TABLE OF CONTENTS

Chapter 1
PHOTOPHYSICS - ENERGY ABSORPTION, DISSIPATION, AND CONVERSION 1
1.1 Absorption of Radiation by Materials 1
1.1.1 Radiative Energy 1
1.1.2 Radiation Intensity 3
1.1.3 Radiation Incidence 4
1.2 Absorption of Radiation 6
1.2.1 General Principles 6
1.2.2 General Model of Molecular Excitation 10
1.3 Radiative Processes 12
1.4 Non-radiative Conversions 22
References 23
Chapter 2
PHOTOCHEMISTRY 25
2.1 General Principles 25
2.2 Primary Photoreactions 26
2.2.1 Cleavage into Free Radicals 26
2.2.2 Abstraction of Hydrogen 28
2.2.3 Photoaddition Reactions 30
2.2.4 Photoisomerism 30
2.2.5 Intramolecular Rearrangement 32
2.2.6 Photodimerization 34
2.2 7 Photoreactions 35
2.3 Secondary Photoreactions 35
Chapter 3
ENVIRONMENTAL CONDITIONS 39
3.1 Solar Radiative Emission 39
3.2 Effect of Orbital Variations on Energy Supply 41
3.3 Scattering of Solar Radiation 42
3.4 Absorption of Solar Radiation 43
3.5 Variations in the Radiative Fluxes 44
3.6 Temperature and Moisture 46
3.7 Atmosphere Composition 47
3.8 Nitrogen Compounds 50
3.9 Oxygen Species 52
3.10 Hydrogen Species 53
3.11 Carbon Oxides 55
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3.12 Sulfur-containing Components 56
3.13 Chlorine-containing Components 57
3.14 Particulate Materials 58
References 59
Chapter 4
CLIMATIC CONDITIONS 61
Chapter 5
ARTIFICIAL WEATHERING EQUIPMENT 95
5.1 Light Sources 95
5.2 Filters 103
5.3 Specimen Racks and Holders 104
5.4 Artificial Weathering Equipment 105
References 107
Chapter 6
MEASUREMENTS IN ASSESSMENT OF WEATHERING CONDITIONS 121
Chapter 7
SAMPLE PREPARATION FOR WEATHERING STUDIES 125
References 139
Chapter 8
NATURAL WEATHERING CONDITIONS 141
8.1 General Description 141
8.2 Methods of Sample Exposure 149
8.2.1 Exposure Site 149
8.2.2 Exposure Racks 149
8.2.2.1 Standard Rack 150
8.2.2.2 Under Glass Exposure 150
8.2.2.3 Black Box Exposure 150
8.2.2.4 Exposure with Spray 151
8.2.2.5 Dry Exposure 151
8.2.2.6 Sun-Tracking Devices 152
8.2.2.7 Light Concentrating Devices 152
8.3 Standards 152
References 153
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Chapter 9
TYPICAL WEATHERING CYCLES 155
References 161
Chapter 10
ARTIFICIAL WEATHERING VERSUS NATURAL EXPOSURE 165
References 179
Chapter 11
IMPORTANT VARIABLES OF WEATHERING 181
11.1 Stress 181
11.2 Molecular Stress 184
11.3 Molecular Mobility 188
11.4 Diffusion, Free-volume, Permeability, Sorption, Density 191
11.5 Chemical Reactivity 194
11.6 Other Variables in Photodegradation 199
References 200
Chapter 12
COLOR FADING IN TEXTILE MATERIALS 203
References 214
Chapter 13
METHODS OF WEATHERED SPECIMEN EVALUATION 217
13.1 Visual Evaluation 218
13.2 Gloss Retention and Surface Roughnes 219
13.3 Surface Morphology and Imaging Techniques 220
13.4 Color Changes 223
13.5 Spectroscopic Methods 225
13.5.1 Visible Spectrophotometry 225
13.5.2 UV Spectrophotometry 226
13.5.3 Infrared Spectrophotometry 228
13.5.4 Nuclear Magnetic Resonance 235
13.5.5 Electron Spin Resonance 236
13.5.6 Chemiluminescence, Fluorescence, and Phosphorescence 239
13.5.7 Reflectance Spectrophotometry 240
13.5.8 Mass Spectrometry 241
13.5.9 Atomic Absorption Spectroscopy 242
13.6 X-ray Analysis 242
13.6.1 WAXS and SAXS 242
13.6.2 X-ray Photoelectron Spectroscopy 243
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13.7 Physical Properties of Materials 245
13.7.1 Mass Change 245
13.7.2 Density 246
13.7.3 Contact Angle 247
13.7.4 Diffusion of Gases and Water Transport in Polymers 248
13.7.5 Electrical Properties 249
13.7.6 Other Physical Parameters 249
13.8 Thermal Methods 250
13.9 Rheological Properties of Materials 251
13.10 Mechanical Properties 252
13.10.1 Tensile Strength 252
13.10.2 Elongation 254
13.10.3 Flexural Strength 255
13.10.4 Other Mechanical Properties 255
13.11 Other Methods of Analysis 258
13.11.1 Molecular Weight Analysis 258
13.11.2 Gas and Liquid Chromatography 260
13.11.3 Titrimetry 261
13.11.4 Dehydrochlorination Rate 261
13.11.5 Gel Fraction 261
13.11.6 Oxygen Uptake 262
References 263
Chapter 14
DATA ON SPECIFIC POLYMERS 275
14.1 Poly(vinyl chloride) 275
14.1.1 Mechanism of Degradation 276
14.1.1.1 Models 276
14.1.1.2 Polymers 276
14.1.2 Effect of Thermal History 280
14.1.3 Characteristic Changes and Properties 281
14.1.4 Data 284
14.2 Poly(vinyl alcohol) 284
14.2.1 Mechanism of Degradation 284
14.2.2 Effect of Thermal History 286
14.2.3 Characteristic Changes and Properties 286
14.2.4 Data 286
14.3 Polystyrenes 288
14.3.1 Mechanism of Degradation 288
14.3.1.1 Models 288
14.3.1.2 Polymers 288
14.3.2 Effect of Thermal History 294
14.3.3 Characteristic Changes and Properties 294
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14.3.4 Data 298
14.4 Polyacrylonitrile 299
14.4.1 Mechanism of Degradation 299
14.5 Acrylic Resins 300
14.5.1 Mechanism of Degradation 300
14.5.2 Effect of Thermal History 303
14.5.3 Characteristic Changes and Properties 303
14.5.4 Data 304
14.6 Polyamides 305
14.6.1 Mechanism of Degradation 305
14.6.1.1 Models 305
14.6.1.2 Polymer 306
14.6.2 Effect of Thermal History 310
14.6.3 Characteristic Changes and Properties 310
14.6.4 Data 312
14.7 Polyurethanes 312
14.7.1 Mechanism of Degradation 313
14.7.1.1 Models 313
14.7.1.2 Polymers 313
14.7.2 Effect of Thermal History 318
14.7.3 Characteristic Changes and Properties 319
14.7.4 Data 319
14.8 Epoxy Resins 322
14.8.1 Mechanism of Degradation 322
14.8.2 Effect of Thermal History 326
14.8.3 Characteristic Changes and Properties 326
14.8.4 Data 328
14.9 Polyethylene 328
14.9.1 Mechanism of Degradation 329
14.9.1.1 Models 329
14.9.1.2 Polymers 330
14.9.3 Effect of Thermal History 333
14.9.4 Characteristic Changes and Properties 334
14.9.5 Data 337
14.10 Polypropylene 338
14.10.1 Mechanism of Degradation 338
14.10.1.1 Model 338
14.10.1.2 Polymers 338
14.10.2 Effect of Thermal History 340
14.10.3 Characteristic Changes and Properties 340
14.10.4 Data 340
14.11 Polyoxymethylene 343
14.11.1 Mechanism of Degradation 343
14.11.2 Effect of Thermal History 345
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14.11.3 Characteristic Changes and Properties 345
14.12 Poly(phenylene oxide) 346
14.12.1 Mechanism of Degradation 346
14.12.1.1 Models 346
14.12.1.2 Polymer 347
14.12.2 Effect of Thermal History 349
14.12.3 Characteristic Changes and Properties 349
14.12.4 Data 350
14.13 Polycarbonates 351
14.13.1 Mechanism of Degradation 351
14.13.1.1 Models 351
14.13.1.2 Polymers 351
14.13.2 Effect of Thermal History 354
14.13.3 Characteristic Changes and Properties 354
14.13.4 Data 357
14.14 Polyesters 357
14.14.1 Mechanism of Degradation 357
14.14.2 Effect of Thermal History 360
14.14.3 Characteristic Changes and Properties 361
14.14.4 Data 361
14.15 Phenoxy Resins 363
14.15.1 Mechanism of Degradation 363
14.16 Polysulfones and Polysulphides 366
14.16.1 Mechanism of Degradation 367
14.16.2 Effect of Thermal History 368
14.16.3 Characteristic Changes and Properties 368
14.16.4 Data 369
14.17 Silicones 371
14.17.1 Mechanism of Degradation 371
14.17.2 Characteristic Changes and Properties 373
14.18 Polyimides 374
14.18.1 Mechanism of Degradation 374
14.18.1.1 Models 374
14.18.1.2 Polymers 375
14.18.2 Characteristic Changes and Properties 375
14.18.3 Data 377
14.19 Polytetrafluoroethylene 377
14.19.1 Mechanism of Degradation 377
14.20 Acrylonitrile Copolymers 378
14.20.1 Mechanism of Degradation 378
14.20.2 Characteristic Changes and Properties 380
14.21 Ethylene-Propylene Copolymers 382
14.21.1 Mechanism of Degradation 382
14.21.2 Characteristic Changes and Properties 383
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14.22 Polymer Blends 385
14.23 Rubbers 391
14.23.1 Mechanism of Degradation 391
14.23.2 Effect of Thermal History 394
14.23.3 Characteristic Changes and Properties 394
14.23.4 Data 395
References 396
Chapter 15
EFFECT OF POLYMER MORPHOLOGY ON PHOTODEGRADATION KINETICS 411
References 422
Chapter 16
EFFECT OF ADDITIVES ON WEATHERING 425
References 434
Chapter 17
WEATHERING OF COMPOUNDED PRODUCTS 437
17.1 Coatings 437
17.2 Paints 444
17.3 Textile Materials 447
17.4 Upholstery Fabrics 450
17.5 Museum Textiles 452
17.6 Coated Fabrics 453
17.7 Geosynthetics 454
17.8 Composites 456
17.9 Space Applications 459
17.10 Building Materials 463
17.11 Sealants 468
17.12 Plastic Pipes 471
17.13 Bituminous Products 472
17.14 Cover Plates for Solar Collectors 475
17.15 Automotive Materials 477
17.16 Vinyl Siding 478
17.17 Films, Cables, and Tapes 479
17.18 Wood 480
17.19 Paper 485
17.20 Data from Medical Applications 485
17.21 Weathering Studies of Other Materials 488
References 490
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Chapter 18
STABILIZATION AND STABILIZERS 497
18.1 Limiting the Incoming Radiation 498
18.2 Deactivation of Excited States and Free-radicals 506
18.3 Elimination of Singlet Oxygen, Peroxide Decomposition, Limiting Oxidative Changes 510
18.4 Defect Removal 513
18.5 Stability of UV Stabilizers 514
18.6 Effect of Stabilization 519
References 520
Chapter 19
BIODEGRADATION 523
19.1 Biodegradation Environment 523
19.2. Enzymatic Reactions 524
19.3 Biodegradation of Materials 526
19.4 Biocides 531
19.5 Methods of Testing 532
References 533
547
G. Wypych
535 International Abbreviations for Polymers
Index
xii