ISBN-10:
1848213360
ISBN-13:
9781848213364
Pub. Date:
04/03/2012
Publisher:
Wiley
Oxydative Ageing of Polymers / Edition 1

Oxydative Ageing of Polymers / Edition 1

by Jacques Verdu
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Product Details

ISBN-13: 9781848213364
Publisher: Wiley
Publication date: 04/03/2012
Series: ISTE Series , #602
Pages: 356
Product dimensions: 6.30(w) x 9.30(h) x 1.10(d)

About the Author

Jacques Verdu obtained the Docteur d'Etat at University of Pierre and Marie Curie (Paris) in 1976 and became Professor at Ecole Nationale Supérieure d'Arts et Métiers in 1981. In 1980 he created a research laboratory, Laboratoire de Transformation et Vieillissement des polymers (LTVP), of which he was the director until 2008 at which point he became Professor Emeritus. He has published about 280 papers in scientific journals, mostly on polymer ageing, with others on polymer physics, mainly network properties, and has co-authored about a dozen of books and about 400 conferences. He has obtained 3 scientific awards and 2 honorary medals.

Table of Contents

Acknowledgements xi

General Introduction xiii

Chapter 1 Methodological Aspects 1

1.1 Definitions 1

1.2 Empirical and semi-empirical models 4

1.2.1 The Arrhenius model 4

1.2.2 The isodose model 5

1.2.3 The overall kinetic model 6

1.2.4 The correlation method 6

1.2.5 Various mathematical "laws" 7

1.2.6 Conclusion 7

1.3 Towards a non-empirical method of lifetime prediction 8

1.3.1 Principles 8

1.3.2 The multiscale model 8

1.3.3 A new philosophy of ageing 10

1.4 Arguments against kinetic modeling 11

1.4.1 Overcomplexity 11

1.4.2 Heterogeneity 12

1.4.3 Conclusion 15

1.5 Principles of model elaboration 15

Chapter 2 Aspects Common to all Oxidation Processes 17

2.1 Oxidation: a radical chain mechanism 17

2.1.1 Radical nature 17

2.1.2 Chain reaction 18

2.2 Propagation 20

2.2.1 Propagation by addition to double bonds 21

2.2.2 Propagation by hydrogen abstraction 22

2.2.3 Propagation by P° radicals 24

2.3 Termination 25

2.3.1 The P° + P° termination 26

2.3.2 The P° + POO° termination 28

2.3.3 The POO° + POO° termination 29

2.4 Initiation 30

2.4.1 Polymer decomposition 30

2.4.2 Decomposition of oxidation products 32

2.5 Thermodynamic aspects 41

2.5.1 Initiation 41

2.5.2 Propagation 42

2.5.3 Termination 43

Chapter 3 Basic Kinetic Schemes 45

3.1 Simplifying hypotheses 45

3.1.1 Hypothesis U: unicity of the reactive site 45

3.1.2 Hypothesis E: Oxygen excess 47

3.1.3 Hypothesis A: constant initiation rate 47

3.1.4 Hypothesis S: stationary state 48

3.1.5 Hypothesis C: constant substrate concentration 48

3.1.6 Hypothesis L: long kinetic chain 49

3.1.7 Hypothesis T: relation between the termination rate constants 49

3.1.8 Hypothesis H: homogeneity of reaction 49

3.1.9 Hypothesis B: "closed loop" scheme 49

3.2 The ASEC scheme 50

3.2.1 Towards an AEC scheme 53

3.3 The ASCTL scheme 54

3.4 The BESC scheme 57

3.4.1 Characteristics common to all BESC schemes 58

3.4.2 Unimolecular decomposition of hydroperoxides 61

3.4.3 Bimolecular decomposition of hydroperoxides 63

3.5 The BASC scheme 66

3.5.1 The unimolecular BASC model 66

3.5.2 Another approach to the BASC schemes 69

3.5.3 How are we to recognize the mechanisms? 71

3.6 Other schemes 74

3.6.1 Consumption of the substrate 74

3.6.2 Unsaturated substrates 76

3.6.3 Intramolecular propagation in polypropylene 79

3.6.4 Co-oxidation 83

3.7 General problems of kinetic analysis of polymer oxidation. The outlines of a new approach 85

3.7.1 Near-universality of the kinetic behavior 86

3.7.2 Rate constants 88

3.7.3 A systematic approach 89

Chapter 4 Oxidation and Oxygen Diffusion 93

4.1 Properties of oxygen transport in polymers 93

4.1.1 Solubility 93

4.1.2 Diffusivity 96

4.2 The reaction/diffusion equation 101

4.2.1 Conventional approach 101

4.2.2 Numerical resolution 107

4.2.3 Thickness of the oxidized layer. Shape and evolution of the profile 108

Chapter 5 Stabilization 111

5.1 Principles of stabilization 111

5.1.1 Action on [O2] 112

5.1.2 Action on radiation 113

5.1.3 Capture or destruction of radicals and hydroperoxides 113

5.2 Action on hydroperoxide decomposition 113

5.2.1 Hydroperoxide decomposers 114

5.2.2 Metal deactivators 116

5.3 Stabilization by capture of P° radicals 117

5.3.1 Carbon black 117

5.3.2 Nitroxide radicals 118

5.4 Stabilization by capture of POO° radicals 119

5.4.1 General 119

5.4.2 POO° radical scavengers 121

5.5 Synergistic mixtures HD + CBA 125

5.6 Polyfunctional stabilizers 126

5.7 Hindered amines 127

5.7.1 Mechanistic aspects 127

5.7.2 Kinetic aspects 129

5.8 Other stabilizing mechanisms 131

5.9 Physical aspects of stabilization by additives 131

5.9.1 Solubility 132

5.9.2 Volatility, evaporation 135

5.9.3 Diffusivity 138

5.9.4 Evaporation-diffusion 141

5.9.5 Demixing and other phenomena 142

Chapter 6 Molecular Mobility and Reactivity 145

6.1 The issue 145

6.2 The chemical way 149

6.2.1 Example of application: oxidation of PE at low temperature 151

6.3 The physical way 154

6.4 Control by diffusion of macromolecular reactive species and heterogeneity 158

6.5 The paradox of thermostability in glassy polymers 161

Chapter 7 Structural Changes Caused by Oxidation 163

7.1 On the molecular scale 163

7.1.1 Absorbed oxygen, oxygenated groups 163

7.1.2 Chemiluminescence 164

7.1.3 Volatile oxidation products 166

7.1.4 How are we to include the formation of the oxidation products in the kinetic model? 169

7.2 On the macromolecular scale 175

7.2.1 Scissions in linear polymers 176

7.2.2 Scissions in three-dimensional polymers 182

7.2.3 Simultaneous crosslinking and scissions 187

7.3 On the morphological scale 192

7.3.1 Amorphous polymers 192

7.3.2 Immiscible mixtures of amorphous polymers 193

7.3.3 Semi-crystalline polymers with a glassy amorphous matrix 193

7.3.4 Semi-crystalline polymers with a rubbery amorphous phase 194

Chapter 8 Effects of Oxidation on Physical and Mechanical Properties 203

8.1 Introduction 203

8.2 Weight changes 204

8.2.1 Particular cases 207

8.3 Changes in density and volume 207

8.4 Optical properties 210

8.4.1 Changes in the refractive index 210

8.4.2 Coloration 212

8.4.3 Surface state 214

8.4.4 Quantifying the effects of oxidation on the optical properties 215

8.5 Electrical properties 215

8.5.1 Dielectrical spectrum 215

8.5.2 Dielectrical fracture 217

8.6 Glass transition and melting 218

8.6.1 Glass transition temperature 218

8.6.2 Melting point 222

8.7 Mechanical properties at low strains 223

8.7.1 Reminders 223

8.7.2 Elastomers, rubbery phases 225

8.7.3 Glassy amorphous phases 226

8.7.4 Semi-crystalline polymers 229

8.8 Fracture properties in the case of homogeneous degradation 230

8.8.1 Glassy and semi-crystalline amorphous linear polymers with a glassy amorphous phase undergoing degradation 230

8.8.2 Semi-crystalline polymers with a rubbery amorphous phase undergoing degradation 234

8.8.3 Elastomers undergoing degradation 236

8.8.4 Thermoset materials undergoing degradation 238

8.8.5 Effects of superficial oxidation on fracture behavior 239

8.9 Fracture properties in the case of homogeneous crosslinking 243

8.9.1 Glassy amorphous polymers 243

8.9.2 Elastomers 245

Chapter 9 Couplings 249

9.1 Introduction 249

9.2 "Spontaneous" cracking 250

9.3 Coupling between cracking and oxidation 252

9.4 Lifetime under static strain and oxidation 254

9.4.1 Mechano-chemical initiation 254

9.4.2 Effect of oxidation on the fracture kinetics 257

9.5 Physical ageing and oxidation 264

9.6 Oxidation during processing - degradation and recycling 266

9.6.1 Thermoplastics 266

9.6.2 Thermoset materials 274

Chapter 10 Oxidation Under Irradiation 277

10.1 Definitions. General aspects 277

10.1.1 Characteristics of radiation 277

10.1.2 Difference between photochemical and radiochemical initiation 278

10.1.3 Quantities characterization the radiation and interaction between the matter and the radiation 279

10.1.4 Quantities characterizing the reaction 282

10.2 Radiochemical initiation 283

10.3 A perculiarity of radiochemical ageing 288

10.3.1 Stabilization 291

10.4 Photochemical initiation 291

10.4.1 Initiation by photolysis of hydroperoxides 292

10.4.2 "Acceleration factor", linked to the intensity 293

10.4.3 Initiation by thermal and photochemical decomposition of POOHs 294

10.4.4 Initiation in an absorbent environment, thickness of the photo-oxidized layer 295

10.4.5 Initiation by other processes 296

10.4.6 Polychromatic light sources 297

10.5 Photostabilization 300

10.5.1 Stabilization by screen effect 300

10.6 Ageing under natural sunlight 308

10.6.1 Solar radiation at the earth's surface 308

10.6.2 Kinetics of polymer photo-ageing 313

10.6.3 Conclusion on photochemical ageing under natural solar radiation 319

Bibliography 321

Appendix 347

Index 353

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