Polymer materials : macroscopic properties and molecular interpretations

433 Pages·2011·27.681 MB·English, French

by  Lauprêtre, Françoise, Monnerie, Lucien, Halary, Jean-Louis

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POLYMER MATERIALS
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POLYMER MATERIALS
Macroscopic Properties and Molecular Interpretations
JEAN LOUIS HALARY
FRANÇOISE LAUPRÊTRE
LUCIEN MONNERIE
A JOHN WILEY & SONS, INC., PUBLICATION
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Translated by Jean Louis Halary and Françoise Lauprêtre and Lucien Monnerie.
Originally published in French under the titles “De la Macromolécule au Matériau Polymère” by Jean Louis Halary and
Françoise Lauprêtre © Editions Belin—Paris (2006) and “Mécanique des Matériaux Polymères” by Jean Louis Halary,
Françoise Lauprêtre, and Lucien Monnerie, ©Editions Belin—Paris (2008).
Copyright © 2011 by John Wiley & Sons, Inc. All rights reserved
Published by John Wiley & Sons, Inc., Hoboken, New Jersey
Published simultaneously in Canada
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Library of Congress Cataloging-in-Publication Data:
Halary, Jean Louis.
[De la macromolécule au matériau polymère. English]
Polymer materials : macroscopic properties and molecular interpretations / Jean Louis Halary, Françoise Lauprêtre, Lucien Monnerie.
p. cm.
Includes index.
ISBN 978-0-470-61619-2 (cloth)
1. Polymers. 2. Macromolecules. I. Lauprêtre, Françoise. II. Monnerie, L. (Lucien) III. Title.
QD381.H34513 2011
541′.2254–dc22
2010023285
Printed in Singapore
ePDF: 978-0-470-92201-9
ePub: 978-0-470-92288-0
10 9 8 7 6 5 4 3 2 1
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CONTENTS
PREFACE xxi
LIST OF SYMBOLS xxiii
Introduction to Polymer Materials 1
I.1. Chronological Landmarks for Polymers, 1
I.2. The Polymer Chain, 2
I.3. The Key Points of Polymer Synthesis, 2
I.3.1. Step Polymerization, 3
I.3.2. Chain Polymerization, 3
I.3.3. Controlled Polymerizations, 4
I.3.4. Ziegler–Natta and Metallocene Polymerizations, 5
I.3.5. Synthesis of Copolymers, 5
I.3.6. Polymer Cross-Linking, 7
I.3.7. The Molecular Weight Distribution, 8
I.3.8. Conclusion, 8
I.4. Major Polymers, 8
I.5. The Lightness of Polymer Materials, 8
I.6. Main Mechanical Aspects of Polymer Materials, 11
I.7. Comprehensive Survey of the Polymer Mechanical Behaviors, 11
Further Reading, 12
PART I 13
1 The Four Classes of Polymer Materials 15
1.1. The Young Modulus, 15
1.2. Un-Cross-Linked Amorphous Polymers, 15
1.3. Semicrystalline Thermoplastics, 17
1.4. Thermosetting Polymers, 17
1.5. Cross-Linked Elastomers, 18
1.6. Conclusions, 19
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vi CONTENTS
2 The Macromolecular Chain in the Amorphous Bulk Polymer: Static
and Dynamic Properties 21
2.1. Conformational Statistics of Isolated Polymer Chains, 21
2.1.1. Freely Jointed Chain, 21
2.1.2. Freely Rotating Chain, 22
2.1.3. Chain with Symmetrically Restricted Internal Rotation, 22
2.1.4. Equivalent Kuhn Chain, 23
2.2. Conformational Energy Calculations, 24
2.2.1. Conformational Energy of Model Molecules, 24
2.2.2. Conformational Energy Maps, 25
2.2.3. NMR Investigation of Polymer Conformations, 27
2.3. Global Properties of an Isolated Chain, 27
2.3.1. Rotational Isomers, Statistical Weights, and Calculation
of 〈R2〉, 28
2.3.2. Construction of an Isolated Chain According to the
Monte-Carlo Method, 28
2.4. Chain Conformations in Bulk Amorphous Polymers, 28
2.4.1. Experimental Investigation by Neutron Scattering, 28
2.4.2. Computer Modeling of an Amorphous Cell, 28
2.5. Local Dynamics of Isolated Chains, 30
2.5.1. Conformational Jumps in Linear Alkanes and Aliphatic
Chains, 30
2.5.2. Molecular Dynamics of Isolated Chains, 32
2.5.3. Cooperative Kinematics Technique, 33
2.6. Local Dynamics of a Polymer Chain in Solution, 34
2.6.1. Experimental Investigation by 13C NMR, 35
2.6.2. Molecular Modeling of Local Chain Dynamics in Solution, 35
2.7. Local Dynamics in Bulk Polymers, 37
2.7.1. Investigation by 13C NMR, 37
2.7.2. Molecular Modeling of Local Chain Dynamics in Polymer
Melts, 37
2.8. Conclusions, 39
References, 39
Further Reading, 40
3 The Glass Transition 41
3.1. Experimental Studies, 41
3.1.1. Temperature Dependence of the Specifi c Volume, 41
3.1.2. Differential Scanning Calorimetry Investigation, 41
3.1.3. Mechanical Observation of the Glass Transition, 42
3.1.3.1. The Young Modulus, 42
3.1.3.2. Dynamic Mechanical Analysis, 42
3.2. Molecular Origin of the Glass Transition Temperature, 43
3.2.1. Cooperative Motions of the Main-Chain Bonds, 44
3.2.2. Time (or Frequency)–Temperature Equivalence, 44
3.3. Overview of the Glass Transition Temperature Theories, 45
3.3.1. The Gibbs–Di Marzio Thermodynamic Theory, 46
3.3.2. Dynamic Free Volume, 47
3.3.3. Computer Simulations, 50
3.3.4. Physical Aging, 51
3.4. Effect of the Polymer Architecture on the Glass Transition
Temperature, 52
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CONTENTS vii
3.4.1. Molecular Weight, 52
3.4.2. Ring and Branches, 53
3.4.3. Cross-Links, 53
3.5. Effect of the Polymer Chemical Structure on the Glass
Transition Temperature, 54
3.6. Glass Transition of Random Copolymers, 54
3.7. Glass Transition of Polymer/Plasticizer Blends, 57
3.7.1. Polymer/Plasticizer Blends, 57
3.7.2. T Dependence on Plasticizer Content, 57
g
3.8. Conclusions, 58
References, 58
Further Reading, 58
4 Secondary Relaxations in Amorphous Polymers 59
4.1. Experimental Evidences of a Secondary Relaxation, 59
4.1.1. Dynamic Mechanical Analysis, 59
4.1.1.1. A Simple Example: The γ Relaxation of
Poly(cyclohexyl methacrylate), 59
4.1.1.2. A More Complex Example: The β Relaxation of
Poly(ethylene terephthalate), 61
4.1.2. Dielectric Analysis, 61
4.1.3. Relaxation Map, 61
4.2. Identifi cation of the Motions that Are Responsible for the
Secondary Relaxations, 61
4.2.1. High-Resolution Solid-State 13C NMR, 62
4.2.1.1. Some General Principles, 62
4.2.1.2. Example of the γ Relaxation of Poly(cyclohexyl
methacrylate), 63
4.2.1.3. Example of the β Relaxation of Poly(ethylene
terephthalate), 64
4.2.2. 2H NMR of Selectively Deuterated Compounds, 66
4.2.3. Comparison of Results Obtained from the Different
Techniques, 66
4.2.4. Use of Antiplasticizers, 67
4.3. Motional Cooperativity Associated with Secondary Relaxations, 67
4.3.1. Starkweather Approach, 68
4.3.2. Nature of the Motional Cooperativity, 69
4.3.2.1. Intermolecular Cooperativity, 69
4.3.2.2. Intramolecular Cooperativity, 69
4.4. Secondary Relaxations of Poly(methyl methacrylate) and Some
of Its Random Copolymers, 69
4.4.1. PMMA, 69
4.4.1.1. Low-Temperature Secondary Relaxations of PMMA, 69
4.4.1.2. DMA and Dielectric Relaxation Evidences of
the β Relaxation of PMMA, 69
4.4.1.3. Identifi cation of Local Motions Responsible for
the β Relaxation of PMMA, 70
4.4.1.4. Information Derived from Molecular Modeling, 71
4.4.2. Methyl Methacrylate-co-N-cyclohexylmaleimide Random
Copolymers, 72
4.4.3. Methyl Methacrylate-co-N-methylglutarimide Random
Copolymers, 73
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viii CONTENTS
4.5. Secondary Relaxation of Neat and Antiplasticized Bisphenol-A
Polycarbonate, 75
4.5.1. Characterization by Dynamic Mechanical Analysis and
Dielectric Relaxation, 75
4.5.2. Identifi cation of Motions, 75
4.5.3. Nature of the Motional Cooperativity, 76
4.5.3.1. Infl uence of Hydrostatic Pressure, 76
4.5.3.2. Effect of Small-Molecule Antiplasticizers, 76
4.5.3.3. Molecular Modeling, 77
4.6. Secondary Relaxations in Neat and Antiplasticized
Aryl-Aliphatic Epoxy Resins, 78
4.6.1. Characterization of the β Relaxation and Motional
Cooperativity, 80
4.6.2. Identifi cation of Local Motions Involved in the β
Relaxation, 81
4.6.3. Characterization of the β Secondary Relaxation of
Antiplasticized Epoxy Networks, 82
4.6.4. Local Motions in Antiplasticized Epoxy Networks, 82
4.6.5. Intermolecular Cooperativity of the β Relaxation
Motions in Neat and Antiplasticized Epoxy Networks, 83
4.7. Conclusions, 83
References, 84
Further Reading, 84
5 Entanglements in Bulk Un-Cross-Linked Polymers 85
5.1. Concept of Entanglement, 85
5.2. Experimental Determinations of M, 87
e
5.2.1. From the Rubbery Plateau, 87
5.2.1.1. Young Modulus, 87
5.2.1.2. Dynamic Shear Modulus, 87
5.2.2. From the Viscosity in the Flow Region, 88
5.2.2.1. Characterization of the Newtonian Viscosity, 88
5.2.2.2. Physical Meaning of Viscosity, 89
5.2.2.3. Molecular Weight Dependence of the Newtonian
Viscosity, 89
5.3. Theoretical Overview of Chain Dynamics, 90
5.3.1. The Rouse Model, 90
5.3.2. de Gennes Reptation Model, 92
5.3.3. The Doi–Edwards Model, 94
5.4. Relationships Between Entanglements and Polymer Chemical
Structure, 95
5.4.1. Values of the Molecular Weight Between Entanglements, 95
5.4.2. Entanglement Density, 95
5.4.3. Number of Bonds Between Entanglements, 96
5.4.4. Number of Equivalent Bonds Between Entanglements, 96
5.4.5. The Example of Random Copolymers, 96
5.5. Conclusions, 98
References, 99
Further Reading, 99
6 Semicrystalline Polymers 101
6.1. Experimental Evidence of Semicrystalline State, 101
6.1.1. Wide-Angle X-Ray Scattering (WAXS), 101
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