Chapter 14:

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 ?

Chapter 14 - 1
 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 9e.

Chapter 14 - 2
 Ancient Polymers
• Originally _______________ were used
– Wood – _________
– Cotton – Wool
– __________ – Silk

• Oldest known uses

– Rubber balls __________
– Noah used ______ (a natural polymer)
for the ark

Chapter 14 - 3
 Polymer Composition
Most polymers are _________________
– i.e., made up of H and C
• Saturated hydrocarbons
– Each __________ singly bonded to four other atoms
– Example:
• Ethane, C2H6

H H
H
C C

H H
H

Chapter 14 - 4
Chapter 14 - 5
 Unsaturated Hydrocarbons
• _______________ somewhat unstable – can
form new bonds
– ______ bond found in ethylene or ethene - C2H4
H H
C C
H H

– ______ bond found in acetylene or ethyne - C2H2

H C C H

Chapter 14 - 6
 Isomerism
• _______________
– two __________ with same ______________ 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

Chapter 14 - 7
 Polymerization and
Polymer Chemistry
• ________________ 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
propagation
H H H H H H H H
dimer
• __________: example - benzoyl peroxide

H H H
C O O C 2 C O =2R
H H H

Chapter 14 - 8
 Chemistry and Structure of
Polyethylene
Adapted from Fig.
14.1, Callister &
Rethwisch 9e.

Note: ___________ is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene

Chapter 14 - 9
Bulk or Commodity Polymers

Chapter 14 - 10
Bulk or Commodity Polymers (cont)

Chapter 14 - 11
Bulk or Commodity Polymers (cont)

Chapter 14 - 12
VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions

Chapter 14 - 13
 MOLECULAR WEIGHT
• Molecular weight, M: ___________________________.

Low M

high M

Not all chains in a polymer are of the same length

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

Chapter 14 - 14
 MOLECULAR WEIGHT DISTRIBUTION
Fig. 14.4, Callister & Rethwisch 9e.

Mi = ___________ molecular weight of size range i

xi = __________________ of chains in size range i
wi = __________________ of chains in size range i
Chapter 14 - 15
 Molecular Weight Calculation
Example: average mass of a class
Student Weight
mass (lb) What is the average
1 104 weight of the students in
2 116
this class:
a) Based on the number
3 140
fraction of students in
4 143
each mass range?
5 180 b) Based on the weight
6 182 fraction of students in
7 191 each mass range?
8 220
9 225
10 380
Chapter 14 - 16
 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 number weight
Calculate the number and weight
range students weight fraction fraction
fraction of students in each weight
Ni Wi xrange
i wi
as follows:
mass (lb) mass (lb)
81-120 2 110 0.2 0.117
121-160 2 142 0.2 0.150
161-200 3 184 0.3 0.294
For example: for the 81-120 lb range
201-240 2 223 0.2 0.237
241-280 0 - 0 0.000
281-320 0 - 0 0.000
321-360 0 - 0 0.000
361-400 1 380 0.1 0.202

total SNi SNi W i total

number 10 1881 weight
Chapter 14 - 17
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

Chapter 14 - 18
 Degree of Polymerization, DP
DP = average number of ___________ 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

Chain fraction mol. wt of repeat unit i

Chapter 14 - 19
Molecular Structures for Polymers

secondary
bonding

Linear B ranched Cross-Linked Network

Adapted from Fig. 14.7, Callister & Rethwisch 9e.

Chapter 14 - 20
 Polymers – Molecular Shape
Molecular Shape (or ______________) – chain
bending and twisting are possible by rotation
of carbon atoms ______________________
– note: not necessary to _______________
to alter molecular shape
Adapted from Fig.
14.5, Callister &
Rethwisch 9e.

Chapter 14 - 21
Chain End-to-End Distance, r

Fig. 14.6, Callister &

Rethwisch 9e.

Chapter 14 - 22
Molecular Configurations for Polymers
___________ – to change must break bonds
• __________________

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

Chapter 14 - 23
 Tacticity
_________ – ___________ or spatial arrangement of
R units along chain

________ – all R groups on _____________ – R groups

same side of chain alternate 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

Chapter 14 - 24
 Tacticity (cont.)
_____ – 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

Chapter 14 - 25
 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 group on H atom and CH3 group on
_____ side of chain _______ sides of chain

Chapter 14 - 26
VMSE: Stereo and Geometrical Isomers

Manipulate and rotate polymer structures in 3-dimensions

Chapter 14 - 27
 Copolymers Fig. 14.9, Callister &
Rethwisch 9e.

two or more monomers random

polymerized together
• ______ – A and B randomly
positioned along chain
• _____________ – A and B
alternate in polymer chain alternating
• _______ – large blocks of A
units alternate with large block
blocks of B units
• _______ – chains of B units
grafted onto A backbone

A– B–
graft

Chapter 14 - 28
 Crystallinity in Polymers
Fig. 14.10, Callister
& Rethwisch 9e.

• Ordered atomic
arrangements involving
_________________
• Crystal structures in terms
of ______________
• Example shown
– ____________ unit cell

Chapter 14 - 29
 Polymer Crystallinity
• Crystalline regions
– thin _________ with chain folds at faces
– ______________ structure

Fig. 14.12, Callister

& Rethwisch 9e.

≈ 10 nm

Chapter 14 - 30
 Polymer Crystallinity (cont.)
Polymers rarely _________________
• Difficult for all regions of all chains to
become aligned crystalline
region
• Degree of crystallinity
expressed as ___________.
-- Some physical properties
depend on % crystallinity.
-- ________________ causes
crystalline regions to grow
and % crystallinity to
increase.
amorphous
region
Fig. 14.11, Callister 6e. (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 - 31
 Polymer Single Crystals
• ____________________ – multilayered single crystals
(chain-folded layers) of polyethylene
• _____________ – only for slow and carefully controlled
growth rates

Fig. 14.11, Callister &

Rethwisch 9e.
[From A. Keller, R. H. Doremus, B.
W. Roberts, and D. Turnbull (Eds.),
Growth and Perfection of Crystals.
General Electric Company and
John Wiley & Sons, Inc., 1958, p.
498. Reprinted with permission of
John Wiley & Sons, Inc.]

1 μm
Chapter 14 - 32
Semicrystalline Polymers
• Some semicrystalline
polymers form
__________ structures
• _______ chain-folded
crystallites and
amorphous regions
• _________ structure for
relatively rapid growth
Spherulite rates
surface

Fig. 14.13, Callister & Rethwisch 9e.

Chapter 14 - 33
Photomicrograph – Spherulites in
Polyethylene
________________ light used
-- a maltese cross appears in each ____________

Courtesy F. P. Price, General Electric Company

100 μm

Fig. 14.14, Callister & Rethwisch 9e.

Chapter 14 - 34