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
Trang 2see 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
Trang 3eutectic 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
Trang 4second 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
Trang 5mathematical 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
Trang 6transition, 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
Trang 7molar-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