CH 4 L 1 (Introduction To Polymers)

Engineering Materials II
Chapter Four
Structure, Characteristics, Applications
and Processing of Polymers
Introduction to Polymers
secondary
bonding
Linear Branched Cross-Linked Network

Why Study Polymer Structures
 A relatively large number of chemical and structural characteristics
affect the properties and behaviors of polymeric materials. Some of
these influences are as follows:
 Degree of crystallinity of semicrystalline polymers on density,
stiffness, strength, and ductility
 Degree of crosslinking on the stiffness of rubberlike materials.
 Polymer chemistry on melting and glass-transition temperatures.
 In this chapter we explore the various structural elements of polymers,

the concepts of crystallinity and crystals in polymers, and how degree
of crystallinity is influenced by these structural elements.
 The manner in which the structural elements affect the properties of

polymer fibers will be discussed
Engineering Materials II 2
Learning Objectives
After studying this chapter you should be able to
 Understand a typical polymer molecule in terms of its chain structure
and, in addition, how the molecule may be generated from repeat
units.
 Understand and Draw repeat units for polyethylene, poly(vinyl

chloride), polytetrafluoroethylene, polypropylene, and polystyrene.
 Understand and briefly describe the types of polymer molecular

structures, stereoisomers, geometrical isomers, and copolymers.
 Understand and Cite the differences in behavior and molecular

structure for thermoplastic and thermosetting polymers.
 Understand and Briefly describe the crystalline state in polymeric

materials.
Introduction
 Polymers are extremely important materials (i.e. plastics)

 Have been known since ancient times – cellulose, wood, rubber, etc..
 Biopolymers – proteins, enzymes, DNA …
 Last ~70 years – tremendous advances in synthetic polymers
 Just like for metals and ceramics, the properties of polymers
 Thermal stability
 Mechanical properties
 Are intimately related to their molecular structure …
Introduction
 Originally natural polymers were used:

 Wood
 Rubber
 Cotton
 Wool
 Leather
 Silk
Introduction
 Polymers are extremely important materials (i.e. plastics)

 Have been known since ancient times – cellulose, wood, rubber, etc..
 Biopolymers – proteins, enzymes, DNA …
 Last ~70 years – tremendous advances in synthetic polymers
 Just like for metals and ceramics, the properties of polymers
 Thermal stability
 Mechanical properties
 Are intimately related to their molecular structure …
Introduction
Date Material Example Use
 1868 Cellulose Nitrate Figurines
 1909 Phenol-Formaldehyde Electrical equipment
 1919 Casein Beauty accessories
 1927 Cellulose Acetate Cellophane package wrapping
 1927 Polyvinyl Chloride Pipe, Synthetic Leather
 1929 Urea-Formaldehyde Lighting fixtures, Plywood glue
 1936 Acrylic Brush backs, displays
 1936 Polyvinyl Acetate Synthetic flooring
 1938 Polystyrene or Styrene Disposable utensils
 1938 Nylon (Polyamide) Hosiery
 1938 Polyvinyl Butyrate Safety glass interlayer
 1939 Polyvinylidene Chloride Saran wrap
 1939 Melamine-Formaldehyde Countertops, Cabinets
Introduction
Date Material Example Use
 1942 Polyester Clothing, Boat hulls
 1942 Polyethylene Milk Jugs
 1943 Fluorocarbon Industrial gaskets, Non-stick liners
 1943 Silicone Gaskets, Tubing, Utensils
 1947 Epoxy Glues
 1948 Acrylonitrile-Butadiene-Styrene Luggage
 1954 Polyurethane or Urethane Foam cushions, Shoe soles, Wheels
 1956 Acetal Automotive parts, Toilet parts
 1957 Polypropylene Living hinges, Safety helmets
 1957 Polycarbonate Water bottles, Eye protection
 1964 Ionomer Golf balls, Skin packages
 1964 Polyimide Gears
Structures of Polymers
 Most polymers are organic in origin
 Many organic materials are hydrocarbons; that is, they are composed
of hydrogen and carbon. Furthermore, the intramolecular bonds are
covalent.
 Each carbon atom has four electrons that may participate in covalent
bonding, whereas every hydrogen atom has only one bonding electron.
 Saturated hydrocarbons
 Each carbon singly bonded to four other atoms
 Example:
 Ethane, C2H6
 Double & triple bonds somewhat unstable
 Thus, can form new bonds H H
 Double bond found in ethylene or ethene - C2H4 C C
H H
 Triple bond found in acetylene or ethyne

Engineering Materials II - C2H2 H C C9 H
Hydrocarbons
 Bonding is highly covalent in hydrocarbons
 Carbon has four electrons that can participate in bonding, hydrogen
has only one H H
C C
 Unsaturated – species contain H H
carbon-carbon double/triple H
Ethylene
H
H
C C
bonds H
 Possible to substitute another H C C H
H
H
Acetylene Ethane
atom on the carbon
 Saturated – carbons have four
atoms attached Unsaturated Saturated
 Cannot substitute another atom
on the carbon
Isomerism
 Hydrocarbon compounds with the same composition having different
atomic arrangements
 For example, there are two isomers for butane; normal butane has the
structure
normal butane isobutane

 Some of the physical properties of hydrocarbons will depend on the
isomeric state
 For example, the boiling temperatures for normal butane and isobutane
are −0.5 𝑎𝑛𝑑 −12.30𝐶, respectively.
 Polymers are molecules (often called macromolecules) formed from a
series of building units (monomers) that repeat over and over again
H H
C *
 polymers can have a range of
* C n
molecular weights
 There are many monomers H H H H
 Can make polymers with different poly-ethylene
monomers, etc.. C
mer unit : C
H H
 n is often a very large number
 Example: we can make polyethylene with MW > 100,000! ~3600 mers
~7200 carbons
Example: ethylene
 Gas at STP
 To polymerize ethylene, typically increase T, P and/or add an initiator
H H H H
C C + R R C C
H H H H
H H H H H
H H H
Propagation
R C C + C C R C C C C
H H H H H
H H H
After many additions of monomer to the growing chain…

R* = initiator; activates the monomer to begin chain growth
 When all of 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
 Functionality is the number of bonds that a given monomer

can form.
 Bifunctional: They have two active bond that may react
to form two covalent bonds with other monomers
forming a two-dimensional chainlike molecular
structure
 Trifunctional: they have three active bonds, from which

a three-dimensional molecular network structure results
Molecular Weight Distribution
total wt of polymer
Mn 
total # of molecules
M n  x i M i
M w  w i M i
Mi = mean (middle) molecular weight of size range i
xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
 The two are different. One is essentially based on mole fractions, and the
other on weight fractions
 They will be the same if all the chains are exactly of the same MW! If not
Mw > Mn
Example Problem
 The following table lists molecular weight data for a polypropylene
material. Compute
a) the number-average molecular weight,
b) the weight-average molecular weight, and
c) the degree of polymerization.
Molecular Structure
 Physical properties of polymers depend not only on their molecular
weight/shape, but also on the difference in the chain structure
 Four main structures
 Linear polymers
 Branched polymers
 Crosslinked polymers
 Network polymers
secondary
bonding
Linear Branched Cross-Linked Network
Branched polymers
 Polymer chains can branch or the fibers may aligned parallel, as in fibers
and some plastic sheets.
 chains off the main chain (backbone)
 This leads to inability of chains to pack very closely together
 These polymers often have lower densities
 These branches are usually a result of side-reactions during the
polymerization of the main chain
 Most linear polymers can also be made in branched forms
Crosslinked polymers
 Adjacent chains attached via covalent bonds
 Carried out during polymerization or by a non-reversible reaction after
synthesis (referred to as crosslinking)
 Materials often behave very differently from linear polymers
 Many “rubbery” polymers are crosslinked to modify their mechanical
properties; in that case it is often called vulcanization
 Generally, amorphous polymers are weak and cross-linking adds
strength: vulcanized rubber is polyisoprene with sulphur cross-links:
Network polymers
 Polymers that are “trifunctional” instead of bifunctional
 There are three points on the mer that can react
 This leads to three-dimensional connectivity of the polymer backbone
 Highly crosslinked polymers can also be classified as network polymers
 Examples: epoxies, phenol-formaldehyde polymers
Molecular Configurations
 For polymers having more than one side atom or group of atoms
bonded to the main chain ((e.g., Cl, CH3), the regularity and symmetry
of the side group arrangement can significantly influence the
properties
 One arrangement is possible when the R side groups of successive

repeat units are bound to alternate carbon atoms as follows:
 This is designated as a head-to-tail configuration
Molecular Configurations
 The head-to-head configuration, occurs when R groups are bound to

adjacent chain atoms:
 In most polymers, the head-to-tail configuration predominates; often

a polar repulsion occurs between R groups for the head-to-head
configuration.
 Isomerism is also found in polymer molecules, wherein different

atomic configurations are possible for the same composition.
Molecular Configurations: Stereoisomerism
 Stereoisomerism denotes the situation in which atoms are linked
together in the same order (head-to-tail) but differ in their spatial
arrangement.
 For one stereoisomer, all of the R groups are situated on the same side
of the chain as follows:
 Isotactic configuration the carbon chain atoms shows the zigzag
pattern.
Molecular Configurations: Stereoisomerism
 Syndiotactic configuration, the R groups alternate sides of the chain.
 Atactic configuration is used for random positioning,
Molecular Configurations: Geometrical Isomerism
 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.
cis Trans
Thermoplastic and Thermosetting Polymers
 Based on how polymers respond to elevated temperatures, they are
classified as Thermoplastic and Thermosetting
Thermoplastics
 Soften when heated, and harden when cooled
 Process is totally reversible; melt and solidify without chemical
change
 This is due to the reduction of secondary forces between polymer
chains as the temperature is increased
 Most linear polymers and some branched polymers are
thermoplastics
 They support hot-forming methods such as injection-molding.
Thermoplastic and Thermosetting Polymers
 Based on how polymers respond to elevated temperatures, they are
classified as Thermoplastic and Thermosetting
Thermosets
 Harden the first time they are heated, and do not soften after
subsequent heating
 During the initial heat treatment, covalent linkages are formed
between chains (i.e. the chains become cross-linked)
 Polymer won’t melt with heating – heat high enough, it will degrade
 Network/crosslinked polymers are typically thermosets
Copolymers
Polymer Crystallinity
 Atomic arrangement in
polymer crystals is more
complex than in metals or
ceramics
 Unit cells are typically large
and complex
Polyethylene
 Polymer molecules are often

partially crystalline (semi-
crystalline), with crystalline
regions dispersed within
amorphous material.
Degree of crystallinity is determined by:
 Rate of cooling during solidification: time is necessary for chains to
move and align into a crystal structure
 Mer complexity: crystallization less likely in complex structures, simple
polymers, such as polyethylene, crystallize relatively easily
 Chain configuration: linear polymers can crystallize, branches inhibit
crystallization, network polymers almost completely amorphous, cross-
linked polymers can be crystalline or amorphous
 Isomerism: isotactic, syndiotactic polymers can crystallize - geometrical
regularity allows chains to fit together, atactic difficult to crystallize
 Copolymerism: crystallize if mer arrangements are more regular -
alternating, block can crystallize more easily as compared to random
and graft
 More crystallinity: higher density, more strength, higher resistance to
dissolution and softening by heating
 Crystalline polymers are denser than amorphous polymers, so the
degree of crystallinity can be obtained from the measurement of
density:
c (  s  a )
% crystallinity   100
 s ( c  a )
 c: Density of perfect crystalline polymer
 a: Density of completely amorphous polymer
 s: Density of partially crystalline polymer that we are analyzing
Molecular Weight & Crystallinity
 Molecular weight, Mw: Mass of a mole of chains.
smaller M w larger M w
 Tensile strength (TS):

 Often increases with Mw.
 Because longer chains are entangled (anchored) better.
 % Crystallinity: % of material that
is crystalline.
crystalline
 TS and E often increase with % region
crystallinity.
 Annealing causes crystalline amorphous
region
regions to grow. % crystallinity
increases.
Stress – Strain Behavior
 Stress-strain behavior can be

 Brittle (A),
 Plastic (B), and
 Highly Elastic (C)
 Curve C is totally elastic
(rubber-like elasticity). This
class of polymers are
elastomers
 Elastic Modulus – defined as for metals

 Ductility (%EL) – defined as for metals
 Yield strength – For plastic polymers (B)
 maximum on curve just after the elastic
region (different from metals)
 Tensile strength is defined at the
fracture point and can be lower than the
yield strength (different from metals)
 Moduli of elasticity
 Polymers: ~ 10 MPa - 4 GPa
 Metals: ~ 50 - 400 GPa
 Tensile strengths
 Polymers: ~ 10 - 100 MPa
 Metals: 100’s - 1000’s MPa
 Elongation
 Polymers: up to 1000 % in some cases
 Metals: < 100%
 Mechanical properties of polymers change dramatically with
temperature, going from glass-like brittle behavior at low temperatures to
a rubber-like behavior at high temperatures.
 Polymers are also very sensitive to

the rate of deformation (strain rate).
Decreasing rate of deformation has
the same effect as increasing T.
 Temperature increase leads to:
 Decrease in elastic modulus
 Reduction in tensile strength
 Increase in ductility
Deformation of Semi-crystalline Polymers
 Semi-crystalline polymers: crystalline regions separated by amorphous
material
 Elastic deformation: Elongation (straightening) of chain molecules in
direction of applied stress.
 Elastic modulus: determined by elastic properties of amorphous and
crystalline regions and the microstructure.
Plastic of Semicrystalline Polymers
 Plastic deformation: defined by interaction between crystalline and
amorphous regions and is partially reversible.
Stages of plastic deformation:

1. elongation of Initial
structure
amorphous tie chains
2. tilting of lamellar
crystallites towards the
tensile axis
3. separation of crystalline
block segments 3 4
4. stretching of crystallites 1 2
and amorphous
Plastic of Semicrystalline Polymers
 Necking : Neck gets stronger since deformation aligns the chains and
increases local strength in the neck region (up to 2-5 times)  neck
expands Chains in neck align along
elongation direction:
strengthening
Elongation by
extension of
neck
 Different from ductile metals where the deformation is confined in the

initial neck region.
Factors that Influence Mechanical properties
 Temperature and strain rate
 Chain entanglement, strong intermolecular bonding (van der Waals,
cross-links) increase strength
 Drawing, analog of work hardening in metals, corresponds to neck
extension. Is used in production of fibers and films. Molecular chains
become highly oriented  properties of drawn material are anisotropic
(perpendicular to the chain alignment direction strength is reduced)
 Heat treatment: changes crystal size and order
 undrawn material: Increasing annealing temperature leads to
 increase in elastic modulus
 increase in yield/tensile strength
 decrease in ductility.
 (changes are opposite to metals)
 drawn material: opposite changes (due to recrystallization and loss of
chain orientation)
Factors that Influence Mechanical properties
 Tensile strength increases with molecular weight – effect of entanglement
 Higher degree of crystallinity – stronger secondary bonding - stronger and
more brittle
Viscoelasticity
 Amorphous polymer: glass at low temperatures, rubber at intermediate
temperatures, viscous liquid at high T.
 Low temperatures: elastic deformation at small strains ( = E).
Deformation is instantaneous when load is applied. Deformation is
reversible.
 High temperatures: viscous. Deformation is time dependent and not
reversible.
 Intermediate temperatures: viscoelastic behavior. Instantaneous elastic
strain followed by viscous time dependent strain.
 Viscoelastic behavior determined by rate of strain (elastic for rapidly
applied stress, viscous for slowly applied stress)
 Rate dependence of
viscoelastic properties in
a silicone polymer (Silly
Putty).
Tensile Response: Brittle and Plastic
Stress-strain curves
Near Failure (MPa)

brittle failure
60 x
near
onset of
failure
necking p lastic failure
40 x
Initial
20 unload/reload
0 
0 2 4 6 8
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Predeformation by Drawing
 Drawing
 stretches the polymer prior to use
 aligns chains to the stretching direction
 Results of drawing:
 increases the elastic modulus (E) in the stretching dir.
 increases the tensile strength (TS) in the stretching dir.
 decreases ductility (%EL)
 Annealing after drawing

 decreases alignment
 reverses effects of drawing.
 Compare to cold working in metals!
Tensile Response: Elastomer Case
Stress-strain curves
(MPa)
x
60 brittle failure
plastic failure
40 x
20 x
elastomer
final : chains
0
0 2 4 6  8
are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, heavily cross-linked. is reversible!
 Compare to responses of other polymers:

 brittle response (aligned, cross linked & networked case)
 plastic response (semi-crystalline case)
Thermoplastics Vs Thermosets
 Thermoplastics: T
 little cross linking Callister,
rubber
viscous
 ductile mobile liquid
Fig. 16.9
Tm
 soften w/heating liquid tough
 polyethylene (#2) plastic
Tg
 polypropylene (#5)
 polycarbonate partially
crystalline
 polystyrene (#6) crystalline
solid
solid
Molecular weight
 Thermosets:
 large cross linking (10 to 50% of mers)
 hard and brittle
 do NOT soften w/heating
 vulcanized rubber, epoxies, polyester resin, phenolic resin
Temperature and Strain Rate: Thermoplastics
 Decreasing T
 increases E
 increases TS
 decreases %EL
 Increasing strain rate...
 same effects as decreasing T.
(MPa)
80 4°C Data for the
semicrystalline
60 polymer: PMMA
20 °C (Plexiglas)
40 40 °C
20
to 1.3
60°C
0
0 0.1 0.2  0.3
Time Dependent Deformation
 Stress relaxation test:  Data: Large drop in Er
(amorphous
 strain to eo and hold. for T > Tg. polystyrene)
 observe decrease in stress with 10 5 rigid solid
E r (10s) (small relax)
time. 3
in MPa 10
transition
tensile test 10 1 region
o strain 10 -1
viscous liquid
( t ) 10 -3 (large relax)
60 10 0 140 180 T(°C)
time Tg
 Sample Tg(C) values:

 Relaxation modulus: -110
PE (low Mw)
(t ) PE (high Mw) - 90
E r (t )  PVC
+ 87
o PS
+100
+150
PC
Summary
 General drawbacks to polymers:
 E, sy, Kc, Tapplication are generally small.
 Deformation is often T and time dependent.
 Polymers benefit from composite reinforcement.
 Thermoplastics (PE, PS, PP, PC):
 Smaller E, sy, Tapplication
 Larger Kc
 Easier to form and recycle
 Elastomers (rubber): Large reversible strains!
 Thermosets (epoxies, polyesters):
 Larger E, sy, Tapplication
 Smaller K

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Engineering Materials II

Linear Branched Cross-Linked Network

 In this chapter we explore the various structural elements of polymers,

 The manner in which the structural elements affect the properties of

 Understand and Draw repeat units for polyethylene, poly(vinyl

 Understand and briefly describe the types of polymer molecular

 Understand and Cite the differences in behavior and molecular

 Understand and Briefly describe the crystalline state in polymeric

 Polymers are extremely important materials (i.e. plastics)

 Originally natural polymers were used:

 Polymers are extremely important materials (i.e. plastics)

 Triple bond found in acetylene or ethyne

normal butane isobutane

After many additions of monomer to the growing chain…

 Chains may be composed of two or more different repeat

 Functionality is the number of bonds that a given monomer

 Trifunctional: they have three active bonds, from which

Linear Branched Cross-Linked Network

 One arrangement is possible when the R side groups of successive

 The head-to-head configuration, occurs when R groups are bound to

 In most polymers, the head-to-tail configuration predominates; often

 Isomerism is also found in polymer molecules, wherein different

 Atactic configuration is used for random positioning,

 Polymer molecules are often

 Tensile strength (TS):

 Stress-strain behavior can be

 Elastic Modulus – defined as for metals

 Polymers are also very sensitive to

Stages of plastic deformation:

 Different from ductile metals where the deformation is confined in the

Near Failure (MPa)

 Annealing after drawing

 Compare to responses of other polymers:

 Sample Tg(C) values:

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