Spectroscopy of Polymer Nanocomposites

Description

Spectroscopy of Polymer Nanocomposites covers all aspects of the spectroscopic characterization of polymer nanocomposites. More than 25 spectroscopy characterization techniques – almost all used in materials science – are treated in the book, with discussion of their potentialities and limitations. By comparing the techniques with each other and presenting the techniques together with their specific application areas, the book provides scientists and engineers the information needed for solving specific problems and choosing the right technique for analyzing the material structure. From this, the dispersion structure of fillers, property relations and filler-polymer interactions can be determined, and, ultimately, the right materials can be chosen for the right applications.

Besides the techniques and structure-property relations, aspects covered include: phase segregation of filler particles, filler agglomeration and deagglomeration, filler dispersion, filler-polymer interactions, surfaces and interfaces. The book also examines recent developments, as well as unresolved issues and new challenges, in the characterization of surfaces and interfaces in polymer nanocomposites. This handpicked selection of topics, and the combined expertise of contributors from industry, academia, government and private research organizations across the globe, make this survey an outstanding reference source for anyone involved in the field of polymer nanocomposites in academia or industry.

Provides comprehensive coverage of spectroscopy techniques for analyzing polymer nanocomposites.
Enables researchers and engineers to choose the right technique and make better materials decisions in research and a range of industries.
Presents the fundamentals, information on structure-property relations, and all other aspects relevant for understanding spectroscopic analyses of nanoreinforced polymers and their applications.

Front Cover 2
Spectroscopy of Polymer Nanocomposites 5
Copyright Page 6
Contents 7
List of Contributors 17
Preface 21
1 Spectroscopy—introducing the advantages and application areas in polymer nanocomposites 23
- 1.1 Introduction 23
- 1.2 Polymer nanocomposites 24
  - 1.2.1 A Large Range of Applications and a Large Market 24
  - 1.2.2 Bringing New Properties to Polymers: Applications of Nanocomposites in Plastics 25
  - 1.2.3 Fabrication and the Challenges Existing in the Field 26
- 1.3 Nanocomposite spectroscopy 27
  - 1.3.2 Various Spectral Techniques and the Advantages 27
  - 1.3.1 What Can Spectroscopy Do? 27

Front Cover 2
Spectroscopy of Polymer Nanocomposites 5
Copyright Page 6
Contents 7
List of Contributors 17
Preface 21
1 Spectroscopy—introducing the advantages and application areas in polymer nanocomposites 23
- 1.1 Introduction 23
- 1.2 Polymer nanocomposites 24
  - 1.2.1 A Large Range of Applications and a Large Market 24
  - 1.2.2 Bringing New Properties to Polymers: Applications of Nanocomposites in Plastics 25
  - 1.2.3 Fabrication and the Challenges Existing in the Field 26
- 1.3 Nanocomposite spectroscopy 27
  - 1.3.2 Various Spectral Techniques and the Advantages 27
  - 1.3.1 What Can Spectroscopy Do? 27
  - 1.3.3 Spectral Applications in Polymers and its Nanocomposites 30
- 1.4 Conclusion 32
- References 32
2 An overview of nanocomposite nanofillers and their functionalization 37
- 2.1 Introduction 37
- 2.2 Overview of nanofillers 38
  - 2.2.1 Inorganic Nanoparticles: Metals and Metalloids 38
    - 2.2.1.1 Nanoparticle structures 38
    - 2.2.1.2 Nucleation and growth 39
    - 2.2.1.3 Physicochemical properties 41
    - 2.2.1.4 Nanoparticle preparation 42
      - 2.2.1.4.1 Metallic nanoparticles 43
        
        2.2.1.4.1.1 Metal salt reduction 43
        
        2.2.1.4.1.2 Organometallic complex reduction/decomposition 44
      - 2.2.1.4.2 Metal oxide nanoparticles 45
    - 2.2.2 Carbon-Based Nano-objects: Fullerenes, Graphene, and Carbon Nanotubes 46
      - 2.2.2.1 Structural considerations 46
      - 2.2.2.2 Properties of carbon-based nanomaterials 49
      - 2.2.2.3 Preparation methods 49
        
        2.2.2.3.1 Fullerene and CNTs 49
        
        2.2.2.3.1.1 Laser ablation 49
        
        2.2.2.3.1.2 Arc discharge 50
        
        2.2.2.3.1.3 Catalyzed chemical vapor deposition 51
        
        2.2.2.3.1.4 Miscellaneous preparation techniques 52
        
        2.2.2.3.2 Graphene 52
      - 2.2.3 Clays 52
        
        2.2.3.1 Clay structures 53
        
        2.2.3.2 Clay modifications 54
      - 2.3 Inorganic Nanoparticles Including Clays: Chemical and Physical Modifications for Their Inclusion as Filler in Nanocompo... 56
        
        2.3.1 Physical Methods of Inclusion 58
        
        2.3.3 Grafting-to or Grafting-from Methods of Inclusion 59
        
        2.3.2 In situ Polymerization with Pre-formed Nanoparticles 59
        
        2.3.4 In situ Nanoparticle and/or Polymer Formation for Nanocomposite Synthesis 61
      - 2.4 Carbon Nanotubes as Fillers in Nanocomposites: The Dispersion Challenge 62
        
        2.4.1 Physical Methods of Dispersion of CNTs 63
        
        2.4.2 Chemical Methods of Dispersion of CNTs 63
        
        2.4.2.1 Chemical functionalization or surface modification of CNTs 64
        
        2.4.2.2 Defect functionalization of CNTs 64
        
        2.4.2.3 Other methods of sidewall and termini functionalization of CNTs 66
        
        2.4.3 Physical Functionalization (or Physical Blending) of CNTs 67
      - 2.5 Graphene as Filler in Nanocomposites: The Behavior of Graphene Layers 68
        
        2.5.1 Surface Modification of Graphene 69
        
        2.5.2 Covalent Functionalization of Graphene and Graphene Oxide Sheets 70
        
        2.5.4 Preparation Methods of Polymer/Graphene Nanocomposites 71
        
        2.5.3 Individualization by π–π Interactions 71
      - 2.6 Conclusion 72
      - References 72
    - 3 Thermodynamics, phase segregation, polymer morphology, and interface/interphases in polymer nanocomposites 87
      - 3.1 Introduction 87
      - 3.2 Thermodynamic solution behavior of nanoparticle systems 89
        
        3.2.1 Static Light Scattering 93
        
        3.2.2 Static Light Scattering: Theory 93
        
        3.2.3 Literature Review: Thermodynamic Solution Behavior of Nanoparticle Systems as Defined with Static Light Scattering an... 96
      - 3.3 Phase segregation and interphases of polymer nanocomposites 98
        
        3.3.1 Segregation and Diffusion of Polymer Chains 99
        
        3.3.2 The Importance of Neutron Reflectivity in Interphase and Phase Segregation Studies 100
        
        3.3.3 Literature Review of Neutron Reflectivity Studies 101
      - Acknowledgments 104
      - References 104
    - 4 Raman and tip-enhanced Raman scattering spectroscopy studies of polymer nanocomposites 110
      - 4.1 Introduction 110
      - 4.2 Examples of raman studies of polymer nanocomposites 112
        
        4.2.1 A Raman Spectroscopy Study on SWCNT/Polystyrene Nanocomposites: Mechanical Compression Transferred from the Polymer t... 112
        
        4.2.2 Raman Study of Interfacial Load Transfer in Graphene Nanocomposites 117
      - 4.3 Raman and TERS Spectroscopy Studies of Polymer Nanocomposites 120
        
        4.3.1 Interaction of SWCNT and PS at the Interface in SWCNT/PS Nanocomposites Studied by Raman and TERS Spectroscopy 120
        
        4.3.2 TERS Spectroscopy Study of Local Interactions at the Interface of SBR/MWCNT Nanocomposites 123
      - References 130
      - 4.4 Conclusions 130
    - 5 Infrared and Fourier transform infrared spectroscopy for nanofillers and their nanocomposites 134
      - 5.2 Introduction to IR spectroscopy 134
        
        5.2.2 Infrared Instruments 135
        
        5.2.2.1 Dispersive IR spectrometers 135
        
        5.2.2.2 Interferometric IR spectrometers: FTIR 135
        
        5.2.2.3 Advantages of FTIR over dispersive IR 136
        
        5.2.1 Basis of Infrared Spectroscopy 135
        
        5.2.3 Sample Preparation 136
      - 5.1 Introduction 134
      - 5.3 FTIR spectroscopy for nanofillers and their nanocomposites 137
        
        5.3.1 Qualitative Analysis 137
        
        5.3.1.1 Nanofiller identification 138
        
        5.3.1.1.1 Metal oxides nanofiller 138
        
        5.3.1.1.2 Clay 140
        
        5.3.1.1.3 Carbonaceous nanofiller 141
        
        5.3.1.1.4 Nanofiller synergy 142
        
        5.3.1.2 Polymer nanocomposite identification 145
        
        5.3.2 Quantitative Analysis 147
      - 5.4 Conclusion 150
      - References 150
    - 6 Ultraviolet and visible spectroscopy studies of nanofillers and their polymer nanocomposites 152
      - 6.1 Introduction 152
      - 6.2 Types of nanocomposites 152
        
        6.2.1 Polymer Matrix Nanocomposites 153
        
        6.2.2 Characterization Techniques 153
        
        6.2.3 Optical Properties of PMC 153
      - 6.3 Nanofillers in PMC 154
        
        6.3.1 Metal Nanoparticles as Nanofillers 154
        
        6.3.2 Semiconductor Nanocrystals as Nanofillers 166
        
        6.3.3 Nano Oxides as Nanofillers 170
        
        6.3.4 Carbon-Based Nanomaterials as Nanofillers 174
      - 6.4 Conclusion 177
      - References 177
    - 7 Fluorescence spectroscopy of nanofillers and their polymer nanocomposites 180
      - 7.1 Introduction 180
      - 7.2 Mechanism of Fluorescence 182
      - 7.3 Instrumentation for fluorescence spectroscopy 183
        
        7.3.3 Detector 184
        
        7.3.1 Light Source 184
        
        7.3.2 Sample Holder 184
      - 7.4 Fluorescence measurement types 185
        
        7.4.2 Time-Resolved Fluorescence 185
        
        7.4.1 Steady-State Fluorescence 185
      - 7.5 Fluorescence spectroscopy for material characteristics 186
      - 7.6 Fluorescence studies of nanofiller and polymer nanocomposites 189
        
        7.6.1 Polymer Composite with Fluorescent Semiconducting Nanofiller 189
        
        7.6.2 Core/Shell Nanofiller-Incorporated Polymer Composite 191
        
        7.6.3 Other Fluorescent Nanofiller-Based Polymer Nanocomposite 193
      - 7.7 Properties of Polymer Nanocomposites Studied from Fluorescence 194
      - 7.8 Advances in fluorescence technologies 195
        
        7.8.1 Multiphoton Fluorescence Microscopy 195
        
        7.8.2 Fluorescence Correlation Spectroscopy 196
        
        7.8.3 Single Molecule Detection 197
      - 7.9 Conclusion 198
      - References 199
    - 8 NMR spectroscopy of polymer nanocomposites 203
      - 8.1 Introduction 203
      - 8.2 Theoretical backgrounds of NMR 204
      - 8.3 NMR analysis of polymer composites 206
        
        8.3.1 Elastomer Nanocomposites 207
        
        8.3.2 Thermoplastic Nanocomposites 210
        
        8.3.3 Biopolymer Nanocomposites 215
      - References 219
      - 8.4 Conclusion 219
    - 9 EPR spectroscopy of polymer:fullerene nanocomposites 224
      - 9.1 Introduction 224
      - 9.2 Theoretical Backgrounds of Electron Paramagnetic Resonance in Polymer Composites 230
        
        9.2.1 Landé Factor 231
        
        9.2.2 Spin Susceptibility 232
        
        9.2.3 Line Shape and Width 236
        
        9.2.4 Dysonian Spectral Contribution 239
        
        9.2.5 Electron Relaxation and Spin Dynamics 240
        
        9.2.6 Mechanism of Charge Transport in Polymers 241
      - 9.3 Magnetic Resonance Parameters of Spin Charge Carriers in Polymer:Fullerene Composites 242
        
        9.3.1 Line Shape and g-Factor 243
        
        9.3.2 Photoinitiation and Recombination of Charge Carriers in Polymer:Fullerene Composites 260
        
        9.3.3 LEPR Line Width 266
        
        9.3.4 Electron Relaxation and Dynamics of Spin Charge Carriers 269
      - 9.4 Utilization of Polymer Composites in Spin-Assisted Molecular Electronics 274
      - 9.5 Summary 283
      - Acknowledgments 285
      - References 285
    - 10 Dielectric spectroscopy and stimulated current analyses of polymer-ceramic nanocomposites 298
      - 10.1 Introduction 298
      - 10.2 Dielectric Analysis of Ceramic Nanofillers 299
      - 10.3 DS of Ceramic Particulates 301
      - 10.4 DS Studies of Nanocomposites 305
      - 10.5 TSC Spectroscopy Studies of Nanodielectrics 315
      - 10.6 Pulsed Electro-Acoustic Analysis of Nanodielectrics 322
      - 10.7 Summary 327
      - Acknowledgment 328
      - References 328
    - 11 Photothermal spectroscopy of polymer nanocomposites 334
      - 11.1 Introduction 334
      - 11.2 Related photothermal studies of composite materials 337
        
        11.2.1 Complex Composites 337
        
        11.2.2 Composites with Defined Microstructure 338
        
        11.2.3 Composites with Random Morphology 340
      - 11.3 Theoretical background for 1D PT response of adiabatic solid slabs 341
        
        11.3.1 Theory of FD- and BD-PT Response with Periodic Excitation 343
        
        11.3.2 Specific Transfer Functions of PT Methods 345
        
        11.3.3 Theory of BD-PT Impulse Response 346
      - 11.4 Materials and methods 347
        
        11.4.1 Motivation for Materials Choice 347
        
        11.4.2 Material Preparation and Properties 348
        
        11.4.3 Experimental Photothermal Setups 351
        
        11.4.4 Flash Method for Thermal Diffusivity Measurement 354
      - 11.5 Frequency- and time-domain PT spectra of nanocomposites 355
        
        11.5.1 PTR Spectra of Nanocomposites with Carbon Fillers 355
        
        11.5.2 Flash Method Spectra of Nanocomposites with Carbon Fillers 357
        
        11.5.3 PTR and PPE Spectra with Optically Thin Samples 358
      - 11.6 Multiscale Analysis of Effective Thermal Conductivity of Nanocomposites 361
        
        11.6.1 Background on Effective Thermal Conductivity Modeling 361
        
        11.6.2 Effective Thermal Conductivity Results and Discussion 364
        
        11.6.3 Indirect Evidence of Thermal Percolation in Composites with EG and CNT Fillers 366
      - 11.7 Discussion of other results of PT spectroscopy 369
      - 11.8 Conclusions 372
      - Acknowledgments 374
      - References 374
    - 12 Brillouin spectroscopy of polymer nanocomposites 384
      - 12.1 Introduction 384
      - 12.2 Brillouin spectroscopy 385
        
        12.2.1 Brillouin Scattering Theory 385
        
        12.2.2 Experimental Setup 387
        
        12.2.2.1 FP Interferometer 388
        
        12.2.2.2 Tandem Interferometry 389
        
        12.2.2.3 Scattering Geometries 391
        
        12.2.2.3.1 90A-Scattering Geometry 391
        
        12.2.2.3.2 180A-Scattering Geometry 393
        
        12.2.2.3.3 RITA-Scattering Geometry 394
        
        12.3 Applications to polymers and nanocomposites 395
        
        12.3.1 Acoustic Wave Velocity 395
        
        12.3.2 Elastic Constants 399
        
        12.3.3 Glass Transition Temperature 402
        
        12.3.4 Refractive Index 404
        
        12.3.5 Coupling of Brillouin and Other Techniques 406
        
        12.3.6 Biological Systems 406
        
        12.4 Concluding Remarks 408
        
        References 409
        
        13 Mössbauer spectroscopy of polymer nanocomposites 415
        
        13.1 Introduction 415
        
        13.2 Basic operational principles of mössbauer spectroscopy 416
        
        13.3 Hyperfine Interactions of the Nucleus with its Surrounding Environment 417
        
        13.3.1 IS Due to Electron Density at the Nucleus 417
        
        13.3.2 QS as a Result of Electric Field Gradient 418
        
        13.3.3 Surrounding Magnetic Field Caused Hyperfine Splitting 419
        
        13.4 General applications of mössbauer spectroscopy 419
        
        13.5 Analysis of PNCs with mössbauer spectroscopy 422
        
        13.5.1 Study of mPNCs by Combining TEM-SAED and Mössbauer Spectroscopy 422
        
        13.5.2 Quantitative Analysis of Iron Speciation with Mössbauer Spectroscopy 423
        
        13.5.3 Characterization of the Surface Layer of Iron Species with Mössbauer Spectroscopy 423
        
        13.5.4 Analysis of Magnetic Carbon Nanostructures with Mössbauer Spectroscopy 426
        
        13.6 Summary 428
        
        References 428
        
        14 X-ray diffraction spectroscopy of polymer nanocomposites 432
        
        14.1 Introduction 432
        
        14.2 Basic principles of XRDS 433
        
        14.3 Variants of XRD Spectroscopy 435
        
        14.4 Wide-angle XRD 436
        
        14.4.1 XRDS of NPs 436
        
        14.4.2 XRDS of PNCs 437
        
        14.4.2.1 Polymer clay nanocomposites 438
        
        14.4.2.2 Silica–PNCs 447
        
        14.4.2.3 Carbon nanotube PNCs 449
        
        14.4.2.4 Graphene PNCs 454
        
        14.4.2.5 Cellulose nanocrystal PNCs 461
        
        14.5 Small-angle X-ray scattering 462
        
        14.6 New Developments in XRD 465
        
        14.7 Summary 465
        
        Abbreviations 466
        
        References 467
        
        15 X-ray photoelectron spectroscopy of nanofillers and their polymer nanocomposites 474
        
        15.1 Introduction 474
        
        15.2 XPS: Tool for characterization of polymer and its composite 475
        
        15.2.1 Basic Principle 475
        
        15.2.2 Basic Components of XPS Measurements 477
        
        15.2.3 Applications 478
        
        15.3 XPS study of PPy 478
        
        15.4 XPS study of WO3 480
        
        15.5 XPS study of PPy–WO3 nanocomposite 482
        
        15.6 XPS study of DBSA-doped PPy–WO3 nanocomposite 484
        
        15.7 Conclusions 486
        
        References 487
        
        Index 491
        
        Back Cover 501

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