Gedde - Polymer Physics PDF

CONTENTS
Preface
1 A brief introduction to polymer science

1.1 Fundamental definitions
1.2 Configurational states
1.3 Homopolymers and copolymers
1.4 Molecular architecture
1.5 Common polymers
1.6 Molar mass
1 . 7 Polymerization
1.8 Thermal transitions and physical structures
1.9 Polymer materials
1.10 A short history of polymers
1.11 Summary
1.12 Exercises
1.13 References
1.14 Suggested further reading
2 Chain conformations in polymers

2.1 Introduction
2.2 Experimental determination of dimensions of chain molecules
2.3 Characteristic dimensions of 'random coil' polymers
2.4 Models for calculating the average end-to-end distance for an ensemble of statistical chains
2.5 Random-flight analysis
2.6 Chains with preferred conformation
2.7 Summary
2.8 Exercises
2.9 References
3 The rubber elastic state

3.1 Introduction
3.2 Thermo-elastic behaviour and thermodynamics: energetic and entropic elastic forces
3.3 The statistical mechanical theory of rubber elasticity
3.4 Swelling of rubbers in solvents
3.5 Deviations from classical statistical theories
3.6 Small-angle neutron scattering data
3.7 The theory of Mooney and Rivlin
3.8 Summary
3.9 Exercises
3.10 References
3. I 1 Suggested further reading
4 Polymer solutions
4.1 Introduction
4.2 Regular solutions
4.3 The Flory-Huggins theory
4.4 Concentration regimes in polymer solutions
4.5 The solubility parameter concept
4.6 Equation-of-state theories
4.7 Polymer-polymer blends
4.8 Summary
4.9 Exercises
4.10 References
5 The glassy amorphous state

5.1 Introduction to amorphous polymers
5.2 The glass transition temperature
5.3 Non-equilibrium features of glassy polymers and physical ageing
5.4 Theories for the glass transition
5.5 Mechanical behaviour of glassy, amorphous polymers
5.6 Structure of glassy, amorphous polymers
5.7 Summary
5.8 Exercises
5.9 References
6 The molten state

6.1 Introduction
6.2 Fundamental concepts in rheology
6.3 Measurement of rheological properties of molten polymers
6.4 Flexible-chain polymers
6.5 Liquid-crystalline polymers
6.6 Summary
6.7 Exercises
6.8 References
7 Crystalline polymers
7.1 Background and a brief survey of polymer crystallography
7.2 The crystal lamella
7.3 Crystals grown from the melt and the crystal lamella stack
7.4 Supermolecular structure
7.5 Methods of assessing supermolecular structure
7.6 Degree of crystallinity
7.7 Relaxation processes in semicrystalline polymers
7.8 Summary
7.9 Exercises
7.10 References
8 Crystallization kinetics
8.1 Background
8.2 The equilibrium melting temperature
8.3 The general Avrami equation
8.4 Growth theories
8.5 Molecular fractionation
8.6 Orientation-induced crystallization
8.7 Summary
8.8 Exercises
8.9 References
9 Chain orientation
9.1 Introduction
9.2 Definition of chain orientation
9.3 Methods for assessment of uniaxial chain orientation
9.4 Methods for assessment of biaxial chain orientation
9.5 How chain orientation is created
9.6 Properties of oriented polymers
9.7 Summary
9.8 Exercises
9.9 References
10 Thermal analysis of polymers

10.1 Introduction
10.2 Thermo-analytical methods
10.3 Thermal behaviour of polymers
10.4 Summary
10.5 Exercises
10.6 References
11 Microscopy of polymers
11.1 Introduction
11.2 Optical microscopy (OM)
11.3 Electron microscopy
11.4 Preparation of specimens for microscopy
11.5 Applications of polymer microscopy
11.6 Summary
11.7 Exercises
11.8 References
12 Spectroscopy and scattering of polymers
12.1 Introduction
12.2 Spectroscopy
12.3 Scattering and diffraction methods
12.4 Summary
12.5 Exercises
12.6 References
13 Solutions to problems given in exercises

Chapter 1
Chapter 2
Chapter 3
Chapter 4
Chapter 5
Chapter 6
Chapter 7
Chapter 8
Chapter 9
Chapter 10
Chapter 11
Chapter 12
References
INDEX
Absorbance, infrared spectroscopy 263 C-axis orientation 205-6 gauche 19, 20

Acrylonitrile-butadiene-styrene plastics, CED, sce Cohesive energy density staggered position 19
glass transition temperatures 81 Cellulose nitrate, history 16 trans 19, 20
Aliphatic polyesters, history 16 Chain branching, polyethylene, Conoscopy 240
Alpha process, relaxation, molecular crystal structure 137 Constitutional repeating unit I
criteria for 163-4 Chain entanglements Copolymer
Anelastic behaviour 89, 90 general 99 alternating 5
Anti-plasticization 82 rheological properties 106 block 5
Anti-Stokes-Raman scattering 260 Chain folding 138, 139, 145, 150, 151 definition 5
Argand plot 225, 226 Chain of hindered rotation graft 5
Arrhenius equation, dielectric independent torsion angle random 5
relaxation 226, 227 ' potentials 26-9 statistical 5
Atacticity 3 interdependent torsion angle terpolymer 5
Attenuated total reflection 262 potentials 29--32 Crankshaft motions 95
Atomic force microscopy 240 Chain orientation Crystal lamella
ATR, see Attenuated total reflection assessment, infrared chain folding 138, 139, 145, 150,
Avrami equation spectroscopy 206-7 151
analysis of crystallization kinetics assessment, sonic modulus 207 crystal thickening 142, 143, 144
data 178 biaxial orientation 208 equilibrium shape 142
athermal nucleation 175, 176 effect on properties 211-14 fundamentals 138-40
exponent values for special growth end-to-end vector orientation 2013-1 history 137-8
cases I77 methods to orient hollow pyramide, polyethylene 139
general 176 polymers 208-11 initial crystal thickness 143
limitations for polymers 177 segmental orientation 200 lateral habit, other polymers,
primary crystallization 177 semicrystalline polymers 207-8 solution-grown 141
secondary crystallization 178 uniaxial orientation 203 lateral habit, polyethylene 139, 140
thermal nucleation 176 Chain with preferred melt-grown 147-51
Axialite 154 conformation 35-6 melt-grown. fold surface 149-51
Chlorosulphonation, staining 248, methods for assessment of
Bakelite, see Phenol-formaldehyde 249 structure 145-6
resin Cholesteric phase 114, 115 polyethylene, annealing of
Bimodal melting 229 Clausius-Mesotti equation 223 monolayer crystals 142, 143
Bingham plastics 101 Cohesive energy density 67 roof-shaped, polyethylene 148
Binodal points 57, 58 Cold-drawing 208-9 rough lateral surfaces 140, 141
Birefringence Cole-Cole equation 225 sectorization, polyethylene 139
assessment, compensator 204-5 Cole-Cole plot, see Argand plot solution-grown 138-41
biaxial orientat~on 208 Cole-Davidson equation 226 Crystal lamella stack
form 204 Compton scattering 270 dominant 149
semicrystalline polymers 204 Configuration general 147-9
uniaxial orientation 202, 203 definition 2 subsidiary 149
Boltzmann superposition head-to-tail 4 Crystal systems 131, 132
principle 90 tacticity 2 Crystal thickening 142, 143, 144. 227
Bonds Conformation Crystallinity
dissociation energy 2 anti-gauche 19 assessment
length 2 definition 4 by calorimetry 158-9, 229
Bragg equation 270 eclipsed position 19 by density measurements 158
Bravais lattices 131. 132 energy map of butane 20 by wide-angle X-ray
Burger's model 91-2 energy map of ethane 20 scattering 157-8
Crystallinity contd Doolittle's viscosity equation 85. 87 Fingerprint texture 115
definition 157 Droplet experiment 286 Flory temperature, see Theta
infrared spectroscopy 265, 266 DSC, see Differential scanning temperature
nuclear magnetic resonance calorimetry Flory theorem 21. 23
spectroscopy 268 DTA, see Differential thermal analysis Flory theory for liquid crystals 1234
polyethylene, dependence on Dyad 3 Flory-Huggins theory
molecular structure 159-60 Dynamic mechanical thermal general 5 8 4 3
thermal treatment 160 analysis 222-3 mixing enthalpy 61-2
polyethylene, effect on mixing entropy 5 9 4 1 , 63
mechanical properties 161 Elasticity rubber materials 48
transport properties 161 compliance, dependence on chain upper critical solution
Crystallite orientation 206 orientation 213 temperature 62
Crystallization, metastable energy-driven 39, 40 Fluids 99
phases 18&9 entropy-driven 39, 40 Focal-conic fan texture 116
Crystallization kinetics, assessment by theoretical 212 FOVE model 68
differential scanning Elastomer 39 Fox equation 70, 82
calorimetry 229-30 Electrically conductive polymers 17 Frank constants 114
Electron diffraction 96. 273 Free volume 79, 80
Degree of polymerization 11 Electron microscopy Freely jointed chain 24-5
Dendrimer 6 history 239 Freely rotating chain 2 5 4
des Cloiseaux' law 66 permanganic acid etching 146. 147
DETA, see Dielectric thermal analysis solution-grown single crystals 145 Gauche state 19, 20
Diamond, maximum modulus 212 staining of semicrystalline Gaussian chain, models 21, 24-35
Die-swell 103 polymers 146 Gel permeation, chromatography, see
Dielectric a process 163 Electron spectroscopy for chemical Size exclusion chromatography
Dielectric constant 225 analysis 269 Gibbs-DiMarzio theory 88-9
Dielectric loss 225 Electron spin resonance Glass transition
Dielectric thermal analysis 223-6 spectroscopy 269 mechanical properties 14
Differential scanning calorimetry Elongational flow 100 semicrystalline polymers 162, 163
amorphous polymers 23CF1 End-to-end distance, chain Glass transition temperature
degree of vulcanization 234 definition 21 effect of
fundamentals 218, 219, 220 experimental methods 21-2 cohesive energy density 79
liquid-crystalline polymers 231, point distribution function 35 crosslink density 81
232 radial distribution function 35 molar mass 80
methods to obtain high accuracy in Enthalpy of isotropization 120 molecular architecture 80
data 220 Entropic crystal growth theory, see pressure 82
molecular fractionation, Sadler-Gilmer theory repe%ing u n ~ tstructure 78-9
polyethylene 193, 194 Entropy of isotropization 120 polymer blends 70, 72, 81, 82
polymer degradation 232, 233 Equation-of-state theories 68-9 Glass transition theory
semicrystalline polymers 2 2 6 3 0 Equilibrium crystallization growth free volume theories 87-8
Differential thermal analysis 218, theories 178 kinetic theories 85-7. 88
219, 220 Equilibrium melting temperature thermodynamic theory 88-9
Diffraction 259 dependence on chain Glassy amorphous polymer
Dilatant liquid 101 structure 172-3 mechanical behaviour 89-90. 92-5
Dilatometry 221-2 diluted systems 174 molecular factors 77, 78
Dimension of Gaussian chains from Hoffman-Weeks plot 172 structure 9 5 4
light scattering 22 from small-molecule data 172 thermal factors 77, 78
long-range effects 22, 33 from Thompson-Gibbs Goler equation 176
small-angle neutron scattering 22 equation 171 GPC, see Size exclusion
theta conditions 22 molar mass dependence 173-4 chromatography
viscometry 22 Equivalent chain model 32 Gutta-percha 3
Disclination 112, 113, 114 Erhrenfest equation 89
Dislocation ESCA, see Electron spectroscopy for Havriliak-Negami equation 226
edge 136 chemical analysis Hermans orientation function
screw 136 ESR spectroscopy, see Electron spin definition 202
DMTA, see Dynamic mechanical resonance spectroscopy optical birefringence 201-2
thermal analysis Etching, electron microscopy 249-51 Higher order interaction 21
Doi theory 123 Extended chain crystals, Hildebrand solubility parameter, see
Doi-Edwards theory 108, 109 polyethylene 174 Solubility parameter
History of polymers 15-18 Leslie-Ericksen theory 123 number average 9
Homopolymer 5 LH theory, see Lauritzen-Hoffman polydispersity index 10
Hyperbranched polymer 6 theory viscosity average 9
Light scattering 22, 70, 72, 273 Z average 9
Infrared dichroism 206-7, 260 Liquid crystal Molar mass distribution functions 1
Infrared spectroscopy history 109 Molar mass segregation 149
chain conformation 265 definition 109 Molecular architecture 6
chain orientation 265 discotic 111 Molecular fractionation
chemical structure analysis 264-5 distortion 114 general 189-93
crystallinity 265, 266 X-ray diffraction patterns 116 methods for assessment 193-4
dichroism 2 0 6 7 , 260 Liquid crystalline polymers theory 190
Fourier transform chemical structure 110 Monomer, definition 1
spectrometers 262 crystal structure, effect of Mooney-Rivlin theory 51
fundamentals 260. 261 copolymerization 121
instrumentation 262 history 17, 18. l I ( t l l Natural rubber
miscibility of polymer 265 main-chain 110, 111 energetic stress ratio 44
polymer blends 71. 72 melting point, effect of history 15, 16
quantitative analysis 262-3 copolymerization 121 structure 39
sample preparation 263 mesogenic group 110 tacticity 3
Injection moulding 21 1 microscopy 253, 254 Necking, cold-drawing 210
Interaction parameter 61 morphology of injection-moulded Nematic phase 112-13
Interlamellar tie chains I51 specimen 211 Network polymer 6
Internal reflection spectroscopy 262 phase diagrams 119, 126 Newtonian liquid 101
iPP, see Polypropylene, isotactic physical structure 111-17 NMR spectroscopy, see Nuclear
IR spectroscopy, see Infrared rheology 121-3 magnetic resonance
spectroscopy side-chain 110. 111 spectroscopy
IRS, see Internal reflection spacer group 110 Non-periodic layer crystallite I21
spectroscopy theory 123-6 Nuclear magnetic resonance
Isotacticity 2, 3 thermal behaviour 117 spectroscopy
Isothermal volume recovery Long-chain branch 6 applications 268-9
memory effect 84 Longitudinal acoustic mode 266 chemical shift 267
phenomenology 83, 84 Lower critical solution chemical structure 268
Isotropization temperature temperature 63, 64, 72 coupling effect 267
definition 113 Lyotropic liquid 109 crystallinity 268
effect of mesogenic group 117-19 fundamentals 2 6 6 7
effect of spacer group I20 Macromolecular concept, history 16 instrumentation 267-8
Maier-Saupe theory 126 nuclear overhauser effect
KAHR model, see Maxwell model (NOE) 268
Kovacs-Aklonis-Hutchinson- dynamic mechanical behaviour 92 polymer blends 71, 72
Ramos model static mechanical behaviour 91 segmental mobility 268
Kevlar 17. 110 Meander model 96 thermal transitions 269
Kinetic crystallization growth Mechanical a process 163 Nucleation, crystal
theories 178-88 Melt-spinning 21 1 fundamentals 169, 170
Kink 137 Meso dyad 3 heterogeneous 170
Kovacs-Aklonis-Hutchinson-Ramos Mesomorphic material 109 homogeneous 170
model 86 Mesophase molecular 190
enantiotropic 117 primary 170
LAM, see Longitudinal acoustic mode monotropic 117 secondary 170
Lattice plane index 134-5 virtual 117 tertiary 170
Laue condition 270 Michel-Levy chart 204, 244
Lauritzen-Hoffman theory Microscopy, different techniques 240 OIT, see Oxidation induction time
experimental data 183-4 Miller's index 134, 135 Oligomer 1
general 178-86 Mixtures of branched and linear Optical microscopy
recent criticism 185-5 PE 191-3 bright-field microscopy 241
recent developments 185 Molar mass condenser 242
regime I growth 181-2 colligative properties 10-11 conjugate planes 242, 243
regime ll growth 182-3 end-group analysis 10 dark-field microscopy 241
regime Ill growth 183 mass average 9 differential interference-contrast
Z test 184 methods for assessment microscopy 244
Optical microscopy contd Poly(1-butene), crystal lamella, heating rate dependence of melting
fundamentals 241-3 solution-grown 141 point 227. 228
history 239 Poly(4-methyl-1-pentene) hexagonal phase 188
numerical aperture 241. 242 crystal lamella, history 16, 17
objective 242 solution-grown 141 maximum modulus 212
phase-contrast microscopy 244 repeating unit 7 molecular fractionation 190, 191,
polarized light microscopy 243-4 Poly(buty1ene terephthalate) 8 192
polymer blends 71, 72 Poly(dimethy1 siloxane) 44 polymerization 13
resolution 241 Poly(ethylene terephthalate) preferred conformation 36
Order parameter crystal lamella, Raman spectroscopy, crystal
definition 112 solution-grown 141 thickness 147
domain, temperature etching techniques for electron repeating unit 7
dependence 113 microscopy 25 1 staining for TEM 249
see also Hermans orientation maximum modulus 212 statistical weight matrix 29
function repeating unit 8 supermolecdar structure 152, 153,
Orientation-induced Poly(n-alkylacrylate) 8 154, 155
crystallization 194-5 Poly(n-alkylmethacrylate) 8 transmission electron
Osmium tetroxide staining 247-8, Poly(viny1 alcohoj) 7 microscopy 252-3, 254
249 Poly(viny1idene dichloride) 8 Polyethyleneoxide
Osmosis 62-3 Poly(viny1idene difluoride) 8 crystal lamella.
Osmotic pressure Polyacrylonitrile 7 solution-grown 141
concentration dependence 65-6 Polyalcohols, staining for TEM 249 equilibrium melting data 173
second virial coefficient 64 Polyaldehydes, staining for TEM 249 repeating unit 8
Ostwald-de Waele equation 102 Polyamide 6 Polyisoprene
Oxidation induction time crystal lamella, repeating unit 7
general 232, 233 solution-grown 141 tacticity 3
temperature dependence 233 maximum modulus 212 Polymer
repeating unit 8 definition 1
PA 6, see Polyamide 6 Polyamide 6.6 names
PA 6.10. see Polyamide 6.10. repeating unit crystal lamella, source-based 6
PA n, see Polyamide n solution-grown 141 stmcture-based 6
PAN, see Polyacrylonitrile equilibrium melting data 173 Polymer blends
Paracrystalline model 147 supermolecular structure 155 electron microscopy 254-5
PBTP, see Poly(buty1ene Polyamide n 8 glass transition temperatures 70,
terephthalate) Polyamide 6.10, repeating unit 8 72
PE, see Polyethylene Polyamides infrared spectroscopy 71. 72
Pentad 3 etching techniques for electron light scattering 70, 72
PEO, see Polyethyleneoxide microscopy 25 1 methods' for the assessment of
Permanganic acid etching 250, 251 repeating unit 8 morphology 70-1
PETP, see Poly(ethy1ene terephthalate) staining for TEM 249 molecular interpretation of
Phantom chain, see Unperturbed chain Polybutadiene 4 miscibility 72
Phenol-formaldehyde resin 16 Polydienes, staining for TEM 249 nuclear magnetic resonance
Physical ageing 82-5 Poly(etherether ketone) spectroscopy 71, 72
Plasticizer 82 etching techniques for electron optical microscopy 71. 72
PMMA, see Polymethylmethacrylate microscopy 25 1 phase diagrams 72
Point groups 132 Polyethylene scanning electron microscopy 71.
Polarization Avrami exponent data 177-8 72
atomic 224 crystal lamella, small-angle X-ray scattering 70,
dipolar 224 solution-grown 138-40 72
electronic 224 crvstal structure 133 transmission electron
Polarized light microscopy temperature dependence 134 microscopy 71, 72
fundamentals 243-4 crystallization kinetics data, LH turbidity measurements 70
molecular fractionation, theory 184-5 wide-angle X-ray scattering 70, 72
polyethylene 194 elastic modulus as function of draw Polymer crystallography 131-7
supermolecdar structure 155, 156 ratio 214 Polymer solutions
Poly(1.4-butadiene) energetic stress ratio 44 concentration regimes 65-6
crystallization via metastable equilibrium melting data 173 dilute 65, 66
phase 188 etching techniques for electron general 58-58
repeating unit 7 microscopy 25 1 semi-dilute 66
Index 297
Polymerization PS, see Polystyrene, isotactic Rubbers
anionic 13 Pseudoplastic liquid 101 energetic stress ratio 43, 44
cationic 13 PTFE, see Polytetrafluoroethylene S t ~ d ~ r 41
e
chain-growth 12-13 PVAc, see Polyvinylacetate, repeating unit swelling in solvents 48
coordination 13 PVAL, see Poly(vinyl alcohol) thermodynamics 41-4
definition 1 PVC, see Polyvinylchloride, repeating unit thermo-elastic behaviour 41
history 16-18 PVDC, see Poly(vinylidene dichloride) Ruthenium tetroxide, staining 248,
radical 12 PVDF, see Poly(vinylidene difluoride) 249
step-growth 12
P~l~methylmeth~acrylate Racemic dyad 3 Sadler-Gilmer theory 1 8 6 8
etching techniques for electron Radius of gyration, definition 21 SALS, see Small-angle light scattering
microscopy 25 1 Raman spectroscopy SAXS, see Small-angle X-ray scattering
relaxation behaviour 93. 94 chemical structure analysis 264 Scanning electron microscopy
repeating unit 7 crystal thickness 147 depth of field 245
Polymorphism fundamentals 260, 261 fundamentals 244, 245
polyethylene 133 sample preparation 263-4 polymer blends 71. 72
polypropylene 133. 134 Random chain, see Gaussian chain preparation of samples 247
P~l~oxymethylene Random-flight analysis 33-5 resolution 245
crystal lamella, Random lamellar structure 154 supermolecular structure 156-7
solution-grown 141 Random switch-board model 145 Scattering 259
equilibrium melting data 173 Reciprocal space 1 3 5 4 Schemer equation 147
maximum modulus 212 Regular solution model Schlieren texture 112. 113
preferred conformation 36 general 55-8 Schultz distribution 12
repeating unit 8 mixing enthalpy 56 Schultz-Flory distribution 12
Polypropylene isotactic mixing entropy 56 SEC, see Size exclusion
cross-hatching 149 upper critical solution chromatography
crystal lamella, temperature 58, 62 Secondary normal stress
solution-grown 141 Relaxation processes coefficient 100
crystal structure 133, 134 molecular interpretation 93-5 Second order interaction 19
equilibrium melting data 173 semicrystalline polymers 162-4 Sectioning 249, 250
etching techniques for electron Relaxation time Sectorization, see Crystal lamella
microscopy 25 1 Arrhenius temperature SEM, see Scanning electron
infrared spectrum, conformational dependence 93 microscopy
analysis 2 6 5 4 dielectric measurements 225, 226 Sheaf structure. see Axialite
maximum modulus 212 Maxwell model 91 Shear modulus
preferred conformation 36 melts, according to reptation complex 101
staining for TEM 249 theory 108 loss 101
supermolecu~arstructure 155 melts, molar mass storage 101
Polypropylene, repeating unit 7 dependence 1 0 5 4 Shear viscosity 100
Polystyrene terminal 104 Shish-kebab 154
glass transition temperature, molar Relaxation time spectrum 92 Short-chain branch, definition 6
mass dependence 81 Reptation model 107-9 Short-fibre composites, assessment of
relaxation behaviour 95 Retardation time, Voigt-Kelvin fibre orientation 255
repeating unit 7 model 91 Single-crystal, see Crystal lamella,
Polystyrene, isotactic Rheology solution-grown
crystal lamella. definition 99 Size exclusion chromatography I I
solution-grown 141 liquid-crystalline polymers 121-3 Small-angle light scattering 156
etching techniques for electron methods for assessment of Small-angle neutron scattering
microscopy 25 1 properties 104-5 deformation of rubbers 51
P~l~tetrafluoroethylene Rheopexi 102 general 22, 260, 272
crystal lamella, Rotational isomeric state glassy amorphous polymers 96
solution-grown 141 approximation 19-20 polyethylene, melt-grown
equilibrium melting data 173 Rotational partitioning function 27 crystals 15C-1
repeating unit 8 Rouse model 107 Small-angle X-ray scattering
Polyvinylacetate, repeating unit 7 Row-nucleated structure 154 crystal thickness 146
P~l~vinylchloride, repeating unit 7 Rubber elastic theory, history 16 instrumentation 272
POM, see Polyoxymethylene Rubber elasticity, statistical molecular fractionation,
PP, see Polypropylene, isotactic mechanical theory 44-8 polyethylene 194
Pr~marynormal stress coefficient 100 Rubber-plateau 14 polymer blends 70, 72
298 Index
Smectic phase 115-16 Mooney-Rivlin theory 5 1 dimensions 23, 24, 65

Solid-state extrusion 209 non-Gaussian statistics 50-1 temperature coefficients 24, 28
Solubility parameter phantom network model 44, 45, Upper critical solution
definition 67 47, 48 temperature 58, 72
Hansen's three-dimensional 67, 68 Thermal analysis Utracki-Jukes equation 70
methods for assessment 67 definition 217 UV-visible spectroscopy 269
Solution, definition 55 methods, summary 217
Solution-spinning 21 1 Thermal conductivity, dependence on Vectra 121
Solvent etching 250, 251 cham orientation 213 Vibrational spectroscopy
Space groups 132 Thermal mechanical analysis 221-2 fundamentals 260-2
Spectroscopic methods, spectral Thermal optical analysis 223 group frequencies 261
ranges 259 Thermo-elastic inversion 41. 42 Viscosity
Spectroscopy, definition 259 Thermogravimetry complex 101
Spherulite content of volatile species 233 dynamic 101
banded 152-3 filler content 233-4 Miesowisz 122
general 152, 153. 155, 156 fundamentals 221 pressure dependence 107
negative 152, 156 oxidation induction time 233 shear 100
non-banded 152 Thermoplastic elastomers 41 steady elongational 100
positive 152. 156 Thermoplastics, definition 15 temperature dependence 107
Spinodal decomposition 56 Thermosets, definition 15 zero-shear-rate 101. 102
Spinodal points 56. 57, 58 Thermotropic llquid 110 Viscosity measurement 22
Stainmg, electron microscopy 247-9 Theta condition 21. 23 Voigt-Kelvin model 91
Statistical weight matrix 29-30 Theta temperature 64. 65 Vulcanization methods 41
Steady elongational viscosity 100 Thixotropy 102
Steady simple shear flow, constitutive Thompson-Gibbs equation 144-5,
Wavenumber 263
equations 96-100 147, 171
WAXS, see Wide-angle X-ray
Steady-state recoverable shear TMA, see Thermal mechanical analysis
scattering
compliance TOA, see Thermal optical analysis
Wide-angle neutron scattering 260,
definition 103 Torsion pendulum 222, 223
272-3
melts, according to reptation Total enthalpy method 158-9
Wide-angle X-ray scattering
theory 108 Trans state, definition 19. 20
molar mass dependence 106 crystal thickness 147
Trans(l,4-polyisoprene). energetic
Stokes-Raman scattering 260 glassy amorphous polymers 95
stress ratio 44
instrumentation 271
Subglass processes Trans-crystalline structure 154
polymer blends 70, 72
amorphous polymers 93-5 Transmission electron microscopy
Willlam-Landel-Ferry equation
semicrystalline polymers 162, 163 artificial structures 251-2
dielectric relaxation 226. 227
Super-folding model 145 dark-held microscopy 246
general 87, 88. 89, 92, 93
'
Superheating, crystal 144, 228 depth of field 245
WLF equation, see
Supermolecular structure fundamentals 244, 245. 246
William-Landel-Ferry
general 151-5 molecular fractionation,
equation
methods of assessing 155-7 polyethylene 194
SWISScheese structure 142 origin of contrast 246
Syndiotacticity 3 polymer blends 71, 72 X-ray scattering
preparation of samples 247-51 fundamentals 269-71
resolution 245 synchrotron source 270
Triad 3
Tacticity 2 Young's modulus 213
TEM, see Transmission electron
Ultra-or~entedpolymers, history 17
microscopy
Ultraviolet microscopy 240 Zero-shear-rate viscosity
Tetrad 3 Unit cell, crystal 131 definition 101, 102
TG, see Thermogravimetry
Universal calibration procedure. melts, according to reptation
Theory of rubber elasticity
SEC 11 theory 108
affine deformation model 44-7
Unperturbed chain molar mass dependence 106
deviations from classical definihon 23 Zimm plot 22
treatment 48-50

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CONTENTS

1 A brief introduction to polymer science

2 Chain conformations in polymers

3 The rubber elastic state

5 The glassy amorphous state

6 The molten state

10 Thermal analysis of polymers

13 Solutions to problems given in exercises

Absorbance, infrared spectroscopy 263 C-axis orientation 205-6 gauche 19, 20

Smectic phase 115-16 Mooney-Rivlin theory 5 1 dimensions 23, 24, 65

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