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Chapter 3
Polymer structure and properties
At the end of this chapter, you should be able to:

 Identify crystalline structures in polymers and how they

differ from metals.

 Understand how the tensile properties of polymers are

affected by microstructure.

 Describe the effects of temperature on polymers.

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Thermoplastic and Thermosetting

Polymers
Thermoplastics
 Soften when heated and harden when cooled (reversibly).
 Temperature is raised, secondary bonding forces are
diminished – molecules easily move against each other.
 Thermoplastics are relatively soft.
Thermosets
 Network polymers, covalent cross-links between adjacent
chains.

 Generally harder and stronger than thermoplastics and

have better dimensional stability.
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Copolymers
Copolymers: Two or more monomers polymerized together.
Random – A and B randomly vary in
chain.
random
Alternating – A and B alternate in polymer
chain.
Block – large blocks of A alternate with
alternating
large blocks of B.
Graft – chains of B grafted on to A
backbone. block

A– B–
graft

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Copolymers

Styrene–butadiene rubber (SBR):

Common random copolymer from

which automobile tires are made.

Nitrile butadiene rubber (NBR):

Automotive transmission belts, hoses,
O rings, gaskets, synthetic leather....

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Polymer crystallinity

Polymers can form crystalline (or

semicrystalline) structures.

Molecular chains ‘pack’ to produce an

ordered atomic array.

Degree of crystallinity can range

from completely amorphous to
almost entirely crystalline

Density of a crystalline polymer will Example: polyethylene unit cell

be greater than an amorphous one

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Degree of crystallinity
May be determined from accurate density measurements.

rc(rs - ra)
% crystallinity =
rs(rc - ra) X 100

rs is the density of a specimen for which the percent

crystallinity is to be determined.
ra is the density of the totally amorphous polymer.
rc is the density of the perfectly crystalline polymer.

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Degree of crystallinity
Crystallinity depends on:

 The rate of cooling during solidification – sufficient time

to allow chains to move and align.

 The nature of the repeat unit. Simple repeat units

crystallise easier

Atactic polymers are difficult to crystallise; isotactic and

syndiotactic polymers crystallise more readily

Bulky / large side groups limit crystallisation

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Polymer crystals
Semicrystalline polymer consists of small crystalline regions
(crystallites).

crystalline
region
Chain folded model

amorphous
region

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Polymer crystals

Spherulites: Fast growth –

forms lamellar (layered)
structures.
Adapted from Fig. 14.14, Callister & Rethwisch 8e.

Spherulite
surface

Photomicrograph of polyethylene using cross

polarised light.
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Polymer Mechanical Properties

Expressed in terms of modulus of
elasticity, and yield and tensile strengths
from the stress–strain test.

Sensitive to:
• Temperature
• The rate of deformation (strain rate)

• The chemical nature of the

environment (the presence of water,
oxygen, organic solvents, etc.)

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Polymer Mechanical Properties

Stress-strain behavior:
Brittle polymer – fractures when
deformed elastically.

Plastic – initially elastic

deformation followed by
plastic.
elastic modulus
less than metal
Elastomer – large
recoverable strains
produced at low stress
levels.

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Polymer Mechanical Properties

TS
σy

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Polymer mechanical properties: Temperature

Influence of T on the stress–strain characteristics of poly(methyl
methacrylate) (PMMA).
X
With an increase in
temperature:

• Decrease in
X
elastic modulus.

• Reduction in
tensile strength.
X
• Enhancement in
ductility.

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Polymer Mechanical Properties:

Viscoelasticity
Polymers can behave as glasses, a rubbery solid or viscous
liquid as a function of temperature.

Viscoelasticity: The behaviour of the polymers as rubbery

solids at an intermediate temperature.
Strain

ta Time, t tr

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Deformation of Semicrystalline Polymers

Mechanism of Elastic Deformation:

Chain molecules in amorphous regions elongate and align in the

direction of the applied tensile stress.
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Deformation of Semicrystalline Polymers

Mechanism of Plastic Deformation:

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Factors that Influence the Mechanical Properties

of Semicrystalline Polymers
 Temperature

 Molecular weight
For some polymers – TS increases with Mn

 Degree of Crystallinity:
Tensile strength increases significantly.
Material tends to become more brittle.

 Heat treating (or annealing):

Can increase the percent crystallinity and size of crystallites

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Summary

 Polymers may exhibit varying degrees of crystallinity.

 Many semicrystalline polymers form spherulites

 Polymers fall into three general categories of stress

strain behaviour; brittle, plastic and highly elastic.

 The deformation of polymers is often both time and

temperature dependent.

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