CHAPTER

11
Polymers

8-1
 Introduction

• What is a polymer?

Poly mer
(many) (repeat unit)

repeat repeat repeat

unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)

8-2
• Originally natural polymers were used
– Wood – Rubber
– Cotton – Wool
– Leather – Silk
 Polymeric Materials

Polymers

Plastics Elastomers

Thermoplastics Thermosetting Plastics

Can be
Cannot be reformed
reheated and
by reheating.
formed
Set by chemical reaction.
into new
materials
• Wide range of • Good insulation.
properties. • Light weight.
• Minimum finishing. • Noise Reduction.
• Minimum lubrication.

Remote Wafer bands

Control Air intake manifold
Figure 7.1
 Polymer Composition

Most polymers are hydrocarbons

– i.e. made up of H and C
• Saturated hydrocarbons
– Each carbon bonded to four other atoms
H H
H
C C

H H
H

CnH2n+2
 Polymer Composition

Unsaturated hydrocarbons

• Double & triple bonds relatively reactive – can form new bonds
– Double bond – ethylene or ethene - CnH2n

H H
C C
H H

H C C H
• 4-bonds, but only 3 atoms bound to C’s
– Triple bond – acetylene or ethyne - CnH2n-2
 Isomerism

• Isomerism
– two compounds with same chemical formula can
have quite different structures
Ex: C8H18
• n-octane
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H
⇓
H3C ( CH2 ) CH3
6

• 2-methyl-4-ethyl pentane (isooctane)

CH3
H3C CH CH2 CH CH3
CH2
CH3
 Chemistry of Polymers

• Free radical polymerization

H H H H
R + C C R C C initiation
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer

• Initiator: example
H H - benzoyl peroxide
H
C O O C 2 C O =2R
H H H
 Adapted from Fig.
14.1, Callister 7e.

Note: polyethylene is just a long HC

- paraffin is short polyethylene
Bulk or Commodity Polymers
 Molecular Weight

• Molecular weight, Mi: Mass of a mole of chains.

Lower M higher M

total wt of polymer
Mn =
total # of molecules

M n = Σx i M i
M w = Σw i M i

Mw is more sensitive to
higher molecular
weights
• 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
 Molecular Weight Calculation

Example: average mass of a class

Ni Mi xi wi
# of students mass (lb)
1 100 0.1 0.054
1 120 0.1 0.065
M n = ∑ xi Mi
2 140 0.2 0.151
3 180 0.3 0.290
M w = ∑ w i Mi
2 220 0.2 0.237
1 380 0.1 0.204

Mn Mw
186 lb 216 lb
 Degree of Polymerization, n

n = number of repeat units per chain

H H H H H H H H H H H H
H C C (C C ) C C C C C C C C H ni = 6
H H H H H H H H H H H H

Mn Mw
nn = ∑ x i ni = nw = ∑ w i ni =
m m

where m = average molecular weight of repeat unit

m = Σfi mi
Chain fraction mol. wt of repeat unit i
 Molecular Structures

• Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.
 Polymers – Molecular Shape

Conformation – Molecular orientation can

be changed by rotation around the bonds
– note: no bond breaking needed
 Polymers – Molecular Shape

Configurations – to change must break bonds

• Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H

A A

C C
E E
B D D B
mirror
plane
 Tacticity

Tacticity – stereoregularity of chain

H H H H H H H H
isotactic – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R

H H H R H H H R
syndiotactic – R groups
C C C C C C C C
alternate sides
H R H H H R H H

H H H H H R H H
atactic – R groups random C C C C C C C C
H R H R H H H R
 cis/trans Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
bulky groups on same bulky groups on opposite
side of chain sides of chain
 Copolymers

two or more monomers random

polymerized together
• random – A and B
randomly vary in chain
• alternating – A and B alternating
alternate in polymer
chain block
• block – large blocks of A
alternate with large
blocks of B
• graft – chains of B
grafted on to A backbone graft
 Polymer Crystallinity

Ex: polyethylene unit cell

• Crystals must contain

the polymer chains in
some way
– Chain folded structure

10 nm
Polymers rarely 100% crystalline
• Too difficult to get all those chains
aligned crystalline
region
• % Crystallinity: % of material
that is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases. amorphous
region
 Polymer Crystal Forms

• Single crystals – only if slow careful growth

 • Spherulites – fast
growth – forms
lamellar (layered)
structures

Spherulite
surface

Nucleation site
 Spherulites – crossed polarizers

Maltese cross
 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.
 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.
 • 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
• 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).
 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. Figure 7.12
 Polymer Additives

Improve mechanical properties, processability,

durability, etc.
• Fillers
– Added to improve tensile strength & abrasion
resistance, toughness & decrease cost
– ex: carbon black, silica gel, wood flour, glass,
limestone, talc, etc.
• Plasticizers
– Added to reduce the glass transition
temperature Tg
– commonly added to PVC - otherwise it is brittle
• Stabilizers
– Antioxidants
– UV protectants
• Lubricants
– Added to allow easier processing
– “slides” through dies easier – ex: Na stearate
• Colorants
– Dyes or pigments
• Flame Retardants
– Cl/F & B
 Thermoplastics

• Polyethylene, polyvinyl chloride (PVC) polypropylene

and polyesters account for most plastic materials sold.
 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.
 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.
 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.
 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.
 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.
 ABS

• ABS = Acrylonitrile + Butadiene + Styrene (Three

monomers).

Table 7.4

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

• Low density, low tensile strength.

• High insulation, good corrosion resistance.
Table 7.5
 Polyamides (Nylons)

• Main chain structure incorporates repeating amide

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

• High thermal and dimensional stability, rigidity,

resistance to creep, light weight.
Table 7.7
 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.
 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.
 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.
 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.
 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
Natural Rubber - Properties
 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 resistance C C C C
to oxygen, ozone, heat and weather.
• Low temperature flexibility, high cost. H Hn
 Vulcanization of Polychloroprene Elastomers

2ZnCl2 + MgO
H2O OH
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
 Mechanical Properties

• i.e. stress-strain behavior of

polymers brittle polymer

σFS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
– less than metal

Strains – deformations > 1000% possible

(for metals, maximum strain ca. 10% or
less)
 Tensile Response: Brittle & Plastic

Near Failure σ(MPa) fibrillar

structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

ε
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
 Tensile Response: Elastomer Case

σ(MPa)
x brittle failure

plastic failure
x
x
elastomer
final: chains
ε are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!

• Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline 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)
• Annealing after drawing...
-- decreases alignment
-- reverses effects of drawing.
• Compare to cold working in metals!
 Thermoplastics vs. Thermosets

T
• Thermoplastics: Callister,
-- little crosslinking viscous rubber
Fig. 16.9
mobile liquid Tm
-- ductile tough
liquid
-- soften w/heating plastic
-- polyethylene Tg
polypropylene
partially
polycarbonate crystalline
polystyrene crystalline
solid
solid

• Thermosets: Molecular weight

-- large crosslinking
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin
 T and Strain Rate: Thermoplastics

• Decreasing T...
σ(MPa)
-- increases E 80 4°C Data for the
-- increases TS semicrystalline
-- decreases %EL 60 polymer: PMMA
20°C (Plexiglas)
• Increasing 40 40°C
strain rate...
-- same effects 20
as decreasing T. to 1.3
60°C
0
0 0.1 0.2 ε 0.3
 Deformation of Thermoplastics

• Below Tg Elastic deformation. Above Tg

Plastic deformation.

Elastic deformation

Elastic or plastic deformation

Plastic deformation
 Melting vs. Glass Transition Temp.

What factors affect Tm and

Tg?
• Both Tm and Tg increase with
increasing chain stiffness
• Chain stiffness increased by
1. Bulky sidegroups
2. Polar groups or sidegroups
3. Double bonds or aromatic
chain groups

• Regularity – effects Tm only

 Time Dependent Deformation

• Stress relaxation test: • Data: Large drop in Er

-- strain to εο and hold. for T5 > Tg. (amorphous
-- observe decrease in 10 rigid solid polystyrene)
Er (10s) 3 (small relax) Adapted from Fig.
stress with time. in MPa 10
15.7, Callister 7e.
transition (Fig. 15.7 is from
tensile test 10 1 region A.V. Tobolsky,
Properties and

εo strain 10-1
Structures of
Polymers, John
viscous liquid Wiley and Sons, Inc.,
σ(t) 10-3 (large relax) 1960.)

60 100 140 180 T(°C)

time Tg
• Relaxation modulus: • Sample Tg(°C) values:
σ(t ) PE (low density) - 110
E r (t ) = PE (high density) - 90
εo PVC + 87
Selected values from
Table 15.2, Callister
PS +100 7e.

PC +150
 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.
 Fracture of Polymers

• Thermosetting plastics Primarily brittle mode.

• Thermoplastics ductile or brittle depending on
the temperature.
 Polymer Fracture

Crazing ≅ Griffith cracks in metals

– spherulites plastically deform to fibrillar structure
– microvoids and fibrillar bridges form

alligned chains

fibrillar bridges microvoids crack

 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.
 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.
 Processing of Plastics

• Thermoplastic –
– can be reversibly cooled & reheated, i.e. recycled
– heat till soft, shape as desired, then cool
– ex: polyethylene, polypropylene, polystyrene, etc.
• Thermoset
– when heated forms a network
– degrades (not melts) when heated
– mold the prepolymer then allow further reaction
– ex: urethane, epoxy
 Processing Plastics - Molding

• Compression and transfer molding

– thermoplastic or thermoset
 Processing Plastics - Molding

• Injection molding
– thermoplastic & some thermosets
Processing Plastics – Extrusion