1 Handbook of EDITORS 1 Multiphase EDITORS …download.e-bookshelf.de/download/0000/5963/97/L-G-0000596397... · P1: OTA/XYZ P2: ABC Trim: 189mm ×246mm JWST068-Vol1-FM JWST068-Boudenne

32mm246 x 189

Cover design: Gary Thompson

E D I T O R S

ABDERRAHIM BOUDENNE

LAURENT IBOS

YVES CANDAUUniversité Paris-Est, CERTES EA 3481– Centre d’Etude et de Recherche en Thermique, Environnement et Systèmes, Créteil, France

SABU THOMASCentre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India

A comprehensive reference guide examining current challenges and opportunities in the fi eld of multicomponent polymer systems.

Multiphase polymer systems are an important research topic from both industrial and fundamental points of view. This new generation of materials offers enhanced physical, mechanical, thermal, electrical, magnetic and optical properties, and fi nds use in many fi elds such as automotive, aeronautics and space industry, cabling, civil engineering and medicine. They cover a wide range of materials such as composites, blends, alloys, gels and interpenetrating polymer networks.

This double-volume book examines the recent advances covering physical, interfacial, and thermophysical properties of multiphase polymer systems. It includes manufacturing and processing techniques, characterization techniques, materials modeling, applications and also ageing, degradation and recycling. It pays particular attention to characterization at different length scales (macro, micro and nano) which is necessary for a full understanding of the structure-property relationships of multiphase polymer systems.

Ideal for researchers in both industry and academia who wish to learn about these promising new materials, the Handbook of Multiphase Polymer Systems is also useful for plastic and rubber technologists, fi ller specialists and researchers in fi elds studying thermal, mechanical and electrical properties.

ABDERRAHIM BOUDENNE

LAURENT IBOS

YVES CANDAU

SABU THOMAS

Handbook ofHandbook of

Multiphase Polymer Systems


E D I T O R S

11 E D I T O R S

BOUDENNE

IBOS

CANDAU

THOMAS

Handbook of

Multiphase Polym

er Systems

1

RED BOX RULES ARE FOR PROOF STAGE ONLY. DELETE BEFORE FINAL PRINTING.

35mm246 x 189

ABDERRAHIM BOUDENNE

LAURENT IBOS

YVES CANDAU

SABU THOMAS

Handbook of


E D I T O R S

2

Cover design: Gary Thompson

E D I T O R S

ABDERRAHIM BOUDENNE

LAURENT IBOS

YVES CANDAUUniversité Paris-Est, CERTES EA 3481– Centre d’Etude et de Recherche en Thermique, Environnement et Systèmes, Créteil, France

SABU THOMASCentre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam, Kerala, India

A comprehensive reference guide examining current challenges and opportunities in the fi eld of multicomponent polymer systems.

Multiphase polymer systems are an important research topic from both industrial and fundamental points of view. This new generation of materials offers enhanced physical, mechanical, thermal, electrical, magnetic and optical properties, and fi nds use in many fi elds such as automotive, aeronautics and space industry, cabling, civil engineering and medicine. They cover a wide range of materials such as composites, blends, alloys, gels and interpenetrating polymer networks.

This double-volume book examines the recent advances covering physical, interfacial, and thermophysical properties of multiphase polymer systems. It includes manufacturing and processing techniques, characterization techniques, materials modeling, applications and also ageing, degradation and recycling. It pays particular attention to characterization at different length scales (macro, micro and nano) which is necessary for a full understanding of the structure-property relationships of multiphase polymer systems.

Ideal for researchers in both industry and academia who wish to learn about these promising new materials, the Handbook of Multiphase Polymer Systems is also useful for plastic and rubber technologists, fi ller specialists and researchers in fi elds studying thermal, mechanical and electrical properties.

Handbook of


2 E D I T O R S

BOUDENNE

IBOS

CANDAU

THOMAS

Handbook of

Multiphase Polym

er Systems

2

RED BOX RULES ARE FOR PROOF STAGE ONLY. DELETE BEFORE FINAL PRINTING.

P1: OTA/XYZ P2: ABC Trim: 189mm × 246mm

JWST068-Vol1-FM JWST068-Boudenne July 8, 2011 13:12 Printer: Yet to come

Handbook of Multiphase Polymer Systems

i



ii




Volume 1

Editors

ABDERRAHIM BOUDENNE, LAURENT IBOS, YVES CANDAUUniversite Paris-Est, Centre d’Etude et de Recherche en Thermique,

Environnement et Systemes, Creteil, France

AND

SABU THOMASCentre for Nanoscience and Nanotechnology, Mahatma Gandhi University,

Kottayam, Kerala, India

A John Wiley & Sons, Ltd., Publication

iii



This edition first published 2011C© 2011 John Wiley and Sons Ltd

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Library of Congress Cataloging-in-Publication Data

Handbook of multiphase polymer systems / editors, Abderrahim Boudenne ... [et al.].p. cm.

Includes bibliographical references and index.ISBN 978-0-470-71420-1 (cloth) – ISBN 978-1-119-97203-7 (ePDF) – ISBN 978-1-119-97202-0 (oBook)

1. Polymeric composites. I. Boudenne, Abderrahim.TA418.9.C6H3426 2012547′.7–dc22

2011011524

A catalogue record for this book is available from the British Library.

Print ISBN: 9780470714201ePDF ISBN: 9781119972037oBook ISBN: 9781119972020ePub ISBN: 9780470714201Mobi ISBN: 9781119972891

Typeset in 10/12pt Times by Aptara Inc., New Delhi, India

iv

http://www.wiley.com



Contents

List of Contributors xix

Foreword xxiii

VOLUME 1

1 Physical, Thermophysical and Interfacial Properties of Multiphase Polymer Systems: Stateof the Art, New Challenges and Opportunities 1Sabu Thomas, Abderrahim Boudenne, Laurent Ibos and Yves Candau

1.1 Introduction 11.2 Multiphase Polymer Systems 2

1.2.1 Polymer Blends 21.2.2 Polymer Composites 21.2.3 Polymer Nanocomposites 21.2.4 Polymer Gels 31.2.5 Interpenetrating Polymer Network System (IPNs) 3

1.3 A Short Survey of the Literature and Applications 51.4 Book Content 7

1.4.1 Modeling and Computer Simulation of Multiphase Composites: From Nanoscale toMacroscale Properties 7

1.4.2 Morphological Investigation Techniques 81.4.3 Macroscopic Physical Characterization 81.4.4 Life Cycling 10

1.5 Future Outlook, New Challenges and Opportunities 10References 12

2 Macro, Micro and Nano Mechanics of Multiphase Polymer Systems 13Alireza S. Sarvestani and Esmaiel Jabbari

2.1 Introduction 132.2 Unentangled Systems 14

2.2.1 Microscopic Structure 152.2.2 Macroscopic Properties 182.2.3 Results 19

2.3 Entangled Systems 212.3.1 Microscopic Structure 222.3.2 Macroscopic Properties 242.3.3 Results 25

2.4 Conclusion 27Acknowledgements 28References 28

v



vi Contents

3 Theory and Simulation of Multiphase Polymer Systems 31Friederike Schmid

3.1 Introduction 313.2 Basic Concepts of Polymer Theory 32

3.2.1 Fundamental Properties of Polymer Molecules 323.2.2 Coarse-Graining, Part I 333.2.3 Ideal Chains 343.2.4 Interacting Chains 363.2.5 Chain Dynamics 38

3.3 Theory of Multiphase Polymer Mixtures 393.3.1 Flory-Huggins Theory 393.3.2 Self-consistent Field Theory 433.3.3 Analytical Theories 493.3.4 An Application: Interfaces in Binary Blends 55

3.4 Simulations of Multiphase Polymer Systems 563.4.1 Coarse-Graining, Part II 563.4.2 Overview of Structural Models 583.4.3 Overview of Dynamical Models 623.4.4 Applications 65

3.5 Future Challenges 70Acknowledgements 70References 71

4 Interfaces in Multiphase Polymer Systems 81Gyorgy J. Marosi

4.1 Introduction 814.2 Basic Considerations 824.3 Characteristics of Interfacial Layers 83

4.3.1 Role of Thermodynamic Factors 854.3.2 Role of Kinetic Factors 874.3.3 Relationship Between Interfacial Structure and Mechanical Response 88

4.4 Interface Modifications: Types and Aims 894.4.1 Interlayers of Controlled Morphology 904.4.2 Interlayers of Modified Segmental Mobility 924.4.3 Interlayers for Improving the Compatibility of the Phases 93

4.5 Interlayers of Modified Reactivity 1004.6 Responsive Interphases 101

4.6.1 Non-reversibly Adaptive Interphases 1014.6.2 Smart Reversibly Adaptive Interphases 103

4.7 Methods of Interface Analysis 1054.8 Conclusions 111

References 112

5 Manufacturing of Multiphase Polymeric Systems 123Soney C. George and Sabu Thomas

5.1 Introduction 123



Contents vii

5.2 Manufacturing Techniques of Polymer Blends 1235.2.1 Solution Blending 1245.2.2 Latex Blending 1255.2.3 Freeze-drying 1265.2.4 Mechanical Blending 1265.2.5 Mechano-chemical Blending 1325.2.6 Manufacturing of Polymer Blends Using Supercritical Fluids 132

5.3 Manufacturing Techniques of Polymer Composites 1335.3.1 Hand Layup Process 1345.3.2 Spray Layup Process 1345.3.3 Vacuum Bag Molding 1355.3.4 Resin Transfer Molding 1365.3.5 Pultrusion 1385.3.6 Filament Winding Process 1395.3.7 Reaction Injection Molding 1405.3.8 Rotational Molding 140

5.4 Manufacturing Techniques of Nanocomposites 1415.4.1 Solution Intercalation 1415.4.2 In Situ Intercalative Polymerization Method 1425.4.3 Melt Intercalation or Melt Blending Method 143

5.5 Manufacturing Techniques of Polymer Gels 1435.5.1 Microgels 1435.5.2 Aerogels 1455.5.3 Xerogels 1455.5.4 Nanostructured Gels 1465.5.5 Topological Networks 1465.5.6 Hydrogels 148

5.6 Manufacturing Techniques of Interpenetrating Polymer Networks (IPNs) 1495.6.1 Full IPNs 1505.6.2 Sequential IPNs 1515.6.3 Simultaneous Interpenetrating Networks (SINs) 1525.6.4 Latex IPNs 1535.6.5 Thermoplastic IPNs 1545.6.6 Semi-IPNs 1545.6.7 Pseudo-IPNs 156

5.7 Conclusion and Future Outlook 156References 157

6 Macro, Micro and Nanostructured Morphologies of Multiphase Polymer Systems 161Han-Xiong Huang

6.1 Introduction 1616.1.1 Polymer Blends 1616.1.2 Polymer and Its Blend Nanocomposites 162

6.2 Morphology Development Mechanisms of Multiphase Polymer Systems During Processing 1646.2.1 Initial Morphology Development in Polymer Blending 1646.2.2 Deformation and Breakup of Droplet 168



viii Contents

6.2.3 Coalescence of Droplet 1746.2.4 Intercalated, Exfoliated, and Dispersed Mechanism of Organoclay During

Melt Mixing 1786.3 Material-Relevant Factors Affecting the Morphology 183

6.3.1 Viscosity of Components 1836.3.2 Elasticity of Components 1876.3.3 Interfacial Tension 1926.3.4 Compatibilization 1976.3.5 Composition 2086.3.6 Nanoparticles 212

6.4 Processing-Relevant Factors Affecting the Morphology 2186.4.1 Flow Field Types 2186.4.2 Chaotic Mixing 2216.4.3 Mixing Sequence 2276.4.4 Processing Parameters 230Nomenclature 231Acknowledgements 234References 235

7 Mechanical and Viscoelastic Characterization of Multiphase Polymer Systems 251Poornima Vijayan P., Siby Varghese and Sabu Thomas

7.1 Introduction 2517.2 Polymer Blends 253

7.2.1 Ultimate Mechanical Properties and Modeling 2537.2.2 Dynamic Mechanical Properties 2717.2.3 Impact Properties 2767.2.4 Nanostructured Polymer Blends 279

7.3 Interpenetrating Polymer Networks (IPNs) 2827.3.1 Modeling of Mechanical Properties of IPNs 287

7.4 Polymer Gels 2907.5 Polymer Composites 293

7.5.1 Mechanical Properties of Polymer Macrocomposites 2957.5.2 Mechanical Properties of Polymer Microcomposites 2987.5.3 Mechanical Properties of Polymer Nanocomposites 2987.5.4 Mechanical Modeling of Polymer Nanocomposites 304

7.6 Conclusion, Future Trends and Challenges 307References 307

8 Rheology and Viscoelasticity of Multiphase Polymer Systems: Blends andBlock Copolymers 311Jean-Charles Majeste and Antonio Santamarıa

8.1 Introduction 3118.2 Morphology of Polymer Blends 313

8.2.1 Morphology Characterization 3138.2.2 Effect of Rheological Parameters on Morphology 315



Contents ix

8.3 Microrheology of Droplet Deformation 3188.3.1 Breakup 3188.3.2 Coalescence 321

8.4 Rheology of Polymer Blends 3228.4.1 Specificity of Blend Rheology 3228.4.2 Blending Laws and Viscoelasticity Models 3268.4.3 Low Frequency Viscoelastic Behavior of Polymer Blends 335

8.5 Microphase Separated Block Copolymers 3398.5.1 Ordered State and Morphologies in Block Copolymers: The Case of SEBS Triblock 339

8.6 Dynamic Viscoelastic Results of SEBS Copolymers 3408.6.1 Low and Intermediate Frequency Viscoelastic Behavior 3408.6.2 Thermorheological Complexity 3418.6.3 Specific Mechanical Relaxation at Low Frequencies 343

8.7 Flow-induced Morphological Changes 3458.7.1 Order–order Transition and Flow Alignment in Block Copolymers 3458.7.2 Flow Alignment in a SEBS Copolymer 345

8.8 Capillary Extrusion Rheometry Results of Block Copolymers 3478.8.1 General Results of Styrenic Block Copolymers 3478.8.2 Viscosity and Flow Instabilities in SEBS Copolymers 350

8.9 Summary 354References 354

9 Thermal Analysis of Multiphase Polymer Systems 359Gyorgy J. Marosi, Alfred Menyhard, Geza Regdon Jr. and Jozsef Varga

9.1 Introduction 3599.2 Thermo-optical Microscopy 3609.3 Differential Scanning Calorimetry 3659.4 Temperature Modulated Differential Scanning Calorimetry 3739.5 Micro- and Nanothermal Analysis 3769.6 Thermal Gravimetric Analysis and Evolved Gas Analysis 3789.7 Conclusions 380

References 381

10 Thermophysical Properties of Multiphase Polymer Systems 387Abderrahim Boudenne, Laurent Ibos and Yves Candau

10.1 Introduction 38710.2 Thermophysical Properties: Short Definitions 38810.3 Measurement Techniques 389

10.3.1 Methods for the Measurement of One Property 38910.3.2 Methods for the Simultaneous Measurement of Several Parameters 393

10.4 Thermophysical Properties of Polymers and Composite Systems 39410.4.1 Neat Polymers (Unfilled Systems) 39410.4.2 Thermophysical Behavior of Composites 395

10.5 Summary 419References 420



x Contents

11 Electrically Conductive Polymeric Composites and Nanocomposites 425Igor Krupa, Jan Prokes, Ivo Krivka and Zdeno Spitalsky

11.1 Introduction 42511.2 Theory 426

11.2.1 Percolation Models 42711.3 Electrically Conductive Fillers 432

11.3.1 Carbon Black 43211.3.2 Metallic Fillers 43511.3.3 Metallized Fillers 43811.3.4 Graphite 43811.3.5 Carbon Nanotubes (CNT) 44311.3.6 Conducting Polymers 44911.3.7 Fillers Coated by Conducting Polymers 451

11.4 Effect of Processing Conditions on the Electrical Behavior of Composites 45211.4.1 Blending of Polymeric Composites 45211.4.2 Effects of the Secondary Processing Steps on Conductivity 45311.4.3 Effect of Polymer Characteristics on the Electrical Conductivity of Composites 45411.4.4 Crystallinity Effect 45411.4.5 Effect of Polymer–Filler Interaction 45511.4.6 Multiphase Morphology of Polymers and Its Influence on the Conductivity

of Composites: Multipercolation Effect 45611.5 Applications 457

11.5.1 EMI 45711.5.2 ESD 45711.5.3 Electrically Conductive Adhesives 45811.5.4 Conductive Rubbers 45811.5.5 Semi-Conductive Cable Compounds 45811.5.6 Fuel Cells 458

11.6 Resistance Measurements 45811.6.1 Two-Probes Method 45911.6.2 Four-Probes Method 46011.6.3 Van der Pauw Method 46511.6.4 Spreading Resistance of the Contacts 46811.6.5 Contact Resistance 470References 472

VOLUME 2

12 Dielectric Spectroscopy and Thermally Stimulated Depolarization Current Analysisof Multiphase Polymer Systems 479Polycarpos Pissis, Apostolos Kyritsis and Daniel Fragiadakis

12.1 Introduction 47912.2 Dielectric Techniques 482

12.2.1 Introduction 48212.2.2 Broadband Dielectric Spectroscopy (DS) 48312.2.3 Thermally Stimulated Depolarization Current (TSDC) Techniques 485



Contents xi

12.3 Copolymers and Interpenetrating Polymer Networks Based on Poly(alkyl acrylate)s andPoly(alkyl methacrylate)s (Mixing and Phase Separation) 48612.3.1 Introduction 48612.3.2 Poly(butyl acrylate)-Poly(butyl methacrylate) Sequential Interpenetrating

Polymer Networks 48812.3.3 Poly(butyl acrylate)-Poly(methyl methacrylate) Interpenetrating Polymer

Networks and Copolymers 49312.3.4 Poly(ethyl methacrylate)-Poly(hydroxyethyl acrylate) Copolymers 49612.3.5 Concluding Remarks 498

12.4 Rubber/Silica Nanocomposites (Interfacial Phenomena) 49912.4.1 Introduction 49912.4.2 TSDC Studies 50012.4.3 Broadband DS Studies 50312.4.4 Concluding Remarks 506

12.5 Polymer Nanocomposites with Conductive Carbon Inclusions (Percolation Phenomena) 50712.5.1 Introduction 50712.5.2 Analysis of DS Data in Terms of the Dielectric Function 50712.5.3 Analysis of DS Data in Terms of ac Conductivity 51012.5.4 Concluding Remarks 512


13 Solid-State NMR Spectroscopy of Multiphase Polymer Systems 519Antonio Martınez-Richa and Regan L. Silvestri

13.1 Introduction to NMR 52013.2 Phases in Polymers: Polymer Conformation 52213.3 High Resolution 13C NMR Spectroscopy of Solid Polymers 525

13.3.1 Chemical Shift 52513.3.2 Polyolefines 52613.3.3 Polyesters 52613.3.4 Carbohydrates 53013.3.5 Conducting Polymers 53013.3.6 Polymer Blends 53113.3.7 Interactions Between Polymers and Low-molecular Weight Compounds 53513.3.8 Miscellaneous Polymers 536

13.4 Additional Nuclei 53613.5 NMR Relaxation 538

13.5.1 NMR Relaxation in the Study of Polymer Blends 53913.5.2 NMR Relaxation in the Study of Copolymers 54213.5.3 NMR Relaxation in the Study of Polymer Composites 54313.5.4 NMR Relaxation in the Study of Polymers for Drug Delivery 543

13.6 Spin Diffusion 54413.7 Concluding Remarks 546

References 546



xii Contents

14 ESR Spectroscopy of Multiphase Polymer Systems 551Srecko Valic, Mladen Andreis and Damir Klepac

14.1 Introduction 55114.2 Theoretical Background 55514.3 Copolymers 56014.4 Grafted Polymers 56914.5 Blends 56914.6 Crosslinked Polymers 57114.7 Semi-Interpenetrating Networks (SIPNs) 57114.8 Composites 57314.9 Nanocomposites 57514.10 Other Polymer Multiphase Systems 57614.11 Conclusion 578

References 579

15 XPS Studies of Multiphase Polymer Systems 585Mohamed M. Chehimi, Fatma Djouani and Karim Benzarti

15.1 Introduction 58515.2 Basic Principles of X-ray Photoelectron Spectroscopy 586

15.2.1 Photoionization 58615.2.2 Surface Specificity of XPS 58715.2.3 Spectral Examination and Analysis 58715.2.4 Quantification 59215.2.5 Determination of Overlayer Thickness 59215.2.6 Instrumentation 597

15.3 Applications of XPS to Polymeric Materials 59915.3.1 Polymer Grafts 60015.3.2 Colloidal Particles 60515.3.3 Epoxy Adhesives 60915.3.4 Conductive Polymers 61315.3.5 Polymer Blends 61915.3.6 Composites 62415.3.7 Interpenetrating Polymer Networks 62715.3.8 Random and Block Copolymers 628

15.4 Conclusion 629Glossary 630References 631

16 Light Scattering Studies of Multiphase Polymer Systems 639Yajiang Huang, Xia Liao, Qi Yang and Guangxian Li

16.1 Introduction 63916.2 Light Scattering Technique 640

16.2.1 Scattering from Multiphase Polymer Systems 64016.2.2 Experiment 64216.2.3 Intensity Calibration 645



Contents xiii

16.3 Phase Behavior of Multiphase Polymer Systems Studied by SALS 64616.3.1 Thermodynamics 64616.3.2 Phase Separation Dynamics 64716.3.3 Reaction-induced Phase Separation 64916.3.4 Phase Behavior of Polymer Blends Under Shear Flow 65116.3.5 Multi-scale Approaches in Studying the Phase Behavior of Polymer Blends 655

16.4 On-line Morphological Characterization of Polymer Blends 65616.5 Light Scattering Characterization of Other Multiphase Polymer Systems 658

16.5.1 Gelation 65816.5.2 Crystallization 660References 663

17 X-ray Scattering Studies on Multiphasic Polymer Systems 669Z. Z. Denchev and J. C Viana

17.1 Introduction 66917.2 Theoretical Background 671

17.2.1 Microfibrillar Reinforced Composites (MCF): Definition and Preparation 67117.2.2 Clay-containing Polymer Nanocomposites 67217.2.3 The use of WAXS and SAXS in Characterization of Polymers 673

17.3 Studies on Multiphase Polymer Systems 67917.3.1 Polyamide 6/montmorillonite Nanocomposites 67917.3.2 Microfibrillar Composites (MFC) 68117.3.3 Immiscible Polymer Blends 69317.3.4 Non-conventional Molding of PP Nanocomposites 69517.3.5 Stretching of Nanoclay PET Nanocomposite 697

17.4 Concluding Remarks 699Acknowledgements 700References 700

18 Characterization of Multiphase Polymer Systems by Neutron Scattering 705Max Wolff

18.1 Introduction 70518.2 Method of Neutron Scattering 705

18.2.1 Scattering Experiment 70618.2.2 Born Approximation 70818.2.3 Elastic and Quasielastic Scattering 71018.2.4 Scattering at Small Momentum Transfer 713

18.3 Experimental Techniques 71618.3.1 Production and Detection of Neutrons 71618.3.2 Instrumentation 71918.3.3 Grazing Incidence Small Angle Scattering 72418.3.4 Comparison of SANS and GISANS for Crystalline Systems 726

18.4 Recent Experimental Results 72918.4.1 Polymer Dynamics 72918.4.2 Contrast Variation 73018.4.3 Effect of Shear 73018.4.4 Near Surface Crystallization of Micelles 733



xiv Contents


19 Gas Diffusion in Multiphase Polymer Systems 749Eliane Espuche

19.1 Introduction 74919.2 Gas Transport Mechanisms in Dense Polymer Films: Definition of

the Transport Parameters 74919.3 Multiphase Polymer Systems for Improved Barrier Properties 752

19.3.1 Introduction 75219.3.2 Dispersion of Impermeable Spheres Within a Polymer Matrix 75219.3.3 Influence of the Shape of the Dispersed Impermeable Phase: Interest of

Oriented Polymer Blends and of the Nanocomposite Approach 75519.3.4 Nanocomposites Based on Lamellar Nanofillers 75719.3.5 Multilayers 76319.3.6 Active Films 76419.3.7 Comparison of the Different Ways Used to Improve Barrier Properties 766

19.4 Multiphase Polymer-based Systems for Improved Selectivity 76719.4.1 Introduction 76719.4.2 Organic–inorganic Materials for Gas Separation Membranes 767

19.5 Conclusion 769References 770

20 Nondestructive Testing of Composite Materials 777Zhongyi Zhang and Mel Richardson

20.1 Introduction 77720.2 Failure Mechanisms in Polymer Composites 779

20.2.1 Matrix Deformation 77920.2.2 Fiber–matrix Debonding 77920.2.3 Matrix Cracking 77920.2.4 Delamination 78020.2.5 Fiber Breakage 78020.2.6 Combination of Different Failure Modes 780

20.3 Visual Inspection 78120.4 Acoustic Emission 78220.5 Ultrasonic Scanning 78320.6 Radiography 78520.7 Thermography 78620.8 Laser Interferometry 78820.9 Electronic Shearography 79020.10 Optical Deformation and Strain Measurement System 79120.11 Summary 795

References 795



Contents xv

21 Ageing and Degradation of Multiphase Polymer Systems 797Xavier Colin, Gilbert Teyssedre and Magali Fois

21.1 Introduction 79721.1.1 Issues Associated With Material Ageing 79721.1.2 Classification of Ageing Types 798

21.2 Physical Ageing 79921.2.1 Ageing Induced by Structural Reorganization 80021.2.2 Ageing Induced by Solvent Absorption 80221.2.3 Ageing Induced by Additive Migration 803

21.3 Chemical Ageing 80621.3.1 General Aspects 80621.3.2 Mechanistic Schemes 816

21.4 Impact of Multiphase Structure on Ageing Processes 82921.4.1 Structural Reorganization 82921.4.2 Diffusion Controlled Processes 831

21.5 Practical Impact of Physical Ageing on Use Properties 83221.5.1 Water-Induced Mechanical Damages in Composites 83221.5.2 Ageing of Electrical Insulations 833

21.6 Concluding Remarks 839References 840

22 Fire Retardancy of Multiphase Polymer Systems 843Michel Ferriol, Fouad Laoutid and Jose-Marie Lopez Cuesta

22.1 Introduction 84322.2 Combustion and Flame Retardancy of Polymers 844

22.2.1 Combustion of Polymers 84422.2.2 Flame Retardancy 845

22.3 Laboratory Fire Testing 84622.3.1 Limiting Oxygen Index (LOI) 84622.3.2 Epiradiator or ‘Drop Test’ 84722.3.3 UL 94 84822.3.4 Cone Calorimeter 848

22.4 Flame Retardant Additives 84922.4.1 Hydrated Fillers 84922.4.2 Halogenated Flame Retardants 85022.4.3 Phosphorus-based Flame Retardants 85022.4.4 Nanometric Particles 852

22.5 Synergistic Effects of Fillers with Flame Retardant Additives 85422.5.1 Definition of Synergistic Effects in Flame Retardant Systems 85422.5.2 Micronic Fillers and Flame Retardants 85422.5.3 Nanometric Fillers and Flame Retardants 856




xvi Contents

23 Applications of Selected Multiphase Systems 865Igor Novak, Volkan Cecen and Vladimır Pollak

23.1 Introduction 86523.2 Construction Applications 866

23.2.1 Automotive Applications 86623.2.2 Marine Applications 87123.2.3 Other Applications 875

23.3 Aeronautics and Spacecraft Applications 88223.3.1 Aeronautics Applications 88223.3.2 Spacecraft Applications 891

23.4 Human Medicine Applications 89523.4.1 Musculoskeletal and Bone Applications 89523.4.2 Dentistry Applications 905

23.5 Electrical and Electronic Applications 90723.6 Conclusion 912

References 913

24 Waste Management, Recycling and Regeneration of Filled Polymers 921Jose-Marie Lopez Cuesta, Didier Perrin, and Rodolphe Sonnier

24.1 Introduction 92124.2 Identification and Sorting 92224.3 Separation of Components 924

24.3.1 Mechanical Separation 92424.3.2 Dissolution of Resin 924

24.4 Feedstock Recycling 92824.5 Thermal Processes 92924.6 Mechanical Recycling of Filled Thermoplastics 932

24.6.1 Degradation During Reprocessing of Filled Thermoplastics and Influenceof Interfacial Agents 932

24.6.2 Properties of Recycled Filled or Reinforced Thermoplastics 93524.6.3 Recycling of Polymer Nanocomposites 940

24.7 Waste Management of Glass Fiber-reinforced Thermoset Plastics 94424.7.1 Waste Management and International Context 94424.7.2 Feedstock Recycling by Pyrolysis 94524.7.3 Solvolysis or Chemical Recycling 94624.7.4 Mechanical Recycling of Glass-reinforced Thermoset Composites 947

24.8 Conclusion 951References 952

25 Nanoparticle Reinforcement of Elastomers and Some Other Types of Polymers 959James E. Mark

25.1 Introduction 95925.2 Fillers in Elastomers 960

25.2.1 Generation of Approximately Spherical Particles 96025.2.2 Glassy Particles Deformable into Ellipsoidal Shapes 96325.2.3 Layered Fillers 964



Contents xvii

25.2.4 Magnetic Particles 96525.2.5 Polyhedral Oligomeric Silsesquioxanes (POSS) 96525.2.6 Nanotubes 96625.2.7 Dual Fillers 96625.2.8 Porous Fillers 96725.2.9 Fillers with Controlled Interfaces 96725.2.10 Silicification and Biosilicification 96725.2.11 Theory and Simulations on Filler Reinforcement 968

25.3 Nanoparticles in Glassy Polymers 97025.4 Nanoparticles in Partially-Crystalline Polymers 97025.5 Nanoparticles in Naturally-Occurring Polymers 97125.6 Nanoparticles in Relatively-Rigid Polymers 97225.7 Nanoparticles in Thermoset Polymers 97225.8 Conclusions 97325.9 Acknowledgements 973

References 973

Index 981



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JWST068-LOC JWST068-Boudenne July 8, 2011 12:3 Printer: Yet to come

List of Contributors

Mladen Andreis, Rudjer Boskovic Institute, Zagreb, Croatia

Karim Benzarti, Laboratoire Central des Ponts et Chaussees, Paris, France

Abderrahim Boudenne, Universite Paris-Est, CERTES EA 3481 – Centre d’Etude et de Recherche enThermique, Environnement et Systemes, Creteil, France

Yves Candau, Universite Paris-Est, CERTES EA 3481 – Centre d’Etude et de Recherche en Thermique,Environnement et Systemes, Creteil, France

Volkan Cecen, Department of Mechanical Engineering, Dokuz Eylul University, Bornova, Izmir, Turkey

Mohamed M. Chehim, ITODYS, Univeresity Paris Diderot and CNRS, Paris, France

Xavier Colin, PIMM, Arts et Metiers Paris Tech, Paris, France

Jose-Marie Lopez Cuesta, CMGD, Ecole des Mines d’Ales, Ales, France

Z.Z. Denchev, Institute for Polymers and Composites, University of Minho, Minho, Portugal

Fatma Djouan, ITODYS, University Paris Diderot and CNRS, Paris, France

Elian Espuche, Ingenierie des Materiaux Polymeres, UMR CNRS 5223, IMP@UCB, Universite de Lyon,Universite Lyon 1, France

Michel Ferriol, LMOPS, UniversitePaul Verlaine Metz, Sain-Avold, France

Magali Fois, Universite Paris-Est, CERTES EA 3481 – Centre d’Etude et de Recherche en Thermique,Environnement et Systemes, Creteil, France

Daniel Fragiadakis, Naval Research Laboratory, Washington, DC, USA

Soney C. George, Department of Basic Science, Amal Jyothi College of Engineering, Kerala, India

Han-Xiong Huang, Laboratory for Micro Molding and Polymer Rheology, South China University of Tech-nology, Guangzhou, China

Yajiang Huang, College of Polymer Science and Engineering, State Key Laboratory of Polymer MaterialsEngineering, Sichuan University, Sichuan, China

Esmaiel Jabbari, Department of Chemical Engineering, University of South Carolina, Columbia, USA

Laurent Ibos, Universite Paris-Est, CERTES EA 3481 – Centre d’Etude et de Recherche en Thermique,Environnement et Systemes, Creteil, France

Damir Klepac, School of Medicine, University of Rijeka, Rijeka, Croatia

Ivo Krivka, Department of Macromolecular Physics, Faculty of Mathematics and Physics, Charles Universityin Prague, Prague, Czech Republic

xix



xx List of Contributors

Igor Krupa, Polymer Institute, Slovak Academy of Sciences, Dubravska, Bratislava, Slovakia

Apostolos Kyritsis, National Technical University of Athens, Athens, Greece

Fouad Laoutid, Materia Nova Asbl, Mons, Belgium

Guangxian Li, College of Polymer Science and Engineering, State Key Laboratory of Polymer MaterialsEngineering, Sichuan University, Sichuan, China

Xia Liao, College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engi-neering, Sichuan University, Sichuan, China

Jean-Charles Majeste, Laboratoire de Rheologie des Matieres Plastiques, CNRS, St Etienne, France

James E. Mark, Department of Chemistry and the Polymer Research Center, The University of Cincinnati,Cincinnati, Ohio, USA

Gyorgy J. Marosi, Budapest University of Technology and Economics, Budapest, Hungary

Antonio Martınez-Richa, Departamento de Quimica, Universidad de Guanajuato, Guanajuato, Mexico

Alfred Menyhard, Jr., Budapest University of Technology and Economics, Budapest, Hungary

Igor Novak, Polymer Institute, Slovak Academy of Sciences, Bratislava, Slovakia

Didier Perrin, CMGD, Ecole des Mines d’Ales, Ales, France

Polycarpos Pissis, National Technical University of Athens, Athens, Greece

Vladimir Pollak, Polymer Institute, Slovak Academy of Sciences, Bratislava, Slovakia

Jan Prokes, Department of Macromolecular Physics, Faculty of Mathematics and Physics, Charles Universityin Prague, Prague, Czech Republic

Geza Regdon, Jr., University of Szeged, Szeged, Hungary

Mel Richardson, Department of Mechanical and Design Engineering, University of Portsmouth, Portsmouth,UK

Antonio Santamarıa, Polymer Science and Technology Department, Faculty of Chemistry, University of theBasque Country, San Sebastian, Spain

Alireza S. Sarvestani, Department of Mechanical Engineering, University of Maine, Orono, Maine, USA

Friederike Schmid, Institute of Physics, Johannes-Gutenberg Universitat Mainz, Germany

Regan L. Silvestri, Department of Chemistry, Baldwin-Wallace College, Berea, Ohio, USA

Rodolphe Sonnier, CMGD, Ecole des Mines d’Ales, Ales, France

Zdeno Spitalsky, Polymer Institute, Slovak Academy of Sciences, Dubravska, Bratislava, Slovakia

Gilbert Teyssedre, Laplace Universite Paul Sabatier, Toulouse, France

Sabu Thomas, Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kerala, India

Srecko Valic, University of Rijeka, Rijeka, Croatia, and Rudjer Boskovic Institute, Zagreb, Croatia

Jozsef Varga, Budapest University of Technology and Economics, Budapest, Hungary



List of Contributors xxi

Siby Varghese, Rubber Research Institute of India, Kottayam, Kerala, India

J.C. Viana, Institute for Polymers and Composites, University of Minho, Minho, Portugal

Poornima Vijayan P, School of Chemical Sciences, Mahatma Gandhi University, Kerala, India

Max Wolff, Department of Phyics, Uppsala University, Uppsala, Sweden

Qi Yang, College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engi-neering, Sichuan University, Sichuan, China

Zhongyi Zhang, Advanced Polymer and Composites (APC) Research Group, Department of Mechanical andDesign Engineering, University of Portsmouth, Portsmouth, UK



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JWST068-Foreword JWST068-Boudenne July 8, 2011 12:8 Printer: Yet to come

Foreword

Multiphase polymer systems have been the focus of recent research and have become an important issue fromboth the industrial and fundamental points of view. The scientific literature devoted to multiphase polymersystems is large and growing as it covers a wide range of materials such as composites, blends, alloys, gelsand Interpenetrating Polymer Networks.

During the last two decades, major opportunities have appeared due to the possibility of tuning the differentrelevant length scales with the promise to produce a new generation of materials displaying enhanced physical,mechanical, thermal, electrical, magnetic, and optical properties. In spite of these intensive investigations,there are still many unresolved problems in this field. One of the main issues is the influence of the shape, sizeand dispersion of the particles in the polymer matrix on the macroscopic behavior of the resulting material.There are many factors which control the dispersion, and one of them is the interaction between the particlesand the polymer phase. Describing the interactions between the various components, the physical attributes ofpolymers and particles, the physical, thermophysical and interfacial properties in a comprehensive universalscheme remains a challenge. This approach requires collecting a large number of experimental data that canbe obtained only by using various and complementary experimental techniques.

Investigations in this field cover different topics, such as polymer blends and composites and nanocom-posites reinforcement, barrier properties, flame resistance, electro-optical properties, etc. Part of these multi-phase polymer materials belong to the so-called smart materials which are materials that have one or moreproperties that can be significantly changed in a controlled fashion by external stimuli. The key to the suc-cess of these smart materials hinges on the ability to exploit the potential of nano-structuring in the finalproduct.

This book discusses many of the recent advances that have been made in the field of morphological,interfacial, physical, rheological and thermophysical properties of multiphase polymer systems. Its content isoriginal in the sense that it pays particular attention to the different length scales (macro, micro and nano) whichare necessary for a full understanding of the structure–property relationships of multiphase polymer systems.It gives a good survey of the manufacturing and processing techniques needed to produce these materials.A complete state-of-the-art is given of all the currently available techniques for the characterization of thesemultiphase systems over a wide range of time and space scales. Theoretical prediction of the properties ofmultiphase polymer systems is also very important, not only to analyze and optimize material performance, butalso to design new material. This book gives a critical summary of the existing major analytical and numericalapproaches dealing with material property modeling. Most of the applications of these smart materials arealso reviewed which shows clearly their important impact on a wide range of the new technologies which arecurrently used in our daily life. Finally, the ageing, degradation and recycling of multiphase polymer systemsis not forgotten and some routes are proposed to avoid environmental contamination.

The 52 contributors of this book are all leading researchers in their respective fields, and I warmlycongratulate the editors Abderrahim Boudenne, Yves Candau, Laurent Ibos and Sabu Thomas for bringingthem together to produce this original and important book dealing on multiphase polymer systems.

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JWST068-Foreword JWST068-Boudenne July 8, 2011 12:8 Printer: Yet to come

xxiv Foreword

I am quite convinced that this book will serve as a reference and guide for those who work in this area orwish to learn about these promising new materials.

Dominique Durand

Laboratoire de Physicochimie Macromoleculaire, Equipe de Recherche Associee au Centre National de laRecherche Scientifique, Faculte des Sciences, Route de Laval, le Mans, France




i



ii




Volume 2

Editors

ABDERRAHIM BOUDENNE, LAURENT IBOS, YVES CANDAUUniversite Paris-Est, Centre d’Etude et de Recherche en Thermique,

Environnement et Systemes, Creteil, France

AND

SABU THOMASCentre for Nanoscience and Nanotechnology, Mahatma Gandhi University,

Kottayam, Kerala, India

A John Wiley & Sons, Ltd., Publication

iii



This edition first published 2011C© 2011 John Wiley and Sons Ltd

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All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic,mechanical, photocopying, recording or otherwise, except as permitted by the UK Copyright, Designs and Patents Act 1988, without the prior permissionof the publisher.

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Designations used by companies to distinguish their products are often claimed as trademarks. All brand names and product names used in this book aretrade names, service marks, trademarks or registered trademarks of their respective owners. The publisher is not associated with any product or vendormentioned in this book. This publication is designed to provide accurate and authoritative information in regard to the subject matter covered. It is sold onthe understanding that the publisher is not engaged in rendering professional services. If professional advice or other expert assistance is required, theservices of a competent professional should be sought.

The publisher and the author make no representations or warranties with respect to the accuracy or completeness of the contents of this work andspecifically disclaim all warranties, including without limitation any implied warranties of fitness for a particular purpose. This work is sold with theunderstanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for everysituation. In view of ongoing research, equipment modifications, changes in governmental regulations, and the constant flow of information relating to theuse of experimental reagents, equipment, and devices, the reader is urged to review and evaluate the information provided in the package insert orinstructions for each chemical, piece of equipment, reagent, or device for, among other things, any changes in the instructions or indication of usage andfor added warnings and precautions. The fact that an organization or Website is referred to in this work as a citation and/or a potential source of furtherinformation does not mean that the author or the publisher endorses the information the organization or Website may provide or recommendations it maymake. Further, readers should be aware that Internet Websites listed in this work may have changed or disappeared between when this work was writtenand when it is read. No warranty may be created or extended by any promotional statements for this work. Neither the publisher nor the author shall beliable for any damages arising herefrom.

Library of Congress Cataloging-in-Publication Data

Handbook of multiphase polymer systems / editors, Abderrahim Boudenne ... [et al.].p. cm.

Includes bibliographical references and index.ISBN 978-0-470-71420-1 (cloth) – ISBN 978-1-119-97203-7 (ePDF) – ISBN 978-1-119-97202-0 (oBook)

1. Polymeric composites. I. Boudenne, Abderrahim.TA418.9.C6H3426 2012547′.7–dc22

2011011524

A catalogue record for this book is available from the British Library.

Print ISBN: 9780470714201ePDF ISBN: 9781119972037oBook ISBN: 9781119972020ePub ISBN: 9780470714201Mobi ISBN: 9781119972891

Typeset in 10/12pt Times by Aptara Inc., New Delhi, India

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