Chemorheology of Thermosetting Polymers Downloaded from pubs.acs.org by YORK UNIV on 12/12/18. For personal use only.
INDEX A AA/BMA—See Poly(butyl methacrylate/co-acrylic acid) films Accelerated aging tests 122 Accelerated epoxy system, isothermal kinetic behavior 192/ Acetylene-terminated quinoxaline— See Quinoxaline resin Acetylene-terminated resins air and nitrogen effects 61-82 dynamic mechanical properties .. 49-60 kinetics 49-60 structure 50 torsion impregnated cloth analysis 50, 54, 57 Acetylene-terminated sulfone 49 See also Sulfone resin cure kinetics 51 degree of cure vs. temperature 58/ glass transition temperature 53-54 vs. conversion 53/ vs. cure in nitrogen 55/ isothermal curing curves 52/ temperature effects 58/ time-temperature-transformation diagram 55/ torsion impregnated cloth analysis 56/ Acrylic acid copolymer adhesive failure 143 wetting results 147 Acrylic ester adhesive failure 143 hydrogen bonding 143 Activation energies 271 dielectric, Narmco 5208 238/ for Narmco 5208 232/ Activation energy terms 313 Actual-use conditions, duplicating.... 290 Adhesive opaque, dynamic mechanical behavior 179 transparent, dynamic mechanical behavior 179 Aerospace industry, epoxy formulations 2 Aged prepreg differential scanning calorimetry ... 14/ high pressure liquid chromatography 11 rheoiogical properties 14/ Aged resin activation energies, chemiluminescence 132/ 319
Aged resin—Continued vaporization gas chromàtography/mass spectrometry ... 134-37 Aging 13 moisture effects 131 Aging tests, accelerated 122 Air, curing quinoxaline resin 75/ sulfone resin 72/ Aliphatic diamines 179 Alkyd resins 201 Arrhenius plots, kinetic parameters .. 305/ ATS—See Acetylene-terminated sulfone Β Benzoyl peroxide 204 4,4'Bis(3-ethynylphenoxy) diphenyl sulfone 50 Blocking effect 108/ in epoxy polymers 105 Butanedial, structure 170 C Charge transport, in viscous medium 241 Chemical events, dielectric property relationship 2 Chemiluminescence activation energies of aged resins.. 132/ data reproducibility 126 least-squares fit 128 of thermosetting resins 121-40 variables 123 Chemiluminescence data, epoxy resin 128/ Chemiluminescence data, TGDDM... 129/ Chemiluminescence intensity-tem perature-time profiles epoxy resins under stress 133/ for epoxy resins 123/, 129/ Chemiluminescence system 123/ Classical polymer phase states 191 Coatings, thermosetting 281-300 leveling vs. fluidity 295/ Conductivity 241 Convectionless entry flow, contours constant temperature 256/ Conversion vs. curing time, TGDDM/DDS resin 87/ Cross-linking, epoxy resin 113-20 Cross-linking effect, glass transition temperature 54 Cure analysis 162
320
CHEMORHEOLOGY OF THERMOSETTING
Cure behavior, model, equation 264 Cure conditions, inductive vs. normal,fluidityvalues 292r Cure curves, with phase transition ... 287/ Cure cycle dielectric scans 6/ differential scanning calorimetry .. 5/ Cure cycle control, using dielectric signals 18 Cure modeling 289-99 Cure profile, thermal 187 Cure rate, factors 264 Cure rheology, intaglio printing inks.... 149-67 Cure transformation diagram, engineering \9Sf Cured epoxy resin, chemilumines cence observed 126 Cured resin oscillatory shear 162 steady shear 159-62 Curezol catalyst 114 Curing agents 172/ Curing polyimide, dielectric rheolog ical response 12/ D DDS—See Diaminodiphenyl sulfone DGEBA/TETA epoxy polymers, loss compliance data 99 DGEBA/TETA resins dynamic mechanical behavior 104/ equilibrium dynamic mechanical data 96 loss compliance 100/ swelling behavior 104/ Diamines, aliphatic 179 Diaminodiphenyl sulfone 7 structure 2, 225 Dicyandiamide, IR studies 7 Dielectric activation energies, Narmco 5208 238/ Dielectric analysis advantages 247 complex capacitance 249 Dielectric cell 227/ Dielectric composite tan delta, Narmco 5208 237/ Dielectric curves 3/ peak discussion 2 Dielectric dissipation factor 12 Dielectric loss factor, separation from conductivity 241 Dielectric monitoring 15,17/18 Dielectric peaks, Arrhenius plots for Narmco 5208 240/ Dielectric properties influence of prepreg aging 13, 16 physical changes 3/
POLYMERS
Dielectric response, isothermal, measurement 226 Dielectric scans, cure cycle 6/ Dielectric signals process control and documentation 15 use in cure cycle control 18, 20/ Differential scanning calorimetry 5/ aged prepreg 14/ catalyst effects on cure 8 problems in data analysis 51 process control 7 for reaction rate determinations .... 31 TGDDM/DDS resin ....85/, 86/, 87/ 88/ Ν,Ν-dimethylaniline 204 Ν,Ν' dimethyldiphenyl sulfone, synthesis 83-84 DSA—See Dynamic spring analysis Dynamic mechanical analysis, for Narmco 5208 232/ Dynamic mechanical moisture sorption/desorption, test chamber .... 97/ Dynamic methods, cure curves 288/ Dynamic spring analysis 226-36 advantages 247 Arrhenius plots of Narmco 5208 230/ 231/ glass transition temperature 229 Narmco 5208 228/ 233/ 235/ sample mounting 224 tan delta peaks 232 Dynamic/isothermal cure, time-tem perature profile 314/ Ε Electrical properties, disagreement on molecular origins Engineering cure transformation diagram Entanglements, relaxation Entry flow centerline temperatures... Environmental effects Epoxy/amine equivalent ratio, in creasing in TGMDA/DDS reactions . Epoxy/amine reaction, exotherm Epoxy-based powder coatings, vis cosity-time data Epoxy phthalic anhydride cure catalyzed, thermogram heats of reaction near IR band ratios near IR data, time effects stepwise mechanism Epoxy polymers blocking effect equilibrium dynamic mechanical data loss compliance data matrix swelling
224 198/ 229 258/ 195 46 37 286 115 114/ 117/ 118/ 118/ 105 96 99 105
321
INDEX
Epoxy polymers—Continued moisture-temperature effects 95-112 polar sites 99 transient dynamic mechanical data 101-11 Epoxy powder coatings, viscometric cure curves 285/ Epoxy resin casting 123 chemiluminescence data 128/ chemiluminescence intensity-temperature-time 123/ chemiluminescence intensity-temperature-time profiles 129/ cross-linking 113-20 with phthalic anhydride—See Epoxy/phthalic anhydride curing cured, chemiluminescence observed 126 dynamic mechanical and dielectric properties during cure .. 223-50 plasticizing and blocking 108/ vaporization gas-chromatography/ mass-spectrometry 125-26 vaporization gas chromatograms ... 135/ volatiles released 137/ Epoxy system, isothermal kinetic phase diagram 193/ Equilibrium dynamic mechanical data of DGEBA/TETA resins % of epoxy polymers % Ester groups, C-0 stretching bands.. 116 3(2-Ethyl-4-methylimidazolyl) propanenitrile 114 See also Curezol catalyst Extent of reaction calculation 32 defined 40
F Ferric acetylacetonate, structure 170 Fiber-reinforced composite hardware, fabrication 21,22/ Filler effect 304 Filler loading effects on induction time 272/ on relaxation spectrum width 274/ on relaxation times 273/ Fingerprinting , 7 Finite element analysis 251-62 computer model 253-54 nonreactive entry flow 255-57 one-dimensional reactive flow ....255-57 streamlines for nonreactive entry flow 256/ two-dimensional nonisothermal reactive flow 257
Finite element method, theoretical background 252-53 First-order kinetic analysis, TGDDM/DDS resin 92/ First-order kinetics 308 Five-parameter model, limitation 308 Flow-cure properties, characterization 283 Fluidity values vs. catalyst levels 293/ Force-voltage analogy 11 Fourier-transform IR spectroscopy, TGDDM/DDS resin 88,89/ 90/ Free volume 99 G
Gel content determination 31 Gel permeation chromatography rate constants for TGMDA/DDS resins 33/ of TGMDA/DDS resins 28-32,29/ Gelation, tan delta 191 Glass transition temperature of acetylene terminated sulfone ...53-54 hard segment 176 rates of change 62 "two part theory'* 54 H Halthanes See also Polyurethane adhesives... aromatic-cycloaliphatic polyurea hard segments cure chemorheology dynamic viscosity isothermal viscosity-time curves ... loss tangent isotherm MDI-butanediol hard segments polyether soft segments viscosity vs. time viscosity-temperature effects with HMDI-aromatic diamine chains Hard segment glass transition temperature Hardware fabrication Heat of curing equation total, equation Heat of reaction, residual High performance liquid chromatography chromatographs High pressure liquid chromatography, of aged prepregs Humidity exposure Hydrogen bonding interference Hylene W, structure
169 169 179 175/ 174/ 173 178/ 173 173 180/ 177/ 181/ 176 1-2 209 209 31 7 9 11 195 146 99 170
322
CHEMORHEOLOGY O F THERMOSETTING I
Impurities effect on TGMDA/DDS resins ....25-48 effects in TGMDA resins Induction time, filler loading effects.. 272/ Initial viscosity, equation for determination 173 Ink behavior 153 Intaglio printing inks behavior 153 composition 152/ cure parameters 165/ excessive drying 165/ measure vs. calculated stress 158/ oscillatory behavior 156 steady flow viscosity vs. cure time 164/ vs. Shear rate 155/ 161/ steady shear flow studies 152/ stress curves 157/ 158/ 163/ stress vs. steady shear flow 154/ viscosity vs. steady shear flow 154/ IR spectroscopy 7 'Isothermal cure predicted vs. experimental viscosity 307/ torsion impregnated cloth analysis 66 Isothermal curve, generation 51 Isothermal dielectric response, measurement 226 Isothermal kinetic diagram, phase precipitation effects 194/ Isothermal moisture transients 103 Isothermal rheological data, applica tion to production cure 16 Isothermal viscosity behavior, equation 301 Izod impact energy, epoxy/amine ratio effects 44 Κ
Kinetic data, from viscosity mea surements, problems 171 Kinetic modeling 263-80 complex viscosity vs. cure time 269/ 270/ shear storage modulus vs. cure time 267/ 268/ 269/ Kinetic parameters, from Arrhenius plots 305/ Kinetic terms 15 Kinetic theory 264-66 Kinetics first order 308 nonisothermal cure 265 nth order 308 L Loss modular, relationship to phase angle
189
POLYMERS
M Mark-Houwink-Sakurada equation .. 142 Material parameters, determination .. 304 MDI—See also Methylene
bis(phenylisocyanate) MDI—butanediol hard segments, vitrification Mechanical testing, of TGMDA/DDS resins Methyl ethyl ketone Methylene bis(phenylisocyanate), structure Moisture sorption Molecular weight, determination, calibration curve MY720, primary constituents
176 32 136 170 99 30/ 225
Ν Narmco 5208 Arrhenius plots, dielectric peaks... 240/ composite loss tangent 226-36 dielectric composite tan delta 237/ dielectric measurements 236-42 dynamic spring analysis 226-36, 228/ 233/ 235/ primary constituents 225 thin-film tan delta 243/ torsion braid analysis 235/ vitrification 229 Nitrogen, curing quinoxaline resin 74/ sulfone resin 70/ 71/ Nonisothermal cure cure model 265 modeling 289 Nonisothermal cure conditions complex viscosity vs. cure time.... 277/ shear storage modulus vs. cure time 277/ Nonisothermal cure kinetics 265 Normal vs. inductive cure condi tions, fluidity values 292/ Ο
One-dimensional reactive flow, de gree of conversion 258/ Opaque adhesive, dynamic mechan ical behavior 179 Oscillatory behavior 156 Oxidative cross-linking, glass transi tion temperature effects 78
PBMA—See Poly(/i-butyl methacry late) films Phase meter, use in dielectric monitoring Phase states, classical polymer
18 191
323
INDEX
Phthalic anhydride, cross-linked with epoxy resin 113-20 See also Epoxy/phthalic anhydride curing Physical changes on dielectric properties 3/ Plasticization, mechanical property changes 103, 105 Plasticizing 108/ Polar groups, in epoxy polymers 99 Polyallyl esters preparation 201 uses 201 Poly(n-butyl methacrylate) films .. 141-48 drying, humidity effects 144/ Poly(butyl methacrylate/co-acrylic acid) films 141-48 drying, humidity effects 145/ Polyester resin heat generated vs. isothermal cure temperature 211/ reaction heat generated 210/ reactivity 216 viscosity vs. cure time 206/ Polyimide curing, dielectric rheological response 12/ dielectnc dissipation factors 12 viscosity 12 Polymer cure dynamics, evaluating 187-200 Polymer and solvent interactions 146 Polyol oligomers 171 Poly(tetramethylene oxide) 170 Poly(urea-urethane) adhesives inverse temperature dependence of initial viscosity 182/ loss tangent data 184/ Polyurea hard segment adhesives curing agents 172/ prepolymers 172/ Polyurethane adhesives See also Halthanes
segmented, curing behavior 169-86 Post-curing, TGMDA resins 44 Precured resins, torsion impregnated cloth analysis 68-78 Precuring, glass transition temperature effects 73 Predictive models, aids in thermoset resin processing 301-18 Prepreg, aged, differential scanning calorimetry 14/ Prepreg aging, influence of dielectric properties 13, 16 Process automation 1-24 Process control 7 and documentation, dielectric signals 15 Propanol 136 Propenal, activation energies for release 136
Q Quadrol effects on viscosity 176 structure 170 Quinoxaline, vitrification time 68 Quinoxaline resin air-cured 75/ 80/ glass transition temperature vs. cure time 79/ nitrogen cured 74/ nitrogen post-curing 80/ structure 62 time to vitrification vs. temperature 69/ torsion impregnated cloth analysis 64/ vitrification 66 R
Rate of reaction definition 32, 40 effects of stoichiometry 37 quenching by vitrification 73 Reactive flows, advantages 251 Reactive systems 251-62 Relaxation function 264 Relaxation spectrum width, filler loading effects 274/ Relaxation time filler loading effects 271, 273/ glassy vs. rubbery state 271 nonisothermal cure 265 Residual heat of reaction 31 Rheological characterization, instrument calibration 190 Rheological cure, varying heat rates 1%/ Rheological cure curve 286 Rheological cure transformation diagrams 187-200 sample handling 189 objectives 188 Rheological events, dielectric property relationship 2 Rheological flow terms 15 Rheometry, advantages 282 Roller's equation 289 application 290 comparison of constants 298/ cure activation energy 293/ cure curves 291/ for inductive cure 291/ use 294 S Segmental chain mobility % Segmented polyurethane adhesives, curing behavior 169-86 Shrinkage 208 Six-parameter model 313 derivation 308 Softening 63
324
CHEMORHEOLOGY OF THERMOSETTING POLYMERS
Solvent and polymer interactions 146 Sorption-desorption process 101, 103 Steady-shear methods, cure curves... 288/ Stoichiometry effect on TGMDA/DDS resins ....25-48 effects, rate of reaction 37 Storage modules, relationship to phase angle 189 Structopendant 202 Structoterminal 204 Subtractive Fourier-transform IR 10 Sulfone resin air-cured 71/, 72/ curing nitrogen 70/ 71/ isothermal cure results 67/ structure 62 thermal stability 66 time to vitrification vs. temperature 70/ torsion impregnated cloth analysis 65/ vitrification temperature 66 vitrification time 69 Τ
Tan delta 191 curve 195 moisture effects 197/ Temperature scans, stages 62 Tetraglycidyldiaminodiphenyl methane/diaminodiphenyl sul fone resin, curing process 83-94 See also TGDDM/DDS resin Tetraglycidyldiaminodiphenyl methane, purification 125 See also TGDDM Tetraglycidylmethylenedianiline, structure 2, 225 see also TGMDA Ν,Ν' tetramethyldiphenyl sulfone, synthesis 84 TGDDM See also Tetraglycidyldiaminodi
phenyl methane chemiluminescence data TGDDM/DDS resin
See also Tetraglycidyldiaminodi
128/
phenyl methane/diaminodi phenyl sulfone conversion vs. curing time 87/ differential scanning calorimetry 85/, 86/, 87/ 88/ first-order kinetic analysis 92/ Fourier-transform IR spectroscopy 88,89/ 90/ viscosity curves 302 viscosity profiles 303/ TGMDA, hydrolysis 26 TGMDA/DDS reactions cure time effects 34/ increasing epoxy/amine ratio 46
TGMDA/DDS resins concentrations vs. cure time 35/ DSC parameters for iso thermal cure 44 effects of impurities 25-48 gel permeation chromatography 28-32, 29/ mechanical testing 323 molecular weight parameters 36/ percent gel vs. cure time 36/ rate constants 33/ rate vs. extent of reaction 38/ reaction rate determination by DSC 31 TGMDA resins by-products effects 40 characteristics 27/ impurities 40 post-curing 44 Thermal cure profile 187 Thermal scans, in air/nitrogen 63-77 Thermogram, of catalyzed epoxy/ phthalic anhydride cure 115 Thermoset resin processing, predictive models 301-18 Thermosetting coatings 281-300 leveling vs. fluidity 295/ Thermosetting resins, chemiluminescence 121-40 TICA—See Torsion impregnated cloth analysis Time average shear rate, equation.... 159 Time-temperature-transformation diagram, of acetylene-terminated sulfone 55/ Torsion braid analysis advantages 247 kinetic effects 236 Narmco 5208 235/ Torsion impregnated cloth analysis of acetylene terminated resins 50,54,57 acetylene-terminated sulfone 56/ isothermal cure 66 precured resins 68-78 quinoxaline resin 64/ softening 63 sulfone resin 65/ Transparent adhesive, dynamic me chanical behavior 179 Transient dynamic mechanical data, epoxy polymers 101-11 Transition, in glassy polymers % Two-dimensional reactive flow isoconversion contours 259/ isothermal contours 260/ U Uncured inks oscillatory shear steady shear
156-59 153, 156
INDEX Uncured resin, temperature scanning Unsaturated polyester resins chemorheology and curing kinetics uses
325
63 201-21 201
V Vaporization gas chromatograms, of epoxy resins 135/ Vaporization gas chromatography/ mass spectrometry aged resin 134-37 of epoxy resins 125-26 Vinyl ester resin 202 heat generated vs. isothermal cure temperature 211/ reaction heat generated 210/ reactivity 216 viscosity vs. cure time 206/
Viscoelastic relaxation, loss peak. :... Viscometric cure curves, for epoxy powder coatings Viscosities, predicted vs. experimental Viscosity initial, equation for determination.. moisture effects polyimide predicted predicting Viscosity measurements, interpretation problems Vitrification effect on reaction rates quenching of reaction rate Volatiles in torsion impregnated cloth analysis released from epoxy resin
242 285/ 306/ 173 197/ 12 15 266 171 57 73 63 137/
