CHAPTER

10
Polymeric Materials

10-1
 Introduction to Polymers

• Polymers many parts

Polymers

Plastics Elastomers

Thermoplastics Thermosetting Plastics

Can be
Cannot be reformed
reheated and
by reheating.
formed
Set by chemical reaction.
into new
materials
10-2
 Plastics - Advantages

• Wide range of • Good insulation.

properties. • Light weight.
• Minimum finishing. • Noise Reduction.
• Minimum lubrication.

Remote Wafer bands

Control Air intake manifold
Figure 7.1
10-3
 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.

10-4
 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.

10-5
 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

10-6
 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
10-7
 Structure of Noncrystalline Linear Polymers

• Zig-Zag configuration in ethylene due to 109 degree

angle between carbon covalent bonds.
• Chains are randomly entangled.

Figure 7.4

Figure 7.5
• Entanglement increases tensile strength.
• Branching decreases tensile strength.

10-8
 Vinyl and Vinylidene Polymers

• Vinyl polymers: One of the hydrogen atom is replaced

by another atom or group of atoms.

Figure 7.6
• Vinylidene Polymers: Both hydrogen of carbon are
replaced by another atom or group of atoms.

Figure 7.7

10-9
 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
10-10
 Other Methods of Polymerization
• Stepwise Polymerization:
Monomers chemically
react with each other to
produce linear polymers
and a small molecule of
byproduct. Figure 7.10

• Network polymerization:
Chemical reaction takes
place in more than two
reaction sites
(3D network). Figure 7.11

10-11
 Industrial Polymerization

Raw Materials:
Granules, pellets,
Natural gas, Petroleum
and coal Polymerizatio powders or liquids.
n
•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. Figure 7.12

10-12
 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

Figure 7.14

• In crystalline thermoplastics, sudden decrease in

specific volume occurs due to more efficient packing of
polymer chains.

10-13
 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.

Polyethylene-folded chain

Figure 7.16 Figure 7.17

After F. Rodriguez, “priciples of Polymer Systems,” 2nd ed., McGraw-Hill, 1982,p.42

10-14 After R. L. Boysen, Olefin Polymers, in “Encyclopedia of Chemical Technology,” vol. 16, Wiley, 1981, p.405.
 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.

Figure 7.19

10-15After G. Crepsi and L. Luciani, in “Encyclopedia of Chemical Technology,” vol. 16, Wiley, 1982, p.454.
 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.

Figure 7.22

Figure 7.21
10-16
 Extrusion, Blow molding and Thermo Forming
• Extrusion: Melted plastic forced by a rotating screw
through a opening and used to produce pipes, rods etc.

Figure 7.23

• 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.
10-17
 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).

Figure 7.25

10-18
 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.

Figure 7.26

• Injection molding is also used to process thermosetting

plastics.
• Special heating-cooling jackets are added to standard
injection molding machine.
10-19
 General Purpose Thermoplastics

• Polyethylene, polyvinyl chloride (PVC) polypropylene

and polyesters account for most plastic materials sold.

Table 7.2
10-20
 Polyethylene
• Clear to whitish translucent thermoplastic.
• Types
 Low density

 High Density

 Linear low density

Table 7.3 Figure 7.28

• Applications: containers, insulation, chemical tubing,

bottles, water pond liners etc.
10-21
 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.

10-22
 Polypropylene

• Methyl group substitute every other carbon

H H
atom in carbon polymer chain.
• High melting (165-1770Cand heat deflection
C C
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.

10-23
 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.

10-24
 Polyacrylonitrile and Styrene-Acrylonitrile (SAN)
Polyacrylonitrile
SAN
H H • Random amorphous
Does not copolymer of styrene
C C Melt. and 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 instrument
and blankets.
lenses, dash components,
Commoner for SAN and knobs, blender and
ABS resins. mixer bowls.
10-25
 ABS

• ABS = Acrylonitrile + Butadiene + Styrene (Three

monomers).

Table 7.4

Figure 7.31
• Applications: Pipe and fittings, automotive parts,
computer and telephone housings etc.

10-26
 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.

10-27
 Fluoroplastics

• Monomers have one or more atoms of fluorine.

• Polytetrafluoroethylene(PTFE):
F F • Exceptionally resistant to
Melting chemicals.
C C Point • Useful mechanical properties
170 C
0
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.

10-28
 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.

10-29
 Engineering Thermoplastics

• Low density, low tensile strength.

• High insulation, good corrosion resistance.
Table 7.5

10-30
 Polyamides (Nylons)

• Main chain structure incorporates repeating amide

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

10-31
 Properties of Nylon
• High strength due to hydrogen bonding between
molecular chain.

Figure 7.35

• Flexibility of carbon chain contributes to molecular

flexibility, low melt viscosity and high lubricity.
• Applications: Electrical equipments, gears, auto parts,
packaging etc.

10-32
 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.

10-33
 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.

10-34
 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.

10-35
 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.

10-36
 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.
10-37
 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)

10-38
 Thermosetting Plastics

• High thermal and dimensional stability, rigidity,

resistance to creep, light weight.
Table 7.7

10-39
 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.

10-40
 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.

10-41
 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.

10-42
 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.

10-43
 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.

Figure 7.41
10-44
 Natural Rubber - Properties

Table 7.8

Figure 7.43

10-45
 Synthetic Rubbers
• Styrene-Butadiene rubber (SBR): Most widely used.
• Greater elasticity than natural
rubbers.
• Tougher and stronger, war
Figure 7.44
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 resistanceC C C C
to oxygen, ozone, heat and weather.
• Low temperature flexibility, high cost.H Hn

10-46
 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

10-47
 Deformation of Thermoplastics

• Below Tg Elastic deformation. Above Tg

Plastic deformation.

Elastic deformation

Elastic or plastic deformation

Plastic deformation

Figure 7.46

Figure 7.45

After T. Alfrey, “mechanical Behavior of Polymers,” Wiley-Interscience, 1967.

10-48
 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.

10-49
 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. Figure 7.49
• Thermosetting plastics can be strengthened by
reinforcements and creation of covalent bonds by
chemical reaction during setting.

10-50After J. A. Sauer and K. D. Pae, in “Introductin to Polymer Science and Technology,” Wiley, 1977, p.331.
 Effects of Temperature on Strength

• Thermoplastics soften as temperature increases.

• Strength dramatically decreases after Tg.

Figure 7.50

• Thermosets also become weaker but not viscous.

• Thermosets are more stable at high temperature than
thermoplastics.
10-51
 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 σ = Stress after time t.
  e0
= 0 Initial stress
Q
1 τ = relaxation time.
 Ce RT
T= temperature, R= molar gas constant.

10-52
 Fracture of Polymers

• Thermosetting plastics Primarily brittle mode.

• Thermoplastics ductile or brittle depending on
the temperature.

Figure 7.52
Figure 7.53

Figure 7.55

10-53
 Biopolymers

• Polymers are used in biomedical applications

 Cardiovascular, Opthalmic and Orthopaedic
implants
 Dental implants, dental cements and denture bases

• Low density, easily formed

and can be made biocompatible.

• Recent development – biodegradable polymers.

 Cardiovascular Applications

• Heart valves can be stenotic or incompetent

• Polymers are used to make artificial heart valves
• Leaflets are made from biometals
• Sewing ring made from PTFE or
PET
Connected to heart tissue
• Blood clogging is side effect
• PTFE is used as vascular graft to bypass clogged arteries.
• Blood oxygenators : Hydrophobic polymer membranes
used to oxygenate blood during bypass surgery
 Air flows on one side and blood on the other side
and oxygen diffuses into blood.
 Opthalmic Applications

• Eye glasses, contact lenses and Intraocular

implants are made of polymers.
• Hydrogel is used to make soft contact lenses
 Absorbs water and allows snug fit
 Oxygen permeable
 Made of poly-HEMA
• Hard lenses made from PMMA
 Not oxygen permeable
 Mixed with Siloxanylalkyl
Metacrylate and metacrylic
acid to make permeable and hydrophilic.
• Intraocular implants are made of PMMA
 Orthopaedic Applications

• Bone cement: Fills space between implant and

bone – PMMA
 Centrifuging and vacuum techniques minimize
porosity
• Used in joint prosthesis (Knee and Hip
replacements)
• Other applications:
 Drug delivery systems: Polymer matrix with
drug implanted inside the body
 Struture materials: High tensile and knot pull
strength.
 Non-absorbable: Polypropylene, Nylon
 Absorbable : Polyglycolic acid.
 Future – Tissue Engineering

• Polymers can be synthesized and blend to suite

the applications
• Biodegradable polymers are used as
scaffolding for generation of new tissues
• In future, tissues can be generated in vivo or in
vitro for repair or replacement.