EMM 3122

Engineering Materials
Chap. 7: Non Metallic Materials
(Polymer)

Mechanical and Manufacturing Engineering Department

Engineering Faculty
University Putra Malaysia (UPM)
 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)

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

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

– Triple bond found in acetylene or ethyne - C2H2

Chapter 14 - 6
 Polymerization and
Polymer Chemistry
• Free radical polymerization

• Initiator: example - benzoyl peroxide

Chapter 14 - 7
Bulk or Commodity Polymers

Chapter 14 - 8
Bulk or Commodity Polymers (cont)

Chapter 14 - 9
Bulk or Commodity Polymers (cont)

Chapter 14 - 10
 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 - 11
 MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 14.4, Callister & Rethwisch 8e.

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 - 12
 Molecular Weight Calculation
Example: average mass of a class
Student Weight
mass (lb) What is the average
1 104 weight of the students in
this class:
2 116
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 - 13
 Molecular Weight Calculation (cont.)
Solution: The first step is to sort the students into weight ranges.
Using 40 lb ranges gives the following table:

Calculate the number and weight

fraction of students in each weight
range as follows:

For example: for the 81-120 lb range

total total
number weight Chapter 14 - 14
Molecular Weight Calculation (cont.)

Chapter 14 - 15
 Degree of Polymerization, DP
DP = average number of repeat units per chain

DP = 6

Chain fraction mol. wt of repeat unit i Chapter 14 - 16

Molecular Structures for Polymers

secondary
bonding

Linear Branche Cross-Linked Network

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

Chapter 14 - 17
 cis/trans Isomerism

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 -
 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 - 19
 Crystallinity in Polymers
• Ordered atomic
arrangements involving
molecular chains
• Crystal structures in terms
of unit cells
• Example shown
– polyethylene unit cell

Chapter 14 -
 Polymer Crystallinity (cont.)
Polymers rarely 100% crystalline
• Difficult for all regions of all chains to
become aligned crystalline
regio
n
• Degree of crystallinity
expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.
amorphou
regio
s
n from Fig. 14.11, Callister 6e.
Adapted
(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 - 21
 Solidification of Thermoplastics
• Glass transition temperature, Tg
🡪 the temperature at which the polymer undergo phase transition from
a rubbery to a glassy state.

Glassy solid Highly

(hard & brittle) Supercooled viscous
below above Rubbery
liquid (rubbery) liquid
Liquid Glassy Tg
(brittle) (flexible)

E.g: Tg for polyethylene is –110 0C and

Poly(vinyl chloride) (PVC) is 82 0C
Solid crystalline
region in a
supercooled liquid
matrix

Solid glassy
region in glassy
matrix

Chapter 14 -
 Solidification of Thermoplastics
• Thermoplastics is either non-crystalline or partly crystalline solid when
solidified from liquid state.
• Non-crystalline thermoplastics (amorphous) 🡪 no sudden change in
specific volume on cooling (line BC).
• Partly noncrystalline thermoplastics 🡪 a sudden decrease in specific
volume on cooling to low T (line BE).
Glassy solid Highly
(hard & brittle) Supercooled viscous
liquid (rubbery) liquid
Liquid

Solid crystalline
region in
supercooled liquid
matrix

Solid glassy
region in glassy
matrix
Chapter 14 -
 Comparison between thermoplastic and thermoset
Thermoplastics Thermosetts

1. Formed by addition polymerisation 🡪 long liner 1. Formed by condensation polymerisation and

chain polymers with no cross-links. 3D-network structure

2. Soften when heating due to secondary bonding 2. Do not soften when heating, on prolong
between the individual chains can break easily Heating 🡪 charring of polymer is caused.
by heat/pressure.

3. Bonding- covalent bonding-secondary bonded by 3. Bonding-covalent bonding-rigid cross-links 🡪

weak Van Der Waals forces. a strong 3D str.

4. Can be reshaped and reused 4. Cannot

5. Soft, weak and less brittle 5. Hard, strong and more brittle

6. Can be recycled from wastes. 6. Cannot

Chapter 14 -
Elastomer

● As rubber.
● Elastic deformation > 200%
● Polymer chain consist of coil like molecules that can be
reversible stretch by applied force.
● Example: Natural rubber (NR), styrene butadiene rubber
(SBR), polysiloxane (Silicone rubber)

Chapter 14 -
TERIMA KASIH

Chapter 14 -