Chapter 5:

Structures of Polymers
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 5 - 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. 5.2, Callister & Rethwisch 9e.

Chapter 5 - 2
 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

Chapter 5 - 3
 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

Chapter 5 - 4
Chapter 5 - 5
 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

– Triple bond found in acetylene or ethyne - C2H2

H C C H

Chapter 5 - 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
ß
H3C ( CH2 ) CH3
6
• 2,4-dimethylhexane
CH3
H3C CH CH2 CH CH3
CH2
CH3

Chapter 5 - 7
 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
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

Chapter 5 - 8
 Chemistry and Structure of
Polyethylene
Adapted from Fig.
5.1, Callister &
Rethwisch 9e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene

Chapter 5 - 9
Bulk or Commodity Polymers

Chapter 5 - 10
Bulk or Commodity Polymers (cont)

Chapter 5 - 11
Bulk or Commodity Polymers (cont)

Chapter 5 - 12
 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 5 - 13
 MOLECULAR WEIGHT DISTRIBUTION
Fig. 5.4, Callister & Rethwisch 9e.

total wt of polymer
Mn =
total #of molecules

Mn = Σx i Mi
MW = Σw i 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
Chapter 5 - 14
 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 5 - 15
 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 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 0.3For example:
0.294 for the 81-120 lb range
201-240 2 223 0.2 0.237
241-280 0 - 0 x 0.000 2
81−120
= = 0.2
281-320 0 - 0 0.000 10
321-360 0 - 0 0.0002 x 110
361-400 1 380 0.1 w 81−120 =
0.202 = 0.117
1881
total ΣN i ΣN i W i total
number 10 1881 weight
Chapter 5 - 16
 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 = ∑ x i 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 = ∑ w i 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 = ∑ w i Mi = 218 lb
Chapter 5 - 17
 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 = Σfi mi
Chain fraction mol. wt of repeat unit i
Chapter 5 - 18
Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

Adapted from Fig. 5.7, Callister & Rethwisch 9e.

Chapter 5 - 19
 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.
5.5, Callister &
Rethwisch 9e.

Chapter 5 - 20
Chain End-to-End Distance, r

Fig. 5.6, Callister &

Rethwisch 9e.

Chapter 5 - 21
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

Chapter 5 - 22
 Tacticity
Tacticity – stereoregularity or spatial arrangement of R
units along chain

isotactic – all R groups on syndiotactic – 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 5 - 23
 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 5 - 24
 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
same side of chain opposite sides of chain

Chapter 5 - 25
 Copolymers Fig. 5.9, Callister &
Rethwisch 9e.

two or more monomers random

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

A– B–
graft

Chapter 5 - 26
 Polymer Crystals
• Crystalline regions
– thin platelets with chain folds at faces
– Chain folded structure

Fig. 5.11, Callister &

Rethwisch 9e.

≈ 10 nm

Chapter 5 - 27
 Polymer Crystals (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
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 5 - 28
 Polymer Single Crystals
• Electron micrograph – multilayered single crystals
(chain-folded layers) of polyethylene
• Single crystals – only for slow and carefully controlled
growth rates

Fig. 5.10, 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 5 - 29
Semicrystalline Polymers
• Some semicrystalline
polymers form
spherulite structures
• Alternating chain-folded
crystallites and
amorphous regions
• Spherulite structure for
relatively rapid growth
Spherulite rates
surface

Fig. 5.12, Callister & Rethwisch 9e.

Chapter 5 - 30
Photomicrograph – Spherulites in
Polyethylene
Cross-polarized light used
-- a maltese cross appears in each spherulite

Courtesy F. P. Price, General Electric Company

100 μm

Fig. 5.13, Callister & Rethwisch 9e.

Chapter 5 - 31
 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 5 - 32