THÈSE DE DOCTORAT DE L'UNIVERSITÉ PARIS VI Adhésion des polymères semi-cristallins ...

260 Pages·2017·8.43 MB·English

by  Gauthier Jarrousse

Self adhesion of semi-crystalline polymers between their
glass transition temperature and their melting
temperature
Gauthier Jarrousse
To cite this version:
Gauthier Jarrousse. Self adhesion of semi-crystalline polymers between their glass transition temper-
ature and their melting temperature. Chemical Sciences. Université Pierre et Marie Curie - Paris VI,
2004. English. ￿NNT: ￿. ￿pastel-00001099￿
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THÈSE DE DOCTORAT DE L’UNIVERSITÉ PARIS VI

Ecole Doctorale de Chimie Physique et Chimie Analytique

Spécialité :

Matière condensée : chimie et organisation

Présentée par :

Gauthier Jarrousse

pour obtenir le titre de :

DOCTEUR DE L’UNIVERSITÉ PARIS VI

Sujet de la thèse :

Adhésion des polymères semi-cristallins entre leur température
de transition vitreuse et leur température de fusion

Self adhesion of semi-crystalline polymers between their glass
transition temperature and their melting temperature

Soutenue le 13 Décembre 2004

devant le jury composé de :

Mme Liliane LEGER, Professeur, Collège de France Co-directrice de thèse
M. Costantino CRETON, Directeur de recherche, ESPCI Directeur de thèse
M. Jean-Claude WITTMANN, Directeur de recherche, Institut Charles Sadron Rapporteur
M. Jean-Yves CAVAILLE, Professeur, INSA de Lyon Rapporteur
M. Alain FRADET, Professeur, Université Paris VI Président
M. John Christopher PLUMMER, Professeur, EPFL Invité
Table of contents

_______________________

i
Introduction

Chapter 1 : Basic concepts and state of the art 4

1.1 Basic concepts 6
1.1.1 Brief introduction to polymers 6
1.1.1.1 Introduction 6
1.1.1.2 Types of polymers and classification 7
1.1.1.3 A few words on polymerization 8
1.1.1.4 Basic considerations of polymer physics 9
1.1.1.4.1 A single chain 9
1.1.1.4.2 Dense system of chains 9
1.1.1.4.3 The amorphous state 11
1.1.1.4.4 Mechanical properties of amorphous polymers 12
1.1.2 Semi-crystalline polymers 16
1.1.2.1 General structure of semi-crystalline polymers 17
1.1.2.2 Theories of crystallization kinetics 18
1.1.2.2.1 General considerations 18
1.1.2.2.2 Overall crystallization kinetics 19
1.1.2.2.3 Molecular mechanisms of crystallization 20
1.1.2.3 Melting 23
1.1.2.4 General mechanical behavior of semi-crystalline polymers 24
1.2 Fracture behavior of polymers 28
1.2.1 Introduction 28
1.2.2 Energy balance approach 29
1.2.3 The stress intensity factor approach 31
1.2.3.1 Plane strain, plane stress and different modes of fractures 31
1.2.3.2 Basic principles of the stress intensity factor approach 33
1.2.4 Relationship between G and K 34
1.2.5 Experimental considerations 35
1.3 Adhesion between polymers 40
1.3.1 Introduction 40
1.3.2 Different fracture mechanisms 41
1.3.2.1 Chain pullout 41
1.3.2.2 Chain scission 42
1.3.2.3 Crazing 42
1.3.2.4 Transition between the different mechanisms 45
1.3.3 Interdiffusion at polymer interfaces 46
1.3.3.1 Polymer interdiffusion 46
1.3.3.1.1 Diffusion at different time scales 47
1.3.3.1.2 Interdiffusion at polymeric interfaces 48
1.3.3.1.3 Fracture toughness and interdiffusion : early studies 50
1.3.4 Polymer adhesion between amorphous polymers : the modern view 51
1.3.4.1 Introduction 51
1.3.4.2 Direct adhesion between amorphous polymers 52
1.3.4.3 Reinforcement of interfaces (immiscible amorphous polymers) 54
1.3.5 Adhesion between semicrystalline polymers 57
1.3.5.1 Reinforcement of incompatible semicrystalline polymers 58
1.3.5.1.1 Compatibilization by formation of a copolymer 58
1.3.5.1.2 Compatibilizing less immiscible semicrystalline polymers 61
1.3.5.2 Self-adhesion of semicrystalline polymers 62
1.4 Conclusions and objectives of the current study 67

ii
Chapter 2 : Characterizations and experimental techniques 68

2.1 Brief review : structure and properties of PBT, PBI and PBT/PBI copolymers 70
2.1.1 PBT 70
2.1.1.1 Introduction 70
2.1.1.2 Crystallinity 70
2.1.1.3 WAXS study on PBT 71
2.1.1.4 The amorphous phase of PBT 72
2.1.1.5 Spherulitic structure 73
2.1.1.5.1 Lamellae 73
2.1.1.5.2 Spherulites 73
2.1.1.6 Crystallization and fusion 74
2.1.1.6.1 Crystallization 74
2.1.1.6.2 Cold crystallization 75
2.1.1.6.3 Fusion 76
2.1.1.6.4 Equilibrium melting temperature and heat of fusion 77
2.1.1.7 Some mechanical properties of PBT 77
2.1.2 PBI 79
2.1.3 PBT-PBI copolymers 81
2.2 Synthesis and molecular characterizations 86
2.2.1 Synthesis 86
2.2.2 End group analysis : determination of M 87
n
2.2.3 Rheology 88
2.2.4 NMR experiments 93
2.3 Bulk characterization 96
2.3.1 Temperature modulated Differential Scanning Calorimetry 96
2.3.1.1 Basic theory 96
2.3.1.2 Experimental procedure 98
2.3.2 Dynamic Mechanical Analysis 100
2.3.2.1 Experimental procedure 100
2.3.2.2 Results 101
2.3.3 X-rays 104
2.3.3.1 Sample preparation and results 104
2.3.3.2 Calculation of the degree of crystallinity 106
2.4 Adhesion : sample preparation and testing 110
2.4.1 Molding and assembling 110
2.4.1.1 Temperature controlled press 110
2.4.1.2 Molding 111
2.4.1.3 Cooling procedure 112
2.4.1.4 Assembling 114
2.4.2 Measurement of the fracture toughness 116
2.4.2.1 DCB tests 116
2.4.2.2 Measurements of the Young’s modulus 118
2.5 Tensile tests 119
2.5.1 Sample preparation 119
2.5.2 Tensile test 120
2.6 Study of the crystallinity at the interface 120
2.6.1 General procedure for optical and electron microscope observations 120
2.6.2 Optical observations 120
2.6.2.1 microtoming the sample 121
2.6.2.2 observation in polarized light microscopy 121
2.6.3 Observation in transmission electron microscopy 122
2.6.3.1 Sample preparation for TEM 122
2.6.3.2 transmission electron microscope observations 124
iii
Chapter 3 : Results 126

3.1 PBT and 15PB 129
3.1.1 Adhesion measurements 119
3.1.2 DSC results 131
3.1.3 Microstructure 135
3.1.3.1 Optical observations 135
3.1.3.2 TEM observations 138
3.1.4 Simultaneous analysis of the different techniques 140
3.1.5 Partial conclusions 142
3.2 35PB and 45PB 144
3.2.1 Adhesion results 144
3.2.2 DSC results 146
3.2.3 Discussion 152
3.2.4 Conclusions 154
3.3 Amorphous 45PB : 45PBa 156
3.3.1 Characterization of the crystallinity of 45PBa by DSC 157
3.3.2 Crystallization kinetics 168
3.3.3 Observations of the samples 172
3.3.4 Tensile tests 175
3.3.5 Crystallinity and mechanical behavior 176
3.3.6 Adhesion results 177
3.3.7 Crack tip observations (optical and TEM) 184
3.3.8 Conclusions 187
3.4 PBI 188
3.4.1 Characterization of the crystallinity of PBI by DSC 188
3.4.2 Crystallization kinetics 193
3.4.3 Samples observations 195
3.4.4 tensile tests 198
3.4.5 Crystallinity and mechanical behavior 199
3.4.6 Adhesion results 200
3.4.7 Crack tip observation and TEM 205
3.4.8 Conclusion 209

Chapter 4 : Discussion 210

4.1 First set :contact between pre-crystallized samples 212
4.1.1 Overview of the results 212
4.1.2 Discussion on the mechanisms 215
4.1.3 Conclusions 219
4.2 Second set : quenched samples of 45PB and PBI 219
4.2.1 Overview of the results 219
4.2.2 Discussion on the mechanisms 223
4.2.3 Conclusions 225
4.3 Outlook and ideas for future studies 225

Conclusion 228

References 234

Extended abstract in French 246

iv
v
Introduction
0
1
Adhesion is an immensely complicated subject concerned with the strength of the
coupling that can occur between any pair of materials. It is also a subject of wide ranging
usefulness with a steadily increasing importance in many technologies. The reason of the
complexity of the science of adhesion lays in the fact that adhesion is at the cross section
of many fundamental sciences, since in order to understand how two materials can be
associated one should be aware of the different chemical or physical coupling that can
occur at the interface.

In the present study, we consider only the adhesion between pairs of polymeric materials,
and more specifically between semicrystalline polymers. This field has been widely but
quite recently studied, since most of the polymers used in the industry are semicrystalline
polymers. For example, the association of two or more polymers in alloys or in blends, to
obtain optimized products by combining their properties, is of great industrial importance.
Some of the industrial processes require a good and rapid adhesion such as the over
molding process, where a polymer melt is injected on top of another polymer which is
solid. In this type of process, the crystallinity at the very surface of the solid polymer is
certainly playing a significant role and a better understanding of the way this crystallinity
acts upon the adhesion is needed.

Although both the mechanisms of reinforcement of an interface between amorphous
polymers and the fracture mechanisms of such interfaces are now relatively well
established, their extension to semicrystalline interfaces is not straightforward. Several
ideas have emerged from the studies of adhesion between semicrystalline polymers, but
still a clear vision of the different mechanisms active for the reinforcement of the
interfaces at the molecular level and the fractures mechanisms of such interfaces, is still
far beyond reach.

The present investigation is a contribution aimed at elucidating the role of crystallinity
upon adhesion and fracture mechanisms between semicrystalline polymers. Since the
adhesion between amorphous polymers has been well described, the natural attempt in
previous studies was to try to apply the mechanisms found in the case of amorphous
polymers to the case of semicrystalline polymers. Although some similarities have been
established, differences have been underlined such as the critical role played by the
crystallinity.

Typically, it is well established that when co-crystallization occurs at the interface, the
fracture toughness of such interfaces is largely increased. However, the conditions which
will allow a co-crystallization are unclear. It has been shown also that the crystalline
orientation at the interface had a great influence on the adhesion. However the reasons of
this influence remain unknown.

Thus, several questions were at the onset of this work. What was the influence on the
level of adhesion of the amorphous part of a semicrystalline polymer welded above T but
g
2