Characteristics, Applications

and Processing of Polymers

 Table of Contents
• Introduction
• The Glass Transition
• Stress strain behavior
• Melting and Glass Transition Temperature
• Macroscopic Deformation
• Viscoelastic Deformation
• Plastics

• Fracture of Polymers • Fibers

• Miscellaneous Mechanical Characteristics • Polymetric Biometers
• Deformation of Semicrystalline Polymers
• Advance Polymetric Materials
• Factors that Influence The Mechanical Properties of
Semicrystalline Polymers • Polymerization
• Deformation of Elasstomers • Polymer Additives
• Crystallization
• Forming Techniques for Platics
• Melting
 Introduction

• This chapter discusses some of the characteristics important

to polymeric materials and the various types of polymers and
their processing techniques.
 Stress-Strain Behavior
• The mechanical properties of polymers are specified with many of the same
parameters that are used for metals that is, modulus of elasticity and yield and
tensile strengths. For many polymeric materials, the simple stress–strain test is
used to characterize some of these mechanical parameters.
 Macroscopic Deformation
• Some aspects of the macroscopic deformation of semicrystalline polymers deserve
our attention. The tensile stress–strain curve for a semicrystalline material that was
initially undeformed is shown in Figure 15.4; also included in the figure are schematic
representations of the specimen profiles at various stages of deformation. Both upper
and lower yield points are evident on the curve, which are followed by a near
horizontal region.
 Viscoelastic Deformation
• An amorphous polymer may behave like a glass at low temperatures, a rubbery solid
at intermediate temperatures [above the glass transition temperature, and a viscous
liquid as the temperature is further raised.
 Viscoelastic Relaxation Modulus
• The viscoelastic behavior of polymeric materials is dependent on
both time and temperature; several experimental techniques may be
used to measure and quantify this behavior. Stress relaxation
measurements represent one possibility.
• The stress necessary to maintain this strain is measured as a function
of time while temperature is held constant. Stress is found to
decrease with time because of molecular relaxation processes that
take place within the polymer.
Er(t)
Er(t) = 𝜎(t)/𝜀0
 Miscellaneous Characteristics
• Impact Strength
The degree of resistance of a polymeric material to impact loading may be of concern
in some applications. Izod or Charpy tests are ordinarily used to assess impact
strength. As with metals, polymers may exhibit ductile or brittle fracture under impact
loading conditions, depending on the temperature, specimen size, strain rate, and
mode of loading, as discussed in the preceding section.
• Fatigue Polymers
may experience fatigue failure under conditions of cyclic loading. As with metals,
fatigue occurs at stress levels that are low relative to the yield strength. Fatigue
testing in polymers has not been nearly as extensive as with metals; however, fatigue
data are plotted in the same manner for both types of material, and the resulting
curves have the same general shape.
 Deformation of SemiCrystalline
Polymers
• each spherulite consists of numerous chain-folded ribbons, or lamellae, that radiate
outward from the center. Separating these lamellae are areas of amorphous
material (Figure 14.13); adjacent lamellae are connected by tie chains that pass
through these amorphous regions.
• Mechanism of Elastic Deformation
As with other material types, elastic deformation of polymers occurs at relatively low
stress levels on the stress–strain curve (Figure 15.1). The onset of elastic deformation
for semicrystalline polymers results from chain molecules in amorphous regions
elongating in the direction of the applied tensile stress. This process is represented
schematically for two adjacent chain-folded lamellae and the interlamellar amorphous
material as Stage 1 in Figure 15.12.
• Mechanism of Plastic Deformation
The transition from elastic to plastic deformation occurs in Stage 3 of Figure 15.13.
(Note that Figure 15.12c is identical to Figure 15.13a.) During Stage 3, adjacent chains in
the lamellae slide past one another (Figure 15.13b); this results in tilting of the
lamellae so that the chain folds become more aligned with the tensile axis. Any chain
displacement is resisted by relatively weak secondary or van der Waals bonds.
 Factors that Influence the Machanical
Properties of Semicrystalline Polymers
• A number of factors influence the mechanical characteristics of polymeric
materials. For example, we have already discussed the effects of temperature and
strain rate on stress–strain behavior (Section 15.2, Figure 15.3). Again, increasing
the temperature or diminishing the strain rate leads to a decrease in the tensile
modulus, a reduction in tensile strength, and an enhancement of ductility.
• Molecular Weight
The magnitude of the tensile modulus does not seem to be directly influenced by
molecular weight. On the other hand, for many polymers it has been observed
that tensile strength increases with increasing molecular weight. T S is a function
of the number average molecular weight, where TS∞ is the tensile strength at
infinite molecular weight and A is a constant. The behavior described by this
equation is explained by increased chain entanglements with rising M n.
• TS = TS∞ − A/Mn
• Degree of Crystallinity
For a specific polymer, the degree of crystallinity can have a significant influence
on the mechanical properties because it affects the extent of the intermolecular
secondary bonding. For crystalline regions in which molecular chains are closely
packed in an ordered and parallel arrangement, extensive secondary bonding
typically exists between adjacent chain segments.
• Predeformation by Drawing
On a commercial basis, one of the most important techniques used to improve
mechanical strength and tensile modulus is to permanently deform the polymer in
tension. This procedure is sometimes termed drawing and it corresponds to the
neck extension process illustrated schematically in Figure 15.4.
• Heat-Treating
Heat-treating (or annealing) of semicrystalline polymers can lead to an increase in
the percent crystallinity and crystallite size and perfection, as well as to
modifications of the spherulite structure.
 Deformation of Elastomers
• One of the fascinating properties of the elastomeric materials is their rubberlike
elasticity that is, they have the ability to be deformed to quite large deformations
and then elastically spring back to their original form. This results from crosslinks in
the polymer that provide a force to restore the chains to their undeformed
conformations.
• In an unstressed state, an elastomer is amorphous and composed of crosslinked
molecular chains that are highly twisted, kinked, and coiled. Elastic deformation
upon application of a tensile load is simply the partial uncoiling, untwisting, and
straightening and resultant elongation of the chains in the stress direction, a
phenomenon represented in Figure 15.15.
• Vulcanization
The crosslinking process in elastomers is called vulcanization, which is achieved by a
nonreversible chemical reaction, typically carried out at an elevated temperature. In most
vulcanizing reactions, sulfur compounds are added to the heated elastomer; chains of sulfur
atoms bond with adjacent polymer backbone chains and crosslink them, which is accomplished
according to the following reaction:

• in which the two crosslinks shown consist of m and n sulfur atoms. Crosslink main-chain sites
are carbon atoms that were doubly bonded before vulcanization but, after vulcanization, have
become singly bonded.
• Unvulcanized rubber, which contains very few crosslinks, is soft and tacky and has poor
resistance to abrasion. Modulus of elasticity, tensile strength, and resistance to degradation by
oxidation are all enhanced by vulcanization. The magnitude of the modulus of elasticity is
directly proportional to the density of the crosslinks.
 Crystallization
• An understanding of the mechanism and kinetics of polymer crystallization is
important because the degree of crystallinity influences the mechanical and
thermal properties of these materials. The crystallization of a molten polymer
occurs by nucleation and growth processes, topics discussed in the context of
phase transformations for metals.
• The time dependence of crystallization is the same as for many solid-state
transformations that is, a sigmoidal-shaped curve results when fraction
transformation is plotted versus the logarithm of time.
y = 1 − exp(−kt^n )
 Melting
• The melting of a polymer crystal corresponds to the transformation of a solid
material, having an ordered structure of aligned molecular chains, into a viscous
liquid in which the structure is highly random. This phenomenon occurs, upon
heating, at the melting temperature, Tm.
 The Glass Transition

• The glass transition occurs in amorphous (or glassy) and semicrystalline polymers
and is due to a reduction in motion of large segments of molecular chains with
decreasing temperature. Upon cooling, the glass transition corresponds to the
gradual transformation from a liquid into a rubbery material and finally into a rigid
solid. The temperature at which the polymer experiences the transition from
rubbery into rigid states is termed the glass transition temperature, Tg.
 Melting and Glass Transition Temperature
• Melting and glass transition temperatures are important parameters relative to
inservice applications of polymers. They define, respectively, the upper and lower
temperature limits for numerous applications, especially for semicrystalline
polymers. The glass transition temperature may also define the upper use
temperature for glassy amorphous materials. Furthermore, Tm and Tg also influence
the fabrication and processing procedures for polymers and polymer–matrix
composites. These issues are discussed in succeeding sections of this chapter.
 FACTORS THAT INFLUENCE MELTING AND GLASS
TRANSITION TEMPERATURES
• Melting Temperature
During melting of a polymer there is a rearrangement of the molecules in the
transformation from ordered to disordered molecular states. Molecular chemistry
and structure influence the ability of the polymer chain molecules to make these
rearrangements and, therefore, also affect the melting temperature.
• Glass Transition Temperature
Upon heating through the glass transition temperature, the amorphous solid polymer
transforms from a rigid into a rubbery state. Correspondingly, the molecules that are
virtually frozen in position below Tg begin to experience rotational and translational
motions above Tg. Thus, the value of the glass transition temperature depends on
molecular characteristics that affect chain stiffness; most of these factors and their
influences are the same as for the melting temperature, as discussed earlier. Again,
chain flexibility is decreased and Tg is increased by the presence of the following:
• 1. Bulky side groups; from Table 15.2, the respective Tg values for polypropylene
and polystyrene are −18°C and 100°C.
• 2. Polar groups; for example, the Tg values for poly(vinyl chloride) and
polypropylene are 87°C and −18°C, respectively.
• 3. Double bonds and aromatic groups in the backbone, which tend to stiffen the
polymer chain.
 PLASTICS
• Possibly the largest number of different polymeric materials come under the
plastic classification. Plastics are materials that have some structural rigidity under
load and are used in general-purpose applications. Polyethylene, polypropylene,
poly(vinyl chloride), polystyrene, and the fluorocarbons, epoxies, phenolics, and
polyesters may all be classified as plastics. They have a wide variety of
combinations of properties. Some plastics are very rigid and brittle Others are
flexible, exhibiting both elastic and plastic deformations when stressed and
sometimes experiencing considerable deformation before fracture.
• Polymers falling within this classification may have any degree of crystallinity, and
all molecular structures and configurations (linear, branched, isotactic, etc.) are
possible. Plastic materials may be either thermoplastic or thermosetting; in fact,
this is the manner in which they are usually subclassified.
 ELASTOMERS
• The characteristics of and deformation mechanism for elastomers were treated
previously (Section 15.9). The present discussion, therefore, focuses on the types
of elastomeric materials.
 FIBERS
• Fiber polymers are capable of being drawn into long filaments
having at least a 100:1 length-to-diameter ratio. Most commercial
fiber polymers are used in the textile industry, being woven or knit
into cloth or fabric. In addition, the aramid fibers are employed in
composite materials.
• While in use, fibers may be subjected to a variety of mechanical
deformations stretching, twisting, shearing, and abrasion. Also
The molecular weight of fiber materials should be relatively high
or the molten material will be too weak and will break during the
drawing process. Also, because the tensile strength increases with
degree of crystallinity, the structure and configuration of the
chains should allow the production of a highly crystalline polymer.
 MISCELLANEOUS APPLICATIONS
• Coatings
Coatings are frequently applied to the surface of materials to serve one or more of
the following functions:
(1) to protect the item from the environment, which may produce corrosive or
deteriorative reactions;
(2) to improve the item’s appearance; and
(3) to provide electrical insulation.
• Adhesives
An adhesive is a substance used to bond together the surfaces of two solid materials
(termed adherends). There are two types of bonding mechanisms: mechanical and
chemical. In mechanical bonding there is actual penetration of the adhesive into
surface pores and crevices
• Films
Polymeric materials have found widespread use in the form of thin films. Films
having thicknesses between 0.025 and 0.125 mm (0.001 and 0.005 in.) are
fabricated and used extensively as bags for packaging food products and other
merchandise, as textile products, and in a host of other uses.

• Foams
Foams are plastic materials that contain a relatively high volume percentage of
small pores and trapped gas bubbles. Both thermoplastic and thermosetting
materials are used as foams; these include polyurethane, rubber, polystyrene, and
poly(vinyl chloride).
 POLYMERIC BIOMATERIALS
• Polymer biomaterials may be divided into two main classifications: synthetic
(manmade) and natural (derived from plants or animals). Furthermore, relative
to degree of stability in the body environment, they may also be further
classified as either biodegradable or nonbiodegradable.
• On the other hand, nonbiodegradable (or biostable) polymers are designed to be
nonreactive with body fluids and tissues; any deterioration of these materials is
imperceptively slow.
• Polypropylene
The salient bioperformance properties of polypropylene include low tissue
reactivity and exceptional flexural fatigue life. On the other hand, in some
environments it experiences oxidation and may crack.
• Ultra-High-Molecular-Weight Polyethylene
Ultra-high-molecular-weight polyethylene (one of the advanced polymeric
materials discussed in Section 15.20) is used in some important biomedical
applications. When crosslinked (chemically or by ionizing radiation), UHMWPE
materials are extremely resistant to wear and abrasion, have very low coefficients
of friction, and offer selflubricating and nonstick surfaces.
• Poly(methyl methacrylate)
Poly(methyl methacrylate) and some of its copolymers possess several desirable
bioperformance attributes to include hardness, chemical inertness,
biocompatibility, optical transparency (of the pure material), and ease of synthesis
and fabrication at room temperature.
• Polytetrafluoroethylene
Polytetrafluoroethylene has a high degree of chemical stability in the body
environment as a result of its strong carbon–fluorine interatomic bonds;
furthermore, PTFE is not wetted by water (is hydrophobic) and has an extremely
low coefficient of friction.
• Silicones
The silicones have a diverse set of desirable bioproperties and are used in a wide
variety of application types. Depending on degree of crosslinking, silicones can be
prepared to exist as elastomers, gels, and fluids.
• Gas-permeable membranes in extended-wear contact lenses and intraocular lenses
• Catheters, drains, and shunts
• Orthopedic implants—hand and foot joints
• Aesthetic implants—breast and facial feature reconstructions (e.g., nose, chin, and
ear)
• Coatings for hypodermic needles, syringes, and blood-collecting devices
• Transdermal drug delivery
• Dental impression materials
• Poly(ethylene terephthalate)
The most notable biomaterial property of poly(ethylene terephthalate) (having the
trade name Dacron) is blood compatibility—when in contact with blood, PET does not
promote clotting.
 ADVANCED POLYMERIC MATERIALS

• A number of new polymers having unique and desirable combinations of properties

have been developed in recent years; many have found niches in new technologies
and/or have satisfactorily replaced other materials.
• Ultra-High-Molecular-Weight Polyethylene
Ultra-high-molecular-weight polyethylene (UHMWPE) is a linear polyethylene that
has an extremely high molecular weight. Its typical Mw is approximately 4 × 106
g/mol, which is an order of magnitude greater than that of high-density polyethylene.
1.An extremely high impact resistance
2. Outstanding resistance to wear and abrasion
3. A very low coefficient of friction
4. A self-lubricating and nonstick surface
5. Very good chemical resistance to normally encountered solvents
6. Excellent low-temperature properties
7. Outstanding sound damping and energy absorption characteristics
8. Electrically insulating and excellent dielectric properties
• Liquid Crystal Polymers
Liquid crystal polymers (LCPs) are a group of chemically complex and structurally
distinct materials that have unique properties and are used in diverse applications.
LCPs are composed of extended, rod-shaped, and rigid molecules.

• Thermoplastic Elastomers
Thermoplastic elastomers (TPEs or TEs) are a type of polymeric material that, at
ambient conditions, exhibits elastomeric (or rubbery) behavior yet is thermoplastic
(Section 14.9). By way of contrast, most elastomers heretofore discussed are
thermosets because they are crosslinked during vulcanization.
 POLYMERIZATION
• The synthesis of these large molecules (polymers) is termed polymerization; it is
simply the process by which monomers are linked together to generate long chains
composed of repeat units. Most generally, the raw materials for synthetic polymers
are derived from coal, natural gas, and petroleum products.

• Addition Polymerization
Addition polymerization (sometimes called chain reaction polymerization) is a
process by which monomer units are attached one at a time in chainlike fashion to
form a linear macromolecule. The composition of the resultant product molecule is
an exact multiple of that of the original reactant monomer.
• Condensation Polymerization
Condensation (or step reaction) polymerization is the formation of polymers by
stepwise intermolecular chemical reactions that may involve more than one
monomer species.
 POLYMER ADDITIVES
• Most of the properties of polymers discussed earlier in this chapter are intrinsic ones
that is, they are characteristic of or fundamental to the specific polymer. Some of
these properties are related to and controlled by the molecular structure.

• Fillers
Filler materials are most often added to polymers to improve tensile and compressive
strengths, abrasion resistance, toughness, dimensional and thermal stability, and
other properties. Materials used as particulate fillers include wood flour (finely
powdered sawdust), silica flour and sand, glass, clay, talc, limestone, and even some
synthetic polymers.
• Plasticizers
The flexibility, ductility, and toughness of polymers may be improved with the aid of
additives called plasticizers. Their presence also produces reductions in hardness and
stiffness. Plasticizers are generally liquids with low vapor pressures and low
molecular weights.
• Stabilizers
Some polymeric materials, under normal environmental conditions, are subject to
rapid deterioration, generally in terms of mechanical integrity. Additives that
counteract deteriorative processes are called stabilizers
• Colorants
Colorants impart a specific color to a polymer; they may be added in the form of dyes
or pigments. The molecules in a dye actually dissolve in the polymer. Pigments are
filler materials that do not dissolve but remain as a separate phase; normally, they
have a small particle size and a refractive index near that of the parent polymer.
• Flame Retardants
The flammability of polymeric materials is a major concern, especially in the
manufacture of textiles and children’s toys.
 FORMING TECHNIQUES FOR PLASTICS
• Quite a variety of different techniques are employed in the forming of polymeric
materials. The method used for a specific polymer depends on several factors: (1)
whether the material is thermoplastic or thermosetting; (2) if thermoplastic, the
temperature at which it softens; (3) the atmospheric stability of the material being
formed; and (4) the geometry and size of the finished product.
• Fabrication of polymeric materials normally occurs at elevated temperatures and
often by the application of pressure. Thermoplastics are formed above their glass
transition temperatures, if amorphous, or above their melting temperatures, if
semicrystalline.
• Compression and Transfer Molding
For compression molding, the appropriate amounts of thoroughly mixed polymer
and necessary additives are placed between male and female mold members, as
illustrated in Figure 15.23. Both mold pieces are heated; however, only one is
movable.
• Injection Molding
Injection molding the polymer analogue of die casting for metals—is the most
widely used technique for fabricating thermoplastic materials. A schematic cross
section of the apparatus used is illustrated in Figure 15.24. The correct amount of
pelletized material is fed from a feed hopper into a cylinder by the motion of a
plunger or ram.
• Extrusion
The extrusion process is the molding of a viscous thermoplastic under pressure
through an open-ended die, similar to the extrusion of metals (Figure 11.9c). A
mechanical screw or auger propels the pelletized material through a chamber, where it
is successively compacted, melted, and formed into a continuous charge of viscous
fluid (Figure 15.25).
• Blow Molding
The blow-molding process for the fabrication of plastic containers is similar to that
used for blowing glass bottles, as represented in Figure 13.15. First, a parison, or
length of polymer tubing, is extruded.

• Casting
Like metals, polymeric materials may be cast, as when a molten plastic material is
poured into a mold and allowed to solidify. Both thermoplastic and thermosetting
plastics may be cast.