additionally obtained by ionic interaction of the carboxyl groups of the polyalkenoic acid
silicate glass filler surrounded by with calcium of hydroxyapatite that remained attached to the collagen fibrils (Yoshida
a silica hydrogel; P= Peritubular & others, 2000) (Figure 18). As mentioned above, for mild self-etch adhesives, this sup-
dentin; S = Smear occluding the plementary chemical attachment may be beneficial particularly in terms of resistance
tubule orifice; U = Unaffected
to rapid hydrolytic degradation (Table 6). Consequently, the underlying mechanism of
intertubular dentin; Bar = 2 µm.
glass ionomer adhesives and “mild” self-etch adhesives may be similar.

Following a total-etch approach, both enamel and dentin are currently etched with
Critical Steps in phosphoric acid in a concentration between 30 and 40%. However, in the early ’90s,
Clinical Bonding lower concentrated (10-20%) phosphoric-acid etchants and phosphoric-acid alterna-
Total Versus Self- tives, such as maleic, citric and nitric acid, were advocated in light of a total-etch tech-
Etching Enamel nique that was not too aggressive to dentin. Consequently, dentin would certainly not
be etched to a depth inaccessible for resin to penetrate up to the complete demineral-
ization depth in a relatively short time. A few years after their introduction, clinical
research has, however, learned that these dentin-kind total-etchants prepare enamel
insufficiently (Swift & Cloe, 1993; Triolo & others, 1993; Van Meerbeek & others, 1994b,
130 Operative Dentistry Supplement 6

Table 6. Plus-Minus Balance of

Plus Minus
“Glass-Ionomer” Adhesives
• Fast and simple application procedure • Adequate adhesion to enamel requires
(new liquid/liquid formulation under development) smear layer removal
• Viscous particle-filled adhesive • Insufficient long-term clinical research
(“shock-absorber”)
• Cariostatic potential by release of fluoride
• Two fold bonding mechanism:
• Ionic bonding to hydroxyapatite
• Micro-mechanical through hybridization

Figure 18. Schematic 1996). Enamel apparently

presentation of the ion- requires more aggressive
exchange process and the etching, such as that pro-
formation of an ionic bond vided by conventional 30-
between the carboxyl groups of 40% phosphoric acid
the polyalkenoic acid with etchants; this not only to
calcium of hydroxyapatite.
remove the smear layer,
but also to produce a
micro-retentive etch-pat-
tern with high surface
energy. When such 30-
40% phosphoric acid
etchants are used on
dentin, over-etching can
best be avoided by apply-
ing the acid first on enamel
Figure 19. Fe-SEM photomicro - so that enamel is etched
graph of an argon-ion-bombarded the longest (for at least 15
resin-enamel interface as seconds) and successively
produced by a “strong” self-
etching adhesive (experimental
dentin is etched for 15
Vivadent). Note that the self- seconds at maximum.
etching approach resulted in a Only sclerotic dentin sur-
clearly detectable effect (arrow - faces can be etched longer
heads) at the enamel surface without the risk of etch-
(E). No separation was ing them too deeply. In
observed between the adhesive
fact, it is even advisable
resin (A) and enamel. The
bonding mechanism is primarily
to etch this hyper-miner-
based on the formation of alized tissue longer to
micro-resin tags. L= Low- make it more receptive to
viscosity resin cured on top of bonding (Van Meerbeek &
the adhesive resin; Bar = 10 µm. others, 1994a, 1998a; Tay
& others, 2000). After etching, the conditioner and its byproducts should be thoroughly
rinsed off prior to application of the primer and adhesive resin. For instance, not rins-
ing off the nitric acid conditioner, as was recommended by the manufacturer of ABC
Enhanced (Chameleon), resulted in an incompletely resin-penetrated demineralized
dentin surface layer or even any significant hybrid layer formation at all (Perdigão,
1995; Eick & others, 1995; Van Meerbeek & others, 1998a). Properly rinsing off the con-
ditioner was sufficient to achieve adequate hybridization.
Concern is often raised regarding the bonding effectiveness of self-etch adhesives to
enamel. Numerous recent laboratory studies provide data that suggests either equal or
reduced enamel bonding effectiveness as compared to conventional phosphoric acid
etching (Perdigão & others, 1997; Hayakawa, Kikutake & Nemoto, 1998; Yoshiyama &
others, 1998; Hannig, Reinhardt & Bott, 1999; Hara & others, 1999; Kanemura, Sano
& Tagami, 1999). Nevertheless, so far, no clinical evidence has been provided that this
self-etch approach guarantees durable bonding to enamel. However, neither has a con-
Van Meerbeek & Others: Adhesives & Cements 131

Figure 20. Fe-SEM photomicro - trolled long-term clinical trial

graph of an argon-ion-bombarded been published that concludes
resin-enamel interface as
produced by a mild self-etching
that self-etched enamel affects
adhesive (Clearfil SE Bond, the clinical longevity of adhesive
Kuraray). Note that the self- restorations. Fe-SEM (Field-
etching approach resulted in a emission Scanning Electron
hardly detectable effect at the Microscopy) interfacial charac-
enamel surface (E). No separa - terization of the resin-enamel
tion was observed between the
interface clearly revealed that
adhesive resin (A) and enamel.
The bonding mechanism is the interaction of self-etch adhe-
primarily based on the formation sives again depends on the pH,
of micro-resin tags. A= Silica- and thus, the etching aggressive-
filled adhesive resin; Bar = 2 µm. ness of the self-etching primer/
adhesive. Whereas strong self-
etch adhesives presented with
the formation of “micro-tags”
(Figure 19), the mild systems hardly showed any detectable interaction with dentin
(Figure 20). Today, any correlation between morphologic findings and bonding effective-
ness has not been provided, making the need for controlled clinical trials to test the self-
etch against the total-etch approach towards enamel urgently needed. Until then, it
remains clinically advisable to employ this simplified application technique first, only on
enamel that has been previously coarsened by bur, second, by applying the self-etch primer
during a sufficiently long time of at least 15 seconds and third, by actively applying it
through rubbing the enamel surface with repeated applications of fresh material.
Alternatively, a separate conventional etchant can be applied prior to the application of
the self-etch primer.
Some of today’s so-called “self-etch primers” are applied prior to the application of poly-
acid modified resin composites or compomers but hardly have a self-etching potential
(Table 1). Nevertheless, manufacturers recommend bonding compomers into mixed
enamel-dentin cavities using these one-step adhesives without any separate acid-etching
step preceding their application. However, morphologic study of the resultant interface
with dentin confirmed their limited etching action (Van Meerbeek & others, 1998a;
Inoue & others, 2000b). A shallow, sub-micron interaction without substantial collagen
fibril exposure was disclosed. Smear debris to keep the dentinal tubules plugged was
observed, and at best was entrapped by resin, forming so-called resin-impregnated
smear plugs. Consequently, these adhesives are certainly not aggressive enough to
expose a highly retentive etch-pattern on the enamel surface. Moreover, recent clinical
trials reported the occurrence of small to severe enamel margin chipping already after
six months of clinical service, that if left untreated, rapidly could lead to marginal dis-
coloration and even caries recurrence (Gladys, 1997; Gladys & others, 1998). These
early enamel margin defects should be ascribed to ineffective etching of enamel using
the weak self-etch primers only. These clinical results were confirmed in vitro, where
the primers provided with compomers produced less effective bonding results on enamel
(Cortes, García-Godoy & Boj, 1993; Fritz, Finger & Uno, 1996; Abate & others, 1997;
Attin, Buchalla & Hellwig, 1996; Ferrari & others, 1998). Most likely, the clinical effec-
tiveness of these polyacid modified composites could be substantially improved by sup-
plementary acid-etching enamel prior to the primer application or by using adhesives
with stronger self-etch potential.

Wet Versus Dry After conditioning following a total-etch approach, the enamel and dentin surface
Bonding should be properly treated to allow full penetration of adhesive monomers. On the
enamel surface, a dry condition is theoretically preferred. On the dentin site, a certain
amount of water is recommended to avoid collapse of the exposed dentin collagen scaf-
fold, thereby, impeding effective penetration of adhesive monomers (Perdigão & others,
1995). Consequently, in most common cavities involving enamel and dentin, the clini-
132 Operative Dentistry Supplement 6

Table 7. Current Adhesives

Categorized Following the Acetone Acetone- Acetone- Ethanol Ethanol- Water
Water Ethanol Water
Type of Solvent of the Primer
or Combined Primer/ ABC Enhanced AQ Bond All-Bond 2 Excite Gluma Amalgambond
Adhesive Resin (Chameleon) (Sun Medical (BISCO) (Vivadent) Comfort Bond Plus (Parkell)
(Kulzer)
EG Bond Reactmer Optibond Solo Optibond FL ART Bond
(Sun Medical) (Shofu) Plus (Kerr) (Kerr) (Coltène)
Gluma One- Tenure Quik PQ1 Permaquik Clearfil SE
Bond (Kulzer) (Den-Mat) (Ultradent) (Ultradent) Bond
(Kuraray)
One Step Quadrant Denthesive II
(BISCO) Unibond (Kulzer)
(Cavex)
Permagen Scotchbond 1 EBS (ESPE)
(Ultradent) (3M)
Prime&Bond Syntac Sprint FujiBond LC
NT (Dentsply) (Vivadent) (GC)
Solid Bond One-coat
(Kulzer) Bond
(Coltène)
Solist (DMG) Prompt L-Pop
1,2 (ESPE)
Stae (SDI) Scotchbond
Multi-Purpose
(3M)
Tenure Quik F Syntac
(Den-Mat) Single-Comp
(Vivadent)

Table 8. Basic Characteristics cian should actually be able

Acetone
of the Three Solvents to balance over a short dis-
Commonly Used in Adhesives Highly volatile, evaporates quickly tance between wet and dry.
Excellent water-chaser Currently, two clinical
Strong drying agent (risk of overdrying dentin) methods exist to achieve
Storage and dispense problems adequate hybridization.
The type of adhesive and, in
Ethanol (Water)
particular, the kind of sol-
Excellent penetration capability vent of the primer (or of the
Good compromise in respect of evaporation primer/adhesive) deter-
Good surface energy for wetting exposed collagen fibril network mines which of the two
Water methods can best be used.
Good penetration capability
One way is to keep the sub-
strate field dry and use
Enables self-etching capability of acid monomers
adhesive systems that pro-
Evaporates slowly consequently more difficult to remove vide water-based primers
Remaining water may hamper resin penetration/polymerization (Table 7) to re-hydrate and
thus re-expand the air-
dried and consequently col-
lapsed collagen network, allowing resin monomers to still interdiffuse efficiently (Van
Meerbeek & others, 1998c). The other alternative is to keep the acid-etched dentin sur-
face moist and to rely on the water-chasing capacity of acetone-based primers (Table 7).
This clinical technique is commonly referred to as wet-bonding and has been introduced
by Kanca (1992a,b,c) and Gwinnett (1992) in the early ’90s.
It is fundamentally important to effective hybridization that the collagen fibril web,
deprived of its mineral support following acid treatment, keep its spongy-like quality,
allowing interdiffusion of resin monomers in the subsequent priming and bonding
steps. Dehydration of the acid-conditioned dentin surface through air-drying is thought
Van Meerbeek & Others: Adhesives & Cements 133

Figure 21. Schematic to induce surface tension stress,

presentation showing the causing the exposed collagen
principle of evaporation of the
solvent during the priming
network to collapse, shrink and
step after it carried the active form a compact coagulate that is
monomers through the impenetrable to resin (Pashley
channels within the exposed & others, 1993; Pashley &
collagen fibril network. Carvalho, 1997). If some water
remains inside the interfibrillar
spaces, the loose quality of the
collagen matrix is maintained
and the interfibrillar spaces are
left open (Perdigão, 1995;
Kanca, 1992c; Perdigão & oth-
Marcos A Vargas 1999 ers, 1995, 1996a). It should,
however, be emphasized that
this wet-bonding technique can
Figure 22. TEM photomicro -
only guarantee efficient resin
graph of the resin-dentin
interface produced by Clearfil interdiffusion if all the remain-
Liner Bond System (Kuraray) ing water on the dentin surface
when applied to 35% is completely eliminated and
phosphoric-acid etched dentin. replaced by monomers during
Due to insufficient resin the subsequent priming step. In
infiltration, a typical hybridoid some of the currently available
zone (H’) was formed
underneath the top area of
adhesive systems, hydrophilic
the hybrid layer (H) which primer monomers are therefore
was stained more electron dissolved in volatile solvents,
dense as sign of adequate such as acetone and ethanol
resin infiltration. A= Adhesive (Abate, Rodriguez & Macchi,
resin; I = Lab-demineralized 2000). These solvents may aid in
intertubular dentin; L= Micro-
displacement of the remaining
resin tag in hybridized lateral
tubule branch; R = Resin tag; water as well as carrying the
W = Hybridized tubule wall; polymerizable monomers into
Bar = 1 µm. the opened dentin tubules and
through the nano-spaces of the
collagen web (Tay & others, 1996a; Tay, Gwinnett & Wei, 1996b, 1997). The primer sol-
vents are then evaporated by gently air-drying, leaving the active primer monomers
behind (Figure 21). The basic characteristics of the three solvents used in commercial
adhesives are summarized in Table 8. When the water inside the collagen network is
not completely displaced, the polymerization of resin inside the hybrid layer may be
affected or, at least, the remaining water will compete for space with resin inside the
demineralized dentin (Jacobsen & Söderhold, 1995). The risk that all moisture on the
dentin surface is not completely replaced by hydrophilic primer monomers is clinically
real and ultra-morphologically documented as overwetting phenomena for adhesive
systems that provide water-free acetone-based primers (Tay & others, 1996a,b, 1997).
In such overwet conditions, excessive water that was incompletely removed during
priming, appeared to cause phase separation of the hydrophobic and hydrophilic
monomer components, resulting in blister and globule formation at the resin-dentin
interface. Such interface deficiencies undoubtedly weaken the resin-dentin bond and
result in incompletely sealed tubules (Tay & others, 1996a,b). On the other hand, even
gentle post-conditioning drying of the dentin surface for as short as three seconds prior
to the application of a water-free, acetone-based primer has been shown to result in
incomplete intertubular resin infiltration. Ineffective resin penetration due to collagen
collapse has been ultra-morphologically observed as the formation of a so-called hybri-
doid zone (Figure 22). These hybridoid zones inside the hybrid layer do not appear elec-
tron dense on demineralized TEM sections. Consequently, this wet bonding technique
appears rather technique-sensitive (Tay & others, 1995, 1996b; Finger & Balkenhol,
134 Operative Dentistry Supplement 6

1999; Frankenberger, Kramer & Petschelt, 1999; Perdigão & others, 1999a), especially in
terms of the precise amount of moisture that should be kept post-conditionally on the
dentin surface. In other words, acid-etched dentin may not be kept too wet, but also may
not be dried too long. A short air blast or blotting the excess water using a dry sponge
or small piece of tissue paper has been recommended as most effective post-condition-
ing wet-bonding procedures.
This wet-bonding technique also has two other disadvantages of clinical importance.
First, acetone quickly evaporates from the primer bottle, so that after the primer solu-
tion is dispensed in a dappen dish, the primer bottle should be immediately closed and
the dispensed primer solution immediately applied to the etched surface. Despite careful
handling, the composition of the primer solution may change after the bottle has been
opened and closed several times due to quick evaporation of solvent out of the recipient.
This will increase the ratio of monomers to the acetone solvent and will definitely have
its effect on the eventual penetrability of monomers in the exposed collagen fibril net-
work. To reduce such a rapid primer solvent volatilization, acetone-based adhesive for-
mulations are also available today in pre-dosed single-patient-use capsules as with
Prime&Bond NT Quix (Dentsply). In this way the capsules can be opened just prior to
application of the “one-bottle” solution, giving the acetone little time to evaporate. A
final clinical disadvantage of keeping the lesion wet after conditioning is that the clini-
cian cannot check if the enamel surface turns white-frosted as clinical proof that enam-
el was efficiently etched.
On the contrary, adhesive systems that provide water-dissolved primers have been
demonstrated to bond equally effective to dry or wet dentin (Van Meerbeek & others,
1998c). In that study, the hybridization effectiveness of two three-step total-etch adhe-
sives, OptiBond Dual Cure (Kerr) and Scotchbond Multi-Purpose (3M), was examined
by TEM. Neither substantial difference in the ultrastructure of the hybrid-layer nor
signs of incomplete resin penetration or collagen collapse were detected when these
water-based adhesives were applied following either a wet- or dry-bonding technique.
Even excessive post-conditioning air-drying of the dentin surface for 15 seconds did not
result in the formation of a hybridoid zone that would have clearly indicated that resin
had ineffectively infiltrated the demineralized collagen network (Tay & others, 1996a).
When both adhesives were bonded to wet dentin, no morphological evidence of over-
wetting phenomena was observed, either. This indicates that the two water-based
primers were capable of sufficiently displacing the water that remained as part of the
wet-bonding technique as well as the additional amount of water that was introduced
with the primers themselves. A potential self-rewetting effect of the primer, which evi-
dently provides sufficient water to re-expand the gently air-dried and collapsed collagen
scaffold, has been advanced as a reasonable explanation for the ability of these systems
to perform equally well in wet or dry conditions. In this regard, air drying of deminer-
alized dentin has been described to reduce its volume by 65%, but the original dimen-
sions can be regained after reimmersion in water (Carvalho & others, 1996).
In contrast to adhesive systems that provide acetone-based primers and show a restricted
window of opportunity as far as a precise amount of water that should remain post-con-
ditionally on the dentin surface for efficient bonding to be achieved, adhesive systems
that provide water-based primers appear less technique-sensitive and bond equally well
to varying degrees of surface dry and wetness. Bonding to dry dentin has the advantage
of being the clinically accepted and utilized standard used by most clinicians. In addi-
tion, dry bonding permits the clinician to verify the frosted appearance of enamel fol-
lowing conditioning as proof of an adequate enamel acid-etch. In addition, dry bonding
does not involve any risks for overwetting. Clinically, a standard dry-bonding procedure
is recommended that involves gentle air drying of the dentin surface after conditioning
for about five seconds or until the glossy wet surface turns dull and the acid-etched
enamel surface appears white and frosted.
Alternatively, conditioned dentin may be air dried and remoistened with water or an
antibacterial solution such as chlorhexidine (Gwinnett, 1992; Kanca, 1992a). In this
Van Meerbeek & Others: Adhesives & Cements 135

regard, a recent study has shown that an aqueous HEMA (35%) solution (Aquaprep,
BISCO) is effective for compensating the dryness induced on the dentin surface by air
blasts from an air syringe after rinsing off the etchant (Perdigão & others, 1999b). The
post-conditioning application of the re-wetting agent significantly improved the bond-
ing effectiveness of some simplified adhesives.

Primer Application Primers should be clinically applied with care to assure that resin effectively infiltrates
the network of interfibrillar collagen channels. A primer application time of at least 15
seconds, as recommended by most manufacturers, should be respected to allow
monomers to interdiffuse up to the complete depth of surface demineralization. When
a dry-bonding technique is followed using self-rewetting water-based primers, this 15-
second primer application time should allow the gently air dried and thus collapsed col-
lagen scaffold to re-expand. Using a wet-bonding technique, the primer should be
applied for sufficiently long time (at least 15 seconds) to displace all remaining surface
moisture through concurrent evaporation of the primer solvent carrier. Moreover,
water-free acetone-based primers, provided with three- and two-step (one-bottle) total-
etch adhesives, should be applied copiously in multiple layers as per the manufacturer’s
instructions. After short and gentle air drying, the primed surface should appear glossy
as a clinical control of an adequate primer application.
Instead of leaving the primer solution untouched on the dentin surface during the
whole application time, an active rubbing application technique with moderate pres-
sure using disposable brushes or sponge applicators may improve and accelerate the
monomer interdiffusion process. In this way, primer monomers may be infused and
aspirated in the network of interfibrillar collagen channels, producing the above-men-
tioned “shag carpet” (Figures 8 and 9).
Acid-etched enamel theoretically does not need separate primer application to achieve
effective bonding when an unfilled or low-filled hydrophobic enamel-bonding agent is
applied on air-dried enamel. On the other hand, primers can be applied on acid-etched
enamel without harming the enamel bonding process. In case the cavity is kept moist
following a wet-bonding technique, primers should, however, always be applied on acid-
etched enamel to displace any residual surface moisture through concurrent evapora-
tion of primer solvent. Eventually, the primer application should always be completed
by short, gentle air drying to volatilize any remaining solvent excess prior to applica-
tion of the adhesive resin.

Adhesive Resin In the final step of the bonding process, the adhesive layer should also be appropriately
Application placed. Spreading the adhesive resin over the surface to which it is bonded should be
done preferentially by
Figure 23. Schematic brush-thinning rather
presentation explaining the
elastic bonding concept in
than by air-thinning. The
which a relatively thick adhesive should be copi-
intermediary resin may ously placed, then evenly
compensate by elastic spread using a brush tip
expansion for the that can optionally be
polymerization shrinkage repeatedly squeezed out
stress induced during
between a paper tissue. In
contraction of the
restorative composite. this way, the adhesive
resin layer will reach an
optimal thickness of about
100 µm (Moon & Chang,
1992). When placed in a
sufficiently thick layer,
the adhesive resin may,
due to its relatively high
136 Operative Dentistry Supplement 6

elasticity, act as a stress-relaxation buffer (Figure 23). This will absorb by elastic elon-
gation, in part, the tensile stresses imposed by polymerization contraction of the resin
composite subsequently placed over the adhesive resin (Kemp-Scholte, 1989; Kemp-
Scholte & Davidson, 1990; Van Meerbeek & others, 1993b; Bayne & others, 1994; Rees,
O’Dougherty & Pullin, 1999; Unterbrink & Liebenberg, 1999). In a recent study, the
polymerization contraction stress generated during the placement of composite restora-
tions was found to be significantly absorbed and relieved by the application of an
increasing thickness of low-stiffness adhesive (Choi, Condon & Ferracane, 2000).
Blowing the adhesive resin layer may reduce its thickness too much, decreasing its elas-
tic buffer potential to relieve polymerization contraction stress. In support of this elas-
tic bonding concept, dentin adhesive systems that provide a low-viscosity resin have
been reported to produce higher bond strengths and less microleakage (Fortin & others,
1994; Inoue & others, 2000a,b). Likewise, microleakage was found to be reduced when
a filled low-viscosity resin was used as an intermediate liner (Swift & others, 1996).
Moreover, this elastic bonding concept can be regarded as an efficient means to not only
counteract the polymerization contraction stress of the resin composite, but also to pos-
sibly aid in absorbing masticatory forces, tooth flexure effects and thermal cycling
shocks which, all during clinical function, may jeopardize the integrity of the resin-
tooth bond. Besides adhesives that provide low-viscosity particle-filled resins, thick
adhesive layers are also placed with polyalkenoic acid-based adhesive systems, such as
Scotchbond Multi-Purpose (3M) and Scotchbond 1 (3M), and with the more recently
developed glass ionomer based adhesives, Fuji Bond LC (GC) and Reactmer (Shofu).
Clinical evidence in support of this elastic bonding concept are the excellent clinical
results that have been reported for Clearfil Liner Bond (Kuraray), Scotchbond Multi-
Purpose (3M) and Optibond Dual Cure (Kerr) in several clinical trials (Van Meerbeek
& others, 1994b, 1996; Bayne & others, 1994; Boghosian, 1996; Trevino & others, 1996;
Peumans & others, 2000).
In theory, chemical and dual-cure adhesive systems that allow small flow-active porosi-
ties to be mixed in the resin layer and the polymerization to progress at a slower rate
than solely light-cure adhesive resins may also contribute to this stress-relaxation
mechanism (Perdigão & others, 1996b; Alster & others, 1992). For the same purpose,
the use of adhesive lining and base cements underneath composite restorations should
be considered as stress-absorbers. The use of an intermediate glass ionomer liner will
reduce the total stiffness and increase the stress-absorption capacity of the restoration.
Resin-modified glass ionomer cements are preferred over conventional glass ionomer
cements because they can chemically co-polymerize with the restorative resin composite
placed over the intermediate cement layer. This so-called “sandwich” technique has, for
instance, been demonstrated to significantly reduce the loss rate of restorations placed
with even an earlier generation adhesive, Scotchbond 2 (3M), when a resin-modified
glass ionomer liner, Vitrebond (3M), was additionally applied as an intermediate liner
(Powell, Johnson & Gordon, 1995). Also the so-called flowable composites are very pop-
ular for use as a stress-absorbing liner in the deepest parts of proximal boxes in poste-
rior restorations (Prager, 1997; Bertolotti & Laamanen, 1999; Bouschlicher, Cobb &
Boyer, 1999; Frankenberger & others, 1999; Murchison, Charlton & Moore, 1999;
Unterbrink & Liebenberg, 1999).
For light-curing bonding agents, the adhesive resin should always be cured prior to the
application of the restorative resin composite. In this way the adhesive resin is not dis-
placed when the restorative resin composite is applied and adequate light intensity is
provided to sufficiently cure the adhesive resin layer (Erickson, 1992). Pre-curing the
adhesive resin will stabilize the resin-tooth bond and consequently activate the elastic
stress-relaxation mechanism.
Because of oxygen inhibition, the top 15 µm of the adhesive resin will not polymerize
(Rueggeberg & Margeson, 1990), but will provide sufficient double methacrylate bonds
for co-polymerization with the subsequently applied restorative resin. Again, brush-
thinning rather than air-thinning may prevent the film thickness from being reduced
Van Meerbeek & Others: Adhesives & Cements 137

Figure 24. Micro-tensile bond

strength to enamel and dentin 70
of 13 contemporary
adhesives classified per 60
adhesive approach.
50

40

30

20

10

Dentin
Enamel

2-Step
GI
Adhesive 1-Step
Self-Etch
Adhesives 2-Step
2-Step 3-Step
Self-Etch
Total-Etch Total
Adhesives
Adhesives Etch
Adhesive

to an extent that the air-inhibited layer permeates the whole resin layer, reducing the
stress-relaxation capacity and bond effectiveness.

Laboratory Bonding The adhesive effectiveness of the self-etching adhesives to enamel and dentin was test-
Effectiveness ed in terms of micro-tensile bond strength (µTBS) using a method introduced by Sano
& others in 1994. This technique was selected as it enables more accurate measure-
ments of tensile bond strength because the typical hourglass design of the specimens
imposes the highest stress during testing to be built-up at the real interface.
The µTBS data clearly indicate that any kind of simplification either following a one-
bottle, self-etch or glass ionomer approach leads to a significant drop in adhesive effec-
tiveness to dentin (Figure 24). Apparently, the conventional three-step procedure allows
a more accurate and less technique-sensitive application that is translated in higher
tensile bond strength to dentin. This difference in effectiveness between conventional
and simplified systems, however, may not be directly relevant in the early years of clin-
ical service, but most likely may shorten the eventual longevity of adhesive restora-
tions. Despite the high turnover of adhesives, there is a high need to re-evaluate long-
term clinical trials since they only allow conclusions to be drawn on the longevity of
adhesive restorations.
Aremarkable concern is the lack of consistency in µTBS recorded with two strong self-
etching adhesives, Prompt L-Pop (ESPE) and NRC/Prime&Bond NT (Dentsply). The
µTBS data mentioned for these two adhesives (Figure 24) did not significantly differ
from the values recorded for the other self-etch adhesives. However, these data only
represent the average bond strength of only 13 out of 17 (75%) Prompt L-Pop speci-
mens, respectively, and 7 out of 14 (50%) NRC/Prime&Bond NT specimens. For both
adhesives, the other specimens did not survive the specimen preparation method and
failed prior to testing. Such inconsistent bonding performance is most likely caused by
the high acidity of unpolymerized monomers remaining after light curing in a relatively
high concentration at the oxygen-inhibited layer (Schiltz & others, 2000; Sanares &
others, 2000). The unreacted acid groups have been hypothesized to attack the poly-
138 Operative Dentistry Supplement 6

Figure 25A(right) 25B

(below). Clinical bonding Bayer exp. 2 (Gluma 2000)
Bayer exp. 1
RETENTION (%)
effectiveness of 14 adhesive-
composite combinations in Tripton
terms of retention (%) in Tenure
Class-V non-carious lesions. Scotchbond 2
The figure at the base of each
Clearfil New Bond 74
data bar represents the year
Gluma 62
when the study was started.
Scotchbond
77 72
100
79
90
46
80

70

60 58

50
33
40

30
Baseline 6 months 1 year 2 year 3 year

Figure 25B. Clinical bonding

effectiveness of 14 adhesive- FujiBond LC 100
composite combinations in Permaquik (+ microfilled composite)
terms of retention (%) in 96
Permaquik (+ hybrid composite)
Class-V non-carious lesions. 98
The figure at the base of each Optibond FL 100
data bar represents the year
Scotchbond Multi-Purp.
when the study was started. 96
Clearfil Liner Bond
100
100

90
RETENTION (%)
80

70

60

50

40

30
Baseline 6 months 1 year 2 year 3 year

merization initiation system of the composite material, especially in the case of pro-
longed contact of the acidic adhesive monomers with the uncured composite material.
Lack of a sufficiently thick and uniform resin layer that stabilizes the hybrid layer may
also have contributed to the lower bond strength values and relatively high number of
pre-testing failures. More recent research has indeed shown that a sufficiently thick
and separately light-cured adhesive (prior to application of the restorative composite),
or the use of an additional intermediary low-viscosity resin reduced or even eliminated
the occurrence of pre-testing failures (unpublished observations). This has been con-
firmed by other researchers (Perdigão & others, 2000). Further research is definitely
needed to elucidate this inconsistency in bonding effectiveness recorded with these two
specific adhesives.
In contrast to the µTBS data recorded to dentin, in general, the adhesives with simpli-
fied application procedures do not underscore against the conventional three-step total-
etch control adhesive with regard to enamel-bonding effectiveness (Figure 24). This is
Van Meerbeek & Others: Adhesives & Cements 139

certainly the case for three out of four “one-bottle” adhesives tested but also for the
strong self-etch adhesive NRC/Prime&Bond NT and even the mild self-etch adhesive
Clearfil SE Bond, of which the µTBS does not significantly differ from that of Optibond
FL. Some pre-testing failures were recorded for the experimental PQ/Universal (three
out of 10 specimens could be tested) when used following a self-etch approach, for One-
up Bond F (six out of 11 were tested) and for Unifil Bond (10 out of 11 were tested). All
adhesives in this study were bonded to enamel on which a 600-grit smear layer was pre-
pared beforehand. In this respect, another study by Kanemura & others (1999) revealed
that two other self-etch adhesives (Clearfil Liner Bond 2, Kuraray; Mac Bond 2,
Tokuyama) scored µTBS data to ground enamel that were comparable to those meas-
ured for two one-bottle adhesives (One-Step, BISCO; Scotchbond 1, 3M) that involved a
separate phosphoric-acid treatment. When the self-etch adhesives were directly bonded
to unground, intact enamel, the resultant µTBS values, however, were significantly
lower. Testing the marginal sealing potential and durability of the self-etching approach
should obviously confirm these promising enamel performance data.

Clinical Bonding At Leuven, the clinical effectiveness of adhesives has been routinely investigated in con-
Effectiveness trolled two-to-three-year follow-up studies using the same experimental protocol for
almost 20 years. The retention rates shown in Figures 25a and 25b clearly illustrate the
significant progress made in adhesive performance when adhesives (Figure 25a) from
prior to versus after 1990 (Figure 25b) were used to restore cervical Class-V non-cari-
ous lesions with their respective restorative composite material. In part, this must be
attributed to the introduction in the early ’90s of the total-etch technique by which phos-
phoric acid is now also applied to dentin. Earlier adhesives often showed many failures
within the first six months when applied strictly to dentin without any selective phos-
phoric acid etching of adjacent enamel (Van Meerbeek & others, 1994b). When following
the same protocol in more recent clinical trials (total-etch systems were applied selec-
tively to dentin), almost any early de-bonding failures were recorded. This must be
attributed to a great extent to the enamel immediately adjacent to dentin always being
(unintentionally) etched and guaranteeing a durable bond to the enamel margin.
Adequate bonding to enamel alone may keep such restorations longer in place.

Conclusions A great diversity in adhesives that can basically be categorized total-etch, self-etch and
glass ionomer adhesives exists. A clear trend exists towards simplified application pro-
cedures with a reduced number of application steps. However, simplification does not
necessarily imply improved or even equal bonding effectiveness.
Conventional three-step total-etch adhesives remain the adhesives of choice for routine
clinical use because of their least technique-sensitivity and their best laboratory and
clinical effectiveness data. Today’s major shortcomings are, amongst others, the rela-
tively high technique-sensitivity of current systems and the apparent difficult-to-solve
compromise to bond equally effective to enamel and dentin. Self-etch adhesives, either
resin- or glass ionomer-based, may be most promising in overcoming these shortcom-
ings. They do not require a rinse phase, which truly saves time and is less prone to
manipulation errors. No discrepancy exists between demineralization and infiltration.
They offer a twofold bonding mechanism based on micro-mechanical interlocking
through hybridization to resist “acute” debonding stress and improved monomer-colla-
gen interaction potentially by primary chemical bonding, which may be helpful to keep
the bonds leakage-free in a long-term perspective.
An adhesive restoration, in conclusion, has many advantages over conventional non-
adhesive restorative techniques except that it cannot yet be realized in a simple way.

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Authors Bart Van Meerbeek, DDS, PhD

Associate Professor
Leuven BIOMAT Research Cluster–Department of Conservative Dentistry
School of Dentistry, Oral Pathology and Maxillo-Facial Surgery
Catholic University of Leuven
Kapucijnenvoer 7, B-3000, Leuven
Belgium
Marcos Vargas, DDS, MS
Associate Professor
Department of Operative Dentistry
College of Dentistry
The University of Iowa
Iowa City, IA
Satoshi Inoue, DDS, PhD
Assistant Professor
Section of Cariology, Operative Dentistry and Endodontics
Department of Oral Health Science
Hokkaido University Graduate School of Dental Medicine
Sapporo, Japan
144 Operative Dentistry Supplement 6

Yasuhiro Yoshida, DDS, PhD

Research Associate
Department of Biomaterials Science
Hiroshima University Faculty of Dentistry
Hiroshima, Japan
Marleen Peumans, DDS, PhD
Research Associate and Clinical Instructor
Leuven BIOMAT Research Cluster–Department of Conservative Dentistry
School of Dentistry, Oral Pathology and Maxillo-Facial Surgery
Catholic University of Leuven
Kapucijnenvoer 7, B-3000, Leuven
Belgium
Paul Lambrechts, DDS, PhD
Professor
Leuven BIOMAT Research Cluster–Department of Conservative Dentistry
School of Dentistry, Oral Pathology and Maxillo-Facial Surgery
Catholic University of Leuven
Kapucijnenvoer 7, B-3000, Leuven
Belgium
Guido Vanherle, MD, DDS
Professor
Leuven BIOMAT Research Cluster–Department of Conservative Dentistry
School of Dentistry, Oral Pathology and Maxillo-Facial Surgery
Catholic University of Leuven
Kapucijnenvoer 7, B-3000, Leuven
Belgium