Polymer

CHAPTER
5
Polymeric Materials
1
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display
Introduction to Polymers
• Polymers many types
Polymers
Plastics Elastomers
Thermoplastics Thermosetting Plastics

Can be
reheated and Cannot be reformed
formed by reheating.
Set by chemical reaction.
into new
materials
2
Foundations of Materials Science and Engineering, 5th Edn. Smith and Hashemi
Plastics - Advantages
• Wide range of properties. • Good insulation.

• Minimum finishing. • Light weight.
• Minimum lubrication. • Noise Reduction.
Remote Wafer bands

Control Air intake manifold
3
Polymerization
• Chain growth polymerization: Small molecules covalently

bond to form long chains (monomers) which in turn bond
to form polymers.
• Example: Ethylene
n=degree of
Polymerization (DP).
H H H H (range: 3500-25000
Heat
n C C C C
Pressure
Catalyst
H H H H n
Molecular mass of polymer(g/mol)
DP = Mass of a mer (g/mer)
• Functionality: Number of active bonds in a monomer.
4
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.
5
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 CH2)n R’

Coupling of two chains
6
Average Molecular Weight
• Average molecular weight determined by special physical

and chemical techniques.
 fi M i M m = average molecular weight of

Mm  thermoplastics.
 fi Mi = Mean molecular weight of each
molecular range selected.
• Example: fi = Weight fraction of the material having
Molecular weights of a selected molecular
Weight range.
= 19,550
Mm
1
= 19,550 g/mol
7
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.
8
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.
9
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).
10
Industrial Polymerization
Raw Materials: Granules, pellets,

Natural gas, Petroleum
and coal 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.
11
Solidification of Thermoplastics.
• There is no sudden change in specific volume on cooling

in noncrystalline thermoplastics.
Tg = glass transition temperature.
Glass below above Rubbery
Tg
brittle
Tg for polyethylene is –1100C

For PVC it is 820C
12
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.
 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
13
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.
14
Processing of Plastic Materials
• Injection Molding: uses

reciprocating screw
mechanism.
• More uniform delivery
of melt for injection.
• High quality, low labor
cost, but high initial cost.
15
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.
16
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).
17
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.
• Injection molding is also used to process thermosetting

plastics.
• Special heating-cooling jackets are added to standard
18 injection molding machine.
General Purpose Thermoplastics
• Polyethylene, polyvinyl chloride (PVC) polypropylene

and polyesters account for most plastic materials sold.
19
Polyethylene
• Clear to whitish translucent thermoplastic.
• Types
 Low density
 High Density
 Linear low density
• Applications: containers, insulation, chemical tubing,

bottles, water pond liners etc.
20
Polyvinyl Chloride and Copolymers
• PVC is amorphous, does not recrystallize.

• 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.
21
Polypropylene
• Methyl group substitute every other carbon

H H
atom in carbon polymer chain.
C C • 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.
22
Polystyrene
H H • Phenyl ring present on every other

carbon atom.
C C • Very inflexible, rigid, clear and brittle.
• Low processing cost and good dimensional
H stability.
n • Poor weatherability and easily attacked
by chemicals.
• Applications: Automobile interior parts, dials and knobs

of appliances and housewares.
23
Polyacrylonitrile and Styrene-Acrylonitrile (SAN)

Polyacrylonitrile
SAN
H H • Random amorphous
Does not copolymer of styrene and
C C Melt. acrylonitrile.
• Better chemical
H C N n resistance, high heat
deflection temperature,
• High strength. toughness and load
• Good resistance to bearing characteristics
moisture and solvents. than polyester alone.
• Applications: sweaters • Applications: Automotive
and blankets. Commoner instrument lenses, dash
components, knobs,
for SAN and ABS resins. blender and mixer bowls.
24
ABS
• ABS = Acrylonitrile + Butadiene + Styrene (Three

monomers).
• Applications: Pipe and fittings, automotive parts, computer

and telephone housings etc.
25
Polymethyl Methacrylate (PMMA)
• An acrylic commonly known as Plexiglas.

H CH3
• Rigid and relatively strong.
C C • Completely amorphous and
O very transparent.
H C
CH3 n
• Applications: Glazing of aircraft, boats, skylights,

advertising signs etc.
26
Fluoroplastics
• Monomers have one or more atoms of fluorine.

• Polytetrafluoroethylene(PTFE):
F F • Exceptionally resistant to
Melting chemicals.
C C Point • 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.
27
Polychlorotrifluroethylene (PCTFE)
F F
Melting • Chlorine atom substitutes
C C Point for every fourth fluorine atom.
2180C •Can be extruded and mold
F Cl n easily.
Applications: Gaskets, chemical processing equipments, seals

and electric components.
28
Engineering Thermoplastics
• Low density, low tensile strength.

• High insulation, good corrosion resistance.
29
Polyamides (Nylons)
• Main chain structure incorporates repeating amide group.

O H
Amide linkage
C N
• Processed by injection molding.
• Examples:
30
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.
31
Polycarbonate
• High strength, toughness and

dimensional stability.
• Very high impact strength.
• high heat deflection
temperature.
• Resistance to corrosion.
• Applications: Precision parts, cams, gears, helmets, power

tool housings and computer terminals.
32
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.
• Applications: Electric connectors, TV tuners, small

machine housing, dashboards and grills.
33
Acetals
• Strongest (68.9 Mpa) and stiffest (2820 Mpa)

thermoplastics.
H 2 Types
Polyoxymethylene • Homopolymers
C O mp: 1750C • Copolymers
H • 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.
34
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.
35
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:-
• Rigid and strong. Mp: 2880C
S
• Highly crystalline.
n
• No chemical can dissolve it below 2000C.

• Applications: Chemical process equipment, emission
control equipment, electrical connectors.
36
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)
37
Thermosetting Plastics
• High thermal and dimensional stability, rigidity, resistance

to creep, light weight.
38
Phenolics
• 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.
39
Epoxy Resins
• Good adhesion, chemical resistance and mechanical

properties. O Epoxide
CH2 C group
• High molecular mobility, low shrinkage during hardening.

• Applications: Protective and decorative coating, drum
lining, high voltage insulators and laminates.
40
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.
41
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.
42
Elastomers (Rubbers)
• Natural rubber: Produced from latex of Havea Brasiliensis

tree.
H CH3 H H
C C C C
H H
n
• Vulcanization: Heating rubber with sulfur and lead

carbonate.
• Increases tensile strength.
• Restricts molecular movement
by crosslinking of molecules.
43
Natural Rubber - Properties
44
Synthetic Rubbers
• 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
45
Vulcanization of Polychloroprene Elastomers
2ZnCl2 + MgO
OH
H2O
2Zn + MgCl
Cl
• Silicone Rubbers: X CH3

• Wide temperature Example
range. Si O Si O
• Used in gaskets,
X n CH3
electric insulation etc. n
46
SKIP FOR LATER
• How much sulfur must be added to 70 g of butadiene

rubber to cross-link 3.0 percent of the mers? (Assume all
sulfur is used to cross-link the mers and that only one
sulfur atom is involved in each cross-linking bond.)
• If 5 g of sulfur is added to 90 g of butadiene rubber, what
is the maximum fraction of the cross-link sites that can be
connected?
• If 3 kg of sulfur is added to 300 kg of butadiene rubber,
what fraction of the cross-links are joined?
• A butadiene-styrene rubber is made by polymerizing one
monomer of styrene with seven monomers of butadiene. If
20 percent of the cross-link sites are to be bonded with
sulfur, what weight percent sulfur is required?
47
Deformation of Thermoplastics
• Below Tg Elastic deformation. Above Tg Plastic

deformation.
Elastic deformation
Elastic or plastic deformation
Plastic deformation
48
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
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
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.
51
Copyright © The McGraw-Hill Companies, Inc.52Permission required for reproduction or display
Fracture of Polymers
• Craze = produce a network of fine cracks on (a surface).

• Thermosetting plastics Primarily brittle mode.
• Thermoplastics ductile or brittle depending on the
temperature.
52
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• Biodegradable plastic is not the best way to

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• 100 words
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CHAPTER

• Polymers many types

Thermoplastics Thermosetting Plastics

• Wide range of properties. • Good insulation.

Remote Wafer bands

• Chain growth polymerization: Small molecules covalently

Chain Polymerization - Steps

• One of free radicals react with ethylene molecule to form

Chain Polymerization – Steps (cont..)

• Propagation: Process of extending polymer chain by

R CH2 CH2 + CH2 CH2 R CH2 CH2 CH2 CH2

• Energy of system is lowered by polymerization.

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

Average Molecular Weight

• Average molecular weight determined by special physical

 fi M i M m = average molecular weight of

Structure of Noncrystalline Linear Polymers

• Zig-Zag configuration in ethylene due to 109 degree angle

• Entanglement increases tensile strength.

Vinyl and Vinylidene Polymers

• Vinyl polymers: One of the hydrogen atom is replaced by

• Vinylidene Polymers: Both hydrogen of carbon are

Other Methods of Polymerization

Raw Materials: Granules, pellets,

• There is no sudden change in specific volume on cooling

Tg for polyethylene is –1100C

Homopolymer and Copolymers

• Homopolymers: Polymer chain is made up of single

Processing of Plastic Materials

• Injection Molding: uses

Extrusion, Blow molding and Thermo Forming

• Extrusion: Melted plastic forced by a rotating screw

• Blow molding: Compressed air is blown into heated

Processes for Thermosetting

• Compression molding: Pressure is applied on

• Injection molding is also used to process thermosetting

General Purpose Thermoplastics

• Polyethylene, polyvinyl chloride (PVC) polypropylene

 Linear low density

• Applications: containers, insulation, chemical tubing,

Polyvinyl Chloride and Copolymers

• PVC is amorphous, does not recrystallize.

• Methyl group substitute every other carbon

H H • Phenyl ring present on every other

• Applications: Automobile interior parts, dials and knobs

Polyacrylonitrile and Styrene-Acrylonitrile (SAN)

• ABS = Acrylonitrile + Butadiene + Styrene (Three

• Applications: Pipe and fittings, automotive parts, computer

Polymethyl Methacrylate (PMMA)

• An acrylic commonly known as Plexiglas.

• Applications: Glazing of aircraft, boats, skylights,

• Monomers have one or more atoms of fluorine.

• Applications: Chemically resistant pipe, parts, molded

Applications: Gaskets, chemical processing equipments, seals

• Low density, low tensile strength.

• Main chain structure incorporates repeating amide group.

• High strength due to hydrogen bonding between

• Flexibility of carbon chain contributes to molecular

• High strength, toughness and

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

Phenyl Oxide Based Resins

• Produced by oxidative coupling of phenolic monomers.

• High rigidity, strength, chemical resistance, dimensional

• Wide temperature range, low creep