Subject Index __________________________________________________________________ 888 reaction 233–238, 233–237 rigid 6 ,7 semicrystalline 488 transitions 536, 537, 537 ultimate strength 533–535, 534, 535 polymerization, degree of 27 emulsion 217, 217 living, see: reaction, chain, without termination Merrifield method 190 –192, 192, 237 of lithium phosphate 201 –206, 202–206 see also: reaction stereo-specific 207, 209 topotactic 510, 511 Ziegler-Natta 209 –211, 210, 211 potentiometer 288 production, of extensive thermodynamic quantities 88, 147, 148, 148 sign of 88 properties, colligative 51, 58, 65, 96 prediction of 226, 227 purity analysis 319–320, 320, 321 pycnometer 295, 296, 296 pyrolysis 232 see also: decomposition pyrometer 289, 819 pyrosynthesis by DTA 354, 354 R radiation, scattering 801–805 electromagnetic 50 electron 66 neutron 66 radius, atomic 3, 302 van der Waals 37, 301, 302 RAF 138, 605 , 607–609, 607–609, 693 , 694, 694 formation on crystallization 608, 609 disappearance on melting 641 , 641 glass transition, see: transition, glass Raoult’s law 708, 708 Rayleigh 51 ratio 54 , 54, 809, 809, 810 derivation 806–810, 807–809 reaction, chain, copolymer 227–229, 227, 228 emulsion polymerization, 217, 217 equilibrium 214 , 214, 215 initiation 208 kinetics 212–214, 213 list of monomers, 212 mass average 225–226, 225, 226 mechanism 206–212, 207 number and mass fraction 221–223, 222 , 223 molar mass fraction 221–223, 222, 223 without termination 215 –216, 216 chemical, by TMDSC 402, 403, 402, 403 interchange, see: transamidation and transesterification kinetics, rate equations 817 molecular length dependence in esters 200 matrix 218–219, 218 polymer 233–238, 233–237 ring-chain 138, 138, 139, 194, 199, 199, 219 step, aromatic polymers 198 conditions 198–199, 199 copolymer 229, 230, 230 equilibrium 219 examples 196–198, 196–198 kinetics 200, 200, 201, 201 lithium phosphate 201–206 mass average 224–225, 224 mechanism 193–195, 194 molar mass 219–221, 221 number and mass fraction 220 polydispersity 224 statistics 195, 196 poymers, produced via chain reactions 216 stepwise 189–193, 190–192 recrystallization 655 -666, 655–665 relaxation 159 time 159–161, 159, 160, 161 Debye 117 , 160 change with temperature 685 process 158–159 see also: stress relaxation Subject Index __________________________________________________________________ 889 see also: thermodynamics, nonequilibrium see also: transition, glass see also: viscoelasticity, relaxation time repeating unit, constitutional 14 , 14, 15, 18–21 flexible to stiff CRUs 49 reptation model 573, 573 revolution, industrial 11 Richards’s rule 182 , 183, 339–341, 340 Rietveld method of X-ray diffraction 504 –506, 505–507 rotation 122 internal 121 rotoreptation 558, 558 rubber elasticity, see: elasticity, entropy run number 762 S sample history, via glass transition 682–700, 683–685, 687–700 saw-tooth modulation 360–362, 361, 362, 837–847, 837–847 SCTA, see: TGA, sample-controlled second, ephemeris 283 Seebeck effect 287, 314, 315 seed material for PP, table 248 self seeding 246, 247, 248 semiconductor 286 , 286 scattering of light 50–58, 52, 806–810, 806–809 angular dependence 56 apparatus 53 intensity 54 molar mass determination 54, 54 size and shape dependence 54–56, 54–56, screw axis 462 , 463 462 relation to helix axis 463, 464, 464 sheet network 25 SI rules and units 75, 76 Simha-Boyer rule 761 skewness 28, 28 solid, see: phase, amorphous see: phase, crystal solution, ideal, regular, real 96 , 710 space groups 462, 462 number of 462, 462, 463 spinodal decomposition 712 , 712 spherulite 240, 499–503, 500–502 growth 259–260, 260 hedgehog-type 500, 501, 500, 501 Popoff-type 500, 501 Staudinger 6 state, functions of, 75 stereoisomer 23, 848 steric hindrance 37–40, 38, 39 stiff chain macromolecules 47–48, 49 strain 404 , 404 release in glasses 605, 605 stress 404 , 404 anomaly 415 conversion factors, table of 404 relaxation 414 , 415 time anomaly 415, 416 Strutt, see: Rayleigh substance, pure 189 subsystem 89, 90, 146, 147 supercooling 243, 255, 266 superposition principle 835 symmetry, axes 460–463, 460, 461 elements 461 symbols for, in crystals 469, 470 product 461, 848 groups 848 operation 460 –463 closed 460 , 460 closed with inversion 461 open 462, 463, 462 translation 462, 462 system, crystal 457, 458, 458 description 88–90, 89 equilibria (thermal, mechanical) 89 isolated 89 open 89, 147, 428 types of 89 multi-component, ideal 96–98, 97 nonideal 98, 98 multi-phase, of small molecules 98–101, 99, 100 right-handed 457 Système International, see: SI T temperature 79–81 Boyle 36 critical, upper and lower 712–714, 712–714 van der Waals 300 Subject Index __________________________________________________________________ 890 eutectic 100, 100, 290, 291, 706, 706, 707, 707 fictive 391, 391, 601, 683 gas 80, 81 isotropization 176 Kauzmann 140 liquidus 290, 291, 706, 706, 707 melting, extrapolation to equilibrium 537 peritectic 706, 706, 707 scale 280 by Celsius 281 by Fahrenheit 281 by Newton 280 by Réaumur 281 gas 282, 282 international, see: ITS 1990 physiological 280 , 280 thermodynamic 80, 282, 282, 283 solidus line 706, 706, 707 theta () 35,36, 36, 64, 713, 713 Theta () 110 Debye 111,112–116, 113 Einstein 110, 110, 111, 111 for crystals of 100 elements and salts 115 for logitudinal and transverse vibrations 115, 115 for chymotrypsinogen 122 for polymethionine 137 for polyoxides 130 for PTFE 134 transition 177 tenacity, see: tensile strength tensile strength 533 –535, 534, 535, 608 TGA 77,77 application 443–449, 444-446 buoyancy correction 437 coupled with, DSC or DTA 428, 431, 432, 433, 433, 444 other techniques 428 mass spectrometry 434, 434 data combined, with DTA 439–445, 440–444 with DTGA 439–441, 440, 441 decomposition 231, 232, 232, 438, 439, 439 of calcium oxalate 444–446, 444–446 fast heating 434 HiRes™ 436 ICTAC recommendations 438, 822, 823 infrared image furnace 434, 435 instrumentation 430–436, 430–436 kinetics, equation 444 by isoconversionion method 448 , 447, 449 by steady-state parameter-jump method 446, 447, 447 lifetime prediction 446 –449, 447, 449 principle 428 , 429, 429 polymer identification with 439 recoil of evolving gases 438, 439 reference materials 437 sample controlled 435, 436 standardization 437, 438, 438 Curie temperature for mass 437, 428 step-wise isothermal 436 technique 437, 438 thermal analysis 77,77 by computer 84–88, 85–87 system, advanced, see: ATHAS techniques 76–79 thermal head 310 thermoacoustimetry 79 thermobalance 430, 437 thermobarometry 79 thermochemistry 320–324 data table 323 Thermochimica Acta 77, 331 thermocouple 287 –289, 288 table of EMF 288 thermodynamic functions, of carbon 325, 326, 325, 326 of paraffins 327–329, 328, 329 thermodynamics, and motion V, 167, 176–178, 591–593, 593 first law 76, 81–84, 83, 90, 91 laws, not so precisely 90, 91 nonequilibrium 146–161, 146–150, 151–161 flux and production 147, 148, 148 internal variables 155–158, 156, 157 melting of lamellar crystals 148–155, 149, 150, 152–155 relaxation times 159–161, 159–161 Subject Index __________________________________________________________________ 891 second law 91–94, 91 Thomson statement 91 Thomson engine 93 third law 94–96, 95, 140 Nernst formulation 95 zeroth law 90, 279 thermoelectrometry 79 thermogravimetry, see: TGA thermoluminescence 79 thermomagnetometry 79 thermometer 80, 279, 280 bimetallic 289 calorimetric 80 gas 289 immersion 285 liquid-in-glass 80, 80, 280, 280 283–285, 285 mercury-in-glass 80, 281 –285, 285 error correction 283–285, 285 noise 289 platinum resistance 286, 818 principle 279–283, 280, 282 quartz 289 resistance 285–287, 286, 287 semiconductor 286, 287, 286 thermocouple 287–289, 288 vapor pressure 289 thermometry 77 application 290–291, 290 contact 279, 280 thermooptometry 79 thermoparticulate analysis 79 thermophotometry 79 Thermophysics of Polymers VII thermorefractometry 79 thermosonometry 79 thermotropic liquid crystal 724 , 724 Thomson, see: Kelvin effect 315 time, scale of, macroscopic V microscopic V, 37 temperature superposition 418, 419 unit, SI, 283, 284 TMA 77,77 applications 408–412, 408–412 instrumentation 406–408, 407 measurement, of the expansivity 298, 298 of the glass transition 298, 298 modes of measurement 407 principle 404–406, 404–406 temperature-modulated 418 time-temperature superposition 418, 419 TMDMA see: DMA, temperature- modulated TMDSC 333, 333, 334 analysis, pseudo-isothermal 369 asymmetry correction 378–379, 379, 380 basic equations 363, 364, 364, 365 calibration with In 375–378, 276, 277 , 397, 397 Cole-Cole plot 383, 384, 383 comparison, of periodic and non- periodic experiments 417 with DMA 418, 419, 609, 610, 610 complex notation 362, 363 data treatment and modeling 369–373, 369 , 370–372 loss of stationarity 371, 371, 372 using spreadsheets 371 Fourier transform 334, 840, 841, 841, 842 frequency correction, - 332, 334, 368 glass transition, measurement 388–396, 389 heat capacity, complex 382–384, 384 measurement 364–369, 365–368, 385–388, 385–388 heat-flow rate 363 , 369–373, 369–372, 386, 386 amplitude dependence 381, 382, 382 contributions on melting 383, 383 frequency dependence 382–384, 382–384 in the transition region 386–388, 387, 388 maximum 370 positive and negative 378, 378 in- and out-of-phase signal 362, 363 instrumental problems 373–384, 374–384 linearity 369 Lissajous figure 266, 379, 380, 380, 381, 386, 397, 397, 398, 626, 742 Subject Index __________________________________________________________________ 892 mathematical treatment 362–369, 363–368 model calculation, heat-flux DSC 365, 366, 366 model calculation, power- compensation DSC 366, 367, 367 tau-correction (-) 367–369, 3 modeling 369–373, 369–372 modulation method 359, 359 complex sawtooth 361, 362 pseudo-isothermal 369 quasi-isothermal 359, 360, 361 sawtooth 359, 361 , 837–847, 837–847 sinusoidal 359 types 360–361 nonreversing signal 358, 386, 389 of chemical reactions 402, 403, 402, 403 of first-order transitions 396–401, 397, 399, 401 irreversible 264, 264, 265, 265, 396, 387, 401, 640 partially irreversible 267, 267 398–401, 399, 401 reversible 255, 255, 256, 375–378, 376, 377, 396–400, 397, 399, 844–846, 844–847 reorganization 400, 401, 401 performance, comparison to DSC 373, 374 limit of amplitude and frequency 373, 374, 374 limit of sample mass 375, 375 principles 359–362, 359–362 pseudo-isothermal analysis 369 reversing signal 334, 369, 370 distinction from reversible 358 stationarity 369 total signal 334, 369, 369 trade name 16 transamidation 230 transesterification 200, 229, 230, 665, 665, 666 transition 176, 177 boiling 182, 183 broadening 554, 555, 555, 597 crystallization and melting 6 entropy, rules of 167, 182, 182, 186 , 541, 544 transition, first-order 181–183, 182, 183, 593–597, 593, 594 see: melting see also: TMDSC, of first order transition glass 6, 178–180, 179, 180, 597 –610, 598–610 analyzed based on TMDSC of PET 392–396, 392–395, 687–689, 688, 689 analyzed based on TMDSC of polystyrene 388–392, 389–391, 600–604, 602–604, 683–685, 684, 685 autocatalytic 683 block copolymer 768–772, 769–771, broadening, absence in copolymers 760 broadening, due to conformational motion 136 broadening, due to crystallinity 695, 695–697, 697 broadening, due to phase size (surface effects) 605, 605, 606, 606, 769–771, 769, 770 broadening in block copolymers 769–771, 769, 770 broadening in polymer solutions 764, 765 by quantitative DSC 354, 355 copolymer 759–762, 759–763 766–768, 767, 772 cooperativity 141, 175, 393, 507, 554, 578, 604 , 772 crystallinity effects and RAF 607, 608, 607, 608, 609, 693–698, 693–698 crystallization at the 592 differences between DSC and DMA 609–610, 610 Doppler-like effect 603, 689 enthalpy relaxation 389, 389, 390, 599–600, 599 enthalpy relaxation, effect of crystallization on 695–697, 696–698 equations for multiple components 759–762, 759, 760, 761, 763 free enthalpy diagram 179, 180, 180 Subject Index __________________________________________________________________ 893 transition, glass, hole model 392-394, 394, 598–600, 598, 686–689, 687–689 hysteresis, see: enthalpy relaxation kinetics 600–604, 602–604 measurement by DSC 179 , 354–355, mesophase 166, 167, 175–177, 176, 547, 548, 559, 560 modeling 686–689, 687–689 molar-mass dependence 193 multi-phase systems 772–773 network effects 698–700, 699, 700 of stereospecific polymers 766, 767 pressure and strain effects 689–692, 690–692 RAF, in semicrystalline poly- mers 605, 607–609, 607–609 ratio to melting transition 179 relaxation time 601, 685, 686 self-retardation 683 seven parameters of 179, 179 size effect 605, 605, 606, 606, 769–771, 770 solubility, partial and 765, 766, 766 solutions and 760–766, 761–766 thermal history evaluation 682 time and temperature effects 682–686, 683–685 gradual 183 liquid-to-gas 164, 165 liquid-to-solid 165 liquid-to-crystal 165 melting, see: melting mesophase 165, 165–167, 167, 547–571 entropy summary 554 multiple, due to mesophases 547–551, 548–551 order of, definition by Ehrenfest 181–182, 182 transport process 158–159, 158 sign of 88 Trouton’s rule 182, 186 539 TTT diagram 402, 403 turbidity 51 , 58, 806, 806 U ultimate strength, see: tensile strength units, human V V van der Waals 163 constants, table of 165 radius, see: radius, van der Waals volume 301 variable, internal 155–158, 156 of state 75–76 variance 28, 28 vernier 294, 294 vibration 109–111, 109 anharmonic 110, 111 acoustic 125 group 124 box distribution 125 harmonic 109–111, 109, 110, 815 skeletal 123 approximation 124–126, 125, 126 spectrum 121–126, 123, 125, 126 zero-point 109 viscoelasticity 416–419, 583–585, 584 data analysis from DMA 417–419, 418, 419 example analyses 584, 584 see also: DMA linear 415 , 416 models 416, 417, 416, 417 relaxation time 417, 416 retardation time 416, 416 spectra 417, 417 stress anomaly 415, 583 time anomaly 415, 583, 584 viscometer 576 Ubbelohde 64 viscosity 415 melt 575–578, 575, 577, 578 molar-mass dependence 193, 576 shear thinning 577 Newtonian 415, 416, 577 range of (list) 577 solution 63–65 freely draining model 64–65, 577, 577, 578, inherent 64 intrinsic 64 Subject Index __________________________________________________________________ 894 molar-mass dependence 64 , 64, 65 relative 64 solid sphere model 64–65 unit of 416 Voigt model, see: viscoelasticity, models volume, excluded 36 calculation 40, 41, 41 , 164 for real gases 163 for macromolecules 35 , 713 measurement 295–298 unit 291 historical 293 volumetric equipment 296 vulcanization 232, 233 W Walden’s rule 541 , 542 water value 309 wave, standing 111 , 112 Wheatstone bridge 287, 287 Wöhler 6 work 76 Wulff construction 168 X–Z X-ray diffraction 851 Young’s modulus, see: modulus, tensile Ziegler 209 Zimm plot 56–58, 56, 57 . 218– 219, 218 polymer 233–238, 233–237 ring-chain 138, 138, 139, 194 , 199 , 199 , 219 step, aromatic polymers 198 conditions 198 199 , 199 copolymer 229, 230, 230 equilibrium 219 examples 196 198 , 196 198 kinetics. 196 198 kinetics 200, 200, 201, 201 lithium phosphate 201–206 mass average 224–225, 224 mechanism 193 195 , 194 molar mass 219 221, 221 number and mass fraction 220 polydispersity 224 statistics 195 ,. 533–535, 534, 535 polymerization, degree of 27 emulsion 217, 217 living, see: reaction, chain, without termination Merrifield method 190 192 , 192 , 237 of lithium phosphate 201 –206, 202–206 see