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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 elastic properties of rubber


3.1. Introduction
3.2. Structure of an ideal rubber
3.3. Entropy elasticity
3.4. Elasticity of a network
3.5. Stress-strain relationship
3.6. ~ n ~ i n e e r rubbers
in~
x 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 xi

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. 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

8. 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
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
Index

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

acrylic polymers 31 biaxial orientation 62, 70, 179. 200. 312


acrylonitrile 28P birefringence 60, 61, 66P
acrylonitrile-butadiene-styrene polymer blends 23, 24
(ABS) 183, 206, 31 1, 31 7P, 327, 328 block copolymer 16, 29P, 92, 160
activation enthalpy 134, 172 blow moulding 70, 3 1 1 -1 3
activation volume 173-6, 205 Boltzmann equation 76
addition polymers 1 1, 12 Boltzmann superposition principle
affine deformation 80 (BSP) 148-54. 348. 349
ageing branching 9, 13. 19. 31, 271
chemical 30, 358 Brownian motion 101
physical 137, 142-5 bulk deformation of melt 267
aircraft 5, 6, 183, 367 butadiene 33
alloys (metal) 1, 8, 16 . butyl rubber 330
amorphous fraction 19, 41, 48-50, 62
anisotropy 38, 60, 200, 208, 221, 350
apparent viscosity 273 capillary flow 273-9
applications of polymers car tyres (reinforcement) 210, 21 1
aircraft 5, 183, 355, 367 carbon black in rubbers 89, 21 1, 2 5 2 4
boats 209, 225 carbon fibre 100. 209. 217-22, 242. 255P
building and construction 283 Carothers 3
cars and vehicles 1, 6, 96, 21 1, 227, 323, cars, use of polymers in 1, 6. 7. 227, 323
324, 329 cellulose nitrate (Celluloid) 2, 3
chemical 323 centrally-cracked plate 183-5
domestic 30 Charpy impact strength 358, 359
electrical 70, 329. 364 chlorine (in PVC) 63P
fibres 70 chloroprene rubbers 92, 93
films 30, 70, 321 chopped strand mat (CSM) 225. 256P
medical 1, 30 Clausius-Clapeyron equation 64P
optical 6 1, 364 coextrusion 321. 322
packaging 30, 70, 321 compact disc (polymer application) 61.
pipes 30, 159, 183 364-7
aramid fibre ( ~ e v l a r ~5,) 209, 2 17, 2 18, 22 1 compact tension (CT) test 192, 193
Arrhenius equation 134, 163, 164, 172, 280 compliance 102, 106, 114, 148
aspect ratio of filler 2 12, 2 13, 245 composite materials 209-63
atactic polymer 19, 20 cost 215
automobiles see cars density 214
Avogadro's number 62P, 93P failure criteria 236, 242
manufacture 223-7
matrices 215, 216, 329
modulus
Baekeland 373 continuous fibres 229-33
Bagley correction 279 discontinuous fibres 247
Bakelite 373 short-fibre 244-52
barrier flight extryder screw 290 thermal expansion 234, 235, 256
compression moulding 224. 226, 3 13-14 dynamic fatigue 197-9. 357-61
computer-aided design (CAD) in of composites 222, 361
moulding 333-6 dynamic properties 1 12-22
condensation polymers 1 1, 14. 15. 19 use of Boltzmann superposition
conformation of molecules 50-2, 55, 56, 62 principle 151, 152
Considere construction 169-7 1
contour length of chain 51, 53, 54
copolymerization 15, 32, 90
copolymers 15, 16, 32, 33, 64P. 90 ebonite 165
costs 215, 327 elastic constraint a t crack tip 189
covalent bond 60, 221 elastomer 96. 97
Cox theory 261 -3 electron (unpaired) 12
crack propagation speed 208 elongation at break 327
crankshaft rotation of molecule 164. 165 elongational flow 268-72
crazing 167-9, 180-3, 202P elongational viscosity 269-72
under biaxial stress 181 end groups 9, 13, 30, 42
environmental 182, 206, 368 end-to-end separation of polymer chain 51 -
under internal stress 18 1 6, 68, 69, 73-8 1, 96P
in rubber-modified plastics 182 energy content 7, 8
creep 101 -8, 126, 145, 148. 345-50 entanglements 73, 167, 281
critical length of fibres 250-2. 263 enthalpy of thermal activation 134-6. 164.
crosslinking 10, 16-18, 29P, 73, 75, 88, 138, 172
165 entropy elasticity 75-8. 97P, 98P
crystallinity 18, 40-2, 46, 63P, 86 epoxy resins 216, 255P, 258, 329, 330
crystallization 34, 42-7 ethylene 9-12. 15
modulus, effect on 140, 142 ethylene oxide 32 I

of rubber 86, 254 ethylene-propylene rubber (EPR) 64, 91,


temperature dependence 4 4 330
yield stress. effect on 179 ethylene-vinyl acetate copolymer 321
crystals 18, 34-42, 61, 62, 64P, 73 ethylene-vinyl alcohol copolymer
(EVAL) 321
expansion, thermal 234, 256, 260, 327
damping 1 12 extension ratio 79, 170
debonding of fibres 248-50 extruder barrel 283, 284
Debye 129, 162 extruder die 2 9 0 4
deflection-limited design 347 drawdown 291 -3
degradation 9. 30. 32. 138. 199 extruder screw 284-90
degree of polymerization 20, 21 extrusion 264, 283-94
density 214. 327 extrusion-blow moulding 3 1 1
density gradient column 41 Eyring theory 172-7
design of polymer products 323-74
die swell 281, 293
dielectric properties 162, 325 failure envelope 181
dipole relaxation 162
distribution
failure of composites 236-44, 361 4
Faraday 3
,,
Gaussian 57, 58, 69, 70 fatigue see dynamic fatigue or static fatigue
o f Kelvin elements 131, 156P fibre composites. design with 350-3
of Maxwell elements 133. 156P. 157P fibre reinforcement 2 12-22
of stress along fibre 245, 246. 249 fibres (polymer) 70
divinyl benzene 17 fibrils 61, 167, 172, 180
dough moulding compound (DMC) 226 filament winding 224, 225, 343
Dow Chemical Company 3 1 film blowing 264, 265
draft angle in injection mould 332 films (polymer) 70, 321
drawing 169. 171 flexural modulus test 344
Du Pont Company 3. 21 7 flow
ductile-brittle transition 196 elongational 268-72
ductility 167 Newtonian 272, 275, 276
Index 387

non-Newtonian 270, 2 7 2 4 , 277, 278, hydrostatic pressure, effect on yield 177-9


316P hysteresis see damping
rate 276, 278, 315P. 316P
shear 272-83
fluorinated rubbers 93 ICI plc 4
fluorine 36 ideal gas 76, 97, 98
folding of molecules 67 ideal rubber 73-88, 94-6P
formaldehyde 30P, 32 impact tests 177, 359
forming processes 264-322 injection blow moulding 3 1 1
for composites 223-7 injection moulding 26, 266, 294-308
fracture energy see GIC clamping 320, 321
fracture mechanics, linear elastic control 302
(LEFM) 183-95, 207 feed hopper 3 19
fracture toughness see KIc gating 299-301, 333
free radical 12, 13, 29P machine 266, 295
freely jointed chain 53 -5 mould filling 300, 301, 332
frequency response 120 mould shrinkage 296, 318P
of Zener model 128-30 packing 297, 298, 303
fringed micelle 38, 39 reinforced thermoplastics 226, 332, 334
functionality 16, 17 RIM 307, 308
runner 296
sprue 296
gauche conformation 65P temperatures 305
Gaussian chain 54-8, 68, 96 thermosets 305-8
GI,, G, 186-9 weld lines 300, 301, 333, 335-7
gel permeation chromatography (GPC) 24, insert moulding 338
25 interfacial shear strength 248-50
Gibbs free energy 35, 163, 164 interfacial shear stress in composites 2 4 4 4 ,
glass fibre 217-19, 222, 255P 248 -50
glass-fibre reinforced plastic (GRP) 209, interlaminar shear strength (ILSS) 363, 364
229, 234, 330 internal stress 18 1
glass-mat reinforced thermoplastics isochronal curves 103, 104, 1 1 1, 345, 346
(GMT) 227 isometric curves 345, 346
glass transition 47-50, 64P, 91, 1 12, 120, isoprene 27P
121, 138, 139 isotactic polymer 19, 20, 48
Goodyear 2, 3 Izod impact strength 327, 3 5 8 4 0
graft copolymer 16, 29P, 160
graphite 220
Griffith fracture theory 183-7, 207 jump frequency 164, 173

kayaks, use of composites in 209, 210


Hancock 2 Kelvin model 125, 156P
hand lay-up 224, 225 generalized 131
hand spray-up 224, 226 ~ e v l a see
r ~ aramid fibre
heat distortion temperature data 327 KIC, Kc 187-95, 208
helicopter rotor blade 367, 368
helix conformation 36-8
Helmholtz free energy 75, 81, 93P lamellae 18, 39, 44, 64P, 172
hexene 27P laminate analysis 350-3, 361
high-impact polystyrene (HIPS) 3 1, 33, 182, latent heat of melting 64P
183, 328, 329 Leadermann 136
Hyatt 3 leaf spring, use of composites 367
hydrocarbon 90, 93 limiting oxygen index (LOI)
hydrogen 35, 63P data 327
hydrogen bonding 38, 179, 221 definition 374
hydrolysis 199 ., linear density 216
388 Index

linear elastic fracture mechanics nitrile rubber (NBR) 89, 90


(LEFM) 183-95, 207 nucleation 46, 47
linear low-density polyethylene (LLDPE) 30 nuclei 42
linear viscoelasticity 103, 122-37 number average molar mass 23-5
logarithmic decrement 1 16-1 8, 120-22 nylon see polyamide

Macintosh 2 orientation (molecular) 58-62, 70, 172, 180,


macromolecules 3 200, 312, 332
materials selection 323 -3 1 orientation factor 59-61, 66P
Maxwell model 125, 156P orientation of fibres
mechanics of fibre reinforcement 227-52 in injection mouldings 332, 334
melamine-formaldehyde resin (MF) 329, 330 in laminates 343
melt elasticity 31, 281 -3, 31 1
melt flow index (MFI) 26, 279, 280
melting 44-6, 64P packaging 70, 321
melting point 43-6, 48, 63P, 64P paraffin 21, 23, 24, 34
metals (comparison with polymers) 1, 2, 8, Paris equation 198
16, 26, 48, 101, 108, 115, 167, 209, 217, Parkes, Parkesine 2, 3
229 pellets, production of 319
metering zone of extruder 283, 285-9 phase angle 6 113, 115, 118, 129
mica 222, 223, 227 phenolic resin 329, 373
Michelin 2 photo-oxidation 89, 358
modified poly(pheny1ene oxide) pipe manufacture 291, 292
(MPPO) 293, 329 plane strain fracture 189, 194
modulus 62 plane stress fracture 188
complex 1 14-2 1, 129, 151 plasticizer 165, 166
of composites 229-33, 247 platelet reinforcement 212, 213, 222, 223
creep 345-8 Plunkett 67
of plastics 209, 327 Poisson's ratio
of polymer crystals 38 of composites 230, 231, 260
of rubbers 83, 84, 94P, 95P of plastics and rubbers 347
measurement of flexural 344 polyacrylonitrile (PAN) 90, 100, 219
relaxed and unrelaxed (definition) 109, polyamide 6 (PA6) 3 1, 63P, 137-9, 327, 329
110 polyamide 1 I (PA 11) 31
stress relaxation 109-12, 158P polyamide 12 (PA 12) 32
variation with angle 256P polyamide 6.6 (PA6.6) 4, 14, 15, 45, 63P,
Mohr's circle, applied to composites 232, 140, 141, 179, 327, 329, 347
233, 242, 243 polybutadiene (BR) 33
molar mass 22-4 polybutene 371, 38, 67
molecular weight see Relative molecular poly(buty1ene erephthalate) (PBT) 327, 329
mass
monomer 9, 1 1-1 7, 27-9P
k
polycarbonat (PC) 175, 196, 324, 329, 373
polychloroprdne 92
Mooney equation 88, 96P, 98, 99 polyester 15, '32, 70 *I
motorcycle drive sprocket, nylon 367 polyester resins 215, 255P, 258, 330
multiaxial stress 177 poly(ether ether ketone) (PEEK) 330, 374
poly(ether sulphone) (PES) 373
polyethylene (PE)
natural rubber (NR) 4, 62, 72, 86-90, 94, branched (LDPE) 9, 30, 45, 46, 122, 123,
137-9, 330, 331 270, 271, 280, 282
carbon black reinforced 210, 21 1, 253, chemistry 9, 12, 13, 21, 50
254 crystallinity 35, 40, 42, 44, 45, 46, 62P,
necking 95P, 168-71 63P
in polymer melt 271, 272 linear (HDPE) 10, 14, 21, 27P, 30, 45, 46,
network elasticity 78-84 108, 122, 123, 270
neutron scattering 50 linear low-density (LLDPE) 30
Index 389

properties 21, 122, 123, 169, 171, 179, reinforced reaction injection moulding
326-8 (RRIM) 224, 226
poly(ethy1ene terephthalate) (PET) 15, 32, relative molecular mass (RMM) 9, 20-6,
45, 62, 63P, 140, 142, 329 44, 48, 199, 280
polyisobutylene 49, 1 1 1, 112, 119, 120 relaxation time 125, 130
polyisoprene 72, 89 relaxations 122
polymer 2, 9, 34, 44 residual stress
polymerization 9-18, 33 in composites 260, 261
poly(methy1 methacrylate) (PMMA) 12, 31 in mouldings 304, 305
37, 121, 141, 165, 181, 200, 280, 281, ribs, stiffening and strengthening with 353
323. 329. 358 Rohm and Haas 3 1
rubbers 2 4 , 72-93, 252-4, 330, 331, 354-7
rubber-toughening 180, 182, 200
poly(parapheny1ene terephthalamide) 221 rule of mixtures 214, 229, 230
poly(pheny1ene oxide) (PPO) 292, 293, 329,
373
poly@henylene sulphide) (PPS) 327, 374
polypropylene (PP) 7, 12, 30, 37, 45, 48, 49, second moment of area
63P, 91, 326-8 of beam 147, 158
polystyrene (PS) 12, 3 1, 167. 182, 183, 31 7P, polar, of shaft 146
328 secondary transitions 121, 122, 138, 165
poly(styrene-co-acrylonitrile) (SAN) 100, shape factor 355, 356
182 shear failure in composites 241, 242, 248,
polysulphone (PSF) 327, 373 363
polytetrafluoroethylene (PTFE) 36, 42, 67, shear flow 272-83
255P, 323, 331 . shear lag theory 245, 261 -3
polyurethane (PU) 1414 , 308, 331 shear modulus
poly(viny1 chloride) (PVC) 12, 31, 62, 63P, of composites 232
1 3 7 4 0 , 145, 198, 326-8, 331, 358 of rubber 83, 84, 94P, 95P
plasticized 33 1 shear thinning 273
poly(viny1 fluoride) (PVF) 62P sheet moulding compound (SMC) 226. 326
poly(viny1idene fluoride) (PVDF) 62P shift factor 134-7
power-law fluid 277, 278 shrinkage 62, 71, 297, 337, 338, 343
press fitting 341, 342 side group motion 122
pressure single edge notch (SEN) test 192
in capillary flow 279 sink marks 337, 338
melting, effect on 64P size coatings 2 16
in polymerization 9 ski bindings 367
in yielding 177-9 snap fitting 341, 343
prices of plastics (data) 327 solubility 100
profiles (extruded) 293 solvent crazing 182, 358
propylene 15, 19 solvent, polymers in 26
pseudoelastic design method 346-50 specific gravity data 327
pseudoplasticity of melts 273 specific stress 2 17, 259
pultrusion 223-5 specific volume 41, 46, 48
Spencer-Gilmore equation 298
spherulites 18, 39, 40, 4 2 4 , 47
spring-dashpot models 123-5
Rabinowitsch equation 278 springs
radiation crosslinking 10 use of composites 367
random copolymer 16, 160 use of rubber 354-6
random walk 68 staking, joining method 339, 340, 342
reaction injection moulding (RIM) 226, 307, static fatigue 197, 359
308, 326 Staudinger 3, 30
recovery 101, 149, 167 stereoregularity 19, 20
Regnault 31 strain hardening 171
390 Index

strain limits 345, 347 three-point bend (3PB) test 192


strain rate effects in yielding 171, 174-7 time-temperature superposition 135-6
strength of composites 2 3 6 4 4 , 250, 257P torsion of shaft 105, 145
stress analysis of polymers 143-54 torsion pendulum 116-18, 121
stress concentration factor 184, 337 toughening 180, 182, 200, 329
stress intensity factor (K) 188, 189, 207 toughness
critical (K,,) 187-97 effect of degradation 199
stress relaxation 109-1 2, 127, 128 effect of orientation 200, 201
in a bolt 159 effect of RMM 199, 200
of Zener model 127, 128 trans conformation 65P
stress-strain curve transfer moulding 3 13
rubbers 85 transient stress, in oscillation 152
viscoelastic polymers 153, 167 true stress 86, 170
Zener model 156 twin screw extruder 290
stretch-blow moulding 3 12
styrene 17, 31
styrene-butadiene rubber (SBR) 33, 89, 91,
330, 331 ultrasonic welding 339, 341
sub-critical crack growth 197, 198, 357, 358 urea-formaldehyde resin (UF) 329, 330, 374
sulphur crosslinking of rubbers 3, 4, 88,
138, 139
surface-to-volume ratio of
reinforcements 212, 2 13 vacuum forming 308
swell ratio 281 -3, 292, 293 van der Waals bonds 60, 99
swelling in liquids 88, 90, 96, 100 vented screw in extruder 286-9
symmetry vinyl polymer 12, 19, 20, 16, 37
in laminates 350 viscoelasticity 101-66
in molecules 18 linear 103-37, 146-58P
syndiotactic polymer 19, 20 non-linear 104, 106, 111, 346
of polymer liquids 281 -3, 31 1
viscosity, apparent
talc 222, 223 definition 273
tan 6 115 determination 273
temperature dependence RMM dependence 280, 282
of compliance 134-6 stress dependence 280-2
of fracture behaviour 199 temperature dependence 280, 281
of modulus 83, 1 3 7 4 3 voids 42, 215, 343, 357
of relaxation times 134, 165 von Mises yield criterion 177
of viscosity 280, 28 1 vulcanization 2, 3, 18, 88
of yield stress 174 ,.'
1
tennis racquet, use of composites 209-1 1
tensile strength i
of composites 2 3 6 4 4 , 250-2, 257P
data for plastics 327
of oriented fibres 62
i
wall shear ate 276, 278, 316P
wall thick ess of mouldings 337, 338
warping 71, 337, 353
r:

tex (unit) 216 water


Tg see Glass transition absorption 32, 141, 144, 345, 347
thermal expansion coefficient 47, 48 formation in polymerization 14, 15
of composites 234, 235 weathering 358
data for plastics 327 weight average molar mass 23-5
thermal stability 32 weld lines 300, 333, 335-7, 357
thermoforming 308-1 1, 332 welding 3 3 8 4 1
thermoplastic (definition) 5, 10 wire coating 294
thermoplastic polyester 32, 70 WLF theory 205, 280, 319
thermoplastic rubber (TR) 33, 90, 91
thermoset polyester see polyester resins
thermosets (definition) 5, 11 X-ray diffraction 34, 38
Index 391

Y (geometrical factor in fracture pressure dependence 177-9


mechanics) 193, 194, 196, 203, 207 strain-rate dependence 174-7
yielding 168-80 temperature dependence 174, 175
under multiaxial stress 177-80 yield zone at crack tip 177, 194
of net section in cracked bar 196
yield stress 171, 174
data for plastics 327 Zener model 124-34
lowering by rubber particles 180 Ziegler-Natta catalysts 10, 14, 19, 30