University of Windsor

MECH 8000 Automotive Materials

Polymers
Polymers
⚫ Polymers are organic ◼ Easy to flow and form
materials composed of ◼ Low stiffness (limits use)
very large chain-like ◼ Soften or decompose at
molecules built from high temperatures
one or more repeating ◼ Corrosion resistant
compared to metals
units called monomers
◼ Not solvent resistant
⚫ Polymers have unique ◆ Nail polish remover can
properties compared to decompose some
other engineering ◆ However, HF acid is
stored in plastic not
materials glass
◼ Lightweight
◼ Electrical and thermal
insulators
Polymerization
⚫ The joining of individual monomers
◼ Example: polyethylene (C2H4) from ethylene
monomer
H H H H
| | | |
C=C —C—C—
| | | |
H H H H
Ethylene Polyethlyene (PE)
 Degree of Polymerization
⚫ Polymers properties are ⚫ A polyethylene sample
determined by the has an average
molecular chain lengths molecular weight of
and the type of chain 25,000 g/mole. What is
linkage the average degree of
MW polymer polymerization
n= ⚫ C2H4 = 2C + 4H
MWmer ◼ 2 x 12.01 g/mole
◼ 4 x 1.008g/mole
⚫ n = degree of
◼ 28.072 g/mole of mers
polymerization
⚫ n = 25,000 / 28.072
⚫ MW = molecular weight
= 891
Addition Polymerization
⚫ Chain growth process ⚫ Example
⚫ 3 stages ⚫ Adding hydrogen
◼ Initiation peroxide (H2O2) to
◼ Propagation ethylene monomers to
◼ Termination form polyethylene
⚫ H2O2 dissociates into 2
hydroxyl groups OH-
⚫ Initiation begins when
an OH- “attacks” an
ethylene monomer
 Initiation
⚫ H2O2 dissociates into 2 hydroxyl groups OH-
⚫ Initiation begins when an OH- “attacks” an
ethylene monomer

H H H H
| | | |
H-O- C = C H – O – C –C –
| | | |
H H H H
Propagation

H H H H
| | | |
H–O–C–C– C=C
| | | |
H H H H

H H H H
| | | |
H–O–C–C–C–C–
| | | |
H H H H
 Termination
H H H H H H H H
| | | | | | | |
H – O – C – C – C – C – …… – C – C – C – C – O – H
| | | | | | | |
H H H H H H H H

⚫ Upon polymerization, the mixture becomes

viscous
⚫ Reaction stops when monomers can no
longer reach the chain ends
 Condensation Polymerization
⚫ Step growth process results in a by-product
which must be removed
◼ Example: Nylon-6 polymerization produces water

water
O O
|| ||
H-N-C-C-C-C-C-C-O-H H-N-C-C-C-C-C-C-O-H
| |
H H
3-Dimensional Polymers
⚫ PE can bond only at the 2 ends of the mer
◼ Produces linear or chain molecule
◼ Referred to a bifunctional
⚫ Crosslinked and network polymers form
additional bonds between mers to provide a
3D structure
⚫ Polyfunctionality required additional bonding
◼ Isoprene rubber has a double bond remaining
after the polymerization
◼ Double bond acts as an additional bonding site
Vulcanized Rubber
⚫ In 1839 Charles isoprene mer
Goodyear discovered H H CH3 H
the vulcanization -C - C = C - C-
process, which forms H H
links between polymer
chains 2 fully crosslinked mers
◼ Polyisoprene
◆ Hevea rubber H H CH3 H
◼ 2 mers linked by 2 sulfur -C - C - C - C-
atoms H H
◼ ~2% sulfur added S S
◼ ~4% of double bonds H H
crosslinked -C - C - C - C-
H H CH3 H
Crosslinked vs. Network
⚫ Isoprene rubber and ⚫ Phenol formaldehyde
synthetic rubbers are ◼ Also called Bakelite
crosslinked ◼ Metallographic mounting
◼ Random links between material
mers
⚫ A polymer molecule
with a high degree of
crosslinking is referred
to as a polymer network
⚫ Epoxy and phenolics
are networked
◼ Tight 3D network
 Bakelite Can Be Networked

H atoms
available for
networking
 Thermoplastic & Thermosetting
⚫ Thermoplastic polymers can be soften and
melt at higher temperatures
◼ Mostly linear polymers, sometimes branched
◼ Chains slide past each other
◼ Polyethylene
⚫ Once thermosetting polymers are formed,
they cannot be softened and reshaped
◼ Decompose and burn at elevated temperatures
◼ Crosslinking prevents chain sliding
◼ Expoxy, bakelite
Configuration
Thermoplastics:
⚫ Homopolymer –all the same mer (PE)
⚫ Copolymers are polymer “alloys”
◼ 2 or more different mers
◼ Alternating
◆ Ordered ABABABA
◆ Block AAABBBAAAABBBAABBBBAAAA
◆ Random AABABABBABABAAB
◼ Branched
 ABS is a Branched Copolymer
⚫ Acrylonitrile-butadiene-styrene ⚫ Acrylonitrile
◼ Good impact, mechanical properties ◼ Heat/chemical
◼ 2% of the polymer market by weight resistance H H
◼ Drainage and vent pipe, telephones | |
◼ B=chain; A,S = branches C=C
| |
⚫ Butadiene = impact strength
⚫ Styrene H C =N
H H H H ◼ Surface gloss
| | | | ◼ Rigidity H H
C=C–C=C | |
| | C=C
H H |
H
Stereoisomerism in Thermoplastics
⚫ Stereoisomerism – ⚫ Syndiotactic
same molecular ◼ Side groups alternate

formula but different R R

architecture C-C-C-C-C-C-C-C-C-C
R R

⚫ Isotactic ⚫ Atactic
◼ Side groups (R) line up ◼ Random position of side
groups

R R R R R R
C-C-C-C-C-C-C-C-C-C C-C-C-C-C-C-C-C-C-C
R R R
Crystallization of Polymers
⚫ Long chains make
crystallization difficult
because bonds can’t be
broken and reformed
⚫ Only isotactic and
syndiotactic can
crystallize
◼ Regular arrangement of
side groups
⚫ Besides crystals, Spherulites (crystals) in
polymers can exist in a low-density polyethylene
kinked or intertwined (LDPE)
state
Polymer Crystallization Models

~ 100 carbon atoms

Lamellar model

Folded-chain model
 Show & Tell

Car Part Polymer

Trim Panels (3) Polypropylene (PP), ABS
Impact Absorber Thermoplastic Olefin (TPO)
Dashboard ABS/Polycarbonate(PC)
Door Outer Panel ABS/Polycarbonate(PC)
Handle Polypropylene (PP)
Fog Light Cover Thermoplastic Elastomeric
Olefin (TEO)
Tire Elastomers
 Application Material Processing Method
Load-Bearing Glass-fiber reinforced Pressing of resin
- bumper beams polyester resins compounds
Moldings/covers Polyurathane Injection Molding
- front apron Polypropylene
- spoiler Polyethlene
- wheel-well liners
- radiator grill
Acrylonitrile-butadiene-
- hood styrene (ABS)
- fenders Polycarbonate
- trunk
- fuel tanks
Protective Polyvinyl chloride Injection Molding/
Moldings Ethylene-Propylene Extrusion
Terpolymers
Energy Polyurethane Liquid Reaction
Absorbing Foam Foaming
Instrument Panels (IP)

⚫ Polycarbonate/ABS resins
⚫ Introduction of airbags in IP design
⚫ Injection Molding vs. Blow Molding
Instrument Panels (IP)
Engine
⚫ ULTEM polyetherimide (PEI) resin to replace
aluminum under the hood for 1st time

• High-performance
amorphous resin from GE

• Complete air
management modules
can be made of
thermoplastic
Throttle Body
#1 Polyethylene
⚫ Largest sales in the ⚫ Flexible chains
world ⚫ Most extensively used
◼ 29% by weight of polymer
polymer market
◼ Electrical insulation on
⚫ 110-137°C melting point wires
⚫ -110°C glass transition ◼ Chemical tubing
temperature ◼ Housewares
◼ Containers and
H H packaging materials
| |
— C—C—
| |
H H
Types of Polyethylene
⚫ High density
polyethylene
(HDPE)(fuel tanks)
◼ Straight chain structure
⚫ Low density
polyethylene (LDPE)
◼ Branched chain structure
⚫ Linear low density
polyethylene (LLDPE)
◼ Linear chain with short
branches
⚫ Process temperature,
pressure vary between
types
#2 Polyvinyl Chloride (PVC)
⚫ 14% by weight of ⚫ Large Cl atom
polymer market ◼ Favours amorphous structure
◼ 2nd behind PE because it is difficult to crystallize
⚫ ~204°C melting point ◼ Strong dipole moment provides
bond strength between chains,
⚫ 82°C glass transition but lowers ductility
temperature ◆ Usually formed with additives
⚫ Common applications ◼ Flame retardant
◼ Home siding
◼ Piping
H H
◼ Upholstery, and shower | |
curtains — C—C—
| |
H Cl
#3 Polypropylene (PP)
⚫ 13% by weight of ⚫ Common applications
polymer market ◼ Housewares
⚫ 165-177°C melting point ◼ Appliance parts
◼ Lab ware, bottles
⚫ -18°C glass transition
◼ Car battery housings
temperature
◼ Carpet backing
⚫ Methyl group (CH3)
restricts chain rotation
◼ Stronger, less flexible H H
⚫ Chemical, moisture, | |
heat resistant —C—C—
⚫ Good flex life | |
H CH3
 #4 Polystyrene (PS)
⚫ 6% by weight of ⚫ Common applications
polymer market ◼ Automotive interior parts
⚫ 150-243°C melting point ◼ Dials and knobs
◼ Cups
⚫ 75-100° glass transition
temperature ⚫ Expandable polystyrene
◼ Pentane or butane added
⚫ Phenylene ring makes
to PS beads
PS rigid and inflexible at H H
room temperature | |
◼ Alloyed with 3-12%
rubber to make impact- —C—C—
resistant styrene | |
H
⚫ Butadiene = impact strength
Other Polymers You Know
⚫ Teflon = polytetrafluoroethylene
◼ PE with the H replaced by F
◼ Nonstick coatings, heat resistant
⚫ Lucite / Plexiglas
◼ Lenses, protective goggles
⚫ Lexan = polycarbonate
◼ transparent thermoplastics
◼ high softening temperature
◼ Impact resistant
◼ Safety shields
Comparison of PE and PS
⚫ Polyethylene ⚫ Polystyrene
⚫ Easy unkinking of ⚫ Bulky side groups make
polymer chains occurs unkinking difficult at
above Tg (-110°C) room temperature
◼ Rubbery, flexible ⚫ Amorphous
⚫ Partially crystalline ⚫ Tg = 100°C
◼ Light scattering from
⚫ Tm = 230°C
crystallites causes loss of
transparency (milk jugs)
⚫ Tm = 135°C

Design a coffee cup and an ice tray with these polymers

Polymer Additives
⚫ Plasticizers ⚫ Reinforcement
◼ Lower MW polymers added ◼ Example: glass fibers
to keep polymers flexible ◼ Good interfacial bonding
⚫ Filler with the polymer gives
◼ Volume replacement with a enhanced strength and
less costly material gives stiffness
dimensional stability by
restricting chain mobility ⚫ Flame retardants
⚫ Colorants ◼ Example: PVC doesn’t
⚫ Stabilizers burn because the
chlorine atoms restrict
◼ Prevent deterioration of
polymer due to combustion
environmental effects ◼ Cl, Br, P based additives
 Stabilizers for Isoprene
⚫ Stabilizers prevent ⚫ Example: isoprene can
degradation absorb 15% oxygen
⚫ Example: oxidation of ◼ 1% oxygen destroys
rubber (corrosion) isoprene’s elastic
properties
◼ UV light causes rubber to
absorb oxygen from the ⚫ Natural latex has
air complex phenyl groups
◼ The tires will become that prevent oxidation
brittle on a bike left ◼ Not effective at elevated
outside year after year temperatures; other
isoprene mer stabilizers are added

H H CH3 H
C - C = C - C-
H H
Colorants
⚫ Pigments
◼ Insoluble, colored material
◆ Trapped between the polymer chains
◼ Powdered form
⚫ Dyes
◼ Soluble organics
◆ Absorbed by the polymers
◼ Transparent colors
Quick Review
⚫ Polymerization ⚫ Thermoplastic and
◼ Addition thermosetting
◼ Condensation ◼ Chain sliding
⚫ Crystalline vs. ◼ Crossliking prevents
amorphous chain sliding
⚫ Common polymers
⚫ Configuration ◼ PE
◼ PVC
◼ Linear
◼ PP
◼ Branched
◼ PS
◼ Crosslinked
◼ Networked
Glass Transition
⚫ Polymer, like glasses
supercooled liquid
exhibit a glass transition
temperature – transition

Specific volume, mL/g

from hard and brittle to
rubbery like material
◼ Amorphous polymers act
like a supercooled liquid
below the melting point
◼ Fully crystalline polymers
show an abrupt increase in
volume at the melting
temperature
◼ Partially crystalline polymers
show some volume increase Tg Tm
at the melting point Temperature
Viscoelastic Modulus
⚫ Polymers exhibit a
viscoelastic modulus,
E = E(t)
◼ Attach a mass, m, to the
polymer sample and let it
L hang
Ao
◼ Measure strain at a fixed
time, t
◼ Repeat for different
mass temperatures, T
⚫ s = Constant stress
⚫ e (t) = ΔL/Lo=time
dependent strain
⚫ E(t) = s/e(t)
 Log Plot of Viscoelastic Modulus
Tg is the boundary
104 between elastic and
plastic behaviour
103

E(t) 102 glassy

MPa rubbery
101 viscous
flow
100
leathery
10-1
Tg Temperature
Behaviour at Temperature
⚫ Glassy region of E(t)
◼ Brittle material
Linear plot of
◼ Highest stiffness 3000 E(t), MPa
⚫ Leathery region of E(t)
◼ Viscoelastic material
◼ Medium stiffness
2000
⚫ Rubbery region of E(t)
◼ Viscoelastic region
◼ Low stiffness
1000
⚫ Viscous flow region of
E(t)
◼ Liquid-like behaviour
0
Tg Temperature
Deformation Mechanisms
⚫ Linear amorphous ⚫ Unkinking of molecules
polymers exhibit three
deformation mechanisms

⚫ Elastic strain

⚫ Viscous flow
Matching Regions & Mechanisms
⚫ Glassy region of E(t) ⚫ Rubbery region of E(t)
◼ Brittle solid ◼ Viscoelastic material
◼ Elastic strain mechanism ◼ Elastic strain
◼ Unkinking of molecules
◼ Small amount of viscous flow
⚫ Leathery region of E(t)
◼ Viscoelastic solid
◼ Elastic strain ⚫ Viscous flow region of E(t)
◼ Unkinking of molecules ◼ Liquid-like behaviour
◼ Unkinking of molecules
◼ Large amount of viscous flow
Effect of Test Time on E(t)
⚫ Unkinking and viscous flow require time
◼ E(t) will change for different test times
◼ More time = more strain = lower modulus

t2 < t1 s = mg / Ao
e = ΔL/Lo
E(t)
E(t) = s/e
MPa
L2 L1

mass

Temperature mass
Effect of Structure on E(t)
⚫ E(t) depends on polymer structure and
crystallinity
linear crystalline
High crosslinking
light crosslinking
E(t)
MPa

linear amorphous – low MW

linear amorphous – high MW

←Loading rate Temperature→

Notes on E(t)
⚫ E(t) increases as the loading rate increases
◼ Viscous flow and unkinking take time
⚫ E(t) increases as the amount of crosslinking
increases
⚫ Linear crystalline polymers act similar to other
solids
◼ Modulus declines with temperature slightly
◼ Large drop approaching melting temperature
 Stress Relaxation: Under a constant
strain the stress level decrease with time
⚫ Stretch an amorphous linear polymer in the leathery
or rubbery region of E(t) to a predetermined strain
level and measure stress necessary to maintain this
strain as a function of time
−t
s=s e
stress so 
T2 o
T1
0.37 so T1>T2>Tg

0
τ1 τ2 time→
Stress Relaxation Time
⚫ Stress relaxation time, τ, is the time required
for the stress to fall to 1/e of its original value
◼ 1/e = 0.37
⚫ Stress relaxation time decreases as
temperature increases
⚫ Stress relaxation time exhibits an Arrhenius
relationship

(1/τ ) = Cexp (- )
Q
RT
Elastic Behaviour
⚫ An elastic solid will elongate when a load is
applied
⚫ The elastic strain will reverse when the stress
is removed
⚫ T < glass transition temperature

strain
load

time time
Leathery Behaviour
⚫ T > Tg ⚫ Immediate recovery of
⚫ Immediate elastic strain elastic strain when
response stress is removed
⚫ Increasing strain with ⚫ Strain lowers due to
time due to unkinking rekinking
stress

strain

time time
Rubbery Behaviour
⚫ T > Tg ⚫ Immediate recovery of
⚫ Immediate elastic strain elastic strain when
response stress is removed
⚫ Increasing strain with ⚫ Strain remains due to
time due to viscous flow chain sliding in viscous
flow
stress

strain

time time
Viscous Flow Behaviour
⚫ Viscous flow occurs during the application of
load
⚫ No strain recovery; chain sliding of viscous
flow cannot be reversed
stress

strain

time time
Tensile Testing of Polymers

YS

UTS
is less than
YS

⚫ Necked region in metals is localized

⚫ Necked region in polymers expands with increasing strain
Necking in Polymers
⚫ Necked region in metals
is localized
⚫ Necked region in
polymers expands with
increasing strain

increasing strain →
Elastomers (Rubber Bands)
⚫ Can be stretched to several 100% of its
original length
⚫ Upon release of the stress,they snap back to
their original dimensions
⚫ Characteristics
◼ Long molecular chains (high polymer)
◼ Flexible chain structure
◼ Above Tg (-72°C for natural rubber)
◼ Very little order in the unstressed state
◼ Lightly crosslinked to prevent permanent
deformation
 Apply Stress to Isoprene, Release

fully crosslinked vulcanized

60 ~4%
crosslinked
45
s,
MPa
30

15 unvulcanized

0
0 200% 400% 600%