Polymer: Structure And

properties

Anshul Gautampurkar
15POL2004
(2015-2017)

High Polymer Chemistry

Department of Polymer and Surface
Engineering
 Learning objectives
 Describe basic features of a polymer
 Name three steps in the addition
polymerization process
 Distinguish between addition and condensation
polymerization
 Describe essential features of condensation
polymerization
 Identify polymerization process used on basis
of polymer composition
 Polymers are large molecules made by
concatenation of many small units
 Building blocks are monomers
 A polymer may contain thousands of
monomers and have a molar mass of hundreds
of thousands
 Homopolymer – the monomers are identical
 Copolymer – the monomers are different (2 or
more)
 Monomer
 A monomer must be capable of forming two
bonds to generate a chain
 A double bond meets that requirement
 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
 Reactive radical to initiate the
process
 Radicals are reactive – contain unpaired electrons
H H H H H H
●
H H H
H H H
R R

R●
 Odd + even = odd: unpaired electron survives
Addition polymerization has three steps

 C2H4 is stable – does not spontaneously change

into polyethylene – requires severe conditions
1. Initiation – create reactive species by
formation of free radical (unpaired electron)
2. Propagation – As chain grows by addition of
C2H4 units, the radical is preserved
3. Termination – radicals eliminated when they
meet
 Polymer properties tuned by
modifying added groups
 Density
 Polarity
 Chain branching
 Cross linking
 Chain length
 Structure is function
 HDPE: the strands pack closely together
 LDPE: branches prevent close packing
Polymers have revolutionized containers
and other household items
Common addition polymers cont’d
 Condensation polymers: another
route to making chains
 Two types of monomer required – each
capable of making two bonds
 Bonding occurs between them by elimination
of components of water
 OH + H = H2O
 Lower temperature process than addition
polymerization
Condensation polymer products
 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

Conformation – Molecular orientation can be

changed by rotation around the bonds
 note: no bond breaking needed

Adapted from Fig.

14.5, 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 – 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
 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 side of bulky groups on opposite sides
chain of chain
 Copolymers Adapted from Fig.
14.9, Callister 7e.

two or more monomers polymerized random

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

A– B–

graft
 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.
 Polymer Crystallinity

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)

 Tensile Response: Brittle & Plastic
Near Failure (MPa) fibrillar
structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

e
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from Figs. 15.12
& 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, Prentice-Hall, Inc., 1974, pp.
500-501.)
 Predeformation by Drawing
• Drawing…(ex: monofilament fishline)
-- stretches the polymer prior to use
-- aligns chains in the stretching direction
• Results of drawing:
-- increases the elastic modulus (E) in the
stretching direction
-- increases the tensile strength (TS) in the
stretching direction Adapted from Fig. 15.13, Callister
-- decreases ductility (%EL) 7e. (Fig. 15.13 is from J.M. Schultz,
Polymer Materials Science, Prentice-
• Annealing after drawing... Hall, Inc., 1974, pp. 500-501.)

-- decreases alignment
-- reverses effects of drawing.
• Comparable to cold working in metals!
 Tensile Response: Elastomer Case
(MPa)
x brittle failure Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset figures
along elastomer curve
(green) adapted from Fig.
15.15, Callister 7e. (Fig.
plastic failure
x 15.15 is from Z.D.
Jastrzebski, The Nature
and Properties of
x Engineering Materials, 3rd
elastomer ed., John Wiley and Sons,
1987.)
final: chains
e are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
 Thermoplastics vs. Thermosets
T
• Thermoplastics: Callister,
-- little crosslinking viscous rubber
mobile Fig. 16.9
-- ductile liquid Tm
liquid tough
-- soften w/heating plastic
-- polyethylene Tg
polypropylene
partially
polycarbonate
crystalline crystalline
polystyrene solid
solid

• Thermosets: Molecular weight

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer, Jr.,
-- large crosslinking Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc., 1984.)
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin
 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.)
 Melting vs. Glass Transition Temp.
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 polystyrene)
-- observe decrease in 10 rigid solid
Er (10s) (small relax) Adapted from Fig.
stress with time. in MPa 10 3
15.7, Callister 7e.
transition (Fig. 15.7 is from A.V.
1 Tobolsky, Properties
tensile test 10 region
and Structures of
eo strain 10 -1
Polymers, John Wiley
and Sons, Inc., 1960.)
viscous liquid
(t) 10 -3 (large relax)
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 Selected values from
PVC + 87 Table 15.2, Callister
7e.
PS +100
PC +150
 Polymer Fracture
Crazing  Griffith cracks in metals
– spherulites plastically deform to fibrillar structure
– microvoids and fibrillar bridges form

alligned chains

Adapted from Fig. 15.9,

fibrillar bridges microvoids crack Callister 7e.
 How polymers are effected
by temperature changes
 Heats solids made of small molecules – melt to form
liquid an eventually boil
 Polymers not so simple
 E.g. rubber cooled in liquid nitrogen becomes brittle
and can be smashed
 It becomes GLASSY
 poly(propene) becomes brittle at about -10 C
 Structure of many polymers mixture of ordered
areas (crystalline) and random (amorphous)
 In glassy state the amorphous regions become
‘frozen’ so cant can’t change shape if it has to move
it does so breaking
 How polymers are effected
by temperature changes
 If you heat the glassy material, polymer
chains reach a temp at which they move
relative to each other. This is the glass
transistion temperature (Tg)

 When polymer is warmer than this, we

see the typical plastic properties we
expect-
 How polymers are effected
by temperature changes
 On further heating we reach the melting
temperature (Tm)

 The crystalline regions break down and

polymer becomes a viscous fluid

 These processes are reversible for

thermoplastics
How polymers are effected
by temperature changes
 How polymers are effected
by temperature changes
 Today’s polymers are designed to have
Tg and Tm values which are suitable for
the manufacturers needs
Matching polymer properties
to needs
 Different polymers with different uses
need polymers with different Tg

 Two important ways of changing Tg is by

using copolymerisation and plasticisers
Matching polymer properties
to needs
 Different polymers with different uses
need polymers with different Tg

 Two important ways of changing Tg is by

using copolymerisation and plasticisers
 Matching polymer properties
to needs
 Pure poly(chloroethene)- PVC has a Tg of about
80 C – rigid and quite brittle at room temp
 Used to make drain pipes
 Sometimes called unplasticised PVC or uPVC
 To make it more flexible the Tg needs to be
lowered.
 One way of doing this is to copolymerise the
chloroethene with a small amount of ethenyl
ethanoate
 Matching polymer properties
to needs

 Introduces different side groups into the

polymer chain
 Chains pack together less well – attractive forces
are weaker
 Polymer is more flexible because the chains can
move over one another more easily
Matching polymer properties
to needs
 Another way is to use a ‘molecular
lubricant’ – a plasticiser
 Allows the PVC chains to slide over each
other more easily

 Diagram shows a plasticiser in place

beween two polymers
Matching polymer properties
to needs

 Plasticiser have to be chosen very

carefully so they are compatible with
the polymer
 Di-(2-ethylhexyl)hexandioate is
commonly used as a plasticiser for PVC
 Important that the plasticisers added
to cling film don’t dissolve in fatty food
as they may be harmful to health
 Section 15.6 Structure–
Property Relationships in Thermoplastics

 Branched polymer - Any polymer consisting of chains that consist

of a main chain and secondary chains that branch off from the
main chain.
 Crystallinity is important in polymers since it affects mechanical
and optical properties.
 Tacticity - Describes the location in the polymer chain of atoms or
atom groups in nonsymmetrical monomers.
 Liquid-crystalline polymers - Exceptionally stiff polymer chains
that act as rigid rods, even above their melting point.

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 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Figure 15.8 Head-to-tail versus head-to-head arrangement of repeat units. The

head-to-tail arrangement is most typical.

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44
(c)atactic.
nonsymmetrical
Figure 15.9 Three

(b)syndiotactic, and
monomers: (a) isotactic,
possible arrangements of
 ©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under
license.

Figure 15.10 Four types of copolymers: (a) alternating monomers, (b) random monomers, (c)
block copolymers, and (d) grafted copolymers. Circles of different colors or sizes represent
different monomers.

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Figure 15.11
Copolymerization
produces the polymer
ABS, which is really
made up of two
copolymers, SAN and
BS, grafted together.

46
 Section 15.7 Effect of
Temperature on Thermoplastics
 Degradation temperature - The temperature above which a polymer
burns, chars, or decomposes.
 Glass temperature - The temperature range below which the amorphous
polymer assumes a rigid glassy structure.

47
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48
behavior of
thermoplastics.
Figure 15.12 The

on the structure and

effect of temperature
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

Figure 15.13 The

effect of temperature
on the modulus of
elasticity for an
amorphous
thermoplastic. Note
that Tg and Tm are not
fixed.

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50
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Figure 15.14 The

relationship between the
density and the
temperature of the
polymer shows the
melting and lass
temperatures. Note that
Tg and Tm are not fixed;
rather, they are ranges of
temperatures.

51
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Figure 15.15 The folded chain ,model for crystallinity in polymers, shown
in (a) two dimensions and (b) three dimensions.

52
Figure 15.16 Photograph of spherulitic
crystals in an amorphous matrix of nylon (
200). (From R. Brick, A. Pense and R.
Gordon, Structure and Properties of
Engineering Materials, 4th Ed., McGraw-Hill,
1977.)

53
 Polymer Structure I

Why most? Because a few

types of polymers may do
under certain circumstances
(we will see how)

amorphous semi-crystalline
polymer polymer

MOST CRYSTALLINE POLYMERS ARE

NOT ENTIRELY CRYSTALLINE !!!
They are either amorphous or semi-crystalline.
The degree of crystallinity varies (From 0 to 90-95 %).
 Polymer Structure II

Shish-kebab morphology

SEM image of a spherulite

SEM image of a chain having
shish-kebab morphology
 Polymer Structure III

Crystallinity of polymers is affected by:

All about the Chemical structure

chain properties Stereochemistry
Molecular weight Hmm…
Temperature
External effects
Processing conditions
 Polymer Structure IV
STEREOCHEMISTRY
(Tacticity)

This is the white, plastic coffee cup

Is polystyrene flat like this?
used everywhere like Fassane.
Strafor kopuk Absolutely NO!
 Polymer Structure V
STEREOCHEMISTRY
(Tacticity)
In the previous picture you see all the phenyl groups are located on the same side of the
polymer chain. But they don't have to be this way. To illustrate let's look at a chain of
polystyrene from above. You can see that the pendant phenyl groups can be either on the
right or left side of the chain.

All phenyl groups Phenyl groups on Phenyl groups

on the same side alternating sides distributed randomly
 Polymer Structure V
STEREOCHEMISTRY
(Tacticity)

The question is, how tacticity helps crystallinity

CRYSTALLINITY ↔ LONG RANGE ORDER ↔ PACKING

Syndiotactic polystyrene: Highly crystalline

Atactic polystyrene: Highly amorphous

Similarly, a linear polymer can pack well, whereas a branched isomer cannot

Highly crystalline Highly amorphous

Polymer Structure VI
Intermolecular forces and crystallinity

(Aromatic ring stacking)

 Polymer Structure VII
 Fibers
 Polymers with regular structure can align themselves very closely for effective
utilization of the secondary intermolecular bonding forces.
 Already stretched out fully, up to 95% crystallinity
 High symmetry, high intermolecular forces.
 Characterized by high modulus, high tensile strength, and moderate extensibilities

Can you stretch this structure???

High density polyethylene

Polypropylene
Nylon
Polyester
Kevlar and Nomex
Polyacrylonitrile
Cellulose
Polyurethanes
 Polymer Structure VIII
 Elastomers (rubbers)
 Polymers with irregular structure, weak intermolecular attractive forces and
flexible chains.
 Can undergo local mobility, but gross mobility of chains is restricted.
 Characterized by high extensibility, low initial modulus in tension but they stifen
when strecthed.

stretch

leave

ENTROPY WORK!
 Polymer Structure IX
 Plastics
 Fall between the elastomers and fibers. However there is no exact boundary
 Harder to stretch than elastomers (Because of crystalline regions?). But preserve
their shape when stretched unlike elastomers (Strain induced crystallization, stiff
chains)
 They are pliable, that is, they can be shaped and molded easily
 Thermoplastics: Melt when heated and can be melted again after cooling
 Thermosets: Undergoes crosslinking when heated, so does not melt again,
decomposes if heated further
 Flexible plastics: Plastics above their Tg. Flexible, soft
 Rigid plastics: Plastics below their glass transition temperature (Tg). Brittle, hard

What are Tg, crosslinking and “melting for polymers” ?

 Polymer Structure X
Glass transition temperature (Tg)

• Different polymers have different segments on their backbones. The ease of movement of these
segments (portions of the chain) depends on the structure, physical environment of the chain etc.
of the segment.

• Any movement of these segments require energy which is kinetic in this case, right? Then each
different polymer would have different energy requirement for the movement of these segments
(different polymer = different structure, different physical environment of the chain etc).

• Below glass transition temperature, these segments do not have sufficient energy to move. So, if
you apply some stress, say if you try to bend a polymer which is below its Tg then the segments
won’t be able to move into new positions to relieve the stress which you have placed on them;
which will make the polymer brittle. Above Tg they would, so they would be flexible.

• Always keep this in mind: Tg IS A PROPERTY RELATED WITH THE AMORPHOUS

REGIONS OF THE POLYMER, NOT CRYSTALLINE!

• So it should now be obvious that elastomers are elastomers above their Tg. Below, they are not
elastomers, they are glassy, because they are not flexible anymore (Remember my experiment
with rubber glove and liquid nitrogen during the lecture).
 Polymer Structure XI
Melting
• Melting is a transition which occurs in crystalline polymers.

• Melting happens when the polymer chains fall out of their crystal structures, and become a
disordered liquid.

• Always keep this in mind: MELTING IS A PROPERTY RELATED WITH THE

CRYSTALLINE REGIONS OF THE POLYMER! So do you think you can melt atactic
polystyrene? (No, because it is not crystalline)

Question: What if I see both

melting and glass transition in the
differential scanning calorimeter
(DSC) spectrum of a polymer
sample???

It is absolutely OK. Remember,

most polymers are semi-
crystalline, i.e. have both
amorphous and crystalline regions
 Polymer Structure XII
Poly (1,4-butadiene)
Crosslinking

Crosslinking
with sulphur
(vulcanization)
Synthetic rubber

This is the tire of your car

Thus, it is possible to produce elastomers via crosslinking!

(In fact, it is not only possible but also the very common way of making elastomers, i.e. rubber)