Interface / Interphase in Polymer Nanocomposites

Anil Netravali is currently the Jean and Douglas McLean Professor in Fiber Science & Apparel Design, Cornell University. His main research is in the field of fiber reinforced composites and green materials and processes. In the past few years, his research group has developed green resins and adhesives from a variety of proteins and starches that have excellent mechanical properties. Dr. Netravali has written over 110 refereed papers and over 20 book chapters.  He has also edited 2 books. He has presented his research at several conferences all over the world and several of them as Keynote addresses as well as plenary and invited lectures.Kashmiri Lal Mittal was employed by the IBM Corporation from 1972 through 1993. Currently, he is teaching and consulting worldwide in the broad areas of adhesion as well as surface cleaning. He has received numerous awards and honors including the title of doctor honoris causa from Maria Curie-Skodowska University, Lublin, Poland. He is the editor of more than 120 books dealing with adhesion measurement, adhesion of polymeric coatings, polymer surfaces, adhesive joints, adhesion promoters, thin films, polyimides, surface modification,surface cleaning, and surfactants. Dr. Mittal is also the Founding Editor of the journal Reviews of Adhesion and Adhesives.

• Preface xiiiPart 1 Nanocomposite Interfaces/Interphases1 Polymer Nanocomposite Interfaces: The Hidden Lever for Optimizing Performance in Spherical Nanofilled Polymers 3Ying Li, Yanhui Huang, Timothy Krentz, Bharath Natarajan, Tony Neely and Linda S. Schadler1.1 Introduction 41.1.1 Dispersion Control 51.1.2 Interface Structure 61.1.3 Interface Properties 61.1.4 Measuring and Modeling the Interface 71.2 Dispersion Control through Interfacial Modification 81.2.1 Introduction 81.2.2 Short Ligands 81.2.3 Polymer Brush 111.2.3.1 Polymer Brush Synthesis Methods 121.2.3.2 Enthalpic and Entropic Contributions of Polymer Brushes to Dispersion Control 131.3 Interface Structure 161.3.1 Introduction 161.3.2 Effects of Particle Size 171.3.3 Effects of Crystallinity and Crosslinking 181.3.4 Effects of Polymer Brush Penetration 191.3.4.1 The Athermal Case 191.3.4.2 The Enthalpic Case 211.3.5 Characterizing the Interface Structure 221.4 Interface Properties and Characterization Techniques 241.4.1 Introduction 241.4.2 Molecular Mobility in Nanocomposite Interfaces 251.4.3 Thermomechanical Properties and Measurements 281.4.3.1 Direct Measurement 301.4.3.2 Indirect Methods 321.4.4 Dielectric Properties and Measurements 401.4.4.1 Effects of Nanofillers 421.4.4.2 Measurement Techniques 431.4.4.3 Indirect Measurement 441.4.4.4 Finite Element Modeling 501.4.5 Remarks on Characterization Methods 521.5 Summary 53Acknowledgements 54References 552 Interphase Engineering with Nanofillers in Fiber-Reinforced Polymer Composites 71József Karger-Kocsis, Sándor Kéki, Haroon Mahmood and Alessandro Pegoretti2.1 Introduction 722.2 Interphase Tailoring for Stress Transfer 742.2.1 Coating with Nanofillers 742.2.2 Creation of Hierarchical Fibers 802.2.2.1 Chemical Grafting of Nanofillers 802.2.2.2 Chemical Vapor Deposition (CVD) 812.2.2.3 Other “Grafting” Techniques 832.2.3 Effects of Matrix Modification with Nanofillers 852.3 Interphase Tailoring for Functionality 872.3.1 Sensing/Damage Detection 872.3.2 Self-Healing/Repair 892.3.3 Damping 912.4 Outlook and Future Trends 912.5 Summary 932.6 Acknowledgements 932.7 Nomenclature 94References 943 Formation and Functionality of Interphase in Polymer Nanocomposites 103Peng-Cheng Ma, Bin Hao and Jang-Kyo Kim3.1 Introduction 1033.2 Formation of Interphase in Polymer Nanocomposites 1053.3 Functionality of Interphase in Polymer Nanocomposites 1113.3.1 Load Transfer in Nanocomposites 1113.3.2 Reduction in Growth Rate of Fatigue Cracks in Nanocomposites 1163.3.3 Controlling the Fracture Behavior of Nanocomposites 1193.3.4 Enhancing the Damping Properties of Nanocomposites 1213.3.5 Channels for the Transport of Ions and Moisture in Nanocomposites 1233.3.6 Phonon Scattering in Nanocomposites 1253.3.7 Electron Transfer in Nanocomposites 1283.4 Summary and Prospects 130Acknowledgements 133References 1334 Impact of Crystallization on the Interface in Polymer Nanocomposites 139Nandika D’Souza Siddhi Pendse, Laxmi Sahu, Ajit Ranade and Shailesh Vidhate4.1 Introduction 1404.2 Thermodynamics of Crystallization 1424.3 Nylon Nanocomposites 1444.4 Dispersion of MLS in Nanocomposites 1454.5 Effect of MLS on Thermal Transitions in Nylon 1464.6 Permeability 1494.7 PET Nanocomposites 1514.8 Dispersion of MLS in Nanocomposites 1514.9 Effect of MLS on Thermal Transitions in PET 1514.10 PEN Nanocomposites 1564.11 Dispersion of MLS in Nanocomposites 1564.12 Effect of MLS on Thermal Transitions in PEN 1574.13 Permeability 1624.14 The Role of the Interface in Permeability: PET versus PEN 1624.15 Summary 167References 1685 Improved Nanofiller-Matrix Bonding and Distribution in GnP-reinforced Polymer Nanocomposites by Surface Plasma Treatments of GnP 171Rafael J. Zaldivar and Hyun I. Kim5.1 Introduction 1725.2 Experimental 1735.2.1 Composite Fabrication 1735.2.2 Image Analysis 1745.2.3 Raman Spectroscopy 1745.2.4 X-ray Photoelectron Spectroscopy (XPS) 1745.2.5 Scanning Electron Microscopy (SEM) 1755.2.6 Mechanical Testing 1755.3 Results 1755.4 Conclusions 187Acknowledgement 187References 1876 Interfacial Effects in Polymer Nanocomposites Studied by Thermal and Dielectric Techniques 191Panagiotis Klonos, Apostolos Kyritsis and Polycarpos Pissis6.1 Introduction 1926.2 Experimental Techniques 1976.2.1 Differential Scanning Calorimetry (DSC) 1976.2.2 Dielectric Techniques 2026.2.2.1 Broadband Dielectric Spectroscopy (BDS) 2036.2.2.2 Thermally Stimulated Depolarization Current (TSDC) Techniques 2076.3 Evaluation in Terms of Interfacial Characteristics 2096.3.1 Analysis of DSC Measurements 2096.3.2 Analysis of Dielectric Measurements 2116.3.3 Thickness of the Interfacial Layer 2136.4 Examples 2146.4.1 DSC Measurements 2146.4.2 Dielectric Measurements 2216.5 Prospects 2356.6 Summary 236Acknowledgements 237References 237Part 2 Techniques to Characterize/Control Nanoadhesion7 Investigation of Interfacial Interactions between Nanofillers and Polymer Matrices Using a Variety of Techniques 251Luqi Liu7.1 Introduction 2517.2 Observation of Interfacial Layer in Nanostructured Carbon Materials-based Nanocomposites 2537.2.1 Characterization of Interface Layer Around CNTs 2537.2.2 Characterization of Interface Layer Around Graphene Sheets 2557.3 Interfacial Properties between Nanofiller and Polymer Matrix 2567.3.1 Theoretical Simulations of CNT and/or Graphene-based Nanocomposites 2567.3.1.1 Theoretical Simulation of CNT-based Nanocomposites 2567.3.1.2 Theoretical Simulation of Graphene-based Nanocomposites 2587.3.2 Experimental Studies to Characterize Interfacial Behavior in CNT and/or Graphene-based Nanocomposite Systems 2607.3.2.1 Indirect Measurement 2617.3.2.2 Direct Measurement 2617.4 Summary 270Acknowledgements 271References 2718 Chemical and Physical Techniques for Surface Modification of Nanocellulose Reinforcements 279Viktoriya Pakharenko, Muhammad Pervaiz, Hitesh Pande and Mohini Sain8.1 Introduction 2798.2 Chemical Surface Modification 2818.2.1 Acetylation 2818.2.2 Silylation 2848.2.3 Bacterial Treatment 2858.2.4 Grafting 2878.2.5 Surfactant Adsorption 2898.2.6 TEMPO-mediated Oxidation 2908.2.7 Click chemistry 2928.3 Physical Surface Modification 2928.3.1 Plasma 2928.3.2 Corona 2978.3.3 Laser 2998.3.4 Flame 2998.4 Use of Ions 3008.5 Summary 300Acknowledgments 301References 3019 Nondestructive Sensing of Interface/Interphase Damage in Fiber/Matrix Nanocomposites 307Zuo-Jia Wang, Dong-Jun Kwon, Jin-Yeong Choi, Pyeong-Su Shin, K. Lawrence DeVries and Joung-Man Park9.1 Introduction 3089.2 Experimental Specimens and Methods 3119.2.1 Gradient Specimen Test 3119.2.2 Dual Matrix Fragmentation Test 3149.3 Damage Sensing Using Electrical Resistance Measurements 3179.3.1 Electrical Resistance Measurement for Strain Sensing Application 3179.3.2 Electrical Resistance Measurement for Interface/Interphase Evaluation 3219.4 Summary 327References 32710 Development of Polymeric Biocomposites: Particulate Incorporation, Interphase Generation and Evaluation by Nanoindentation 333Oisik Das and Debes Bhattacharyya10.1 Introduction 33410.2 The Definitions of Composite and its Constituents 33710.2.1 Composite 33710.2.2 Biocomposite 33710.2.3 The Reinforcement 33710.2.4 The Matrix 33810.3 Physical and Chemical Structures of Bio–based Reinforcements 33910.3.1 Plant/Vegetable-based Reinforcements/Fibres 33910.3.1.1 Physical Structure 33910.3.1.2 Chemical Structure 33910.3.2 Animal-based Reinforcements/Fibres 34210.3.2.1 Physical Structure 34210.3.2.2 Chemical Structure 34310.4 Particulate and Short Fibre Composites 34410.4.1 Biochar as Potential New Bio-based Particulate Reinforcement 34510.4.2 Properties of Particulate-based Composites: Governing Factors 35110.4.2.1 Particulate Properties 35110.4.2.2 Particulate Structure 35510.5 Nanoindentation Technique to Determine Interphase and Composite Properties 35810.5.1 The Technique and Theory of Nanoindentation 35810.5.1.1 Different Types of Indenter Tips 36010.5.1.2 Nanoindentation Theory 36210.5.1.3 Nanoindentation Instrument 36410.5.2 Nanoindentation on Polymeric Composites and their Interphase 36410.5 Concluding Remarks 369References 37011 Perspectives on the Use of Molecular Dynamics Simulations to Characterize Filler-Matrix Adhesion and Nanocomposite Mechanical Properties 375Sanket A. Deshmukh, Benjamin J. Hanson, Qian Jiang and Melissa A. Pasquinelli11.1 Introduction 37611.2 Overview of Molecular Dynamics (MD) Simulations 37711.3 Characterization of Interfacial Adhesion with MD Simulations 38111.3.1 Quantifying Adhesion Strength 38111.3.2 Effect of the Strength of Matrix-Filler Interactions 38311.3.3 Effect of Filler Geometry 38611.3.4 Effect of Ordering and Crosslinking within the Polymer Matrix 38811.4 Characterization of Mechanical Properties with MD Simulations 39111.4.1 Predicting Static Mechanical Properties 39211.4.2 Predicting Dynamic Mechanical Properties 39511.5 Prospects 39911.6 Summary 400Acknowledgements 400References 400

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