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 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) Polyvinyl chloride (PVC) 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
– 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 bonded to four other atoms

H H
H
C C

H H
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 H
C C
H H

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

H C Cor H
– Triple bond – acetylene ethyne - CnH2n-2

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-methyl-4-ethyl pentane (isooctane)
CH3
H3C CH CH2 CH CH3
CH2
CH3
Chapter 14 - 7
 Chemistry of Polymers
• 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 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 xi wi
# of students mass (lb)
1 100 0.1 0.054
1 120 0.1 0.065
M n   xi Mi
2 140 0.2 0.151
3 180 0.3 0.290
M w   w i Mi
2 220 0.2 0.237
1 380 0.1 0.204

Mn Mw
186 lb 216 lb

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

Mn Mw
nn   xi ni  nw   w i ni 
m m

where m  average molecular weight of repeat unit

m  fi mi
Chain fraction mol. wt of repeat unit i
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 Branched 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 H H H R
C C C C or C C
H R
H R H H

A A

C C
E E
B D D B
mirror
plane
Chapter 14 - 19
 Tacticity
Tacticity – stereoregularity of chain
H H H H H H H H
isotactic – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R

H H H R H H H R
syndiotactic – R groups
C C C C C C C C
alternate sides
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 CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain

Chapter 14 - 21
 Copolymers Adapted from Fig.
14.9, Callister 7e.

two or more monomers random

polymerized together
• random – A and B randomly
vary in chain
• alternating – A and B
alternate in polymer chain alternating
• block – large blocks of A
alternate with large blocks of block
B
• graft – chains of B grafted
on to A backbone

A– B–
graft
Chapter 14 - 22
 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 - 23
 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 - 24
 Polymer Crystal Forms
• Single crystals – only if slow careful growth

Adapted from Fig. 14.11, Callister 7e.

Chapter 14 - 25
 Polymer Crystal Forms
• Spherulites – fast
growth – forms lamellar
(layered) structures

Spherulite
surface

Nucleation site Adapted from Fig. 14.13, Callister 7e.

Chapter 14 - 26
Spherulites – crossed polarizers
Maltese cross

Adapted from Fig. 14.14, Callister 7e. Chapter 14 - 27

 ANNOUNCEMENTS
Reading:

Core Problems:

Self-help Problems:

Chapter 14 - 28