CHAPTER 14:

POLYMER STRUCTURES
ISSUES TO ADDRESS...
What are the basic microstructural features?
How are polymer properties effected by
molecular weight?
How do polymeric crystals accommodate the
polymer chain?

Chapter 14 - 1

Chapter 14 Polymers
What is a polymer?
Poly
many

mer
repeat unit

repeat
unit

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Polyvinyl chloride (PVC)

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Adapted from Fig. 14.2, Callister 7e.

Chapter 14 - 2

Ancient Polymer History

Originally natural polymers were used
Wood
Rubber
Cotton
Wool
Leather
Silk
Oldest known uses
Rubber balls used by Incas
American Indians used natural rubber on
the soles of their feet
Chapter 14 - 3

Polymer Composition
Most polymers are hydrocarbons
i.e. made up of H and C
Saturated hydrocarbons
Each carbon bonded to four other atoms
H

H
C

H
C
H

CnH2n+2
Chapter 14 - 4

Chapter 14 - 5

Unsaturated Hydrocarbons
Double & triple bonds relatively reactive can
form new bonds
Double bond ethylene or ethene - CnH2n

H
C C

4-bonds, but only 3 atoms bound to C s

Triple bond acetylene or ethyne - CnH2n-2

H C C H
Chapter 14 - 6

Isomerism
Isomerism
two compounds with same chemical formula can
have quite different structures
Ex: C8H18
n-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-dimethyl hexane
CH3
H3C CH CH2 CH CH3
CH2
CH3

Chapter 14 - 7

Chemistry of Polymers
Free radical polymerization
R

H H
H H

H H

C C

R C C

H H
monomer
(ethylene)

free radical

R C C

H H

initiation

H H

H H

H H H H

C C

R C C C C

H H

H H H H

propagation

dimer

Initiator: example - benzoyl peroxide

H

C O O C
H

H
2

Q: how does termination take place?

C O

= 2R

H
8
Chapter 14 -

Chemistry of Polymers
Adapted from Fig.
14.1, Callister 7e.

Note: polyethylene is just a long HC

- paraffin is short polyethylene
Chapter 14 - 9

Bulk or Commodity Polymers

Chapter 14 - 10

Chapter 14 - 11

Chapter 14 - 12

MOLECULAR WEIGHT
Molecular weight, Mi: Mass of a mole of chains.
Lower M

higher M

total wt of polymer
Mn =
total # of molecules

M n = !x i M i
M w = !w i M i
Mw is more sensitive to
higher molecular weights
Adapted from Fig. 14.4, Callister 7e.

Chapter 14 - 13

Molecular Weight Calculation

Example: average mass of a class
Ni

Mi

# of students

mass (lb)

1
1
2
3
2
1

100
120
140
180
220
380

xi

wi

0.1
0.1
0.2
0.3
0.2
0.1

0.054
0.065
0.151
0.290
0.237
0.204

Mn

Mw

186 lb

216 lb

M n = ! xi Mi
M w = ! w i Mi

Chapter 14 - 14

Degree of Polymerization, n
n = 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

ni = 6

H H H H H H H H H H H H

H n

Poly dispersity (DP) =Mw/Mn

n=6

and is typically ~2-3

Chapter 14 - 15

End to End Distance, r

Adapted from Fig.

14.6, Callister 7e.

Chapter 14 - 16

Molecular Structures
Covalent chain configurations and strength:

secondary

bonding

Linear

B ranched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.

Chapter 14 - 17

Polymers Molecular Shape

Conformation Molecular orientation can be
changed by rotation around the bonds
note: no bond breaking needed

Adapted from Fig.

14.5, Callister 7e.

Chapter 14 - 18

Polymers Molecular Shape

Configurations to change must break bonds
Stereoisomerism
H

H
C C

H H

H R
or

C C
R

C C

H R

H H

mirror
plane
Chapter 14 - 19

Tacticity
Tacticity stereoregularity of chain
isotactic all R groups on
same side of chain

syndiotactic R groups
alternate sides

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

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

atactic R groups random

C C C C C C C C
H R H R H H H R
Chapter 14 - 20

cis/trans Isomerism

CH3

H
C C

CH2

CH2

CH3

C C

CH2

CH2
H

cis

trans

cis-isoprene
(natural rubber)

trans-isoprene
(gutta percha)

bulky groups on same side

of chain

bulky groups on opposite

sides of chain

Chapter 14 - 21

Polymer Topology

crosslink-point
Topology or skeletal structure of a polymer molecule:
main-chain
branch-point

Linear
(thermopastics, eg. nylon)

Branched
(thermoplastics)

Network
(thermosets, e.g. epoxy)
(elastomers, e.g. rubber)

Soluble, Tm

Soluble, Tm

insoluble, no Tm
Chapter 14 -

Polymer Types and Properties?

Thermoplastics
Thermosets
Elastomers
Chapter 14 -

Copolymers
two or more monomers
polymerized together
random A and B randomly
vary in chain
alternating A and B
alternate in polymer chain
block large blocks of A
alternate with large blocks of
B
graft chains of B grafted
on to A backbone
A

Adapted from Fig.

14.9, Callister 7e.

random

alternating
block

graft
Chapter 14 - 24

Polymer Crystallinity

Adapted from Fig.

14.10, Callister 7e.

Ex: polyethylene unit cell

Crystals must contain the
polymer chains in some
way
Chain folded structure
Adapted from Fig.
14.12, Callister 7e.

10 nm

Chapter 14 - 25

Polymer Crystallinity
Polymers rarely 100% crystalline
Too difficult to get all those chains
aligned
crystalline
region

Crystallinity: % of material

that is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases.
amorphous
region
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.)

Chapter 14 - 26

Polymer Crystal Forms

Single crystals only if slow careful growth

Adapted from Fig. 14.11, Callister 7e.

Chapter 14 - 27

Polymer Crystal Forms

Spherulites fast
growth forms lamellar
(layered) structures

Spherulite
surface
Nucleation site

Adapted from Fig. 14.13, Callister 7e.

Chapter 14 - 28

Spherulites crossed polarizers

Maltese cross

Adapted from Fig. 14.14, Callister 7e.

Grain boundary!

Chapter 14 - 29

Summary
Polymers are long entangled chains, typically comprised
of C,H, O and N (covalent bonding!)
linear, branched, network, hyperbranched.
Isomers are possible: Tacticity! Syndio-, Iso-, A-tactic
Polymers are a mixture of chain lengths: Mn, Mw, PD
Random, homopolymers, block-co-polymers, alternating.
Polymers can crystallize but are seldom 100% crystalline

Adapted from Fig. 14.14, Callister 7e.

Chapter 14 - 30