UNIT VI.

POLYMERIC MATERIALS

Topic Outline:

⚫ Polymers
⚫ Types of polymer molecular structures
⚫ Stereoisomerism of polymers
⚫ Mechanical properties of polymers
⚫ Types of polymeric materials
⚫ Polymer synthesis and processing

Learning Objectives:

After careful study of this chapter, you should be able to do the following:

✓ Describe a typical polymer molecule in terms of its chain structure and, in addition,
how the molecule may be generated from repeat units;
✓ Name and briefly describe: (a) the four general types of polymer molecular structures,
(b) the three types of stereoisomers, (c) the two kinds of geometrical isomers and (d)
the four types of copolymers;
✓ Cite the differences in behavior and molecular structure for thermoplastic and
thermosetting polymers;
✓ Make schematic plots of the three-characteristic stress–strain behaviors observed for
polymeric materials;
✓ Cite the seven different polymer application types and, for each, note its general
characteristics;
✓ Briefly describe addition and condensation polymerization mechanisms;
✓ Name the five types of polymer additives and, for each, indicate how it modifies the
properties and;

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✓ Name and briefly describe five fabrication techniques used for plastic polymers.
POLYMER MOLECULES

Polymers are gigantic in comparison to the hydrocarbon molecules because of their

size they are often referred to as macromolecules. These long molecules are composed of
structural entities called repeat units, which are successively repeated along the chain. The
term monomer refers to the small molecule from which a polymer is synthesized. Hence,
monomer and repeat unit mean different things, but sometimes the term monomer or
monomer unit is used instead of the more proper term repeat unit.

Polymers can be classified as organic and inorganic polymers:

⚫ Inorganic polymers – cement, glass, sand, clays

⚫ Organic polymer can be synthetic or natural:

➢ Synthetic polymers – adhesives, fibers, coatings, rubbers

➢ Natural polymers – polysaccharides, proteins, DNA, polyisoprene rubber

Figure 1. Schematic representation of repeat unit.

Adapted from Materials science and engineering
an introduction (7th ed.) (page 494)., by W. D.
Callister, Jr., 2007, John Wiley & Sons, Inc.

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Table 6.1 Common polymeric materials and structure of repeat unit. Adapted from
Materials science and engineering an introduction (7th ed.) (page 497)., by W. D. Callister,
Jr., 2007, John Wiley & Sons, Inc.

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A. Types of polymer molecular structures

⚫ Linear polymers are those in which the repeat units are joined together end to end in
single chains. These long chains are flexible and may be thought of as a mass of
spaghetti, where each circle represents a repeat unit.

⚫ Polymers may be synthesized in which side-branch chains are connected to the main
ones; these are fittingly called branched polymers. The branches, considered to be part
of the main-chain molecule, may result from side reactions that occur during the
synthesis of the polymer.

⚫ In crosslinked polymers, adjacent linear chains are joined one to another at various
positions by covalent bonds. The process of crosslinking is achieved either during
synthesis or by a nonreversible chemical reaction. Often, this crosslinking is
accomplished by additive atoms or molecules that are covalently bonded to the chains.
Many of the rubber elastic materials are crosslinked; in rubbers, this is called
vulcanization.

⚫ Multifunctional monomers forming three or more active covalent bonds, make three-
dimensional networks and are termed network polymers. Actually, a polymer that is
highly crosslinked may also be classified as a network polymer. These materials have
distinctive mechanical and thermal properties; the epoxies, polyurethanes, and phenol-
formaldehyde belong to this group.

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 Figure 6.2 Schematic representations of (A) linear, (B) branched, (C) crosslinked, and
(D) network (three-dimensional) molecular structures. Circles designate individual repeat
units. Adapted from Materials science and engineering an introduction (7th ed.) (page
502)., by W. D. Callister, Jr., 2007, John Wiley & Sons, Inc.
B. Types of polymers based on stereoisomerism

For one stereoisomer, all the R groups are situated on the same side of the chain as
follows:

or

This is called an isotactic configuration.

In a syndiotactic configuration, the R groups alternate sides of the chain:

or

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 And for random positioning, the term atactic configuration is used.

or

C. Types of polymers based on geometrical stereoisomerism

Other important chain configurations, or geometrical isomers, are possible within
repeat units having a double bond between chain carbon atoms. Bonded to each of the
carbon atoms participating in the double bond is a side group, which may be situated on
one side of the chain or its opposite. Consider the isoprene repeat unit having the structure

in which the CH3 group and the H atom are positioned on the same side of the double bond.
This is termed a cis structure, and the resulting polymer, cis-polyisoprene, is natural
rubber. For the alternative isomer

the trans structure, the CH3 and H reside on opposite sides of the double bond. Trans-
polyisoprene, sometimes called gutta percha, has properties that are distinctly different
from natural rubber as a result of this configurational alteration. Conversion of trans to cis,
or vice versa, is not possible by a simple chain bond rotation because the chain double bond
is extremely rigid.

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D. Types of copolymer types

When all the repeating units along a chain are of the same type, the resulting polymer is
called a homopolymer. Chains may be composed of two or more different repeat units, in
what are termed copolymers.

-AAABAABBBAABBAAABBBBBAAAABAB- → Random copolymer: two different

units are randomly dispersed along the chain.

-ABABABABABABABABABABABABABAB- → Alternating copolymer: two repeat

units alternate chain positions.

-AAAABBBBAAAABBBBAAAABBBB- → Block copolymer: identical repeat units

are clustered in blocks along the chain.

→Graft copolymer of molecular chains to

produce an ordered atomic array: homopolymer
side branches of one type may be grafted to
homopolymer main chains that are composed of
a different repeat unit.

THERMOPLASTICS AND THERMOSETTING POLYMERS

The response of a polymer to mechanical forces at elevated temperatures is related to
its dominant molecular structure. In fact, one classification scheme for these materials is
according to behavior with rising temperature. Thermoplastics (or thermoplastic
polymers) and thermosets (or thermosetting polymers) are the two subdivisions.
Thermoplastics soften when heated (and eventually liquefy) and harden when
cooled—processes that are totally reversible and may be repeated. Irreversible degradation
results when a molten thermoplastic polymer is raised to too high of a temperature. In
addition, thermoplastics are relatively soft. Most linear polymers and those having some
branched structures with flexible chains are thermoplastic. These materials are normally
fabricated by the simultaneous application of heat and pressure. Most linear polymers are
thermoplastics. Examples of common thermoplastic polymers include polyethylene,
polystyrene, poly (ethylene terephthalate), and poly (vinyl chloride).

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 Thermosetting polymers are network polymers. They become permanently hard
during their formation, and do not soften upon heating. Thermoset polymers are generally
harder and stronger than thermoplastics and have better dimensional stability. Network
polymers have covalent crosslinks between adjacent molecular chains. During heat
treatments, these bonds anchor the chains together to resist the vibrational and rotational
chain motions at high temperatures. Thus, the materials do not soften when heated.
Crosslinking is usually extensive, in that 10 to 50% of the chain repeat units are
crosslinked. Only heating to excessive temperatures will cause severance of these crosslink
bonds and polymer degradation. Most of the crosslinked and network polymers, which
include vulcanized rubbers, epoxies, and phenolics and some polyester resins, are
thermosetting.
MECHANICAL PROPERTIES OF POLYMERS

⚫ Stress-strain behavior
Three typically different types of stress–strain
behavior was found for polymeric materials. Curve
A illustrates the stress–strain character for a brittle
polymer, in as much as it fractures while deforming
elastically. The behavior for a plastic material, curve
B, is similar to that for many metallic materials; the
initial deformation is elastic, which is followed by
yielding and a region of plastic deformation. Finally,
the deformation displayed by curve C is totally
elastic; this rubber-like elasticity (large recoverable
strains produced at low stress levels) is displayed by
a class of polymers termed the elastomers. For plastic polymers (curve B), the yield point
is taken as a maximum on the curve, which occurs just beyond the termination of the linear-
elastic region. The stress at this maximum is the yield strength (σy). Furthermore, tensile
strength (TS) corresponds to the stress at which fracture occurs; TS may be greater than or
less than σy. Strength, for these plastic polymers, is normally taken as tensile strength.

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⚫ 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. For relatively small deformations,
the mechanical behavior at low
temperatures may be elastic; that is, in
conformity to Hooke’s law. At the highest
temperatures, viscous or liquidlike
behavior prevails. For intermediate temperatures the polymer is a rubbery solid that
exhibits the combined mechanical characteristics of these two extremes; the condition is
termed viscoelasticity.

⚫ Miscellaneous Mechanical Properties

1. Impact strength – the degree of resistance of a polymeric material to impact loading

may be of concern in some applications. 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.
Both semicrystalline and amorphous polymers are brittle at low temperatures, and both
have relatively low impact strengths. However, they experience a ductile-to-brittle
transition over a relatively narrow temperature range, similar to that shown for a steel.
Of course, impact strength undergoes a gradual decrease at still higher temperatures
as the polymer begins to soften. Ordinarily, the two impact characteristics most sought
after are a high impact strength at the ambient temperature and a ductile-to-brittle
transition temperature that lies below room temperature.

2. 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.

3. Tear strength and hardness – Other mechanical properties that are sometimes
influential in the suitability of a polymer for some particular application include tear
resistance and hardness. Tear strength, the mechanical parameter that is measured, is
the energy required to tear apart a cut specimen that has a standard geometry. The

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 magnitude of tensile and tear strengths are related. As with metals, hardness represents
a material’s resistance to scratching, penetration, marring, and so on.

POLYMERIC MATERIAL TYPES

• Plastics – 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.

• Elastomers – Natural rubber is still utilized to a large degree because it has an

outstanding combination of desirable properties. However, the most important
synthetic elastomer is styrene-butadiene copolymer (SBR), which is used
predominantly in automobile tires, reinforced with carbon black. Acrylonitrile-
butadiene copolymer (NBR), which is highly resistant to degradation and swelling,
is another common synthetic elastomer.

• Fibers – The 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
utilized in the textile industry, being woven or knit into cloth or fabric. In addition,
the aramid fibers are employed in composite materials. To be useful as a textile
material, a fiber polymer must have a host of rather restrictive physical and
chemical properties. While in use, fibers may be subjected to a variety of
mechanical deformations—stretching, twisting, shearing, and abrasion.
Consequently, they must have a high tensile strength (over a relatively wide
temperature range) and a high modulus of elasticity, as well as abrasion resistance.
These properties are governed by the chemistry of the polymer chains and also by
the fiber drawing process.

• 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
that may produce corrosive or deteriorative reactions; (2) to improve the item’s
appearance; and (3) to provide electrical insulation. Many of the ingredients in
coating materials are polymers, the majority of which are organic in origin. These
organic coatings fall into several different classifications, as follows: paint, varnish,
enamel, lacquer, and shellac.

• 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. For mechanical there is actual penetration of the adhesive
into surface pores and crevices. Chemical bonding involves intermolecular forces

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 between the adhesive and adherend, which forces may be covalent and/or van der
Waals; degree of van der Waals bonding is enhanced when the adhesive material
contains polar groups.

• Films – Films are 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 a host of other uses. Important characteristics
of the materials produced and used as films include low density, a high degree of
flexibility, high tensile and tear strengths, resistance to attack by moisture and other
chemicals, and low permeability to some gases, especially water vapor. Some of
the polymers that meet these criteria and are manufactured in film form are
polyethylene, polypropylene, cellophane, and cellulose acetate.

• 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). Foams are commonly used as cushions in
automobiles and furniture as well as in packaging and thermal insulation. The
foaming process is often carried out by incorporating into the batch of material a
blowing agent that, upon heating, decomposes with the liberation of a gas. Gas
bubbles are generated throughout the now-fluid mass, which remain in the solid
upon cooling and give rise to a spongelike structure. The same effect is produced
by dissolving an inert gas into a molten polymer under high pressure. When the
pressure is rapidly reduced, the gas comes out of solution and forms bubbles and
pores that remain in the solid as it cools.

POLYMER SYNTHESIS AND PROCESSING

The large macromolecules of the commercially useful polymers must be synthesized

from substances having smaller molecules in a process termed polymerization.
Furthermore, the properties of a polymer may be modified and enhanced by the inclusion
of additive materials. Finally, a finished piece having a desired shape must be fashioned
during a forming operation. This section treats polymerization processes and the various
forms of additives, as well as specific forming procedures.

⚫ 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 for that of the original reactant monomer. Three

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 distinct stages—initiation, propagation, and termination—are involved in addition
polymerization. During the initiation step, an active center capable of propagation is
formed by a reaction between an initiator (or catalyst) species and the monomer unit.
Propagation involves the linear growth of the polymer chain by the sequential addition
of monomer units to this active growing chain molecule. Propagation may end or
terminate in different ways. First, the active ends of two propagating chains may link
together to form one molecule according to the following reaction.

⚫ Condensation polymerization – Condensation (or step reaction) polymerization is

the formation of polymers by stepwise intermolecular chemical reactions that may
involve more than one species. There is usually a small molecular weight byproduct
such as water that is eliminated (or condensed). No reactant species has the chemical
formula of the repeat unit, and the intermolecular reaction occurs every time a repeat
unit is formed. For example, consider the formation of the polyester, poly(ethylene
terephthalate) (PET), from the reaction between ethylene glycol and terephthalic acid;
the intermolecular reaction is as follows:

POLYMER ADDITIVES

⚫ Fillers – Fillers are 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. Often the fillers are inexpensive materials that replace some
volume of the more expensive polymer, reducing the cost of the final product.

⚫ 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 having low vapor pressures
and low molecular weights. The small plasticizer molecules occupy positions between
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 the large polymer chains, effectively increasing the interchain distance with a
reduction in the secondary intermolecular bonding. Plasticizers are commonly used in
polymers that are intrinsically brittle at room temperature, such as poly(vinyl chloride)
and some of the acetate copolymers. The plasticizer lowers the glass transition
temperature, so that at ambient conditions the polymers may be used in applications
requiring some degree of pliability and ductility. These applications include thin sheets
or films, tubing, raincoats, and curtains.

⚫ 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 to that of the parent
polymer. Others may impart opacity as well as color to the polymer.

⚫ Flame retardants – The flammability of polymeric materials is a major concern,

especially in the manufacture of textiles and children’s toys. Most polymers are
flammable in their pure form; exceptions include those containing significant contents
of chlorine and/or fluorine, such as poly(vinyl chloride) and polytetrafluoroethylene.
The flammability resistance of the remaining combustible polymers may be enhanced
by additives called flame retardants. These retardants may function by interfering with
the combustion process through the gas phase, or by initiating a different combustion
reaction that generates less heat, thereby reducing the temperature; this causes a
slowing or cessation of burning.

Reference:
Callister, Jr. W. D. (2007) Materials science and engineering an introduction (7th ed).
York, PA: John Wiley and Sons.

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