Engineering Material Technologies

(EMT 520S)
B.Tech Semester 2 - 2022

Polymers

Polymers 1
 Introduction
Polymers are long-chain molecules that are found naturally or
synthesized chemically.
• Lightweight, ductile, and easily shaped.
• Low melting point and mechanical strength.

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Polymers
 Polymers
Polymers
Macromolecules consisting of many repeated basic units or
monomers.

Synthesized from monomers in a process called

polymerisation.
1. In step-growth polymerisation, small chains of monomers
combine to form large chains.
2. In chain-growth polymerisation, growth of the polymer
chain is by individual monomer addition.

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Polymers
 Polymers
Natural polymers - Include natural rubber, wool, and cellulose.

Synthetic polymers - Include polyethylene, polystyrene,

polypropylene, and polyvinyl chloride.

Length of a polymer chain is expressed by degree of

polymerisation (number of polymers in the chain) or molecular
weight.

Increasing chain length increases viscosity, melting and

boiling point, glass transition temperature, strength, and
toughness.

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Polymers
 Chemistry
Homopolymers
• Contain a single type of repeated unit.

Copolymers
• Contain mixed repeated units.

Block copolymers
• Form when blocks of two or more homopolymers bond
covalently.

Graft copolymers
• Have side chains with different units.

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Polymers
 Chemistry
Tacticity
Described as the relative stereochemistry of chiral centers in
neighboring structural units of a polymer.
• Isotactic: all substituents are on the same side.
• Atactic: substituents are randomly placed.
• Syndiotactic: substituents are alternatively placed.

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Polymers
 Chemistry
Polyethylene is classified based on density and molecular
weight.
• Ultra-high molecular weight polyethylene (used in
automobile parts and bulletproof vests)
• High-density polyethylene (used in plastic furniture, water
pipes, and containers)
• Medium-density polyethlylene (used in gas pipes and
packing film)
• Low-density polyethylene (used in retail store bags and
squeeze bottles)

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Polymers
 Chemistry
Polymers can be crystalline and/or amorphous, which strongly
affects properties.

Crystalline melting point (Tm)

The temperature where a crystalline phase is transformed into
an amorphous phase.

Glass transition temperature (Tg)

When an amorphous polymer transitions from a viscous liquid
to an amorphous solid upon cooling.
Generally 0.5 – 0.8Tm (Kelvin).

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Polymers
 Chemistry
Plasticisers are additives that:
• Improve flexibility and reduce cracking.
• Decrease glass transition temperature
• Reduce cracking of plastic automobile parts under cold
temperatures.

Sulphur is added through vulcanisation, and increases

hardness of rubber.

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Polymers
 Mechanical Properties
Tensile strength is low compared to metals, but ductility can
be very large.
• Cross-linking and length of polymer chains contributes to
tensile strength.
• Crystalline polymers have higher tensile strength than
amorphous polymers.
• Tensile strength is increased by pre-deformation (similar to
strain hardening).

Polymer fracture involves: (1) crack initiation, (2) crack

propagation, and (3) failure.
Fracture can be ductile or brittle depending on polymer type
and environment.
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Polymers
 Mechanical Properties– Stress-Strain Behavior

Fracture strengths of polymers ~ 10% of those for metals

Some polymers can deform > 1000%
• for most metals, deformation strains < 10%
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Polymers
 Mechanisms of Deformation — Brittle Crosslinked and
Network Polymers

Stress (MPa)

Strain

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Polymers
 Mechanisms of Deformation — Semicrystalline (Plastic)
Polymers

Stress (MPa)

Strain

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Polymers
 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
• decreases ductility (%EL)

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Polymers
 Predeformation by Drawing
Heat-treating (or annealing) of semicrystalline polymers can lead to:
increase in the percent crystallinity, and
• crystallite size and perfection,
• as well as modifications of the spherulite structure.

Undrawn materials that are subjected to constant-time heat

treatments, leads to the following:
(1) An increase in tensile modulus,
(2) an increase in yield strength, and
(3) a reduction in ductility.

Contrast to effects of in metals!

Annealing after drawing.

Decreases chain alignment
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Polymers
 Mechanisms of Deformation— Elastomers

Stress (MPa)

Strain

Compare elastic behavior of elastomers with the:

• brittle behavior (of aligned, crosslinked & network
polymers), and
• plastic behavior (of semicrystalline polymers) (as shown on
previous slides)
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Polymers
 Thermosetting and Thermoplastic Polymers
Thermosetting polymers
Become hard once cured and cannot be remolded or melted.
Break down when overheated (not recyclable).
Molded into different shapes and sizes by a process called
curing.
Include polyurethanes, bakelite, and polyimides.

Thermoplastic polymers
Soften and form a viscous liquid when heated.
Can be melted and remolded, and are recyclable.
Include polyethylene, polyvinyl chloride, polypropylene, and
polystyrene.

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Polymers
 Thermoplastics vs. Thermosets
Thermoplastics:
• little crosslinking
• ductile
• soften with heating

Examples:
• polyethylene
• polypropylene
• polycarbonate
• Polystyrene

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Polymers
 Thermoplastics vs. Thermosets
Thermosets:
• significant crosslinking (10 to 50% of repeat units)
• hard and brittle
• do NOT soften with heating

Examples:
• vulcanized rubber,
• epoxies,
• polyester resin, and
• phenolic resin.

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Polymers
 Thermoplastics vs. Thermosets

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Polymers
 Influence of T and Strain Rate on Thermoplastics
Decreasing T:
• increases E
• increases TS

Stress (MPa)
• decreases %EL

Increasing strain rate.

Same effects as
decreasing T:
Strain
• increases E
• increases TS
• decreases %EL

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Polymers
 Melting & Glass Transition Temperatures
What factors affect Tm and Tg?
Both Tm and Tg increase with
increasing chain stiffness
Chain stiffness increased by
presence of
• Bulky sidegroups
• Polar groups or sidegroups
• Chain double bonds and
aromatic chain groups

Regularity of repeat unit

arrangements – affects Tm only

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Polymers
 Degradation
Can be caused by long-term exposure to heat, light, or
chemicals.

Leads to reduction in chain length and causes failure or

cracking.

Main mechanism of degradation is scission (breaking of

bonds) of polymer chains.
• In random scission, breaking of bonds occurs randomly.
• In specific scission, breaking of bonds occurs at the
chain end and forms monomers.

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Polymers
 Degradation
Step-growth polymers degrade by hydrolysis in acidic or
basic environments.

Polymers may undergo degradation in the presence of

oxygen at high temperatures.

Chain-growth polymers are not stable at high

temperatures.

Microorganisms in soil or water can cause biodegradation

of polymers.

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Polymers
 Time-Dependent Deformation
Stress relaxation test:
Strain in tension to εo and hold.
Observe decrease in stress with time.

𝜀0
Relaxation modulus:
𝜎(𝑡)
𝐸𝑟 𝑡 =
𝜀0

𝐸𝑟 𝑡 Viscoelastic Relaxation Modulus

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Polymers
 Time-Dependent Deformation
There is a large decrease
in Er for T > Tg.

Representative Tg
values (°C):
Polyethylene (low density) -110
Polyethylene (high density) -90
Poly(vinyl chloride) (PVC) +87
Polystyrene +100
Polycarbonate +150
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Polymers
 Crazing During Fracture of Thermoplastic Polymers
Craze formation prior to cracking
• during crazing, localized plastic deformation
• and formation of microvoids and Fibrillar bridges

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Polymers
 Polymer Types – Fibers
Fibers - length/diameter >100
• Primary use is in textiles.

Fiber characteristics:
• high tensile strengths
• high degrees of crystallinity
• structures containing polar groups

Formed by spinning
• extrude polymer through a spinneret (a die containing
many small orifices)
• the spun fibers are drawn under tension
• leads to highly aligned chains

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Polymers
 Polymer Types – Miscellaneous
Coatings thin polymer films applied to surfaces (i.e.,
paints, varnishes)
• protects from corrosion/degradation
• decorative
• improves appearance
• can provide electrical insulation

Adhesives bonds two solid materials (adherands)

Bonding types:
• Chemical – involves intermolecular forces between the
adhesive and adherend (van der Waals forces)
• Mechanical – penetration into pores/crevices

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Polymers
 Polymer Types – Miscellaneous
Films
Produced by blown film extrusion.
Used as bags for packaging food products and other
merchandise.
Characteristics:
low density, a high degree of flexibility,
high tensile and tear strengths, resistance to attack by
moisture and other chemicals, and low permeability to
some gases, especially water vapor.

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Polymers
 Polymer Types – Miscellaneous
Foams
Gas bubbles incorporated into plastic.
Thermoplastic and thermosetting materials are used as
foams.
Used as cushions in automobiles and furniture as well as
in packaging and thermal insulation.

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Polymers
 Advanced Polymers
Ultrahigh Molecular Weight Polyethylene (UHMWPE)
Molecular weight ca. 4x106 g/mol

Outstanding properties
• high impact strength
• resistance to wear/abrasion
• low coefficient of friction
• self-lubricating surface

Important applications
• bullet-proof vests
• golf ball covers
• hip implants (acetabular cup)

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Polymers
 Advanced Polymers
Thermoplastic Elastomers
Styrene-butadiene block copolymer

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Polymers
 Summary
Limitations of polymers:
E, σy, Kc, Tapplication are generally small.
Deformation is often time and temperature dependent.

Thermoplastics (PE, PS, PP, PC):

Smaller E, σy, Tapplication
Larger KIC
Easier to form and recycle

Elastomers (rubber):
Large reversible strains!

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Polymers
 Summary
Thermosets (epoxies, polyesters):
Larger E, σy, Tapplication
Smaller KIC

Polymer applications:
• elastomers
• fibers
• coatings
• adhesives
• films
• foams
• advanced polymeric material
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Polymers