Chapter 14:

Polymer Structures
ISSUES TO ADDRESS...
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
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)

Poly(vinyl 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 & Rethwisch 8e.

Chapter 14 - 2

Ancient Polymers
Originally natural polymers were used
Wood
Rubber
Cotton
Wool
Leather
L th
Silk
Old
Oldestt known
k
uses
Rubber balls used by Incas
Noah used pitch (a natural polymer)
for the ark
Chapter 14 - 3

Polymer Composition
Most polymers are hydrocarbons
i.e., made up
p of H and C
Saturated hydrocarbons
Each carbon singly bonded to four other atoms
Example:
Ethane, C2H6
H

H
C

H
C
H

Chapter 14 - 4

Chapter 14 - 5

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

H
C C

Triple bond found in acetylene or ethyne - C2H2

H C C H
Chapter 14 - 6

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
2 4 dimethylhexane
CH3
H3C CH CH2 CH CH3
CH2
CH3
Chapter 14 - 7

Polymerization and
Polymer Chemistry
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
H

C O

=2R

H
Chapter 14 - 8

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
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: 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

Chapter 14 -14

MOLECULAR WEIGHT DISTRIBUTION

Adapted from Fig. 14.4, Callister & Rethwisch 8e.

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
Chapter 14 -15

Molecular Weight Calculation

Example: average mass of a class
Student

Weight
mass (lb)

104

116

140

143

180

182

191

220

225

10

380

What is the average

weight of the students in
this class:
a) Based on the number
fraction of students in
each mass range?
b) Based on the weight
fraction of students in
each mass range?

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
range

number of
students

mean
weight

Ni

Wi
mass (lb)

81-120
121-160
161 200
161-200
201-240
241-280
281 320
281-320
321-360
361-400

2
2
3
2
0
0
0
1

110
142
184
223
380

total
number

Ni
10

NiWi
1881

mass (lb)

number
Calculateweight
the number and weight
fraction
fraction
fraction of
students in each weight
xirange as follows:
wi
NiWi
Ni
wi
xi
0.2
Ni
NiWi
0.117
0.2
0.150
03
0.3
0 294
0.294
For example:
for the 81-120 lb range
0.2
0.237
2
0 x
0.000

0.2
81120
10
0
0 000
0.000
0
0.0002 x 110

0.117
0.1 w 81120
0.202

1881

total
weight

Chapter 14 -17

Molecular Weight Calculation (cont.)

weight
range

mean
weight

mass (lb)

Wi
mass (lb)

81-120
121-160
161-200
201-240
241-280
281 320
281-320
321-360
361-400

110
142
184
223
380

number
fraction
xi

weight
fraction
wi

0.2
0.2
0.3
0.2
0
0
0
0.1

0.117
0.150
0.294
0.237
0.000
0 000
0.000
0.000
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
M w wi Mi 218 lb

+ 0.237 x 223 + 0.202 x 380) = 218 lb

Chapter 14 -18

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

Chapter 14 -19

Molecular Structures for Polymers

secondary

bonding

Linear

Branched

Cross-Linked

Network

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

Chapter 14 -20

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.

Chapter 14 -21

Chain End-to-End Distance, r

Adapted from Fig.

14.6, Callister &
Rethwisch 8e.

Chapter 14 -22

Molecular Configurations for Polymers

Configurations to change must break bonds
Stereoisomerism
H

H
C C

H H

H R
or

C C
R

Stereoisomers are mirror

images cant superimpose
ith t breaking
b ki a b
bond
d
without

C C

H R

H H

mirror
plane
Chapter 14 -23

Tacticity
Tacticity stereoregularity or spatial arrangement of R
units along chain
isotactic all R groups on
same side of chain

syndiotactic R groups
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.)
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

Chapter 14 -25

cis/trans Isomerism

CH3

H
C C

CH2

CH2

CH3
C C

CH2

CH2

cis

trans

cis-isoprene
(natural rubber)

trans-isoprene
(gutta percha)

H atom
t
and
d CH3 group on
same side of chain

H atom
t
and
d CH3 group on
opposite sides of chain

Chapter 14 -26

VMSE: Stereo and Geometrical Isomers

Manipulate and rotate polymer structures in 3-dimensions

Chapter 7
19
14- -27

Copolymers
two or more monomers
polymerized together
random A and B randomly
positioned along chain
alternating A and B
alternate in polymer chain
block large blocks of A
units alternate with large
blocks of B units
graft chains of B units
grafted
f d onto A backbone
b kb
A

Adapted from Fig.

14.9, Callister &
R th i h 8
Rethwisch
8e.

random

alternating

block

graft
Chapter 14 -28

Crystallinity in Polymers

Adapted from Fig.

14 10 Callister
14.10,
C lli t &
Rethwisch 8e.

Ordered atomic
g
involving
g
arrangements
molecular chains
Crystal structures in terms
of unit
nit cells
Example shown
polyethylene unit cell

Chapter 14 -29

Polymer Crystallinity
Crystalline regions
thin platelets with chain folds at faces
Chain folded structure
Adapted from Fig.
14.12, Callister &
Rethwisch 8e.

10 nm

Chapter 14 -30

Polymer Crystallinity (cont.)

Polymers rarely 100% crystalline

Difficult for all regions of all chains to

become aligned
crystalline
region

Degree of crystallinity

expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.

amorphous
region

Adapted
p
from Fig.
g 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 -31

Polymer Single Crystals

Electron micrograph multilayered single crystals
((chain-folded layers)
y ) of polyethylene
p y y
Single crystals only for slow and carefully controlled
growth rates

Adapted from Fig. 14.11, Callister & Rethwisch 8e.

Chapter 14 -32

Semicrystalline Polymers

Spherulite
surface

Some semicrystalline
y
form
polymers
spherulite structures
Alternating chain-folded
crystallites and
amorphous regions
Spherulite
p
structure for
relatively rapid growth
rates

Adapted from Fig. 14.13, Callister & Rethwisch 8e.

Chapter 14 -33

Photomicrograph Spherulites in
Polyethylene
Cross-polarized light used
-- a maltese cross appears in each spherulite

Adapted from Fig. 14.14, Callister & Rethwisch 8e.

Chapter 14 -34

ANNOUNCEMENTS
Reading:

Core Problems:

Self help Problems:

Self-help

Chapter 14 -35