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Introduction to Polymers
Contents
• Introduction to Polymers
– Polymer study
– Polymer definition
– Polymer composition
– Molecular weight
– Degree of polymerization
– Molecular structure
– Molecular shape
– Mechanical properties
– Tg Vs Tm
– Processing of Plastics
 P o l ym e r s t u d y
• Basic microstructural features of a polymer
• Polymer properties affected by molecular weight
• Polymeric materials accommodating the polymer chain
• Tensile properties of polymers and how are they affected by basic microstructural
features
• Changing Polymer Properties: Hardening, anisotropy, and annealing in polymers.
• The elevated temperature mechanical response of polymers compare to ceramics
and metals
• Primary polymer processing methods
P o l ym e r s
• A polymer (Greek poly - "many" + mer - "parts") is a large molecule, or
macromolecule, composed of many repeated subunits.

• Because of their broad range of properties, both synthetic and natural polymers
play an essential and ubiquitous role in everyday life.

Definition: a substance which has a molecular structure built up chiefly or

completely from a large number of similar units bonded together, e.g. many
synthetic organic materials used as plastics and resins.
E x a m p l e o f p o l ym e r

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)
Polymer Composition
Most polymers are hydrocarbons
– i.e. made up of H and C
(we also recognize Si-H ‘silicones’)

• Saturated hydrocarbons
– Each carbon bonded to four other atoms

H H
H
CnH2n+2
C C

H H
H
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 = xi Mi
M w = w i Mi

Mw is more sensitive to
higher molecular
weights Adapted from Fig. 14.4, Callister 7e.
D e g r e e o f P o l ym e r i z a t i o n , 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
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.
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
Tacticity

Tacticity – stereo regularity 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
Copolymers
Adapted from Fig.
14.9, Callister 7e.

two or more monomers polymerized random

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

A– B–

graft
P o l ym e r C r ys t a l l i n i t y
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.
P o l ym e r C r ys t a l l i n i t y

Polymers rarely exhibit 100% crystalline

• Too difficult to get all those chains aligned
crystalline
region
• % Crystallinity: how much
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.)
Mechanical Properties
• i.e. stress-strain behavior of polymers

brittle polymer

FS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
– less than metal

Adapted from Fig. 15.1,

Strains – deformations > 1000% possible Callister 7e.

(for metals, maximum strain ca. 100% or less)

T and Strain Rate: Thermoplastics

• Decreasing T...
(MPa)
-- increases E 80 4°C Data for the
-- increases TS semicrystalline
-- decreases %EL 60 polymer: PMMA
20°C (Plexiglas)
• Increasing 40 40°C
strain rate...
-- same effects 20
as decreasing T. to 1.3
60°C
0
0 0.1 0.2 e 0.3
Adapted from Fig. 15.3, Callister 7e. (Fig. 15.3 is from T.S. Carswell and
J.K. Nason, 'Effect of Environmental Conditions on the Mechanical
Properties of Organic Plastics", Symposium on Plastics, American Society
for Testing and Materials, Philadelphia, PA, 1944.)
M e l t i n g v s . G l a s s Tr a n s i t i o n Te m p .

What factors affect Tm

and Tg?
• Both Tm and Tg increase with
increasing chain stiffness

• Chain stiffness increased by

1. Bulky sidegroups
2. Polar groups or
sidegroups
3. Double bonds or
aromatic chain groups

• Regularity (tacticity) – affects

Tm only
Adapted from Fig. 15.18,
Callister 7e.
Time Dependent Deformation
• Stress relaxation test: • Data: Large drop in Er
-- strain to eo and hold. for T > Tg. (amorphous
5
-- observe decrease in 10 rigid solid polystyrene)
Er (10s) (small relax) Adapted from Fig.
stress with time. in MPa 10
3
15.7, Callister 7e.
transition (Fig. 15.7 is from
tensile test 101 region A.V. Tobolsky,
Properties and
eo strain 10-1
Structures of
Polymers, John
viscous liquid Wiley and Sons, Inc.,
(t) 10-3 (large relax) 1960.)

60 100 140 180 T(°C)

time Tg
• Relaxation modulus: • Sample Tg(C) values:
(t ) PE (low density) - 110
E r (t ) = PE (high density) - 90
eo PVC + 87
Selected values from
Table 15.2, Callister
PS +100 7e.

PC +150
Processing of Plastics

• Thermoplastic –
– can be reversibly cooled & reheated, i.e. recycled
– heat till soft, shape as desired, then cool
– ex: polyethylene, polypropylene, polystyrene, etc.
• Thermoset
– when heated forms a network
– degrades (not melts) when heated
– mold the prepolymer then allow further reaction
– ex: urethane, epoxy
Two main synthetic approaches

• Addition polymerization
• Simply adding monomers
together – synthetic plastics
• Condensation polymerization
• Combination by exclusion of a
small molecule (usually water) –
extensively used by nature
 Molecular weight

CH4 ----------------------------------------- 16 increasing

CH3 - CH3 -------------------------------- 30 molecular weight
Gases
CH3 - CH2 _ CH3 ------------------------ 44
CH3 - CH2 - CH2 - CH3 --------------- 58

Liquids
CH3 - (CH2)6 _ CH3 --------------- 114

"Semi-solid"
CH3 - (CH2)30 _ CH3 --------------- 450

Solids
CH3 - (CH2)30000 _ CH3 ---------- 420030

Increasing
Molecular Weight
 Molecular weight

Chains have different

molecular weights

There is a distribution
26

Cross linking adds tensile

strength
 Thermoplastics (80%)

• No cross links between chains.

• Weak attractive forces between chains broken by
warming.
• Change shape - can be remoulded.
• Weak forces reform in new shape when cold.
 Thermosets

• Extensive cross-linking formed by covalent

bonds.
• Bonds prevent chains moving relative to
each other.
• What will the properties of this type of plastic
be like?
 Polymer properties tuned by modifying added
groups
• Density
• Polarity
• Chain branching
• Cross linking
• Chain length
Polymers have revolutionized containers and other
household items
Common addition polymers cont’d
Thank you