Edited by Avraam I. Isayev. Encyclopedia of Polymer Blends

Transcription

1 Edited by Avraam I. Isayev Encyclopedia of Polymer Blends

2 Related Titles Isayev, Avraam I. (ed.) Encyclopedia of Polymer Blends Volume 1: Fundamentals 2010 PRINT ISBN: Isayev, Avraam I. (ed.) Encyclopedia of Polymer Blends Volume 2: Processing 2011 PRINT ISBN: Elias, H. Macromolecules Volume 1: Chemical Structures and Syntheses 2005 Print ISBN: Elias, H. Macromolecules Volume 2: Industrial Polymers and Syntheses 2007 Print ISBN: Elias, H. Macromolecules Volume 3: Physical Structures and Properties 2007 Print ISBN: Elias, H. Macromolecules Volume 4: Applications of Polymers 2008 Print ISBN:

3 Edited by Avraam I. Isayev Encyclopedia of Polymer Blends Volume 3: Structure

4 The Editor Prof. Avraam I. Isayev The University of Akron Department of Polymer Engineering 250 South Forge Street Akron, OH USA All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library. Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at < Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, Weinheim, Germany All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form by photoprinting, microfilm, or any other means nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law. Print ISBN: epdf ISBN: epub ISBN: Mobi ISBN: obook ISBN: Cover Design Adam-Design, Weinheim, Germany Typesetting Thomson Digital, Noida, India Printed on acid-free paper

5 V Contents Preface XIII List of Contributors XVII 1 Glass-Transition Phenomena in Polymer Blends 1 Ioannis M. Kalogeras 1.1 Introduction Phenomenology and Theories of the Glass Transition Thermodynamic Phase Transitions Structural, Kinetic, and Thermodynamic Aspects Relaxation Dynamics and Fragility Relaxations in Glass-Forming Materials The Concept of Fragility Theoretical Approaches to the Glass Transition General Overview Energy Landscapes and Many-Molecule Relaxation Dynamics Approaches with an Underlying Avoided Dynamical Transition Models Showing a Thermodynamic (or Static) Critical Point Percolative Phenomena in Glass Formation Manipulating the Glass Transition Effects of Chemical Structure Externally Controlled Processes or Treatments Pressure Effects Crystallization Effects Plasticizer Effects Filler Effects Cross-linker Effects Geometric Confinement Effects Experimental Means of Determination Calorimetric Techniques Thermomechanical Analysis (TMA) Dynamic Mechanical Analysis (DMA) 60

6 VI Contents Dielectric Analysis (DEA) Blend Morphology and Glass Transitions Miscibility and Phase Boundaries in Polymer Blends State of Dispersion and the Glass Transition Analyzing Glass Transitions in Single-Phase Systems Shape Characteristics and Strength of the Transition Description and Interpretation of T g versus Composition Behaviors Specific Volumes or Flexible Bonds Additivity Models Additivity of Free Volumes Predictions Based on Thermodynamic Considerations Empirical Concentration Power T g (w) Equations and Systems Complexity Dynamically Heterogeneous Miscible Blends Case Studies Miscibility Achievement via Chemical Modification Microstructure of the Amorphous Phase in Semicrystalline Blends Ternary Polymer Blends: Phase Behavior and Glass Transitions Concluding Remarks 115 Abbreviations 117 Symbols 119 Greek Symbols 121 References Crystallization and Melting Behavior in Polymer Blends 135 Saleh A. Jabarin, Kazem Majdzadeh-Ardakani, and Elizabeth A. Lofgren 2.1 Introduction Miscibility of Polymer Blends Miscible Blends Crystalline/Amorphous Polymer Blends Glass Transition and Melting Behavior Melting Point Depression Crystallization Spherulite Growth Rate of the Crystallizable Component Overall Crystallization Kinetics Isothermal Kinetics Nonisothermal Kinetics Crystalline/Crystalline Polymer Blends Immiscible Blends Blends with an Amorphous Dispersed Phase in a Crystallizable Matrix Nucleation of the Crystalline Phase Spherulite Growth Rate of the Crystalline Phase Overall Crystallization Kinetics Glass Transition of the Amorphous Component and Melting Behavior of the Crystalline Matrix in Immiscible Polymer Blends 163

7 Contents VII Blends with a Crystallizable Dispersed Phase in an Amorphous Matrix Fractionated Crystallization Determination of the Number Density of Heterogeneities Effect of the Fillers on the Crystallization of Immiscible Polymer Blends Compatibilized Polymer Blends Addition of Blocks or Graft Copolymers Reactive Compatibilization Reactive Compatibilization in Bio-based Polymer Blends Crystallization of Compatibilized Blends Differences Between the Crystallization Behaviors of Polymer Blends and Copolymers The role of Transesterification on the Miscibility and Morphology of Polyester Blends Summary and Conclusions Nomenclature Abbreviations Notations Symbols Roman Letters Greek Letters 179 References Morphology and Structure of Crystalline/Crystalline Polymer Blends 191 Zhaobin Qiu and Shouke Yan 3.1 Introduction Systems with Small Melting Point Difference Preliminary Study on Morphology and Structure of PES/PEO Blends Effect of Blend Composition on the Formation of Interpenetrating Spherulites of PES/PEO Blends Effect of Crystallization Temperature on the Crystalline Morphologies of PES/PEO Blends Systems with Large Melting Point Difference Crystallization Behavior of the High-T m Component in Miscible Polymer Blends Crystallization Behavior of Low-T m Component in Miscible Polymer Blends Morphology and Structure of Blend Systems with Large Melting Point Difference Concluding Remarks 225 Acknowledgment 226 References 226

8 VIII Contents 4 Rubber Plastic Blends: Structure Property Relationship 229 Sudhin Datta 4.1 Introduction: Key Challenges Rubber Toughening of Thermoplastics Mechanism Morphology Failure Process Models for Rubber Toughening of Plastics Crazing Model Interparticle Distance Model Percolation Models Characterization of Rubber Plastic Blends Glass Transition Dynamic Mechanical Characterization Calorimetric Methods Dielectric Characterization Morphology/Microscopy Optical Microscopy Transmission Electron Microscopy Scanning Electron Microscopy Atomic Force Microscopy Scanning Tunneling Microscopy X-Ray Microscopy Scattering Methods: Light, X-Ray, and Neutron X-Ray Scattering Neutron Scattering Neutron Reflectivity Neutron Spin Echo Spectroscopy Nuclear Magnetic Resonance Spectroscopic Methods Infrared Spectroscopy UV Visible Spectroscopy Raman Spectroscopy Fluorescence Spectroscopy: Nonradiative Energy Transfer and Excimer Fluorescence X-Ray Photoelectron Spectroscopy and Secondary Ion Mass Spectroscopy Vapor Sorption and Solvent Probe Techniques Characterization of Interfacial Properties Experimental Rubber Plastic Blends Early Work Blends of Polyvinyl Chloride Blends of Polystyrene and Styrene Copolymers Blends of Polyamides Blends of Isotactic Polypropylene 269

9 Contents IX With Ethylene Propylene Copolymer Rubber With Ethylene Isotactic Propylene Copolymers With Higher α-olefin Rubber With Ethylene Butene-1 Copolymer With Ethylene Hexene-1 Copolymer With Ethylene Octene-1 Copolymer Tensile Properties Structure in Injection-Molded Specimens Impact Performance Poly(butene-1) as Semicrystalline Rubber Styrene Block Polymer Rubber Thermoplastic Vulcanizates Nonpolar Rubber with Nonpolar Thermoplastic EPDM Elastomer with ipp Thermoplastic Natural Rubber Elastomer with PE Thermoplastic Natural Rubber Elastomer with Polypropylene Thermoplastic Butyl Rubber Elastomer with Polypropylene Thermoplastic Polar Rubber with Nonpolar Plastic NBR Elastomer with ipp Thermoplastic Acrylate Rubber with ipp Thermoplastic Nonpolar Rubber with Polar Thermoplastic EPDM Rubber with PA6 Thermoplastic EPDM Rubber with PBT Thermoplastic EPDM Rubber with ipp + PA6 Thermoplastic Polar Rubber with Polar Thermoplastic Acrylate Elastomer with Polyester Thermoplastic Blends Made during Polymerization Gum Elastomers Diene Rubbers Ethylene-Based Elastomers Ethylene Copolymers Ionomers Emulsion Rubbers Core Shell Graft Polymers Block Polymers Butadiene Styrene Block Copolymers Conclusions 288 References Morphology of Rubber/Rubber Blends 299 Avraam I. Isayev and Tian Liang 5.1 Introduction Characterization Techniques for Rubber Blends Optical Microscopy 300

10 X Contents Transmission Electron Microscopy Scanning Electron Microscopy Atomic Force Microscopy Dynamic Testing Thermal Analysis Effect of Material Parameters and Processing on Structure and Morphology of Rubber Blends Distribution of Fillers and Cure Balance in Rubber Blends Distribution of Fillers in Rubber Blends Migration of Curatives in Rubber Blends Morphology and Properties of Different Rubber Blends Blends Containing NR Blends Containing BR Blends Containing SBR Blends Containing EPDM Blends Containing Butyl Rubber Blends Containing NBR Blends Containing CR Blends Containing Silicone Rubber Blends Containing Hydrogenated Nitrile Butadiene Rubber (HNBR) Conclusions 328 References Phase Morphology and Properties of Ternary Polymer Blends 335 V.N. Kuleznev and Yu. P. Miroshnikov 6.1 Introduction Miscibility of Polymers in Ternary Polymer Blends Formation of Phase Morphology Prediction of Phase Morphologies of Polymer Blends Binary Blends Ternary Polymer Blends Encapsulated Morphologies: Influence of Different Factors Blend Composition Kinetic Factors Morphological Types Multiple Percolated Structures Partial Wetting Morphology Ternary Blends with Separated Dispersed Phases Effects of Interaction between Dispersed Phases Ternary Systems with One Solid Phase Proof of the Mechanism of Phase Interaction Properties of Ternary Polymer Blends Conclusions and Future Development 393 References 395

11 Contents XI 7 Morphology and Structure of Polymer Blends Containing Nanofillers 401 Hossein Nazockdast 7.1 Introduction Type of Nanofiller Used in Polymer Nanocomposite Structure and Characteristic of Layered Silicate Surface Modification of Layered Silicates The Structure of Polymer-Silicate Nanocomposites Structure and Characteristic of Carbon Nanotube Surface Modification of Carbon Nanotube Structure and Characteristics of Silica Nanoparticles Nanostructural Characterization X-Ray Diffraction Transition Electron Microscopy (TEM) Differential Scanning Calorimetry The Linear Rheological Measurements Partially Miscible Polymer Blends Containing Nanoparticle The Effect of Nanoparticles on Phase Separation of Partially Miscible Polymer Blends The Effect of Silica Nanoparticles on Phase Separation of PMMA/Polyvinyl Acetate Effect of Nanosilica on Phase-separation Behavior of PMMA/SAN Blends Effect of Addition of Nanoparticles on Phase-separation Behavior of PS/PVME Immiscible Polymer Blends Containing Nanoparticle Introduction Parameters Determining Localization of Nanoparticles Thermodynamic Parameters (Wetting Parameters) Kinetic Parameters (Dynamic Processes) Effect of Feeding Sequence Effect of Viscosity Rheology of Immiscible Polymer Blends Containing Nanoparticle Polymer Blends Containing Nanosilica Polymer Blends Containing Nanoclay Polymer Blends Containing Carbon Nanotubes The Role of Nanoparticles on the Morphology Evolution of Nanofilled Polymer Blends Nanoparticle Migration (Dynamic and Transfer of Nanoparticles) The Compatibilizing Effect of Nanoparticles 464 References 473 Index 483

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13 XIII Preface Encyclopedia of polymer blends will include scientific publications in various areas of blends. Polymer blends are mixtures of two or more polymers and/or copolymers. Polymer blending is used to develop new materials with synergistic properties that are not achievable with individual components without having to synthesize and scale up new macromolecules. Along with a classical description of polymer blends, articles in the encyclopedia will describe recently proposed theories and concepts that may not be accepted yet but reflect future development. Each article provides current points of view on the subject matter. These up-to-date reviews are very helpful for understanding the present status of science and technology related to polymer blends. The encyclopedia will be the source of existing knowledge related to polymer blends and will consist of five volumes. Volume 1 describes the fundamentals including the basic principles of polymer blending, thermodynamics, miscible, immiscible, and compatible blends, kinetics, and composition and temperature dependence of phase separation. Volume 2 provides the principles, equipment, and machinery for polymer blend processing. Volume 3 deals with the structure of blended materials that governs their properties. Volume 4 describes various properties of polymer blends. Volume 5 discusses the blended materials and their industrial, automotive, aerospace, and other high technology applications. Individual articles in the encyclopedia describe the topics with historical perspective, the state-of-the-art science and technology and its future. This encyclopedia is intended for use by academicians, scientists, engineers, researchers, and graduate students working on polymers and their blends. Volume 3 is devoted to the structure of blended materials that governs their properties and consists of seven chapters. These chapters cover glass transition phenomena, crystallization and melting behavior, structure property relationship, morphology and structure of polymer blends, and blends containing various nanofillers. Existing theoretical approaches to describe morphology and structure of blends are extensively discussed. The importance of flow, rheology of components, and rheological aspects of blends is emphasized. These aspects are detailed below and build on each other. Chapter 1 addresses a number of topics, including general phenomenology, theories, and metrology of the glass transition of polymer blends. The theoretical

14 XIV Preface foundations and practical examples from the analysis of experimental data for miscible systems including binary polymer blends, oligomer/polymer mixtures, and copolymers are critically reviewed. The applicability ranges of important theoretical, semi-empirical, or purely phenomenological mixing rules used for describing the compositional dependence of the glass transition are explored. Examples demonstrating the physical meaning of model parameters are given. A number of case studies involving hydrogen-bonding binary polymer blends and ternary polymer systems are presented. The chapter ends by summarizing general rules that relate the results of glass-transition studies with structural characterizations and miscibility evaluations of polymer blends. Chapter 2 deals with crystallization and melting behavior of crystalline/ amorphous and crystalline/crystalline polymer blends that are strongly influenced by the miscibility and morphology of the polymers. The interspherulitic and intraspherulitic segregations are considered in the case of crystalline/ amorphous polymer blends. The crystallization and morphology of crystalline/ crystalline polymer blends related to differences in the melting points of each of component, thermodynamic, and kinetic factors during crystallization are discussed. The influence of the composition, rheological characteristics, the interfacial tension, and processing conditions on the superstructures of immiscible polymer blends is presented. Immiscible blends with a crystallizable matrix and an amorphous dispersed phase, and blends with an amorphous matrix and a crystallizable dispersed phase are discussed. The effect of the addition of a copolymer as a compatibilizer that decreases or increases the tendency for crystallization of polymer blends is considered. Reactive compatibilization of polymer blends and its influence on crystallization and morphology are discussed. In addition, the effect of the fillers on the crystallization of immiscible polymer blends is presented. Chapter 3 is devoted to the morphology and structure of crystalline/crystalline polymer blends with strong emphasis to the recent progress in this field. It focuses mainly on the influence of crystallization on the microphase separation and the effect of phase separation on the crystallization of the blending components. Special attention is given to the various possible crystalline morphologies and phase structures formed in different crystalline/crystalline polymer blends under controlled crystallization conditions. The mechanism of the formation of specific morphologies, such as interpenetrating spherulites, is discussed with elaborately selected model systems. Also, examples of specific polymer blends are presented along with their morphology and structure. Chapter 4 describes the physics and chemistry of rubber plastic blends and their structure property relationship. A greater attention is paid to understanding the interface and the role of the physical process in enabling and extending the interfacial effects of rubber plastic blends. Various models for the rubber toughening of plastics are described. Numerous techniques that are for the characterization of rubber plastic blends are provided. Many industrially important examples of many rubber plastic blends are given along with their structure and morphology.

15 Preface XV Chapter 5 deals with the current state of knowledge on the structure and morphology of rubber rubber blends. Characterization techniques suitable for the study of these blends are introduced. The effect of material parameters and processing conditions on the structure and morphology of rubber rubber blends is discussed along with the issues related to the filler distribution and curative migration in blends. Various blends containing different pairs of rubbers are presented. When dealing with specific rubber rubber blends, the characteristics of each rubber component in the blends, such as the crystallization behavior, curing state, and preference of filler distribution is considered, since all these factors influence the blend morphology and structure. Chapter 6 deals with the miscibility, phase morphology, and properties of ternary polymer blends. A number of interesting cases of miscibility and immiscibility in ternary blends are examined. It is stressed that a simple summation of the contributions of binary interactions to the free energy of mixing in ternary polymer blends is a simplification. The review is devoted to the prediction and formation of phase morphologies in immiscible binary and ternary polymer blends. The theory of spreading coefficients is analyzed in detail and the formation of all the possible morphological types is discussed. Particularly, phase morphologies with separated, fully encapsulated, and partially capsulated dispersed phases are described. Effects of blend composition, kinetic factors as well as the interaction of droplets upon mixing cycle are discussed in detail. An attempt is made to provide the understanding of the principles of the blend formation influencing the mechanical properties of ternary blends. Several cases of property composition relationships for ternary composition are revised. A hypothesis is offered claiming that the experimental values of the properties of the ternary blends are much closer to those calculated by the additivity properties of the corresponding binary blends. Chapter 7 deals with the morphology and structure of polymer blends containing various nanofillers. This subject area is increasingly growing due to the interest in polymer nanocomposite indicating that small addition of nanoparticles can dramatically change various properties of a polymer matrix including electrical and thermal conductivity, dielectric and magnetic permeability, gas barrier properties, and mechanical performances. A combination of polymer blending and nanoscale filler reinforcement has received a special attention due to the fact that the addition of nanofillers into multiphase polymer blends is proved to be an efficient strategy to develop a new family of polymer nanocomposites with a great tailoring potential for producing products with a combination of prescribed properties. Among various nanofillers considered in this chapter are silica nanoparticles (hydrophilic and hydrophobic), layered silicate, surface modified nanosilicates (nanoclays), single and multiwalled carbon nanotubes, and graphene along with their surface modification. There are many people who contributed to the completion of this volume. I wish to express my profound appreciation to the contributors of the various chapters for being patient with my requests for revisions and corrections. I would also like to thank Dr. David Simmons for providing excellent review. I am

16 XVI Preface thankful to Wiley-VCH Publishers for undertaking this project and for their patience, understanding, and cooperation with the authors at all stages of preparation. Finally, the support and patience of my family and the families of all the chapter authors contributed to the completion of this volume. Akron, OH, USA October 2015 Avraam I. Isayev

17 XVII List of Contributors Sudhin Datta ExxonMobil Chemical Co. GCR-Product Fundamentals 5200 Bayway Drive Baytown, TX USA Avraam I. Isayev The University of Akron Department of Polymer Engineering 250 South Forge Street Akron, OH USA Saleh A. Jabarin University of Toledo Polymer Institute Department of Chemical and Environmental Engineering 2801 W. Bancroft Street Toledo, OH USA Ioannis M. Kalogeras University of Athens Faculty of Physics Department of Solid State Physics Zografos, Athens Greece V.N. Kuleznev Lomonosov State University of Fine Chemical Technology Prospekt Vernadskogo Moscow Russia Tian Liang The University of Akron Department of Polymer Engineering 250 South Forge Street Akron, OH USA Elizabeth A. Lofgren University of Toledo Polymer Institute Department of Chemical and Environmental Engineering 2801 W. Bancroft Street Toledo, OH USA Kazem Majdzadeh-Ardakani University of Toledo Polymer Institute Department of Chemical and Environmental Engineering 2801 W. Bancroft Street Toledo, OH USA

18 XVIII List of Contributors Yu. P. Miroshnikov Lomonosov State University of Fine Chemical Technology Prospekt Vernadskogo Moscow Russia Hossein Nazockdast Amirkabir University of Technology Department of Polymer Engineering 424 Hafez Ave Tehran Iran Zhaobin Qiu Beijing University of Chemical Technology State Key Laboratory of Chemical Resource Engineering 15 North Third Ring Road East Chaoyang District Beijing China Shouke Yan Beijing University of Chemical Technology State Key Laboratory of Chemical Resource Engineering 15 North Third Ring Road East Chaoyang District Beijing China