Thermal Analysis of Polymeric Materials

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

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

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

156, 157

melting of lamellar crystals 148–155, 149, 150,

152–155

relaxation times 159–161,

159–161

time-temperature superposition

374–384 linearity 369

Lissajous figure 266, 379, 380,

380, 381, 386, 397, 397, 398, 626, 742

mathematical treatment 362–369,

363–368

model calculation, heat-flux DSC 365, 366, 366

model calculation, powercompensation 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

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 polymers 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

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