CL309 Materials Science

Module4
Principles of polymer, Structure and
Property relation of polymers, molecular
weight and MWD, Glassy state, glass
transition, Rheological and Mechanical
Properties, Thermodynamics of Polymer
Solutions, Properties of
PE,PP,PVC,PS,PMMA,PET,NYLON,PTFE,
Properties of elastomer (NR, SBR, Silicone
Rubber)
Where does the field stand?
 Polymer ?

One brick = monomer

Cement mixture=chemical bond (covalent/ionic)
Property of wall ( polymer) = strength
Property of brick (monomer) = no/low strength
 How do we get Polymers?
Gas monomer

Processing

Solid Granules

Films
 Classification of Polymers
Source

Are we eating Polymers? YES, in the form of cellulose, starch, protein etc.
Synthetic Polymers
 Synthesis route

• Addition Polymerization- Vinyl POlymers

 Chemical Structure of some Vinyl polymers
PE
PP PMMA

PS

PVAc

PVC

PVA
Condensation POlymerization
 Chemical Structure of some condensation
polymers

PET Nylon6

PBT

nylon11
Unsaturated Polyester
Thermoset (Condensation) Polymers

PHENOLIC RESIN

EPOXY RESIN
crosslinked
Thermal behaviour
Linear chains
Upon heating
 PE,PP, PS, PVC,
PMMA,etc.

Vinylacetate-maleic anhydride-copolymers

ABS, SAN, PLA-co-PGA

polystyrene-b-poly(methyl methacrylate)
 Homopolymers

Copolymer
Properties Comparison
Transparent MABS(MMA+ABS) can
outperform polystyrene, SAN and
PMMA for impact resistance and
has similar heat distortion
temperatures. Polycarbonate can
outperform clear ABS for both
impact resistance and high
temperature performance
 Uses

SAN

ABS
Crystallinity of Polymers
 Factors affecting degree of crystallinity
• Chemical structure of repeat unit-homopolymer
[Link]
• Linearity/branching/crosslinking
• Tacticity
• Geometric isomerism
• Molecular weight
• Intermolecular interaction-H-bonding, dipole-dipole etc.
• Rate of cooling
• Presence of foreign material
• Total time of cooling
• Mould temperature
Application
Uses
FIBRE

FABRIC
Comparison between rubber, Plastics and Fibres
Tg/Tm Molecular Crystallinity at RT
weight

Rubber -40 to -80C >105 Amorphous

Plastics >RT 105 Crystalline/Amorphous

Fibres Tm>200C 104 - 105 Crystalline

 PMMA, PS

HDPE
Polymer structure
LDPE

NR

PF

PAN(polyacrylonitrile)
 Calculation of Molecular weight of Polymers
Number of Mass of Each Total Mass Weight (WiMi)=
Molecules, Molecule, Mi of Each Type Fraction (NiMi)xMi
Ni of Molecule, Type of
NiMi =Wi Molecule
(NiMi/NiMi)
1 800,000 800,000 0.016 12,800
3 750,000 2,250,000 0.045 33,750
5 700,000 3,500,000 0.070 49,000
8 650,000 5,200,000 0.104 67,600
10 600,000 6,000,000 0.120 72,000
13 550,000 7,150,000 0.143 78,650
Polydispersity
MWD

Factors controlling Molecular Weight & MWD of Polymers:

•Rate of polymerization
•Reactivity of functional groups which are involved in
polymerization
•Concentration of monomer
•Use of chain transfer agents
•Condition of reaction- Temperature &Pressure
•Purity of reactants(monomer, solvents etc.)
•Catalysts used
I Glass Transition
2

5
3
4

6
 Significance
I. Elastic deformation-bend &
stretch of bonds
II. Secondary transtion-
Excitation of internal bond
rotation-side groups
III. Primary transition-main
chain bond rotation-glass
transition
IV. Highly elastic-rubbery-large
scale (segmental mobility)
mobility
V. Flow-chain slippage-high
viscosity liquid
VI. Degradation
Effect of free volume on glass transition point of polymers

Greater the free volume easier the

segmental mobility lower the Tg

Plasticization

•Bulkier side group and

repeat unit more free
volume
•More the number of
chain end groups more
the free volume
Glass transition: Why is it second order transition?
Parameters e.g. Entropy, sp.
Volume and enthalpy undergo
change of slope at Tg

Parameters e.g. Heat capacity

Cp, coefficient of thermal
expansion (),isothermal
compressibility (K) undergo
sharp discontinuity at Tg which
are second derivatives of free
energy

Thermomechanical Property of
polymers
 =

Isothermal Compressibility, K=
 Molecular weight and Tg

Value of K depends upon the number of end groups in polymer

chain-more the number less is the Tg
Effect of molecular weight of polymers on thermal
behaviour
Effect of crosslinking on thermal properties
Effect of crystallinity on glass transition temperature of
polymers

Crystallinity-crystallite regions act as points to tie the molecules

against deformation-greater elasticity
 Effect of chemical structure of monomers/repeat unit
on thermal properties

• Chemical structure intermolecular

interaction (polarity) 3D rearrangement
of polymer chains Crystallinity
Less possibility of repeat unit mobility------rigid
chain--------higher glass transition

•Isotactic Polymer has higher Tm than atactic due to

crystallinity(PP,PS)
•Copolymers have lower Tg than Homopolymers due to chain
flexibility and reduced chain regularity (ABS /PS)
 •Large repeat unit
•More free volume
•But rigid repeat unit
Polycarbonate •So high Tg (146C)
 Polyacrylamide 160C -85C
-60C

Nylon6(polycaprolactum) 54C
120-160C
 Tg 76.8C
Tm 100-250C
Tg-18C
Tm 250C

Polyvinylidine chloride Polyvinyl Chloride

HDPE -120C Atactic PP -20C -45C

LLDPE -120C
Isotactic PP 100C
 Structure Property Relation
Factors affecting Glass Transition
• Chemical Structure of repeat unit
• Crystallinity
• Molecular Weight
• Polarity
• Substituent group-steric effect
• Main chain rigidity/flexibility
• Plasticization(wide MWD/
additive/copolymerization)
 Difference between softening and melting

• Softening occurs in most metals when heated to a point

where stresses are relieved in the crystal structure that
results in reduced hardness often arbitrarily defined as
a percentage loss of hardness or tensile strength
• Melting Point is the temperature where metals begin to
change phase from solid ot liquid …most commercially
prepared metals are alloys and will melt over a range of
tempertaure, where the metal is partly liquid and partly
solid until it becomes completely liquid.
 Condensation polymers

Melting point
Rigidity

Tm=595K,Tg=410K
Aromatic polyamides have excellent dimensional stability, low creep at elevated
temperatures and good chemical resistance
 Why is nylon66 high melting solid?

•Chain regularity
•Polar –NHCO- along chain causing high intermolecular forces of attraction
•Interchain H-bonding further increases that
•Even number of –CH2- in between any two successive –NHCO-
•Both Nylon 6 and Nylon 66 -excellent mechanical properties including high tensile
strength, high flexibility, good resilience, low creep and high impact strength
(toughness).
• easy to dye and exhibit excellent resistance to wear , low coefficient of friction
(self-lubricating).
• high melting temperature (227 – 267C) and glass transition temperature
•good resistance to oils, bases, fungi, and many solvents.
•strong moisture sensitivity (water acts as a plasticizer) and the resulting changes in
mechanical properties
•Nylon 6,12- less hydrophilic than Nylons 6,6 and 6 due to the larger number of
methylene groups in the polymer backbone.
 A. Polyamides with adipic acid
B. Polyamides with sebacic acid

Polymers with even number of

methylene groups in between two
successive amide linkages-higher
melting points
Moisture absorbed by the plastic act as plasticizer-reduces tensile
strength, electrical insulation, increases impact strength

Dry

Wet
Mechanical Properties of Polymers
[Link],PF
[Link]
[Link]
[Link], NR
• In elastic regime atomic bonds are stretching, so elastic behavior occurs
• In plastic regime, atomic bonds are broken and reformed and the material
strength increases during this time because of dislocation pile-up. Strain
hardening, or work hardening, will continue until the material breaks.
• Due to pulling of the material, the cross-sectional area decreases. Since we
assume the cross-sectional area stays the same, the stress appears to
decrease- necking-all of the stress is concentrated in this thin part.
A. elastic region.
B. Yield(plastic)
C. Necking
D. Cold
drawing(working)
E. Strain Hardening
F. Break
semi-crystalline
high molecular
weight
polymer
T4>T3>T2>T1
 A: minimum molecular weight -1000
Above “A” mechanical str. Increases
with molecular weight
B:Critical point –sufficient value to
exhibit sufficient str-mechanical Str
increases more slowly above B-(5000-
10000)
C: limiting value-maximum strength

•The plot in this figure shifts to right side if the intermolecular interaction
decreases-NYLON, Polyesters can show sufficient str at lower molecular
weight than PE
•Few properties may increase with MW to a maximum value and then
decrease –like processability(viscosity)
 Stress-strain curve for rubber
1. In no part of the curve, strain changes
linearly with change in applied stress.
2. During unloading, the curve does not retrace
its path.
[Link] done by the material in returning to its
original shape is less than the work done by
the deforming force when it is deformed. A
particular amount of energy is absorbed by the
material. This phenomenon is called elastic
hysteresis.

Due to high
molecular weight
and steric hindrance
of cis- isomer less
crystallinity at room
temperature
 Strain Induced Crystallization of natural rubber
B C

Dipped in
hot water

Upon dipping in hot water crystalline polymer(C)

becomes again flexible –as crystalline zones melt and
chains become entangled like the initial state
Crystallization of Polymers by DSC
Solution of Polymers
 Mechanism of solution formation
•Below the entanglement length, a thin swollen layer forms
almost instantaneously, which allows for the outside-in
mechanism to start in a few tens of nanoseconds after the
polymer–solvent initial contact.
•After this initial transient time the two mechanisms are
concurrent:
(1) the solvent diffuses into the polymer, leading to osmotic
driven swelling and progressive chain dilution (inside-out
mechanism);
(2) polymer chains are solvated, detach from the interface and
move into the solvent before the film is completely swollen
(outside-in mechanism).
 Quality of solvent
Good-interaction between polymer segments with
solvent molecules
Poor-low or no interaction
Theta-equilibrium( during reversible process)
 Factors affecting polymer and solvent
interaction
• Polarity-solubility parameter
PVA dissolves in water, PE dissolves in hot Xylene
• Molecular weight-lower molecular wt. dissolves quicker

• Crosslinking-difficult to dissolve
• PF does not dissolve, PE dissolves
• Crystallinity-more crystalline-difficult to dissolve
• NYLON dissolves in strong acid at elevated temperature
• PS dissolves in toluene at 80 C
 Thermodynamics of Polymer solution

So,
Lattice model of solubility
 Flory Huggins Theory

• Based on the lattice model

• Configurational entropy change, , obtained from the
statistical evaluation of the number of arrangement possible
on the lattice

• Where i= volume fraction of ith component, ni- no. of moles

of ith component

Where xi=no. Of segments in the species, for monomers x1=1

For polymers x2= average degree of polymerization=
>0

 =solubility parameter of
the ith component

So, >0
• For a linear and branched polymer greatest tendency to dissolve
in a specific solvent will be seen when 1=2

•For lightly crosslinked polymer even if 1=2 the polymer swells

most , does not dissolve
Flory Huggin’s
Equation
Effect of branching on solubility