CHAPTER 14:

POLYMER STRUCTURES
ISSUES TO ADDRESS...

•Basic microstructural features:

•Polymeric reaction
•Molecular shape and structure
•Thermoplastic and Thermosetting Polymers
•Co-polymers
•Polymer crystals

Chapter 14 - 1
 Chapter 14 – Polymers

What is a polymer?

Poly mer (meros – part)

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
 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 - 3
 Polymers
• Carbon bonds (primary bonds) form the backbone of polymeric
structures
• In the process of polymerization, none of the atoms are lost and none
are gained
• Each unit is called Monomer
• Chain of Polymers are attached with weak bonds (secondary bonds)
• Primary bonds are much stronger than secondary bonds Anisotropy
• Polymers can be crystalline, semi-crystalline, amorphous or a mixture all
three

Ethylene Polyethylene Styrene Polystyrene MIT, OCW

Table 14.3 for a list of 10 most common polymers and their monomers

Chapter 14 - 4
Common Polymers

MIT, OCW

Chapter 14 - 5
 MOLECULAR WEIGHT
• All chains do not grow to the same length  How to define
molecular weight in the units of gram/mol?
• 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 xi number fraction of
weight Mi
wi weight faction of
M w  w i M i weight Mi

Mw is more sensitive to
higher molecular
weights Adapted from Fig. 14.4, Callister 7e. Chapter 14 - 6
 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
Total = 10 Total =1860
Mn Mw
186 lb 216 lb

Chapter 14 - 7
 Degree of Polymerization (DP), 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
n
m mol. wt of repeat unit

Example: (14.1 Callister)

Polymer = PVC  Monomer (repeating unit)= vinyl chloride (CH2=CHCl)
In part (a), it was calculated that the Mn = 21,150g/mol
Molar weight of the repating unit, m = 2x12.01+3x1.01 + 35.45 g/mol = 62.50 g/mol
 DP, n = 21,150/62.50 = 338

Chapter 14 - 8
 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 - 9
 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.

Adapted from Fig.

14.6, Callister 7e.

Chapter 14 - 10
 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 - 11
 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 - 12
 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 - 13
 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 - 14
 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 - 15
 Polymer Crystal Forms
• Single crystals – only if slow careful growth

Adapted from Fig. 14.11, Callister 7e.

Chapter 14 - 16
 Polymer Crystal Forms
• Spherulites – fast
growth – forms lamellar
(layered) structures

Spherulite
surface

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

Chapter 14 - 17
Spherulites – crossed polarizers
Maltese cross

Adapted from Fig. 14.14, Callister 7e. Chapter 14 - 18