Contents

0. Introduction
0.1. The past
0.2. Engineering plastics

1. Structure of the molecule

1 . 1 . Introduction
1.2. Addition polymers
1.3. Condensation polymers
1.4. Copolymers
1.5. Cross-linked polymers
1.6. Molecular symmetry and the tendency to form crystals
1.7. Distribution of relative molecular mass
Problems
Notes
Structure of polymeric solids
2.1. Introduction
2.2. Structure of the crystal
2.3. Crystal shape
2.4. Crystallinity
2.5. Crystallization and melting
2.6. The glass transition temperature
2.7. Molecular conformation in the amorphous polymer
2.8. The freely jointed chain
2.9. The Gaussian chain
2.10. Molecular orientation
Problems
Notes

3.

The
3.1.
3.2.
3.3.
3.4.
3.5.
3.6.

elastic properties of rubber

Introduction
Structure of an ideal rubber
Entropy elasticity
Elasticity of a network
Stress-strain relationship
~ n ~ i n e e r rubbers
in~

Contents

Problems
Notes
4.

Viscoelasticity
4.1. Introduction
4.2. The nature of viscoelasticity
4.2.1. Creep
4.2.2. Stress relaxation
4.2.3. Dynamic properties
4.3. Theory of linear viscoelasticity
4.3.1. The Zener model
4.3.2. Distribution of relaxation times
4.3.3. Origin of temperature dependence
4.4. Polymer selection: stiffness
4.4.1. Temperature dependence
4.4.2. Stress analysis
Problems
Notes

5.

Yield and fracture

5.1. Introduction
5.2. Yielding
5.2.1. Considhe's construction
5.2.2. Eyring's model of the flow of solids
5.2.3. Yielding under multiaxial stresses
5.3. Crazing
5.4. Fracture mechanics
5.4.1. Measurement and application of KIc
5.5. Fracture properties of polymers
Problems
Notes

6.

Reinforced polymers
6.1. Introduction
6.2. Reinforced plastics
6.2.1. Polymer matrices
6.2.2. Fibrous reinforcement
6.2.3. Platelet reinforcement
6.3. Forming of reinforced plastics
6.3.1. Pultrusion
6.3.2. Filament winding
6.3.3. Hand lay-up
6.3.4. Hand spray-up

Contents

6.3.5. Compression moulding

6.3.6. Reinforced reaction injection moulding ( R R I M )
6.3.7. Reinforced thermoplastics
6.4. The mechanics of fibre reinforcement
6.4.1. Continuousfibres
6.4.2. Discontinuous fibres
6.5. Reinforced rubbers
Problems
Notes
7.

8.

Forming
7.1. Introduction
7.2. The flow properties of polymer melts
7.2.1. Bulk deformation
7.2.2. Elongational~ow
7.2.3. Shear flow
7.3. Extrusion
7.3.1. Extruder barrel
7.3.2. Extruder screw
7.3.3. Die and calibration equipment
7.4. Injection moulding
7.4.1. Hot runner moulds
7.4.2. The gate
7.4.3. Control of pressure, temperature, and time
7.4.4. Thermosets
7.4.5. Reaction injection moulding ( R I M )
7.5. Thermoforming
7.6. Blow moulding
7.7. Compression and transfer moulding
7.7.1. Compression moulding
7.7.2. Transfer moulding
Problems
Notes
Design

8.1. Introduction
8.2. Materials selection
8.2.1. The selection procedure
8.2.2. The 'big four' commodity thermoplastics
8.2.3. The engineering thermoplastics
8.2.4. Thermosets and composites
8.2.5. Rubbers

xi

xii

Contents

8.3. Designing for manufacture

8.3.1. Injection moulding
8.3.2. Joining and fbstening
8.3.3. Thermosetting polymers
8.4. Designing for stiffness
8.4.1. PIastics
8.4.2. Fibre composites
8.4.3. Rubbers
8.5. Designing for strength
8.6. Case histories
8.6.1. Optical memory devices (compact discs)
8.6.2. Motorcycle drive sprocket
8.6.3. Cross-country ski bindings
8.6.4. Glass fibre -epoxy composite leaf spring
8.6.5. Helicopter blade
8.6.6. Cautionary tale no. I
8.6.7. Cautionary tale no. 2
Problems
Notes
Further reading
Answers t o problems
Index

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Note: the letter P after a page number indicates that the reference is to one of the set problems.

acrylic polymers 31
acrylonitrile 28P
acrylonitrile-butadiene-styrene polymer
(ABS) 183, 206, 31 1, 31 7P, 327, 328
activation enthalpy 134, 172
activation volume 173-6, 205
addition polymers 1 1, 12
affine deformation 80
ageing
chemical 30, 358
physical 137, 142-5
aircraft 5, 6, 183, 367
alloys (metal) 1, 8, 16 .
amorphous fraction 19, 41, 48-50, 62
anisotropy 38, 60, 200, 208, 221, 350
apparent viscosity 273
applications of polymers
aircraft 5, 183, 355, 367
boats 209, 225
building and construction 283
cars and vehicles 1, 6, 96, 21 1, 227, 323,
324, 329
chemical 323
domestic 30
electrical 70, 329. 364
fibres 70
films 30, 70, 321
medical 1, 30
optical 6 1, 364
packaging 30, 70, 321
pipes 30, 159, 183
aramid fibre ( ~ e v l a r ~5,) 209, 2 17, 2 18, 22 1
Arrhenius equation 134, 163, 164, 172, 280
aspect ratio of filler 2 12, 2 13, 245
atactic polymer 19, 20
automobiles see cars
Avogadro's number 62P, 93P

Baekeland 373
Bagley correction 279
Bakelite 373
barrier flight extryder screw 290

biaxial orientation 62, 70, 179. 200. 312

birefringence 60, 61, 66P
blends 23, 24
block copolymer 16, 29P, 92, 160
blow moulding 70, 3 1 1 -1 3
Boltzmann equation 76
Boltzmann superposition principle
(BSP) 148-54. 348. 349
branching 9, 13. 19. 31, 271
Brownian motion 101
bulk deformation of melt 267
butadiene 33
butyl rubber 330
capillary flow 273-9
car tyres (reinforcement) 210, 21 1
carbon black in rubbers 89, 21 1, 2 5 2 4
carbon fibre 100. 209. 217-22, 242. 255P
Carothers 3
cars, use of polymers in 1, 6. 7. 227, 323
cellulose nitrate (Celluloid) 2, 3
centrally-cracked plate 183-5
Charpy impact strength 358, 359
chlorine (in PVC) 63P
chloroprene rubbers 92, 93
chopped strand mat (CSM) 225. 256P
Clausius-Clapeyron equation 64P
coextrusion 321. 322
compact disc (polymer application) 61.
364-7
compact tension (CT) test 192, 193
compliance 102, 106, 114, 148
composite materials 209-63
cost 215
density 214
failure criteria 236, 242
manufacture 223-7
matrices 215, 216, 329
modulus
continuous fibres 229-33
discontinuous fibres 247
short-fibre 244-52
thermal expansion 234, 235, 256

compression moulding 224. 226, 3 13-14

computer-aided design (CAD) in
moulding 333-6
condensation polymers 1 1, 14. 15. 19
conformation of molecules 50-2, 55, 56, 62
Considere construction 169-7 1
contour length of chain 51, 53, 54
copolymerization 15, 32, 90
copolymers 15, 16, 32, 33, 64P. 90
costs 215, 327
covalent bond 60, 221
Cox theory 261 -3
crack propagation speed 208
crankshaft rotation of molecule 164. 165
crazing 167-9, 180-3, 202P
under biaxial stress 181
environmental 182, 206, 368
under internal stress 18 1
in rubber-modified plastics 182
creep 101 -8, 126, 145, 148. 345-50
critical length of fibres 250-2. 263
crosslinking 10, 16-18, 29P, 73, 75, 88, 138,
165
crystallinity 18, 40-2, 46, 63P, 86
crystallization 34, 42-7
modulus, effect on 140, 142
of rubber 86, 254
temperature dependence 4 4
yield stress. effect on 179
crystals 18, 34-42, 61, 62, 64P, 73
damping 1 12
debonding of fibres 248-50
Debye 129, 162
deflection-limited design 347
degradation 9. 30. 32. 138. 199
degree of polymerization 20, 21
density 214. 327
density gradient column 41
design of polymer products 323-74
die swell 281, 293
dielectric properties 162, 325
dipole relaxation 162
distribution
Gaussian 57, 58, 69, 70
o f Kelvin elements 131, 156P
of Maxwell elements 133. 156P. 157P
of stress along fibre 245, 246. 249
divinyl benzene 17
dough moulding compound (DMC) 226
Dow Chemical Company 3 1
draft angle in injection mould 332
drawing 169. 171
Du Pont Company 3. 21 7
ductile-brittle transition 196
ductility 167

dynamic fatigue 197-9. 357-61

of composites 222, 361
dynamic properties 1 12-22
use of Boltzmann superposition
principle 151, 152

ebonite 165
elastic constraint a t crack tip 189
elastomer 96. 97
electron (unpaired) 12
elongation at break 327
elongational flow 268-72
elongational viscosity 269-72
end groups 9, 13, 30, 42
end-to-end separation of polymer chain 51 6, 68, 69, 73-8 1, 96P
energy content 7, 8
entanglements 73, 167, 281
enthalpy of thermal activation 134-6. 164.
172
entropy elasticity 75-8. 97P, 98P
epoxy resins 216, 255P, 258, 329, 330
ethylene 9-12. 15
ethylene oxide 32
I
ethylene-propylene rubber (EPR) 64, 91,
330
ethylene-vinyl acetate copolymer 321
ethylene-vinyl alcohol copolymer
(EVAL) 321
expansion, thermal 234, 256, 260, 327
extension ratio 79, 170
extruder barrel 283, 284
extruder die 2 9 0 4
drawdown 291 -3
extruder screw 284-90
extrusion 264, 283-94
extrusion-blow moulding 3 1 1
Eyring theory 172-7

failure envelope 181

failure of composites 236-44, 361 4
Faraday 3
fatigue see dynamic fatigue or static fatigue
fibre composites. design with 350-3
fibre reinforcement 2 12-22
fibres (polymer) 70
fibrils 61, 167, 172, 180
filament winding 224, 225, 343
film blowing 264, 265
films (polymer) 70, 321
flexural modulus test 344
flow
elongational 268-72
Newtonian 272, 275, 276

,,

Index

non-Newtonian 270, 2 7 2 4 , 277, 278,

316P
rate 276, 278, 315P. 316P
shear 272-83
fluorinated rubbers 93
fluorine 36
folding of molecules 67
formaldehyde 30P, 32
forming processes 264-322
for composites 223-7
fracture energy see GIC
fracture mechanics, linear elastic
(LEFM) 183-95, 207
fracture toughness see KIc
free radical 12, 13, 29P
freely jointed chain 53 -5
frequency response 120
of Zener model 128-30
fringed micelle 38, 39
functionality 16, 17

gauche conformation 65P

Gaussian chain 54-8, 68, 96
GI,, G, 186-9
gel permeation chromatography (GPC) 24,
25
Gibbs free energy 35, 163, 164
glass fibre 217-19, 222, 255P
glass-fibre reinforced plastic (GRP) 209,
229, 234, 330
glass-mat reinforced thermoplastics
(GMT) 227
glass transition 47-50, 64P, 91, 1 12, 120,
121, 138, 139
Goodyear 2, 3
graft copolymer 16, 29P, 160
graphite 220
Griffith fracture theory 183-7, 207

Hancock 2
hand lay-up 224, 225
hand spray-up 224, 226
heat distortion temperature data 327
helicopter rotor blade 367, 368
helix conformation 36-8
Helmholtz free energy 75, 81, 93P
hexene 27P
high-impact polystyrene (HIPS) 3 1, 33, 182,
183, 328, 329
Hyatt 3
hydrocarbon 90, 93
hydrogen 35, 63P
hydrogen bonding 38, 179, 221
hydrolysis 199 .,

387

hydrostatic pressure, effect on yield 177-9

hysteresis see damping
ICI plc 4
ideal gas 76, 97, 98
ideal rubber 73-88, 94-6P
impact tests 177, 359
injection blow moulding 3 1 1
injection moulding 26, 266, 294-308
clamping 320, 321
control 302
feed hopper 3 19
gating 299-301, 333
machine 266, 295
mould filling 300, 301, 332
mould shrinkage 296, 318P
packing 297, 298, 303
reinforced thermoplastics 226, 332, 334
RIM 307, 308
runner 296
sprue 296
temperatures 305
thermosets 305-8
weld lines 300, 301, 333, 335-7
insert moulding 338
interfacial shear strength 248-50
interfacial shear stress in composites 2 4 4 4 ,
248 -50
interlaminar shear strength (ILSS) 363, 364
internal stress 18 1
isochronal curves 103, 104, 1 1 1, 345, 346
isometric curves 345, 346
isoprene 27P
isotactic polymer 19, 20, 48
Izod impact strength 327, 3 5 8 4 0
jump frequency 164, 173
kayaks, use of composites in 209, 210
Kelvin model 125, 156P
generalized 131
~ e v l a see
r ~ aramid fibre
KIC, Kc 187-95, 208
lamellae 18, 39, 44, 64P, 172
laminate analysis 350-3, 361
latent heat of melting 64P
Leadermann 136
leaf spring, use of composites 367
limiting oxygen index (LOI)
data 327
definition 374
linear density 216

388 Index
linear elastic fracture mechanics
(LEFM) 183-95, 207
linear low-density polyethylene (LLDPE) 30
linear viscoelasticity 103, 122-37
logarithmic decrement 1 16-1 8, 120-22
Macintosh 2
macromolecules 3
materials selection 323 -3 1
Maxwell model 125, 156P
mechanics of fibre reinforcement 227-52
melamine-formaldehyde resin (MF) 329, 330
melt elasticity 31, 281 -3, 31 1
melt flow index (MFI) 26, 279, 280
melting 44-6, 64P
melting point 43-6, 48, 63P, 64P
metals (comparison with polymers) 1, 2, 8,
16, 26, 48, 101, 108, 115, 167, 209, 217,
229
metering zone of extruder 283, 285-9
mica 222, 223, 227
Michelin 2
modified poly(pheny1ene oxide)
(MPPO) 293, 329
modulus 62
complex 1 14-2 1, 129, 151
of composites 229-33, 247
creep 345-8
of plastics 209, 327
of polymer crystals 38
of rubbers 83, 84, 94P, 95P
measurement of flexural 344
relaxed and unrelaxed (definition) 109,
110
stress relaxation 109-12, 158P
variation with angle 256P
Mohr's circle, applied to composites 232,
233, 242, 243
molar mass 22-4
molecular weight see Relative molecular
mass
monomer 9, 1 1-1 7, 27-9P
Mooney equation 88, 96P, 98, 99
motorcycle drive sprocket, nylon 367
multiaxial stress 177

natural rubber (NR) 4, 62, 72, 86-90, 94,

137-9, 330, 331
carbon black reinforced 210, 21 1, 253,
254
necking 95P, 168-71
in polymer melt 271, 272
network elasticity 78-84
neutron scattering 50

nitrile rubber (NBR) 89, 90

nucleation 46, 47
nuclei 42
number average molar mass 23-5
nylon see polyamide
orientation (molecular) 58-62, 70, 172, 180,
200, 312, 332
orientation factor 59-61, 66P
orientation of fibres
in injection mouldings 332, 334
in laminates 343
packaging 70, 321
paraffin 21, 23, 24, 34
Paris equation 198
Parkes, Parkesine 2, 3
pellets, production of 319
phase angle 6 113, 115, 118, 129
phenolic resin 329, 373
photo-oxidation 89, 358
pipe manufacture 291, 292
plane strain fracture 189, 194
plane stress fracture 188
plasticizer 165, 166
platelet reinforcement 212, 213, 222, 223
Plunkett 67
Poisson's ratio
of composites 230, 231, 260
of plastics and rubbers 347
polyacrylonitrile (PAN) 90, 100, 219
polyamide 6 (PA6) 3 1, 63P, 137-9, 327, 329
polyamide 1 I (PA 11) 31
polyamide 12 (PA 12) 32
polyamide 6.6 (PA6.6) 4, 14, 15, 45, 63P,
140, 141, 179, 327, 329, 347
polybutadiene (BR) 33
38, 67
polybutene
poly(buty1ene erephthalate) (PBT) 327, 329
polycarbonat (PC) 175, 196, 324, 329, 373
polychloroprdne 92
polyester 15, '32, 70
*I
polyester resins 215, 255P, 258, 330
poly(ether ether ketone) (PEEK) 330, 374
poly(ether sulphone) (PES) 373
polyethylene (PE)
branched (LDPE) 9, 30, 45, 46, 122, 123,
270, 271, 280, 282
chemistry 9, 12, 13, 21, 50
crystallinity 35, 40, 42, 44, 45, 46, 62P,
63P
linear (HDPE) 10, 14, 21, 27P, 30, 45, 46,
108, 122, 123, 270
linear low-density (LLDPE) 30

371,

Index

properties 21, 122, 123, 169, 171, 179,

326-8
poly(ethy1ene terephthalate) (PET) 15, 32,
45, 62, 63P, 140, 142, 329
polyisobutylene 49, 1 1 1, 112, 119, 120
polyisoprene 72, 89
polymer 2, 9, 34, 44
polymerization 9-18, 33
poly(methy1 methacrylate) (PMMA) 12, 31
37, 121, 141, 165, 181, 200, 280, 281,
323. 329. 358
poly(parapheny1ene terephthalamide) 221
poly(pheny1ene oxide) (PPO) 292, 293, 329,
373
poly@henylene sulphide) (PPS) 327, 374
polypropylene (PP) 7, 12, 30, 37, 45, 48, 49,
63P, 91, 326-8
polystyrene (PS) 12, 3 1, 167. 182, 183, 31 7P,
328
poly(styrene-co-acrylonitrile) (SAN) 100,
182
polysulphone (PSF) 327, 373
polytetrafluoroethylene (PTFE) 36, 42, 67,
255P, 323, 331 .
polyurethane (PU) 1414 , 308, 331
poly(viny1 chloride) (PVC) 12, 31, 62, 63P,
1 3 7 4 0 , 145, 198, 326-8, 331, 358
plasticized 33 1
poly(viny1 fluoride) (PVF) 62P
poly(viny1idene fluoride) (PVDF) 62P
power-law fluid 277, 278
press fitting 341, 342
pressure
in capillary flow 279
melting, effect on 64P
in polymerization 9
in yielding 177-9
prices of plastics (data) 327
profiles (extruded) 293
propylene 15, 19
pseudoelastic design method 346-50
pseudoplasticity of melts 273
pultrusion 223-5

Rabinowitsch equation 278

radiation crosslinking 10
random copolymer 16, 160
random walk 68
reaction injection moulding (RIM) 226, 307,
308, 326
recovery 101, 149, 167
Regnault 31

389

reinforced reaction injection moulding

(RRIM) 224, 226
relative molecular mass (RMM) 9, 20-6,
44, 48, 199, 280
relaxation time 125, 130
relaxations 122
residual stress
in composites 260, 261
in mouldings 304, 305
ribs, stiffening and strengthening with 353
Rohm and Haas 3 1
rubbers 2 4 , 72-93, 252-4, 330, 331, 354-7
rubber-toughening 180, 182, 200
rule of mixtures 214, 229, 230

second moment of area

of beam 147, 158
polar, of shaft 146
secondary transitions 121, 122, 138, 165
shape factor 355, 356
shear failure in composites 241, 242, 248,
363
shear flow 272-83
shear lag theory 245, 261 -3
shear modulus
of composites 232
of rubber 83, 84, 94P, 95P
shear thinning 273
sheet moulding compound (SMC) 226. 326
shift factor 134-7
shrinkage 62, 71, 297, 337, 338, 343
side group motion 122
single edge notch (SEN) test 192
sink marks 337, 338
size coatings 2 16
ski bindings 367
snap fitting 341, 343
solubility 100
solvent crazing 182, 358
solvent, polymers in 26
specific gravity data 327
specific stress 2 17, 259
specific volume 41, 46, 48
Spencer-Gilmore equation 298
spherulites 18, 39, 40, 4 2 4 , 47
spring-dashpot models 123-5
springs
use of composites 367
use of rubber 354-6
staking, joining method 339, 340, 342
static fatigue 197, 359
Staudinger 3, 30
stereoregularity 19, 20
strain hardening 171

390

Index

strain limits 345, 347

strain rate effects in yielding 171, 174-7
strength of composites 2 3 6 4 4 , 250, 257P
stress analysis of polymers 143-54
stress concentration factor 184, 337
stress intensity factor (K) 188, 189, 207
critical (K,,) 187-97
stress relaxation 109-1 2, 127, 128
in a bolt 159
of Zener model 127, 128
stress-strain curve
rubbers 85
viscoelastic polymers 153, 167
Zener model 156
stretch-blow moulding 3 12
styrene 17, 31
styrene-butadiene rubber (SBR) 33, 89, 91,
330, 331
sub-critical crack growth 197, 198, 357, 358
sulphur crosslinking of rubbers 3, 4, 88,
138, 139
surface-to-volume ratio of
reinforcements 212, 2 13
swell ratio 281 -3, 292, 293
swelling in liquids 88, 90, 96, 100
symmetry
in laminates 350
in molecules 18
syndiotactic polymer 19, 20
talc 222, 223
tan 6 115
temperature dependence
of compliance 134-6
of fracture behaviour 199
of modulus 83, 1 3 7 4 3
of relaxation times 134, 165
of viscosity 280, 28 1
of yield stress 174
tennis racquet, use of composites 209-1 1
tensile strength
of composites 2 3 6 4 4 , 250-2, 257P
data for plastics 327
of oriented fibres 62
tex (unit) 216
Tg see Glass transition
thermal expansion coefficient 47, 48
of composites 234, 235
data for plastics 327
thermal stability 32
thermoforming 308-1 1, 332
thermoplastic (definition) 5, 10
thermoplastic polyester 32, 70
thermoplastic rubber (TR) 33, 90, 91
thermoset polyester see polyester resins
thermosets (definition) 5, 11

three-point bend (3PB) test 192

time-temperature superposition 135-6
torsion of shaft 105, 145
torsion pendulum 116-18, 121
toughening 180, 182, 200, 329
toughness
effect of degradation 199
effect of orientation 200, 201
effect of RMM 199, 200
trans conformation 65P
transfer moulding 3 13
transient stress, in oscillation 152
true stress 86, 170
twin screw extruder 290

ultrasonic welding 339, 341

urea-formaldehyde resin (UF) 329, 330, 374

vacuum forming 308

van der Waals bonds 60, 99
vented screw in extruder 286-9
vinyl polymer 12, 19, 20, 16, 37
viscoelasticity 101-66
linear 103-37, 146-58P
non-linear 104, 106, 111, 346
of polymer liquids 281 -3, 31 1
viscosity, apparent
definition 273
determination 273
RMM dependence 280, 282
stress dependence 280-2
temperature dependence 280, 281
voids 42, 215, 343, 357
von Mises yield criterion 177
vulcanization 2, 3, 18, 88
,.'

wall shear ate 276, 278, 316P

wall thick ess of mouldings 337, 338
warping 71, 337, 353
water
absorption 32, 141, 144, 345, 347
formation in polymerization 14, 15
weathering 358
weight average molar mass 23-5
weld lines 300, 333, 335-7, 357
welding 3 3 8 4 1
wire coating 294
WLF theory 205, 280, 319
X-ray diffraction 34, 38

r:

Index

Y (geometrical factor in fracture

mechanics) 193, 194, 196, 203, 207
yielding 168-80
under multiaxial stress 177-80
of net section in cracked bar 196
yield stress 171, 174
data for plastics 327
lowering by rubber particles 180

pressure dependence 177-9

strain-rate dependence 174-7
temperature dependence 174, 175
yield zone at crack tip 177, 194
Zener model 124-34
Ziegler-Natta catalysts 10, 14, 19, 30

391