Description of Materials

1. Polymeric Materials
2. Ceramics
3. Composite Materials

1. polymeric materials
(1) introduction
elastomers (or rubbers)
polymers
thermoplastics
plastics
thermosetting plastics
(or thermosets)
thermoplastics
can be reheated and formed into new shapes
consist of very long main chains of carbons
covalently bonded together
long molecular chains are bonded to each
other by secondary bonds
thermosetting plastics
set by chemical reaction
cannot be reformed by reheating
consist of a network of carbons covalently
bonded into a thermoset network structure
engineering plastics
2

(2) polymerization reactions

chain growth polymerization small molecules
(monomers) covalently bond to form very long
chains (polymers)
ex. polyethylene

n : degree of polymerization (DP)

ex. a particular type of polyethylene has a
molecular mass of 150,000 g/mol, what is
its degree of polymerization?
molecular mass of polymer
150000
DP = =
mass of monomer
28
= 5357

(a) chain polymerization steps

(i) initiation: a radical is needed
ex.

one of free radicals react with ethylene

molecule to form new longer chain free
radical

(ii) propagation process of extending

polymer chain by addition of monomers
energy of system is lowered by
polymerization
RCH2CH2 + CH2=CH2
RCH2CH2CH2CH2
(iii) termination
by addition of termination free radical
combining of two chains
R(CH2CH2)m + R(CH2CH2)n
R(CH2CH2)m(CH2CH2)n R
(iv) average molecular weight
average molecular weight determined by
special physical-chemical techniques
average molecular weight of thermoplastic
fi Mi
Mm =
fi
Mi = mean molecular weight of each
molecular range selected
fi = weight fraction of the material
having molecular weights of a
5
selected molecular weight range

ex. calculate the average molecular weight

Mm for a thermoplastic material that has
the mean molecular weight fractions fi for
molecular weight ranges list below

fi Mi 19550
Mm = = = 19550 g/mol
fi
1.00
(b) functionality of a monomer
functionality number of active bonds in a
monomer
bifunctional : two active bonds for the
polymerization of long chains
ex. ethylene
trifunctional: three active bonds to form a
network polymeric material
ex. phenol C6H5OH
6

(c) structure of noncrystalline linear polymers

zig-zag configuration in ethylene due to 109o
angle between carbon covalent bonds

on a larger scale the polymer chains are

randomly entangled
entanglement increases
tensile strength
branching decreases
tensile strength
(d) vinyl and vinylidene polymers
vinyl polymers one of the hydrogen atom is
replaced by another atom or group of atoms

ex.

vinylidene polymers both hydrogen of

carbon are replaced by another atom or group
of atoms

ex.

(e) homopolymers and copolymers

homopolymers polymer chain is made up of
single repeating units
AAAAAAAA
copolymers polymer chains made up of two
or more repeating units
random copolymers different monomers
randomly arranged in chains
ABBABABBAAAAABA

alternating copolymers definite ordered

alterations of monomers
ABABABABABAB
block copolymers different monomers
arranged in long blocks
AAAAA.BBBBBBBB

 graft copolymers one type of monomer

grafted to long chain of another
AAAAAAAAAAAAAAAAAAA
B
B
B
B
B
B

ex. a copolymer consists of 15 wt% polyvinyl

acetate (PVA) and 85 wt% polyvinyl
chloride (PVC), determine the mole
fraction of each component

No. of mole of PVA = 15/86 = 0.174 mole

No. of mole of PVC = 85/62.5 = 1.36 mole
mole fraction of PVA = 0.174/1.534 = 0.113
mole fraction of PVC = 1.36/1.534 = 0.887

10

ex. determine the mole fraction of vinyl

chloride and vinyl acetate in a copolymer
having a molecular weight of 10,520 g/mol
and a degree of polymerization of 160
MWav = fvc MWvc + fva MWva = fvc MWvc + (1 - fvc) MWva
MWav(polymer)
10520
MWav = = = 66.75 g/mol
DP
160
66.75 = fvc (86) + (1 - fvc)(62.5)
fvc = 0.86
fva = 0.14

ex. a PVC-PVA copolymer has a ratio of 10:1

vinyl chloride to vinyl acetate and a
molecular weight of 16000 g/mol, what is
its degree of polymerization
MWav = 10/11(62.5) + 1/11(86) = 64.6 g/mol
DP = 16000/64.6 = 248

11

(f) other methods of polymerization

stepwise polymerization monomers
chemically react with each other to produce
linear polymers and a small molecule of
byproduct condensation polymerization

network polymerization chemical reaction

takes place in more than two reaction sites
(3D network)

12

(3) industrial polymerization

raw materials: natural gas,
petroleum and coal
polymerization
granules, pellets, 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

13

(4) crystallinity and stereoisomerism in some

thermoplastics
(a) solidification of thermoplastics
there is no sudden change in specific
volume on cooling in noncrystalline
thermoplastics

glass transition temperature Tg

above Tg, show viscous or rubbery behavior
below Tg, show glass-brittle behavior
polyethylene -110oC
polypropylene -18oC
PVA 29oC
polystyrene 75~100oC
PVC 82oC
polymethyl methacrylate 72oC

in partly crystalline thermoplastics, sudden

decrease in specific volume occurs due to
more efficient packing of polymer chains 14

(b) structure of partly crystalline thermoplastics

the 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, a transition
from crystalline to noncrystalline regions can
be formed

15

(c) 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 pendent methyl group is

always on same side of the carbon chain

syndiotactic stereoisomer pendant group

regularly alternates from one side of the chain
to the other side

16

(5) general purpose thermoplastics

polyethylene, polyvinyl chloride (PVC)
polypropylene and polystyrene account for
most plastic materials sold
some properties of general-purpose
thermoplastics are considered:
density: relatively low (~ 1)
tensile strength: relatively low
impact strength
dielectric strength: generally good insulator
maximum-use temperature: relatively low
(54 ~ 149oC)

17

(a) polyethylene
mp : 110 ~ 137oC
clear-to-whitish translucent
thermoplastic material
types of polyethylene
low-density: has a branched-chain structure
high-density: has a straight-chain structure
linear-low-density

applications: containers, insulation,

chemical tubing, bottles, water pond liners18

(b) polyvinyl chloride and copolymers

mp : ~ 204oC
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
(i) plasticizers impart flexibility
phthalate esters are commonly used
(ii) heat stabilizers prevent thermal
degradation typical stabilizers are
organometallic compounds of Pb and Sn
(iii) lubricants aid in melt flow of PVC
waxes, fatty esters and metallic soaps
(iv) fillers lower the cost.
calcium carbonate
(v) pigments give color, opacity and
weatherability
19

(c) polypropylene
mp : 167 ~ 177oC
methyl group substitute every
second carbon atom in carbon
polymer chain
high heat deflection temperature
low density, good chemical resistance,
moisture resistance and heat resistance
good surface hardness and dimensional
stability
applications: housewares, appliances,
packaging, laboratory ware, bottles, etc.
(d) polystyrene
mp : 150 ~ 243oC
phenyl ring present on every
other carbon atom
very inflexible, rigid, 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
20

(e) polyacrylonitrile
often in the form of fibers
high strength
good resistance to moisture
and solvents
applications: sweaters and blankets
comonomer for SAN and ABS resins.
(f) styrene-acrylonitrile (SAN)
random amorphous copolymer of styrene
and acrylonitrile
better chemical resistance, high heatdeflection temperature, toughness and load
bearing characteristics than polyester alone
applications: automotive instrument lenses,
dash components, knobs, blender and mixer
bowls

21

(g) ABS
ABS : acrylonitrile + butadiene + styrene

good impact and mechanical strength, with

ease of processing

ABS can be considered a blend of a glassy

copolymer (SAN) and rubbery domains
(butadiene polymer)
applications: pipe and fittings, automotive
parts, computer and telephone housings

22

(h) polymethyl methacrylate (PMMA)

mp : 160oC
an acrylic commonly
known as Plexiglas.
rigid and relatively strong
completely amorphous and
very transparent
applications: glazing of aircraft, boats,
skylights, advertising signs etc.
(i) fluoroplastics
monomers have one or more atoms of F
polytetrafluoroethylene (PTFE)
a crystalline polymer
soften at 370oC
useful mechanical properties at
a wide temperature range
exceptionally resistant to chemicals
high impact strength, low tensile strength
good wear and creep resistance
applications: chemically resistant pipe,
parts, molded electrical components,
nonstick coating
23

polychlorotrifluoroethylene (PCTFE)
mp : 218oC

less crystalline and more moldable

applications: chemical processing
equipments, electrical applications,
gaskets, O rings, seals, electrical
components

24

(6) engineering thermoplastics

low density
low tensile strength
high insulation
good corrosion resistance

25

(a) polyamides (Nylons) ()

main chain structure incorporates
repeating amide group
amide linkage
produced by stepwise polymerization of a
dibasic organic acid with a diamine
ex. Nylon 6, 6 mp: 250~266oC

also produced chain polymerization of ring

compound containing both acid and amine
ex. Nylon 6, 6 mp: 216~225oC

properties of nylon
NHO type of hydrogen bonding between
molecular chain results in high strength,
high heat-deflection temperature and good
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chemical resistance

flexibility of carbon chain produces

molecular flexibility which leads to low melt
viscosity, easy processibility and high
lubricity
applications: electrical equipments, gears,
auto parts, packaging
(b) polycarbonate
basic repeating unit
mp: 270oC

high tensile strength, impact strength,

toughness and dimensional stability
high heat deflection temperature

27

 good electrical insulating property

resistance to corrosion
applications: safety shields, cams and gears,
helmets, aircraft components, boat
propellers, housings for power tool and
computer terminals
(c) phenyl oxide based resins
basic repeating unit

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
28

(d) acetals
basic repeating unit
polyoxymethylene
mp: 175oC

the strongest (68.9 Mpa) and stiffest in

flexure (2820 Mpa) thermoplastics
excellent long term load carrying capacity
and dimensional stability
two basic types: homopolymer (du Pont
Delrin), and copolymer (Celeanese Celcon)
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

29

(e) thermoplastic polyesters

two important polyesters:
polyethylene terephthalate (PET)

polybutylene terephthalate (PBT)

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

30

(f) polysulfone
basic repeating unit

mp : 315oC

phenylene rings provide high strength and

rigidity
para-oxygen atom provides high-oxidation
stability
can be used for long timse at 150~174oC
high heat-deflection temperature, high
tensile strength, low tendency to creep
applications: electrical connectors, cores,
circuit boards, pollution control equipments
(g) polyphenylene sulfide
basic repeating unit
mp : 228oC
rigid and strong highly crystalline.
no chemical can dissolve it below 200oC
applications: chemical process equipment,
emission control equipment, electrical
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connectors

(h) polyetherimide

high heat and creep resistance and rigidity

good electric insulation.
applications: high voltage circuit breaker
housing, coils etc.
(i) polymer alloys
polymer alloys mixture of structurally
different homopolymers or copolymers
optimizes properties
some degree of compatibility needed.

32

(7) thermosetting plastics

high thermal rigidity
high dimensional stability
resistance to creep and deformation
light weight
electric and thermal insulation

(a) phenolics
low cost, good electric and heat insulating
properties and mechanical properties
produced by polymerization of phenol and
formaldehyde
33

 two-stage (novolac) phenolic resins

in the first stage, a brittle thermoplatic resin
is produced
addition of hexamethylenetetramine (as
basic catalyst) creates methylene crosslinkages to form thermosetting material
various types of phenolic molding
compounds are manufactured:
(i) general-purpose compounds: usually wood
flour filled to increase impact resistance
(ii) high-impact-strength compounds: filled
with cellulose and glass fibers to provide
impact strength
(iii) high electrical insulating compounds:
mineral (Mica) filled to increase electrical
resistance
(iv) heat-resistant compounds: mineral
(asbetos) filled to withstand long-term
exposure to 150~180oC
applications: wiring devices, telephone relay
system, auto transmission parts, plywood
lamination, adhesives, shell molding
34

(b) epoxy group

epoxy group

general chemical structure:

cross-linking (curing) of two linear epoxy

molecules with ethylene diamine:

good adhesion, chemical resistance and

mechanical properties
high molecular mobility, low shrinkage
during hardening
applications: protective and decorative
coating, drum lining, high voltage insulators
35
and laminates

(c) unsaturated polyesters

ester linkage reaction of alcohol with acid

unsaturated polyester resin can be formed by

reaction of diol with diacid that contains
reactive double carbon-carbon bonds

36

 linear unsaturated polyesters are usually

cross-linked with vinyl-type molecules:

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

37

(d) amino resins (ureas and melamines)

formed by reaction of formaldehyde with
compounds having NH2 group

melamine reacts with formaldehyde:

combined with cellulose fillers to produce

low cost products with good rigidity,
strength, and impact resistance
applications: electrical wall plates, molded
dinnerware, buttons, control buttons, knobs,
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flooring

(8) elastomers (rubbers) ()

polymers whose dimensions can be greatly
changed when stressed and which return to
original dimensions when the deforming
stress is removed
(a) natural rubber produced from latex of
Havea Brasiliensis tree
repeating structural unit:
cis-1,4-polyisoprene

vulcanization heating rubber with sulfur

and lead carbonate

39

cross-linking of cis-1,4-polyisoprene chains

by sulfur atoms

cross-linking of molecules restricts

molecular movement and increases tensile
strength

properties of natural rubber

40

(b) synthetic rubber

styrene-butadiene rubber (SBR)

most widely used synthetic rubber

greater elasticity than natural rubbers
tougher and stronger, war resistant
disadvantage : absorbs organic solvents and
swell
nitrile rubbers
55~82% butadiene + 45~18% acrylonitrile
resistance to solvents and wear
less flexible
polychloroprene (neoprene)
increased resistance to
oxygen, ozone, heat and
weather
low temperature flexibility, high cost
41

vulcanization of polychloroprene elastomers

instead of S, Zn and MgO are used

(c) silicone rubbers

based on Si and O in the main chain
basic repeating structural unit

polydimethyl siloxane

wide temperature range

used in gaskets, electric insulation

42

ex. how much sulfur must be added to 100 g

of polyisoprene rubber to cross-link 5%
of the mers?
MW for isoprene : 68 g/mol
(100/1.68) 0.05 32 = 2.35 g

ex. a butadiene-styrene rubber is made by

polymering 1 monomer of styrene and 8
monomers of butadiene, how much S is
required to react with 100 g of this rubber
to cross-link 20% of the cross-link sites?
wt% of butadiene in copolymer =
(8 54)/ (8 54 + 104) = 0.806
amount of S required for 20% cross-linking =
100 0.806
32 = 9.55 g
54

43

(9) deformation of thermoplastics

elastic deformation
below Tg
stretching out of the covalent bonds within
the molecular chains

plastic deformation
above Tg
sliding of molecular chains past each other
by the breaking and remaking of secondry
dipole bonding forces

combination of elastic deformation and

plastic deformation
uncoiling of the linear polymers

44

 tensile stress vs. strain for PMMA

(b) strengthening of thermoplastics

seven factors to determine the strength of
thermopalstics :
increasing average molecular mass increases
strength up to a certain critical mass.
as degree of crystallinity increases, tensile
strength, tensile modulus of elasticity and
density of material increase
chain slippage during permanent
deformation can be made more difficult by
introduction of pendant atomic groups to
45
main carbon chain

 strength can be increased by bonding highly

polar atoms on the main carbon chain
strength can be increased by introduction of
O and N atoms into main carbon chain
introduction of phenylene ring into main
polymer chain in combination with other
elements (As, O, N, S) increases strength
adding plastic fibers increases the strength
polymer
PE
PVC
polyoxy methylene (acetal)
nylon 6, 6
nylon 6, 6 (with 40% glass fiber)
phenylene oxide- based material
thermoplastic polyester
polycarbonate

tensile strength
2.5~5 ksi
6~11 ksi
9~10 ksi
9~12 ksi
30 ksi
7.8~9.6 ksi
10 ksi
9 ksi

(c) strengthening of thermosetting plastics

can be made by reinforcements and
creation of covalent bonds by chemical
reaction during setting
46

(d) 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

47

(10) creep and fracture of polymers

creep deformation of polymer under a constant
applied load at a constant temperature
continues to increase with time
ex. creep curve for polystyrene at 77oF

creep increases with increased applied stress

and temperature.
creep rate is relatively low below Tg
at Tg, deformation is more easily and is
referred to as viscoelastic behavior
above Tg, deformation is viscous flow
the creep of polymer is measured by the
creep modulus which is the ratio of initial
applied stress o to creep strain (t)
a high value for creep modulus implies a
48
low creep rate

 glass fiber reinforcements decreases creep

stress relaxation decrease in stress with
time under constant strain
stress relaxation due to breaking and
reforming of secondary bonds
decrease in stress with time is given by

= 0 e t/
1
= C e Q/RT

: stress after time t

: relaxation time

0 : initial stress
T : temperature

R : molar gas constant

ex. a stress of 1100 psi is applied to an
elastomer at constant strain, after 40 days
at 20oC, the stress decreases to 700 psi
(a) what is the relaxation time? (b) what
will be the stress after 60 days t 20oC?
(a) = 0 e t/
700 = 1100 e 40/
ln(700/1100) = -40/
= 40ln(1100/700) = 88.5 days
(b) = 1100 e t/88.5 = 1100 e 60/88.5 = 559 psi

49

ex. relaxation time for an elastomer at 25oC is

40 days, while at 35oC relaxation time is
30 days, calculate the activation energy
for this stress-relaxation process.
1
= C e Q/RT

1
Q
1
1
= exp[ ( )]
2
R T1 T2

40
Q
1
1
= exp[ ( - )]
30
8.314 298 308
Q = 22,000 J/mol = 22 kJ/mol

fracture of polymers
two extreme modes: brittle or ductile
for thermosetting plastics, primarily brittle
mode
for thermoplastics, depending on temperature:
below Tg primarily brittle mode
above Tg primarily ductile mode
surface energy required to fracture a glassy
polymer is about 1000 times greater than
that would be required for the fracture just
involved simple CC bond breaking
a craze in glassy thermoplastic is formed in
a highly stressed region and consist of
alignment of molecular chains combined
with a high density of interdispersed voids50

the structure of a craze near the end of a crack

in a glassy thermoplastic

above Tg, thermoplastics can exhibit plastic

yielding before fracture, molecular linear
chains uncoil and slip past each other and
gradually align closer together

51

(11) polymers in biomedical applications

biopolymer majority are thermoplastics
advantages : low density, ease of forming,
and can be made for maximum biocompatible
recent development : biodegradable polymers
(a) cardiovascular
artificial heart valves

flange and leaflets are made from biometals

(Ti or Co-Cr alloy)
sewing ring made from PTFE or PET
polymers are only materials that make
connection of the valve to heart tissue
PTFE is used as vascular graft to bypass
clogged arteries
hydrophobic polymer (polypropylene)
membranes are used to oxygenate blood
52
during bypass surgery

(b) opthalmic
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 lens are made of PMMA
(c) drug-dilevery
biodegradable polymer polylactic acid
(PLA), polyglycolic acid (PGA)
(d) suture used to close wounds and incisions
nonabsorbable suture : polypropylene, nylon,
polyethylene terephthalaate, polyethylene
absorbable suture : polyglycolic acid

53

(e) orthopaedic
bone cement a structure material to fill the
space between the implant and the bone
PMMA is the primary material used in this
purpose

54