Chapter Four

Polymer Structures
 WHY STUDY Polymer Structures?
• Large number of chemical and structural
characteristics affect the properties and behaviors
of polymeric materials.
 Degree of crystallinity of semi-crystalline polymers on
density, stiffness, strength, and ductility
 Degree of crosslinking on the stiffness of rubber-like materials
 Polymer chemistry on melting and glass-transition
temperatures
 Polymer Structures

ISSUES TO ADDRESS...
• What are the general structural and chemical
characteristics of polymer molecules?
• What are some of the common polymeric
materials, and how do they differ chemically?
• How is the crystalline state in polymers
different from that in metals and ceramics ?

3
 What is a Polymer?

Poly mer
many repeat unit

repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister & Rethwisch 8e.

4
 Ancient Polymers
• Originally natural polymers were used
– Wood – Rubber
– Cotton – Wool
– Leather – Silk

• Oldest known uses

– Rubber balls used by Incas
– Noah used pitch (a natural polymer)
for the ark
5
 Polymer Composition
Most polymers are hydrocarbons
– i.e., made up of H and C
• Saturated hydrocarbons
– Each carbon singly bonded to four other atoms
– Example:
• Ethane, C2H6

H H
H
C C

H H
H

6
7
 Unsaturated Hydrocarbons
• Double & triple bonds somewhat unstable –
can form new bonds
– Double bond found in ethylene or ethene - C2H4

H H
C C
H H

H C C H

– Triple bond found in acetylene or ethyne - C2H2

8
 Isomerism
• Isomerism
– two compounds with same chemical formula can have
quite different structures
for example: C8H18
• normal-octane
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H 
H3C ( CH2 ) CH3
6
• 2,4-dimethylhexane CH3
H3C CH CH2 CH CH3
CH2
CH3
9
 Polymerization and
Polymer Chemistry
• Free radical polymerization
H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer
• Initiator: example - benzoyl peroxide
H H H
C O O C 2 C O =2R
H H H
10
Chemistry and Structure of Polyethylene
Adapted from Fig.
14.1, Callister &
Rethwisch 8e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene

11
Bulk or Commodity Polymers

12
Bulk or Commodity Polymers (cont)

13
Bulk or Commodity Polymers (cont)

14
VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions

15
 MOLECULAR WEIGHT
• Molecular weight, M: Mass of a mole of chains.

Low M

high M

Not all chains in a polymer are of the same length

— i.e., there is a distribution of molecular weights

16
 MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 14.4, Callister & Rethwisch 8e.

total wt of polymer
Mn 
total # of molecules

M n  xi Mi
M w  wi Mi

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

17
 Molecular Weight Calculation

Example: average mass of a class

Student Weight
What is the average
mass (lb)
weight of the students in
1 104 this class:
2 116 a) Based on the number fraction
of students in each mass
3 140 range?
4 143 b) Based on the weight fraction of
5 180 students in each mass range?
6 182
7 191
8 220
9 225
10 380
18
 Molecular Weight Calculation (cont.)
Solution: The first step is to sort the students into weight ranges. Using 40 lb
ranges gives the following table:

weight number of mean numberCalculateweight

the number and weight
range students weight fraction fraction
fraction of students in each weight
Ni Wi xirange as follows:
wi
mass (lb) mass (lb) Ni NiWi
xi  wi 
81-120 2 110 0.2 0.117
Ni  NiWi
121-160 2 142 0.2 0.150
161-200 3 184 0.3
For example:0.294 for the 81-120 lb range
201-240 2 223 0.2 0.237
241-280 0 -  0  2
x811200.000
  0.2
281-320 0 - 0 0.00010
321-360 0 - 0 0.0002 x 110
361-400 1 380 0.1 w 81120 
0.202  0.117
1881
total Ni NiWi  total
number 10 1881 weight 19
 Molecular Weight Calculation (cont.)
weight mean number weight
range weight fraction fraction
Wi xi wi
mass (lb) mass (lb)
81-120 110 0.2 0.117
121-160 142 0.2 0.150
161-200 184 0.3 0.294
201-240 223 0.2 0.237
241-280 - 0 0.000
281-320 - 0 0.000
321-360 - 0 0.000
361-400 380 0.1 0.202
M n   xi Mi  (0.2 x 110  0.2 x 142 + 0.3 x 184 + 0.2 x 223 + 0.1 x 380) = 188 lb

M w   wi Mi  (0.117 x 110  0.150 x 142 + 0.294 x 184

+ 0.237 x 223 + 0.202 x 380) = 218 lb
M w   wi Mi  218 lb
20
 Degree of Polymerization, DP
DP = average number of repeat units per chain

H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H DP = 6
H H H H H H H H H H H H

Mn
DP 
m

where m  average molecular weight of repeat unit

for copolymers this is calculated as follows:
m  fi mi
Chain fraction mol. wt of repeat unit i 21
Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

Adapted from Fig. 14.7, Callister & Rethwisch 8e.

22
 Polymers – Molecular Shape
Molecular Shape (or Conformation) – chain
bending and twisting are possible by rotation
of carbon atoms around their chain bonds
– note: not necessary to break chain bonds to alter
molecular shape
Adapted from Fig.
14.5, Callister &
Rethwisch 8e.

23
Chain End-to-End Distance, r

Adapted from Fig.

14.6, Callister &
Rethwisch 8e.

24
 Molecular Configurations for Polymers

Configurations – to change must break bonds

• Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H

A A
Stereoisomers are mirror
images – can’t superimpose C C
without breaking a bond E E
B D D B
mirror
plane

25
 Tacticity
Tacticity – stereoregularity or spatial arrangement of R
units along chain
isotactic – all R groups on same side syndiotactic – R groups alternate
of chain sides

H H H H H H H H H H H R H H H R
C C C C C C C C C C C C C C C C
H R H R H R H R H R H H H R H H

26
Tacticity (cont.)
atactic – R groups randomly
positioned

H H H H H R H H
C C C C C C C C
H R H R H H H R

27
 cis/trans Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
H atom and CH3 H atom and CH3 group
group on same side of on opposite sides of chain
chain

28
VMSE: Stereo and Geometrical Isomers

Manipulate and rotate polymer structures in 3-dimensions

Chapter 7 - 19 29
 ThermToplastic 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.
 Copolymers
Copolymers
Copolymers: Two or more
monomers polymerized together. random

Random – A and B randomly vary in

chain.
Alternating – A and B alternate in alternating
polymer chain.
Block – large blocks of A alternate block
with large blocks of B.
Graft – chains of B grafted on to A
backbone.
A– B– Adapted from Fig.
14.9, Callister & graft
Rethwisch 8e.
 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....
 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 Example: polyethylene unit cell

will be greater than an amorphous
one Adapted from Fig.
14.10, Callister &
Rethwisch 8e.
 Degree of crystallinity

May be determined from accurate density measurements.

c(s - a)
% crystallinity = X 100
s(c - a)

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.
 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

 Polymer crystals

Semicrystalline polymer consists of small crystalline regions

(crystallites).

crystalline
region
Chain folded model

Adapted from Fig. amorphous

14.12, Callister & region
Rethwisch 8e.

Adapted from Fig. 14.11, Callister 6e. (Fig. 14.11 is from H.W. Hayden, W.G.
Moffatt, and J. Wulff, The Structure and Properties of Materials, Vol. III,
Mechanical Behavior, John Wiley and Sons, Inc., 1965.)
 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.
Adapted from Fig. 14.13, Callister & Rethwisch 8e.
 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.)
 Polymer mechanical properties
Stress-strain behavior: Adapted from Fig. 15.1,
Callister & Rethwisch 8e.
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.
 Polymer mechanical properties

TS
σy

Adapted from Fig. 15.02,

Callister & Rethwisch 8e.
 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. Adapted from Fig. 15.03,
Callister & Rethwisch 8e.
 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.

viscoelastic
Strain

purely elastic system, totally viscous

ta Time, t tr
 Deformation of semicrystalline
polymers
Mechanism of Elastic Deformation:

Chain molecules in amorphous regions elongate and align in

the direction of the applied tensile stress.
Adapted from Fig. 15.12,
Callister & Rethwisch 8e.
 Deformation of semicrystalline
polymers
Mechanism of Plastic Deformation:

Adapted from Fig. 15.13,

Callister & Rethwisch 8e.
 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
 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.
Polymer processing and applications
 Intended Learning Outcomes

At the end of this section, you will be able to:

• Describe typical polymer applications in

relation to polymer classes.

• Describe some of the commonly used

polymer processing techniques.
 Melting and glass
transition temperatures

Tg and Tm define the upper

and lower working
temperature limits

Specific volume (ν) is the

volume occupied by a unit of
mass of a material.

Adapted from Fig. 15.18,

Callister & Rethwisch 8e.
 Factors that influence melting and
glass transition temperatures
Melting: Rearrangement of the molecules, in a
transformation from an ordered to disordered molecular state.

• Presence of double bonds - increase Tm

• Bulky or large side groups - increase Tm

• Polar groups – increase Tm

• Molecular weight (when relatively low) increases Tm

• Degree of branching - introduces defects in crystalline polymers and lowers Tm

 Factors that influence melting and
glass transition temperatures
Glass Transition Temperature: Solid polymer transforms from a
rigid to a rubbery state.

Tg increases with:
• Presence of double bonds in the backbone.
• Bulky side groups
• Polar groups
• Increasing the molecular weight

Branching - small amount lowers Tg, high amount

however elevates Tg.
Crosslinking - raises Tg .
High density of crosslinks - no glass transition.
 Polymer types

Seven categories:

Plastics
Elastomers (or rubber) Dowcorning.com

Fibres
Coatings
Adhesives
Foams Pittsburghplastics.com

Films

Wisegeek.com
 Polymer types: Plastics
Plastics:
Solid materials that have some structural rigidity under load
and are used in general-purpose applications.

Variety of properties possible!

• Rigid and brittle.
• Flexible, exhibiting both elastic and
plastic deformations.
• May have any degree of crystallinity.
• Linear or branched.

Thermoplastic or Thermosetting
 Polymer types: Elastomers

Elastomers: Experience large and reversible elastic deformations

• Natural rubber styrene

• Synthetic rubber
butadiene
• Silicone rubber

Example: polydimethylsiloxane (PDMS)

 Polymer types: Fibres

Fibres: Length/diameter ratio >100

Mainly used in the textile industry and in the manufacture of

composites (aramid fibres)

Must have high tensile strength:

• Usually highly crystalline

• Formed of linear, symmetrical chains

• Regular repeat units

• Polar function groups

 Polymer types: Other

Coatings:
Thin film of polymer on surfaces - i.e. paint, varnish.
Used to protect item, improve appearance, provide electrical insulation.

Adhesives:
Produce bond between two adherends.
Bonded via mechanical or chemical mechanism.

Films:
Blown film extrusion for packaging, etc.

Foams:
Gas bubbles in plastic for packaging, insulation.
 Polymer additives

Additives are used to improve mechanical properties, processing,

durability, etc.

Fillers:
Added to improve tensile strength & abrasion resistance,
toughness & decrease cost.
Example: carbon black in rubber

Plasticizers:
Added to reduce the glass transition temperature Tg
Migration of plasticizers can be problematic
 Polymer additives

Stabilizers:
Antioxidants
UV protectants

Lubricants:
Added to allow for easier handling during processing i.e.
‘slides’ through dies easier. Example: Na stearate.

Colorants:
Dyes or pigments for aesthetic purposes.

Flame Retardants:
Cl/F & B
 Polymer Processing

Thermoplastics Thermosets
Soften upon heating, Degrade or burn upon
harden when cooled reheating

General process: General process:

• Heat until soft • Prepolymer is
• Shape molded
• Set via cooling • Set via cooling
 Processing of polymers: Molding

Compression and transfer molding:

Used for both thermoplastics or thermosets.
Male mold

Female
mold

Adapted from Fig. 15.23,

Callister & Rethwisch 8e.
 Processing of polymers: Molding

Injection molding:
Used for thermoplastics and some thermosets (RIM)

Adapted from Fig. 15.24,

Callister & Rethwisch 8e.
Processing of polymers: Extrusion

Adapted from Fig. 15.25, Callister &

Rethwisch 8e. (Fig. 15.25 is from
Encyclopædia Britannica, 1997.)
Blown-Film Extrusion

Adapted from Fig. 15.26, Callister &

Rethwisch 8e. (Fig. 15.26 is from
Encyclopædia Britannica, 1997.)
 Summary

• Polymers are widely used as plastics,

elastomers, fibres, coatings, adhesives, films
and foams.

• Typical polymer processing includes

compression and injection moulding, extrusion
and blown film extrusion.
Thank you