INDEX

A Bloembergen-Purcell-Pound (BPP) theory, 250

Abb6 refractometer, 395-7, 400
Acetone, 378
Acrylamide, 19, 93
2-Acrylamide-2-methylpropane sulfonic acid,
18-19
Acrylic acid, 19, 79
Acrylonitrile, 19
Addition condensation reaction, 99
Aerogels, 10
Agar, 112
Agaropectin, 112
Agarose, 112, 287, 353, 355
Aggregation model, 130-4
Aggregation process, 132, 213
Amorphous polystyrene (a-PS), gelation, 191-2
Angular frequency, 322
Anisotropically shaped gels, 89-90
Anomalous viscosity, 112
Arginic acid salt, 114
Atago refractometer, 395, 397
Atomic force microscopy (AFM), 221,235-49
application to gels, 245-7
fundamental principles, 242-4
Autocorrelation function (ACF), 195, 205
B Cellulose derivatives, 137
Babinet's compensator, 400-1
Baratron pycnometer, 380
Basal cells, 148
z-Benzyl-L-glutamate (PBLG), 106, 200
Bernoulli statistics, 184
Bifunctional monomers, 130
Bimodal distributions, 39
Biopolymers, 112-16, 146-70, 213
Birefringence measurement, 399-401
Bonding probability, 131
Boyle temperature, 67
Branched polymers, 125
Branching, 35-7
Bulk copolymerization, 46
C
13C CP/MAS NMR spectrum, poly(vinyl
alcohol) (PVA), 259-61
Cahn's theory, 200
Caldron, 285-7
Carbon bond, 337
S-Carboxymethylalanyl disulfide (CMAD), 165
Carboxymethylalanyl disulfide keratin
(CMADK), 165-6, 168
Cardrun, 285, 286
Carr-Purcell-Meiboom-Gill technique (CPMG),
266
Carrageenan, 113, 354
dielectric spectrum, 375
phase transition, 374
Cascade theory, 125
CASING, 20, 108-9
Catalytic polymerization, 102
Cell membrane complex (CMC), 147
Characterization techniques, 172-412
see also specific techniques
Chemical bonding, 14, 16
Chemical crosslinking, 106
Chemical gels, 15, 16, 138, 140, 353
Chemical reactions, 104-6
Chemical shift, conformation dependent, 282
C-hordein, 288
Cluster-cluster aggregation, 132, 133

413
414 Index

Coil/spring composite insulator, 346 poly(vinyl alcohol) (PVA), 259-6 1

Cole--Cole plot, 367 three-dimensional, 10-12
Collagen, 113, 114 Crosslinked polymer, schematic diagram, 30
Complex bonding, 98 Crosslinking, 35-7, 125
Complex dielectric constant, 363-4, 378 association of molecular chains, 353-6
Complex modulus, 339 conformational changes, 356-7
Compositional drit~ of copolymers during coordination bonding, 22
polymerization reaction, 44 helix formation, 22-3
Condensation polymerization, 16, 99 hydrogen bonding, 20-1
Confocal laser scanning microscopy (CLSM), hydrophobic bonding, 25
220-8 ion pair formation, 357-8
conceptual diagram, 222 ionic bonds, 21-2
cornea of pig, 228 microcrystallite formation, 359
future development, 228 phase separation, 358-9
observation of polymer gels, 223-8 Crosslinking agent, 19, 101, 102
Conformation, gel networks, 283-90 Crosslinking formation
Conformation dependent chemical shitS, 282 classification, 14-25
Conformational changes, crosslinking, 356-7 covalent bonds, 138
Conformational order, 180-8 Cross-polarization magic angle spinning. See
i-PS/CS2 solution, 188-90 CP/MAS technique
CONTIN method, 201 Cyclic voltametry, 310
Cooperative diffusion of networks, 84-5 Cyclic voltammogram, 305, 313, 315
Coordination bonding, 6, 21, 109, 111, 114 Cyclization, 48
crosslinking, 22 Cystine, 150, 156, 157
Copolymerization reactivity ratio, 44
Cottrell equation, measurement principles D
309-11 Damping ratio, 332, 334
Coulombic bonding, 21 DD-MAS, 283, 285, 287, 288, 290
Coulombic field of polymer electrolytes, 371-2 Debye-Buiche equation, 195-6
Covalent bonding, 16, 99-109, 123 Debye-Waller factor, 214, 217
crosslinking formation, 138 Deformation entropy of networks, 70
Covalent crosslinking networks, 139 Degree of polymerization, 99, 125, 128, 130, 133
CP/MAS technique, 258, 281,285, 287, 288, distribution, 37-41
290 number average, 31-5
Critical angle method for refractive index, 395-6 total probability, 32
Critical chain length, 176 weight average, 31-5, 36
determination, 177-9 Deoxyribonucleic acid (DNA), 356
Critical index, 127, 128 Dielectric constant, 363-4, 390
Critical point, 76 Dielectric properties, 363-79
drying method, 229 measurement techniques, 368-71
Critical relaxation, 90-2 high-frequency range, 369-71
Crosslink density and relaxation time, 373 low-frequency range, 368-9
Crosslink formation, 5-7 Dielectric relaxation spectra, 371-7
Crosslink points, schematic diagram, 8 Dielectric spectrum
Crosslink points per primary polymer at gelation, carrageenan, 375
34 polyacrylamide, 377
Crosslink structure, 7-9, 37-4 1 Differential scanning calorimetry (DSC), 349,
formation, 41-7, 98 351,353, 354, 358-61
hair, 149-54 Diffusion coefficient, 86, 90, 93, 95, 303, 310,
molecular conformation, s-PS/CHC13, 186 313, 314, 317, 318

Diffusion equation, 86
Diffusion-limited aggregation (DLA), 131, 132,
134
Dihedral angle, 282
Dispersion curves, 175
D-monomer, 178
Domain formation, 135
Domain volume fraction, 153
Donnan effect, 74, 82
Dynamic dielectric constant, 364
Dynamic light scattering (DLS)
ACF, 196-7
measurement examples, 200-7
technique, 195
Dynamic structure, 137-45
classification, 137--40
definition, 137-40
E Gel fixation, 306-9
Einstein-Stokes equation, 196
Elastic deformation, 89
Eldridge-Ferry plot, 355-6
Electrochemical cell, equivalent circuitry, 305
Electrochemical techniques, 302-18
Electrode method, 380
Electrode reaction, 305
Electromagnetic wave scattering, 207-9
Electron microscopy, 221
Electropolymerization, 104
Elemental analysis, 220
Entangled networks, 138-40
Epoxy resin, 99
Equilibrium swelling line, 77
Excluded volume and temperature, 66-7
Exponential type gels, 330
F Gellan aqueous solution, 328, 329
fifunctional condensation polymerization, 130,
132
flfunctional monomers, 124
flfunctional random polycondensation
polymerization, 124
flshift, 322
Fallen ball method, 58
Falling impact testing system, 348
Field-ion microscope, 239
Finite element analysis (FEM), 345, 348
Flory distribution, 34
Flory-Stockmayer model (FS model), 127, 128,
130, 134, 135, 144, 209, 213
Index 415
Flory-Stockmayer theory, 43, 122
Focal point method for refractive index, 392
Force curves, 246-7
Formaldehyde, 99
Fractal heterogeneous structure, 144-5
Free energy of elasticity, 68-71
Free energy of mixing, 67-8, 76
Free induction decay (FID), 250
Free radical copolymerization, 41-8
Free radical initiators, 17
Free radical polymerization, 17-18, 101, 105
Friction force microscopy (FFM), 235
G
Gases
permeability, 379-90
permeation coefficient, measurement
techniques, 380-9
Gel models, scattering, 209-15
Gel networks. See Network(s)
Gel point, evaluation, 51-64
Gel preparation, 51, 98-117
Gel time measurement method, 60
Gelatin, 113, 114
chemically crosslinked, 205
quasi-dilute solution, 197, 198
scattering intensity, 198
Gelation
amorphous polystyrene (a-PS), 191-2
i-PS/CS2 solution, 188-90
measurements, 353-9
poly(ethylene oxide) (PEO), 192-4
terminology, 145
theory, 27-117, 29-50
viscoelasticity during, 326-30
Gellan gum, 37, 354
chemical repeat unit, 241
crosslink domain, 243
crosslinking mechanism, 243
gelation, 216
structure analysis, 215-17
Gellan gum-K aqueous solution, small angle
X-ray scattering profile, 219
Gellan gum-TMA aqueous solution, 216
small angle X-ray scattering profile, 218
Gels
classification, 5-10
definition, 4, 122, 380
416 Index
Gels (cont.) Hydroxylethylcellulose, 115
formation, 5-7 Hydroxylpropylcellulose, 115
schematic diagram, 5
Gibbs free energy, 67
I
Glass transition temperature, 360-1
i-PS/CS2
Globular gels, 213
conformational order, 188-90
Globular proteins, 116
gelation behavior, 188-90
Gluronic acid, 357
infrared spectra, temperature dependence,
190, 192
I-I Ideal networks, 143
Habiriyaku-Negami equation, 367 Impact reduction gels, 347-9
Hair, 146-70 Index of refraction see Refractive index
change of structure and properties, 162-3 Infinite chain, molecular vibration, 176-7
characterization of crosslinking by physical Infinite structure, 123
means, 151-4 Infrared spectra, 173--6
crosslink structures, 149-54 i-PS/CS2, temperature dependence, 190, 192
follicle, 148 poly(ethylene oxide) (PEO), 193
formation, 148-9 polystyrene, 182
properties, 155-8 Infrared spectroscopy, 172-94, 220
protein component, 149-51 Inhomogeneous structure, 134-7
proteins, 149-54 Instantaneous crosslink density, 42
small angle neutron scattering (SANS), Interference method for refractive index, 393-5
158-62 Intermediate filament adhesive protein (IFAP),
small angle X-ray scattering (SAXS), 58-62 151, 158
structure, 147-8 Intermolecular interaction, 123
Haviviliyaku-Negami equation, 367 Intermolecular linkages, 109
Havriliak-Negami equation, 367 Intermolecular physical bonding, 109-16
Heat capacity, 351 Interpenetrating polymer networks (IPN), 112
Heat flux, 350 Inverted test tube method, 52-8
Helix formation, crosslinking, 22-3 Ion complex gels, 94-5
Heterogeneous crosslinking, 10 Ion effect, 74-5, 79, 80
structure formation, 44 Ion exchange resins, 92-3
Heterogeneous structure, 144 Ion pair formation, crosslinking, 357-8
Heterogenous gel model, 36 Ionic bonding, 14
High-power decoupling magic angle spinning crosslinking, 21-2
(DD-MAS) technique, 281 Irreversible gels, 14
High-resolution solid-state NMR, 257-62, 281 Isopressure technique
H-monomer, 178 direct method, 381-5
Homogeneous branched structure, 36 indirect method, 385-9
Homogeneous crosslink structure, 40 Isotactic polystyrene (i-PS), 177
HOPG, 240, 242
Hydrocolloids, 114
J
Hydrogels, 10, 336
Junction zone, 15-20
Hydrogen bonding, 6, 14, 21, 98, 109, 110,
model, 55
112-14
crosslinking, 20-1
Hydrophilic membrane materials, 379, 389 K
Hydrophobic bonding, 98, 109, 115 Keratin, 148-51,153, 154, 157
crosslinking, 25 Keratin protein model gel, structure and
Hydrophobic groups, 81 properties, 163-7
 Index 417
Konyak mannan, 114 Molecular entanglement, 112
Kratky plot, 199, 200, 217 Molecular vibration
infinite chain, 176-7
polymer chains, 173-6
L Molecular weight distribution, 47-8
Langrnuir-Blodgett technique, 239 Monomer residue, temperature dependence of
Laophilization, 20 weight fraction, 191
Latent crosslink density, 42
Lecithin gels, 375-6
Lennard-Jones type potential, 66
LiC104, 312, 316
Light scattering, 194-207
N
theoretical background, 195-7
Lightly heterogeneous gels, 145 N-Ferrocenylmethyl-N,N,N-trimethyl
Lorentz-Lorenz formula, 391 ammonium hexafluorophosphate (Fc),
Loss dielectric constant, 364 312
Lower critical solution temperature (LCST)-type N-isopropylacrylamide (NIPAAm) gel, 78, 79,
phase diagrams, 359 226
Lyopic gels, 10 internal structure, 226
reconstructed, 3D image, 227
Natural gels, 7
M Natural polymers, 112-16
Mach-Zehnder interference microscope, 393-4 NMR, 279-90
McLaud pycnometer, 380 Network state, polymer gels, 376-7
Macrogels, 9-10 Network structure, 11, 98, 101
Manuronic acid, 357 and superposition principle, 324-6
Maxwell model, 321 dynamics, 290
Mechanical models, 319-21 Networks
Mechanically weak gels, 140 conformation, 209-15, 283-90
Medium, 10 cooperative diffusion of, 84-5
Melamine resin, 99 models, 124
Membrane materials, hydrophilic, 379, 389 size, 7-9
Methacrylic acid, 19 swelling, 84
4-Methyl ammonium salt (TMA), 215, 356 swelling kinetic theory, 83-90
Methylcellulose, 115, 358, 359 Neutral networks in pure solvents, 73-4
Micro-Brownian motion, 142, 340 Neutron scattering, 207
Microcrystallite formation, crosslinking, 359 Newtonian viscosity, 351
Microdisk electrode, 307 Nuclear magnetic relaxation time, 283
gel treated, 315 Nuclear magnetic resonance (NMR)
manufacture, 307 classification methods, 250
Microelectrode natural polymers, 279-90
characteristics, 304-6 parameters, 279-83
gel-treated, 313 Nuclear magnetic resonance (NMR) imaging,
preparation, 306 262-78
Microgels, 9-10 characteristics, 263-4
Microscopy, 220--49 polymer gels, 265-7
Minimum angular deviation method for principles, 264-5
refractive index, 392 Nuclear magnetic resonance (NMR)
Molecular aggregation, 182 spectroscopy, 220, 249-90
Molecular conformation, 172 synthetic polymers, 249-78
s-PS/CHCI3, crosslink structure, 186 Nuclear Overhauser effect (NOE), 258, 290
418 Index
O Poly(N,N-dimethylacrylamide) (PDAAm), 256,
Optical properties, 390--403 257
Ordered conformation, 184 Polydimethylsiloxane (PDMS), 60, 62, 199, 201,
Organogels, 10 203, 204
Orientation polarization, 364--6 Polyelectrolyte complex gels, 22
Omstein-Zemike equation (OZ), 195-7 Polyethylene, 108, 175
Osmotic pressure, 72, 73 Polyethylene-carbon disulfide gel, 57
Oxygen permeability, 385 Poly(ethylene glycol), 201
measurement, 381-5 Poly(ethylene oxide) (PEO)
gelation, 192-4
infrared spectra, 193
P temperature variation, 193
p value, 187, 188 Polyethylene-toluene gels, 55, 57
temperature dependence, 189 Poly(hydroxyethyl methacrylate), 12
PBLG, 106, 200 Poly(2-hydroxyethyl methacrylate) (PHEMA),
Pectin, 114 322-3, 379
Percolation PolyfN-isopropylacrylamide) (PNIPAAm), phase
cluster, 144-5 transition, 251-2
examples, 129 Poly(N-isopropylacrylamide) solution, sol-gel
model, 128-30 transition, 250-1
terminology, 145 Polymer chains, 6, 14
Permeability of gases, 379-90 crosslinking, 19-20
Permeation coefficient of gases, measurement molecular vibration of, 173-6
techniques, 380-9 Polymer electrolytes
Permittivity, 390 coulombic field of, 371-2
Phase separation, 90-2 sol-gel transition, 372-4
crosslinking, 358-9 Polymer gels, 353
Phase transition, 76, 79 characteristics, 13-14
carrageenan, 374 classification, 14
mixed solvents, 79 network state, 376-7
poly(N-isopropylacrylamide) (PNIPAAm), NMR imaging, 265-7
251-2 phase transition, 376-7
polymer gels, 376-7 properties, 14
Phenolic resin, 99 water molecules movement, 375--6
Photocrosslinking, 20, 106-7 Polymer networks, 10-12, 14
Photodimerization, 107 Polymer-solvent interaction parameter, 71-3
Photopolymerization, 18, 102 Polymerization reactions, 16-19
Physical gels, 14, 20-5, 137, 140, 323, 353 Poly(methacrylic acid) (PMAA), 112, 265-7
Plasma crosslinking, 20, 108-9 1H spin density image, 267-71
Plasma polymerization, 18-19, 103-4 1H spin-spin relaxation time (T2) enhanced
Polyacrylamide, dielectric spectrum, 377 image, 271-3
SDS-Polyacrylamide electrophoresis, 165 shrinkage behavior of double-layered
Polyacrylamide (PAAm), 201,304, 309, 311, structured gel, 274-8
312, 314-16 Polysaccharides, 112, 213,282-8, 353, 354, 356,
Polyaddition polymerization, 99 372-4
Poly(g-benzyl-L-glutamate), 202 Polystyrene, 200, 203, 245
Polybenzyl-trimethyl-ammonium (PVBMA)- infrared spectra, 182
polystyrene sodium sulfonate (PNaSS), translational diffusion coefficient, 206
111 Polystyrene-carbon disulfide gels, 55, 56
Polycondensation polymerization, 99 Poly(tetrafluoro ethylene), 109
 Index 419
Polyurea, 99 Relaxation time, 377
Polyurethane, 99 and crosslink density, 373
Poly(vinyl acetate), 199, 200 Relaxation-type dispersion, 364-6
Poly(vinyl alcohol) (PVA), 9, 20, 94-5, 108, 110, empirical equation, 366-7
200, 202, 204, 258-9 Reversible gels, 15
analysis of dynamics, 261-2 Rubber elasticity, 142-5
aqueous system, 58 Rubber front factor, 143
~3C CP/MAS NMR spectrum, 259-61
crosslink structure, 259-61 S
Poly(vinyl alcohol) (PVA)/sodium borate, s-PS, gelation of, 180-8
self-correlation function, 205 s-PS/CC14 system, 183-4
Poly(vinyl alcohol) (PVA)-water gel, 57 s-PS/CDC13 system, 185
Poly(vinyl chloride) (PVC), 109, 324 molecular conformation, crosslink structure,
Poly(vinyl methylether) (PVME), 108, 245 186
Porod law, 212 SAN, 196
Porod region, 196 Scanning electron microscopy (SEM), 228-34
Proportionality equations, 127 lens-type, 234
Protein gels, 288-90 low-vacuum, 229-30
Proteins, 282 Scanning probe microscopy (SPM), 235
Pulse saturation transfer (PST)/MAS Scanning tunneling microscopy (STM), 235-49
technique, 258 application on gels, 240-2
Pulsed NMR technique, 250-2 combination of field ion microscope, 239
self-diffusion coefficient, 252-7 fundamental principles, 236-40
Pulsed-field-gradient spin echo (PGSE) Scattering, gel models, 209-15
technique, 254-7 Scattering amplitude, 210
measurement examples, 257 Scattering angle, 207, 208
pulse sequence, 255 Scattering function, 212, 213, 215, 217
Scattering intensity, 207-11
Q Scattering points, 210
Quantitative analysis, 172 Scattering profile, 207, 211, 213
Quasi-gels, 138-40 Scattering vector, 208
SCE (saturated Calomel electrode), 308
Schulz-Zimm distribution, 37
R Secondary bonds, 323
Radiation crosslinking, 19-20, 107-8 Self-diffusion coefficient, pulsed NMR
Radiation polymerization, 18, 102-3 technique, 252-7
Raman spectra, 174 Shear modulus, 86, 96
Random branching polymers, 125 Shrinkage behavior of double-layered PMAA
Random crosslinking, 30-41 gel, 274-8
Rapid freeze etching method, 230-4 Signal intensity, 279-81
Rayleigh scattering, 194 Silica gel, self-correlation function, 206
Reaction-limited aggregation (RLA), 131, 134 Silicone gel, 338, 340
Redox initiated polymerization, 102 structure, 336
Reentrant phase transition, 80 viscoelastic properties of, 341-3
Refraction, 390 Siloxane bond, 337, 340
Refractive index, measurement methods, 390-9 Simplified conditions, 43-7
Refractive index distribution, measurement, Size exclusion chromatography (SEC), 38
396-9 Skewed distribution, 39
Refractive index gradient, 399 Small angle neutron scattering (SANS), 185,220
Relaxation intensity, 377 hair, 158-62
420 Index
Small angle X-ray scattering (SAXS), 220
hair, 158-62
Small angle X-ray scattering (SAXS) profile
gellan gum-K aqueous solution, 219
gellan gum-TMA aqueous solution, 218
Smoluchowski equation, 132
Sodium acrylate, 372
Sol-gel transition, 6, 99, 144, 326-30
exponential law, 330
poly(N-isopropylacrylamide) solution, 250-1
polymer electrolytes, 372-4
Special reaction conditions, 43
Spherical symmetric gels, 85-9
Spin echo method, 255
Spin echo pulse sequence, 265
Spin-lattice relaxation time, 250
Spin-spin relaxation, 255
Spin-spin relaxation time, 250
Static bonding, 98, 109-11
Static light scattering (SLS) technique, 195
measurement examples, 197-200
Static properties, 65-82
Static structure, 123-37
Stereoregular gels, 104
Stereoregular polystyrene, 177
Strain relaxation, 89
Strong gels, 140, 141
Structural analysis, 172
Structure, 122-46
classical model, 123-7 see also
Characterization techniques
Structure analysis, application examples
215-17
Styrene, 19
Superabsorbent polymers
testing methods, 292
water absorption rate test method, 298-302
water uptake testing method, 292-8, 294-8
Superposition principle, 321-6
and network structure, 324--6
Surface effect factor, 133
Suspension polymerization, 45, 46
Swelling, 279-81,291-302, 312, 314
fundamental theory, 66-73
kinetic theory, 82-97
networks, 83-90
main characteristic, 86
networks, 84
phenomenology, 82-3
solute in gels, 311-18
theory, 65-97
Swelling curves for neutral NIPAAm gel, 77
Swelling equation, 86
Swelling equilibrium, 71, 73-5, 79, 81
Swelling relaxation time, 86
Sylpinski gasket, 137
Syndiotactic polystyrene, 177
Syndiotactic polystyrene/o-dichlorobenzene
solutions, 360
Synthetic gels, 7
Synthetic polymers, 110-12
nuclear magnetic resonance spectroscopy
(NMR), 249-78
T
TF theory, 93
TG-type conformational chains, 177
TG-type i-PS, 179
TG-type stereoregular chain, 191
Thermal analysis, 353
Thermal polymerization, 99-102
Thermal properties, 349-63
measurement techniques, 349-52
Thermodynamically weak gels, 140
Thermomechanical analysis, 349, 351-3, 356
Three-dimensional crosslink structure, 10-12
Time-concentration superposition principle,
321-3
Time-temperature superposition principle,
321-3, 324
Transmission electron microscopy (TEM), 234
Transparency of gels, 401-3
Tree model, 126
TT-type chain, 177
TT-type s-PS, 179
TTG-type homogeneous helix, 194
TTG-type ordered conformation, 194
TTGG conformation, 184
TTGG-type chain, 177, 180
TTGG-type conformational order, 185, 187
TTGG-type s-PS, 179
U
U-shaped tube method, 59
Urea resin, 99
V
van der Waals bonding, 98, 109, 111-12
van der Waals forces, 356
van't Hoff equation, 72, 354
 Index 421
Vibration Viscosity coefficient, 351
prevention, 331 Volumetric phase transition, 75-81
transferability, 332, 333
Vibration absorbing gel, viscoelastic properties W
of, 338-43 Water absorption rate test method,
Vibration absorption, mechanism, 331-6 superabsorbent polymers, 298-302
Vibration damping device, 335 Water condition, 361-3
Vibration damping gels, 331-49 Water-medium gels, 10
characteristics, 336-8 Water molecules movement, polymer gels, 375-6
viscoelasticity, 344-9 Water uptake testing method, superabsorbent
Vibration damping material, 335 polymers, 292-356, 357
Vinyl monomers, 101
Vinyl polymerization, 99
Viscoelastic behavior, 60, 63 X
Viscoelastic properties Xanthan, 356, 357
silicone gels, 341-3 Xanthan gum, 116, 354
vibration absorbing gel, 338-43 Xerogels, 10
Viscoelastic relaxation, 321 X-ray scattering, 207
Viscoelasticity, 318-49 Xylene, 359
during gelation, 326-30
vibration damping gels, 344-9 Z
Viscoelasticity method, 59-63 Zehner model, 320