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CHAPTER

8
Polymeric Materials

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Introduction to Polymers

Polymers

many types
Polymers

Plastics

Thermoplastics
Can be
reheated and
formed
into new
materials
2

Elastomers

Thermosetting Plastics
Cannot be reformed
by reheating.
Set by chemical reaction.
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Plastics - Advantages

Wide range of properties.


Minimum finishing.
Minimum lubrication.

Remote
Control
3

Good insulation.
Light weight.
Noise Reduction.

Wafer bands
Air intake manifold
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Polymerization

Chain growth polymerization: Small molecules covalently


bond to form long chains (monomers) which in turn bond
to form polymers.
Example: Ethylene
H
n

H
Heat

Pressure
Catalyst

H n

DP =

n=degree of
Polymerization (DP).
(range: 3500-25000

Molecular mass of polymer(g/mol)


Mass of a mer (g/mer)

Functionality: Number of active bonds in a monomer.


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Chain Polymerization - Steps

Initiation:
A Radical is needed.
Example H2O2

In General

One of free radicals react with ethylene molecule to form


new longer chain free radical.
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Chain Polymerization Steps (cont..)

Propagation: Process of extending polymer chain by


addition of monomers.
R CH2

CH2 + CH2

CH2

R CH2 CH2 CH2 CH2

Energy of system is lowered by polymerization.


Termination: By addition of termination free radical.
Combining of two chains
Impurities.

R(CH2 CH2)m + R(CH2 CH2)n

R(CH2 CH2)m R (CH2

Coupling of two chains


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CH2)n R

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Average Molecular Weight

Average molecular weight determined by special physical


and chemical techniques.

Mm

fi M i
fi

Example:

M m = average molecular weight of


thermoplastics.
Mi = Mean molecular weight of each
molecular range selected.
fi = Weight fraction of the material having
Molecular weights of a selected molecular
Weight range.

Mm

= 19,550
1
= 19,550 g/mol

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Structure of Noncrystalline Linear Polymers

Zig-Zag configuration in ethylene due to 109 degree angle


between carbon covalent bonds.
Chains are randomly entangled.

Entanglement increases tensile strength.


Branching decreases tensile strength.
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Vinyl and Vinylidene Polymers

Vinyl polymers: One of the hydrogen atom is replaced by


another atom or group of atoms.

Vinylidene Polymers: Both hydrogen of carbon are


replaced by another atom or group of atoms.

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Homopolymer and Copolymers

Homopolymers: Polymer chain is made up of single


repeating units.
Example: AAAAAAAA
Copolymers: Polymer chains made up of two or more
repeating units.

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Random copolymers: Different monomers randomly arranged in


chains. Eg:- ABBABABBAAAAABA
Alternating copolymers: Definite ordered alterations of
monomers. Eg:- ABABABABABAB
Block copolymers: Different monomers arranged in long blocks.
Eg:- AAAAA.BBBBBBBB
Graft copolymers: One type of monomer grafted to long chain of
another. Eg: AAAAAAAAAAAAAAAAAAA
B
B
B
B
B
B
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Other Methods of Polymerization

Stepwise Polymerization:
Monomers chemically
react with each other to
produce linear polymers
and a small molecule of
byproduct.

Network polymerization:
Chemical reaction takes
place in more than two
reaction sites
(3D network).
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Industrial Polymerization
Raw Materials:
Natural gas, Petroleum
and coal

Granules, pellets,
Polymerization powders or liquids.

Bulk polymerization :
Monomer and activator
mixed in a reactor and
heated and cooled as desired
Solution polymerization: Monomer
dissolved in non-reactive solvent
and catalyst.
Suspension polymerization: monomer
and catalyst suspended in water.
Emulsion polymerization: Monomer
and catalyst suspended in water along with emulsifier.
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Solidification of Thermoplastics.

There is no sudden change in specific volume on cooling


in noncrystalline thermoplastics.
Tg = glass transition temperature.
Glass
brittle

below

Tg

above

Rubbery

Tg for polyethylene is 1100C


For PVC it is 820C

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In crystalline thermoplastics, sudden decrease in specific


volume occurs due to more efficient packing of polymer
chains.

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Structure of Partly Crystalline Thermoplastics

Longest dimension of crystalline region is 5-50 nm.


Fringed micelle model: Long polymer chains of 5000 nm
wandering successively through a series of disordered and
ordered region.
Folded chain model: sections of molecular chains folding
on themselves.

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Stereoisomerism in Thermoplastics

Stereoisomer:- Same chemical composition but different


structural arrangements.
Atactic stereoisomer:- Pendent methyl
group of polypropylene is randomly
arranged on either side of main carbon
chain.
Isotactic stereoisomer:- The pendent
methyl group is always on same side
of the carbon chain.
Syndiotactic stereoisomer:- The
pendant group regularly alternates
from one side of the chain to the
other side.

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Processing of Plastic Materials

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Injection Molding: uses


reciprocating screw
mechanism.
More uniform delivery
of melt for injection.
High quality, low labor
cost, but high initial cost.

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Extrusion, Blow molding and Thermo Forming

Extrusion: Melted plastic forced by a rotating screw


through a opening and used to produce pipes, rods etc.

Blow molding: Compressed air is blown into heated


cylinder or pipe of plastic to press it against the wall of
mold.
Thermoforming: heated plastic sheet is forced into contours
of a mold by pressure.
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Processes for Thermosetting

Compression molding: Pressure is applied on


heated plastic by upper mold and the molten plastic
fills the cavities.
Low initial cost, simple.
Less wear and abrasion
of molds.
Difficult to mold complex
parts
Creates flash (spills).

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Transfer Molding

A plunger forces plastic resin, placed outside mold, into mold


cavities through
runners and gate.
No flash formed.
Multiple parts at a
time.
Can be used for small
and intricate parts.

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Injection molding is also used to process thermosetting plastics.


Special heating-cooling jackets are added to standard injection
molding machine.

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General Purpose Thermoplastics

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Polyethylene, polyvinyl chloride (PVC) polypropylene


and polyesters account for most plastic materials sold.

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Polyethylene

Clear to whitish translucent thermoplastic.


Types
Low density
High Density
Linear low density

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Applications: containers, insulation, chemical tubing, bottles,


water pond liners etc.
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Polyvinyl Chloride and Copolymers


PVC is amorphous, does not recrystallize.
Chlorine atoms produce large dipole moments and also
hinder electrostatic repulsion.
PVC homopolymer has high strength (7.5 to 9 KSI) and is
brittle.
Compounding of PVC: Modifies and improves properties.
Plasticizers: Impart flexibility. Eg Phthalate.
Heat Stabilizers: Prevent thermal degradation. Eg lead and tin
compounds.
Lubricants: Aid in melt flow of PVC. Eg Waxes and fatty esters.
Fillers: Lower the cost. Eg Calcium Carbonate.
Pigments : Give color.

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Polypropylene
H

Methyl group substitute every other carbon


atom in carbon polymer chain.
High melting (165-1770C) and heat deflection
temperature.

H CH3 n

Low density, good chemical resistance, moisture


resistance and heat resistance.
Good surface hardness and dimensional stability.
Applications: Housewares, appliances, packaging,
laboratory ware, bottles, etc.

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Polystyrene
H

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Phenyl ring present on every other


carbon atom.
Very inflexible, rigid, clear and brittle.
Low processing cost and good dimensional
stability.
Poor weatherability and easily attacked
by chemicals.

Applications: Automobile interior parts, dials and knobs


of appliances and housewares.

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Polyacrylonitrile and Styrene-Acrylonitrile (SAN)


Polyacrylonitrile
H
C

H
C

Does not
Melt.

H C N n
High strength.
Good resistance to
moisture and solvents.
Applications: sweaters
and blankets. Commoner
for SAN and ABS resins.
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SAN

Random amorphous
copolymer of styrene and
acrylonitrile.
Better chemical
resistance, high heat
deflection temperature,
toughness and load
bearing characteristics
than polyester alone.
Applications: Automotive
instrument lenses, dash
components, knobs,
blender and mixer bowls.

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ABS

ABS = Acrylonitrile + Butadiene + Styrene (Three


monomers).

Applications: Pipe and fittings, automotive parts, computer


and telephone housings etc.
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Polymethyl Methacrylate (PMMA)

An acrylic commonly known as Plexiglas.


H CH3
C

C
O

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Rigid and relatively strong.


Completely amorphous and
very transparent.

CH3 n

Applications: Glazing of aircraft, boats, skylights,


advertising signs etc.

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Fluoroplastics

Monomers have one or more atoms of fluorine.


Polytetrafluoroethylene(PTFE):
F F
Exceptionally resistant to
Melting
chemicals.
Point
C C
Useful mechanical properties
0
170 C
at a wide temperature range.
F F n
High impact strength but low
tensile strength.
Good wear and creep resistance.

Applications: Chemically resistant pipe, parts, molded


electrical components, nonstick coating etc.
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Polychlorotrifluroethylene (PCTFE)
F

Cl n

Melting
Point
2180C

Chlorine atom substitutes


for every fourth fluorine atom.
Can be extruded and mold
easily.

Applications: Gaskets, chemical processing equipments, seals


and electric components.

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Engineering Thermoplastics

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Low density, low tensile strength.


High insulation, good corrosion resistance.

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Polyamides (Nylons)

Main chain structure incorporates repeating amide group.


O
H
Amide linkage
C
N
Processed by injection molding.
Examples:

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Properties of Nylon

High strength due to hydrogen bonding between


molecular chain.

Flexibility of carbon chain contributes to molecular


flexibility, low melt viscosity and high lubricity.
Applications: Electrical equipments, gears, auto parts,
packaging etc.
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Polycarbonate
High strength, toughness and
dimensional stability.
Very high impact strength.
high heat deflection
temperature.
Resistance to corrosion.

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Applications: Precision parts, cams, gears, helmets, power


tool housings and computer terminals.

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Phenyl Oxide Based Resins

Produced by oxidative coupling of phenolic monomers.

High rigidity, strength, chemical resistance, dimensional


stability and heat deflection temperature.
Wide temperature range, low creep
High modulus.

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Applications: Electric connectors, TV tuners, small


machine housing, dashboards and grills.

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Acetals

Strongest (68.9 Mpa) and stiffest (2820 Mpa)


thermoplastics.
2 Types
H
Homopolymers
Polyoxymethylene
Copolymers
mp: 1750C
C O

Excellent long term load carrying capacity


n
and dimensional stability.
Homopolymer is harder and rigid than copolymer.
Low wear and friction but flammable.
Applications: Fuel systems, seat belts, window handles of
automobiles, couplings, impellers, gears and housing.
H

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Thermoplastic Polyesters
Phenylene ring provides rigidity.
Good strength and resistant to most chemicals.
Good insulator: independent of temperature and humidity.
Applications: Switches, relays, TV tuner components,
circuit boards, impellers, housing and handles.

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Polysulfone and Polyphenylene Sulfide.

Polysulfone: Phenylene ring provides high strength and


rigidity.
Can be used for long time
at high temperature.

Applications: Electrical connectors, cores, circuit boards,


pollution control equipments.
Polyphenylene Sulfide:0
Mp:
288
C
Rigid and strong.
S
Highly crystalline.
n

37

No chemical can dissolve it below 2000C.


Applications: Chemical process equipment, emission
control equipment, electrical connectors.
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Polyetherimide and Polymer Alloys


Polyetherimide:

High heat and creep resistance and rigidity.


Good electric insulation.
Applications: High voltage circuit breaker housing, coils etc.
Polymer alloys: Mixture of structurally different homopolymers
or copolymers
optimizes properties.
Some degree of compatibility needed.
Example:- Bayblend MC2500 (ABS/Polycarbonate)
38

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Thermosetting Plastics

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High thermal and dimensional stability, rigidity, resistance


to creep, light weight.

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Phenolics

40

Low cost, good insulating and mechanical properties.


Produced by polymerization of phenol and formaldehyde.
General purpose compounds: Usually wood flour filled to
increase impact resistance.
High impact strength compounds: Filled with cellulose and
glass fibers.
High electrical insulating compounds: Mineral (Mica) filled.
Heat resistant compounds: Mineral filled.
Applications: Wiring devices, auto transmission parts,
plywood lamination, adhesives, shell molding.

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Epoxy Resins

Good adhesion, chemical resistance and mechanical


properties.
O
Epoxide
CH2
C
group
H

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High molecular mobility, low shrinkage during hardening.


Applications: Protective and decorative coating, drum
lining, high voltage insulators and laminates.

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Unsaturated Polyesters

Have reactive double


Carbon-Carbon covalent
bonds.

Low viscosity and can be reinforced with low viscosity


materials.
Open mold lay up or spray up techniques are used to
process many small parts.
Compression molding is used for big parts.
Applications: Automobile panels and body parts, boat
hulls, pipes, tanks etc.
42

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Amino Resins (Ureas and Melamines)

Formed by reaction of formaldehydes with compounds


having NH2 group.

Combined with cellulose fillers to produce low cost


products with good mechanical properties.
Applications: Electrical wall plates, molded
dinnerware, buttons, control buttons, knobs, flooring
etc.
43

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Elastomers (Rubbers)

Natural rubber: Produced from latex of Havea Brasiliensis


tree.
H
C
H

CH3
C

H
C

H
C
H

Vulcanization: Heating rubber with sulfur and lead


carbonate.
Increases tensile strength.
Restricts molecular movement
by crosslinking of molecules.

44

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Natural Rubber - Properties

45

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Synthetic Rubbers

46

Styrene-Butadiene rubber (SBR): Most widely used.


Greater elasticity than natural
rubbers.
Tougher and stronger, war
resistant.
Absorbs organic solvents and swell.
Nitrile Rubbers: 55-82% Butadiene and 45-18%
acrylonitrile.
Resistance to solvents
H Cl H H
and wear. Less flexible.
Polychloroprene: Increased resistance
C C C C
to oxygen, ozone, heat and weather.
Low temperature flexibility, high cost.
H
Hn
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Vulcanization of Polychloroprene Elastomers

2ZnCl2 + MgO
OH
H2O
2Zn
+ MgCl
Cl

Silicone Rubbers:
Wide temperature
range.
Used in gaskets,
electric insulation etc.
47

X
Si
X

CH3
Example

Si
n

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi

CH3

O
n

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Deformation of Thermoplastics

Below Tg
deformation.

Elastic deformation. Above Tg

Plastic

Elastic deformation

Elastic or plastic deformation

Plastic deformation

Tensile stress vs strain curves for polymethyl methacrylate


(PMMA) at various temperature.

48

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Strengthening of Thermoplastics
Increasing average molecular mass increases strength
upto a certain critical mass.
Degree of crystallinity increases strength, modulus
of elasticity and density.
Chain slippage during permanent deformation can
be hindered by introduction of pendant atomic
groups to main carbon chain.
Strength can be increased by bonding highly polar
atoms on the main carbon chain.

49

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Strengthening of Thermoplastics (Cont..)

Strength can be increased by introduction of oxygen and


nitrogen atoms into main carbon chain.
Introduction of phenylene
ring into main polymer
chain with other elements
increases strength.
Adding plastic fibers
increases the strength.
Thermosetting plastics can be strengthened by
reinforcements and creation of covalent bonds by chemical
reaction during setting.
50

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Effects of Temperature on Strength

Thermoplastics soften as temperature increases.


Strength dramatically decreases after Tg.

Thermosets also become weaker but not viscous.


Thermosets are more stable at high temperature than
thermoplastics.
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Creep and Stress Relaxation of Polymers

Creep increases with increased tensile stress and


temperature.
Creep is low below Tg. Above Tg, the behavior is
viscoelastic.
Glass fiber reinforcements decreases creep.
Stress relaxation: Decrease in stress at constant
strain.
Due to breaking and formation of secondary
bonds.
t
= Stress after time t.
0 = Initial stress
0e

1
Ce
52

Q
RT

= relaxation time.
T= temperature, R= molar gas constant.

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Fracture of Polymers
Thermosetting plastics
Primarily brittle mode.
Thermoplastics
ductile or brittle depending on the
temperature.

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Exercise
1.
2.
3.
4.
5.
6.
7.
8.

54

Define and differentiate polymers, plastics, and elastomers.


What is the functionality of a monomer? Distinguish between a
bifunctional and trifunctional monomer.
Distinguish between a homopolymer and a copolymer.
What are three basic raw materials used to produce the basic chemicals
needed for the polymerization of plastic materials?
Describe and illustrate the fringed-micelle and folded-chain models for
the structure of partly crystalline thermoplastics.
Describe the extrusion process for processing thermoplastics.
Define an engineering thermoplastic. Why is this definition arbitrary?
What is the basic repeating chemical structural unit for polycarbonates?
What is the carbonate linkage? What are the common trade names for
polycarbonate?

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Exercise
7.
8.
9.
10.
11.
12.

13.

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What are the two most important engineering thermoplastic polyesters? What
are their repeating chemical structural units?
What is the repeating chemical structural unit for polysulfone?
What are elastomers? What are some elastomeric materials?
What are chemical structural isomers?
(a) What are SAN resins? (b) What desirable properties do SAN thermoplastics
have? (c) What are some of the applications for SAN thermoplastics?
(a) What do the letters A, B, and S stand for in the ABS thermoplastic? (b) Why
is ABS sometimes referred to as a terpolymer? (c) What important property
advantages does each of the components in ABS contribute? (d) Describe the
structure of ABS.
(a) What is the repeating chemical structural unit for polymethyl methacrylate?
(b) By what trade names is PMMA commonly known? (c) What are some of the
important properties of PMMA that make it an important industrial plastic?

Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi