Oxydative Ageing of Polymers

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.

• Acknowledgements xiGeneral Introduction xiiiChapter 1. Methodological Aspects 11.1. Definitions 11.2. Empirical and semi-empirical models 41.3. Towards a non-empirical method of lifetime prediction 81.4. Arguments against kinetic modeling 111.5. Principles of model elaboration 15Chapter 2. Aspects Common to all Oxidation Processes 172.1. Oxidation: a radical chain mechanism 172.2. Propagation 202.3. Termination 252.4. Initiation 302.5. Thermodynamic aspects 41Chapter 3. Basic Kinetic Schemes 453.1. Simplifying hypotheses 453.2. The ASEC scheme 503.3. The ASCTL scheme 543.4. The BESC scheme 573.5. The BASC scheme 663.6. Other schemes 743.7. General problems of kinetic analysis of polymer oxidation. The outlines of a new approach 85Chapter 4. Oxidation and Oxygen Diffusion 934.1. Properties of oxygen transport in polymers 934.2. The reaction/diffusion equation 101Chapter 5. Stabilization 1115.1. Principles of stabilization 1115.2. Action on hydroperoxide decomposition 1135.3. Stabilization by capture of P° radicals 1175.4. Stabilization by capture of POO° radicals 1195.5. Synergistic mixtures HD + CBA 1255.6. Polyfunctional stabilizers 1265.7. Hindered amines 1275.8. Other stabilizing mechanisms 1315.9. Physical aspects of stabilization by additives 131Chapter 6. Molecular Mobility and Reactivity 1456.1. The issue . 1456.2. The chemical way . . 1496.3. The physical way . . 1546.4. Control by diffusion of macromolecular reactive species and heterogeneity 1586.5. The paradox of thermostability in glassy polymers 161Chapter 7. Structural Changes Caused by Oxidation 1637.1. On the molecular scale 1637.2. On the macromolecular scale 1757.3. On the morphological scale 192Chapter 8. Effects of Oxidation on Physical and Mechanical Properties 2038.1. Introduction 2038.2. Weight changes 2048.3. Changes in density and volume 2078.4. Optical properties 2108.5. Electrical properties 2158.6. Glass transition and melting 2188.7. Mechanical properties at low strains 2238.8. Fracture properties in the case of homogeneous degradation. 2308.9. Fracture properties in the case of homogeneous crosslinking 243Chapter 9. Couplings 2499.1. Introduction 2499.2. “Spontaneous” cracking  2509.3. Coupling between cracking and oxidation 2529.4. Lifetime under static strain and oxidation 2549.5. Physical ageing and oxidation 2649.6. Oxidation during processing – degradation and recycling 266Chapter 10. Oxidation Under Irradiation 27710.1. Definitions. General aspects 27710.2. Radiochemical initiation 28310.3. A perculiarity of radiochemical ageing 28810.4. Photochemical initiation 29110.5. Photostabilization 30010.6. Ageing under natural sunlight 308Bibliography 321Appendix 347Index 353