Aging of Industrial Polymers 1

Emmanuel Richaud is Professor in Arts et Métiers Sciences and Technologies, and Researcher in the Process and Engineering in Mechanics and Materials lab (PIMM), France. His research focuses on predicting the service life of polymer materials and composites.

• Foreword xiSamuel FORESTIntroduction xvEmmanuel RICHAUDChapter 1 Mechanistic and Kinetic Aspects of Oxidative Aging 1Emmanuel RICHAUD1.1 Introduction 11.2 Oxidation mechanisms 21.2.1 General mechanism 21.2.2 Kinetic aspects 81.2.3 Control by oxygen diffusion 101.3 Kinetic modeling 131.3.1 Introduction 131.3.2 Standard scheme 131.3.3 Strategy for estimating rate constants and orders of magnitude 191.4 Conclusion 211.5 References 21Chapter 2 Polymer Aging in the Presence of Water 25Emmanuel RICHAUD2.1 Introduction 252.2 Physical aging of polymers in the presence of water 252.2.1 Water solubility in the polymers 262.2.2 Diffusivity of water into polymers 302.2.3 The consequences of physical aging by water absorption on the mechanical properties of polymers 322.3 Chemical aging in the presence of water (hydrolysis) 342.3.1 General case 352.3.2 Some practical cases of hydrolysis 362.3.3 Consequences for mechanical properties 402.3.4 Stabilization against hydrolytic aging 412.4 Conclusion 422.5 References 43Chapter 3 Polymers Under Ionizing Radiations: Introduction and Basic Principles 47Yvette NGONO3.1 Introduction 473.2 Overview of ionizing radiation 533.2.1 Definition 533.2.2 Sources of ionizing radiations 553.2.3 Quantifying energy deposition and radiation effects on matter 563.3 Interactions between ionizing radiation and polymers: initial processes 583.3.1 Photon‒polymer interactions 583.3.2 Interactions between particles and polymers 603.3.3 Differences and similarities between various types of ionizing radiation 673.4 Evolution of polymers under ionizing radiation 683.4.1 Primary species 693.4.2 Evolution of primary species 693.4.3 Evolution of radicals: defect formation 723.4.4 Parameters influencing the stability of polymers under radiation 763.4.5 Specificity of swift heavy ions 883.5 Conclusion 913.6 Acknowledgments 933.7 References 94Chapter 4 Stabilization 99Emmanuel RICHAUD4.1 Introduction 994.2 Chemical reactions of stabilization against thermo-oxidative aging 994.2.1 Strategy of stabilization against oxidative aging 994.2.2 Kinetic aspects 1054.3 Stabilization against photochemical aging 1084.3.1 UV absorbers 1084.3.2 Quencher 1094.3.3 Pigments 1104.4 Synergies/antagonism 1104.5 Example of specific stabilizations 1114.5.1 PVC stabilization against dehydrochlorination 1114.5.2 Stabilization against depolymerization 1134.6 Physical phenomena involved in the external stabilization of polymers 1144.6.1 Solubility of stabilizers 1144.6.2 Volatility/surface loss of stabilizers 1154.6.3 Diffusivity of stabilizers 1174.6.4 Kinetic analysis of migration phenomena 1194.7 Methods for antioxidant detection and evaluation 1194.8 Conclusion 1214.9 References 122Chapter 5 Effect of Chemical Aging on Mechanical Properties 125Emmanuel RICHAUD5.1 Introduction 1255.2 Thermoplastics 1265.2.1 Change in the average molar mass 1265.2.2 Glass transition temperature 1275.2.3 Viscosity of the molten state 1285.2.4 Fracture properties 1295.3 Networks 1325.3.1 Networks in the rubbery state: elastomers 1325.3.2 Networks in the glassy state: thermosets 1345.4 Conclusion 1385.5 References 138Chapter 6 Physical Aging by Structural Relaxation in Polymers 141Blandine QUÉLENNEC, Nicolas DELPOUVE and Laurent DELBREILH6.1 Introduction: glass transition and the glassy state 1416.1.1 Glass transition 1426.1.2 Characteristics of the glassy state 1546.2 Historical landmarks in the study of physical aging 1556.2.1 Tool’s observations and the concept of fictive temperature 1556.2.2 The limits stated by Ritland 1556.2.3 Kovacs’ experiments 1566.2.4 Theoretical contributions 1596.2.5 Monitoring the mechanical properties 1696.3 Experimental methods for studying physical aging 1716.3.1 Differential scanning calorimetry 1716.3.2 Fast scanning calorimetry 1766.3.3 Broadband dielectric spectroscopy 1776.3.4 Thermally stimulated depolarization currents 1796.3.5 Dynamic mechanical analysis 1826.3.6 Nuclear magnetic resonance spectroscopy 1836.3.7 Positron annihilation lifetime spectroscopy 1856.3.8 Ellipsometry 1856.3.9 Raman spectroscopy 1876.4 Physical aging in glassy systems 1886.4.1 Thermosetting polymers 1886.4.2 Amorphous thermoplastic polymers 1886.4.3 Semicrystalline polymers 1926.4.4 Copolymers 1946.4.5 Composites and nanocomposites 1956.4.6 Polymers and model systems: chalcogenide glasses 1966.5 For a better comprehension of physical aging 1986.5.1 Nature of relaxation dynamics in the glassy state 1986.5.2 An equilibration kinetics in several stages 2006.5.3 Sensitivity of aging by structural relaxation to scale effects and the behavior of a confined polymer 2026.5.4 Possibility of crystallization following aging by structural relaxation 2036.5.5 Predicting the influence of environmental factors on physical aging 2046.6 Conclusion 2066.7 References 208Chapter 7 Several Aspects of Elastomer Fatigue 229Stéphane MÉO, Alexis DELATTRE, Jean-Louis POISSON, Florian LACROIX and Stéphane LEJEUNES7.1 Introduction 2297.2 Problem formulation 2317.2.1 Fatigue in general terms 2317.2.2 Elastomer fatigue 2317.2.3 An example of a crack initiation study 2417.3 Conclusion 2547.4 References 254Chapter 8 Influence of Polyamide 6,6 Molecular Mobility on Mechanical Behavior 261Agustín RIOS DE ANDA, Louise-Anne FILLOT and Paul SOTTA8.1 Introduction 2618.2 Materials and techniques 2658.3 Sorption and plasticizing effect of pure polar and apolar solvents and of mixtures of solvents on pure PA6,6 2708.4 Properties of additivated or chemically modified PA6,6 2808.5 Conclusion 2888.6 References 290Chapter 9. Statistic Approach to Polymer Network Degradation .. 295Pierre GILORMINI9.1 Introduction 2959.2 Numerical simulation 2979.3 Probabilistic approach to degradation 2989.4 First example: trifunctional network with one or two reactive groups per chain 3009.5 Second example: trifunctional network with more than two reactive groups per chain 3029.6 Third example: a tetrafunctional network 3059.7 Conclusion 3079.8 References 308List of Authors 309Index 311