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 8e.

Chapter 14 - 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 14 - 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 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 H
C C
H H

– 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
CH3
H3C CH CH2 CH CH3
CH2
CH3
Chapter 14 - 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
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 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
 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 -13
 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
Chapter 14 -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 14 -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 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 0.3For example:
0.294 for the 81-120 lb range
201-240 2 223 0.2 0.237
  2
241-280 0 - 0 x 
0.000
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 Ni NiWi  total
number 10 1881 weight Chapter 14 -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
Mn   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
Mw   wi Mi  218 lb
Chapter 14 -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  fi mi
Chain fraction mol. wt of repeat unit i Chapter 14 -18
Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

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

Chapter 14 -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.

14.5, Callister &
Rethwisch 8e.

Chapter 14 -20
Chain End-to-End Distance, r

Adapted from Fig.

14.6, Callister &
Rethwisch 8e.

Chapter 14 -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 14 -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 14 -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 14 -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 14 -25
 Copolymers Adapted from Fig.
14.9, Callister &
Rethwisch 8e.

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 14 -26
 Crystallinity in Polymers Adapted from Fig.
14.10, Callister &
Rethwisch 8e.

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

Chapter 14 -27
 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 -28
 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 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 -29
 Polymer Single Crystals
• Electron micrograph – multilayered single crystals
(chain-folded layers) of polyethylene
• Single crystals – only for slow and carefully controlled
growth rates

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

Chapter 14 -30
Semicrystalline Polymers
• Some semicrystalline
polymers form
spherulite structures
• Alternating chain-folded
crystallites and
amorphous regions
• Spherulite structure for
relatively rapid growth
Spherulite rates
surface

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

Chapter 14 -31
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 -32