Authors
Peiluo Shi, Hélène Montes, François Lequeux, Régis Schach, Etienne Munch
- Bibliographic Reference
- Peiluo Shi, Hélène Montes, François Lequeux, Régis Schach, Etienne Munch. Linear and non linear mechanical properties of miscible polymer blends near glass transition. Polymers. Université Pierre et Marie Curie - Paris VI, 2013. English. ⟨NNT : ⟩. ⟨pastel-00920019⟩
- HAL Collection
- ['PASTEL - ParisTech', 'ParisTech', 'Université Pierre et Marie Curie', 'Sorbonne Université', 'ESPCI ParisTech', 'CNRS - Centre national de la recherche scientifique', "Thèses de l'Université Pierre et Marie Curie", 'Sciences et Ingénierie de la Matière Molle - Physico-chimie des Polymères et Milieux Dispersés', 'Université Paris sciences et lettres', 'Thèses de Sorbonne Université', 'SORBONNE université <2018', 'Faculté des Sciences de Sorbonne Université', 'Sciences - Sorbonne Université', 'Ecole Supérieure de Physique et de Chimie Industrielles de la Ville de Paris - PSL', 'Sorbonne Université - Texte Intégral', 'Alliance Sorbonne Université']
- HAL Identifier
- 920019
- Institution
- ['Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris', 'Société Michelin']
- Laboratory
- ['Laboratoire de Physico-Chimie des Polymères et des Milieux Dispersés', 'Centre de Technologie de Ladoux']
- Published in
- France
Table of Contents
- Remerciements 4
- 1. 9
- General introduction 10
- 12
- 1. Introduction 12
- 1.1. What is a glass? 12
- 1.1.1. Non equilibrium aspects of the glass transition 13
- 1.1.2. Dynamic aspects of the glass transition 14
- 1.2. Glass transition: specificities in polymer materials 17
- 1.2.1. Structure of a polymer 17
- 19
- 1.2.2. Rubber elasticity 20
- 1.2.3. Linear properties in glassy polymers 25
- 1.2.4. Nonlinear properties in glassy polymers 29
- 1.2.5. Theoretical interpretations of plasticity 32
- 1.3. Miscible polymer blends 37
- 1.4. Problematics 41
- 43
- 2. Materials and methods 44
- 2.1. PB/SBR sample preparation 44
- 2.1.1. Structure 44
- 2.1.2. Blend preparation 45
- 2.1.3. Gluing to metal holders 45
- 2.2. Experimental techniques and sample geometries 46
- 49
- 50
- 3. Measurements of linear properties of the PB/SBR blends in the glass transition zone 50
- 3.1. Introduction 50
- 3.2. Overview of the samples and experimental techniques 51
- 3.3. Calorimetric properties of PB/SBR blends 52
- 3.3.1. Position and width of the glass transition 52
- 3.3.2. Influences of the crosslinking 54
- 3.3.3. Physical aging 55
- 3.4. Linear viscoelastic measurements 60
- 3.4.1. Rheological data 60
- 3.4.2. Time-temperature superposition 61
- 3.4.3. Influence of crosslinking and sample preparations 65
- 3.4.4. Broadening of the glass transition zone 68
- 3.5. Linear dielectric measurements 71
- 3.5.1. Main characteristics of the dielectric responses 71
- 3.5.2. -relaxation and -relaxation separation 74
- 3.5.3. Evolution of the position of-relaxation in PB/SBR blends 78
- 3.6. Conclusions on linear measurements 81
- 4. Interpretation of the linear properties of PB/SBR blends in the glass transition zone 82
- 4.1. Tg distribution P(Tg) from calorimetry 83
- 4.2. Microscopic organization: what length scale for glass transition? 87
- 4.2.1. Model description 87
- 4.2.2. Evolution of P(eff) with the length scale 89
- 4.2.3. Length scale of PB/SBR blends 91
- 4.3. Tg distribution and linear dielectric properties 94
- 4.3.1. How to relate P(Tg) to the macroscopic dielectric measurements? 94
- 4.3.2. Prediction of dielectric properties of PB/SBR blends 96
- 4.4. Tg distribution and linear properties: from DSC to rheology 99
- 4.4.1. Estimation of the viscoelastic spectra of a local domain of Tg. 100
- 4.4.2. Description of the macroscopic mechanical response of the blends 102
- 4.4.3. Conclusion on the interpretation of viscoelastic response and its relation to calorimetry 106
- 4.5. Conclusions on linear properties of PB/SBR blends 107
- 5. Nonlinear properties of PB/SBR blends in the glass transition zone 108
- 5.1. Experimental difficulties 108
- 5.1.1. Adiabatic self-heating 108
- 5.1.2. Non homogeneous deformation 110
- 5.2. Simple extension experiments 111
- 5.2.1. Measurement procedure 111
- 5.2.2. Determination of reliable experimental windows 111
- 5.2.3. Role of linear viscoelasticity in extension test 117
- 5.2.4. Nonlinearity in extension test 123
- 5.2.5. Evolution of structural nonlinearity 130
- 5.3. Cyclic shear Nonlinearities 132
- 5.4.1. Physical interpretation of Aent+Aplast 141
- 5.4.2. What is the relation between structural nonlinearity and plasticity? 144
- 6. General conclusion 149
- Résumé 152
- Annex A. Infrared camera and calibration 158
- Annex B. Kuhn lengths of PB and SBR 162
- Annex C. Calculation of heat transfer 164
- Annex D. Analytic form of viscoelastic relaxation 168
- Annex E. Determination of the evolution of the structural non linearity parameters Aent+Aplast 170
- Annex F. Details of cyclic shear measurements 173
- Annex G. Nonlinear time-temperature superposition in extension 179
- References 182