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Graphite Fibers and Filaments 石墨纤维和长丝
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Graphite Fibers and Filaments M. S. Dresselhaus . G. Dresselhaus K. Sugihara· I. L. Spain· H. A. Goldberg Professor Dr. Mildred S. Dresselhaus Dr. Gene Dresselhaus Dr. Ko Sugihara Massachusetts Institute of Technology, Cambridge, MA 02139, USA 1. Introductory Material on Graphite Fibers and Filaments 1 1.1 Introductory Discussion of Structure of Carbon Filaments 4 1.1.1 Ex-polymer Fibers . . . . . 4 1.1.2 Arc-Grown Carbon Whiskers 9 1.1.3 CCVD Filaments. . . . . . 10 2. Synthesis of Graphite Fibers and Filaments 12 2.1 Carbon Fibers from Polymeric Precursors 12 2.1.1 Ex-rayon Fibers 13 2.1.2 Ex-PAN Fibers. . . 14 2.1.3 Ex-pitch Fibers 2.2 Carbon Filaments by CCVD 2.2.1 General Considerations 2.2.2 Detailed Considerations 2.2.3 Growth Mechanisms 2.2.4 Growth Conditions . . 2.3 Carbon-Coated Filaments . . 2.4 Filaments Prepared from Carbon Arcs. 2.5 Synthesis by Ion Bombardment . . . . 3. Structure. . . . . . . . . . . 3.1 Graphite and Its Defect Structures 3.1.1 Structure of Ideal Graphite 3.1.2 Basic Scattering Concepts 3.1.3 Point Defects 3.1.4 Dislocations . . . . . 3.1.5 Boundaries . . . . . 3.1.6 Turbostratic Graphite. 3.1.7 Partial Graphitization. 3.2 Structure of Fibers and Filaments 3.2.1 Defects in Filaments with Partially Graphitic Structure . . . . . . . . . . . . . 3.2.2 Highly Disordered Fibers and Filaments 3.3 Density . . . . . . . . . . . . . . . . . 3.4 X-Ray Diffraction. . . . . . . . . . . . . . . 50 3.4.1 Interlayer Spacing . . . . . . . . . . . 50 3.4.2 X-Ray Studies of Turbostratic and Partially Graphitized Carbon ....... 51 3.4.3 Preferred Orientation of the c-Axes . 55 3.4.4 Crystalline Structures of Finite Size. 57 3.5 Small Angle Scattering 59 3.6 Optical Microscopy . . . . . 65 3.7 Electron Microscopy .... 66 3.7.1 SEM Characterization 66 3.7.2 High Resolution Transmission Electron Microscopy 69 3.7.3 Microstructure of the CCVD Filaments 79 3.7.4 EELS. . . . . . . . . . 82 3.8 Other Spectroscopies . . . . . . 83 3.9 Other Characterization Techniques 83 4. Lattice Properties ........ 85 4.1 Elastic Parameters of Single Crystal Graphite 85 4.2 Lattice Dynamics of Single Crystal Graphite . 87 4.2.1 Lattice Vibrations in the Long Wavelength Approximation . . . . . . . . . . . . . 89 4.3 Models for the Elastic and Lattice Properties of Fibers 90 4.3.1 Effect of Defects on Elastic Parameters of Crystallites 90 4.3.2 Models for Young's and Torsional Moduli of Fibers 92 4.3.3 Rayleigh Waves in Thin Carbon Films 95 4.4 Raman Effect for Single Crystal Graphite 97 4.5 Raman Effect in Disordered Carbons 98 4.5.1 Raman Spectroscopy of Fibers 98 4.6 Photoconductivity in Graphite Fibers 103 5. Thermal Properties . 106 5.1 Specific Heat . . . 106 5.2 Thermal Expansion 109 5.3 Thermal Conductivity 114 6. Mechanical Properties . . . . . 120 6.1 Elastic Parameters . . . . . . 123 6.1.1 Experimental Techniques 123 6.1.2 Experimental Observations 125 6.1.3 Internal Friction . . . . . 131 6.1.4 Comparison of Elastic Moduli with Theory 132 6.2 Fracture, Stress and Strain. . . . 136 6.2.1 Experimental Observations ....... 136 6.2.2 Models of Fracture Processes in Ex-polymer Fibers 144 6.3 Mechanical Properties of CCVD Fibers 148 7. Electronic Structure . . . . . . . . . 153 7.1 Introduction and Overview. . . . . . 153 7.2 The Slonczewski-Weiss Model for Graphite. 161 7.3 Electronic Structure in a Magnetic Field. . 166 7.3.1 Landau Levels in Three-Dimensional Graphite 167 7.3.2 Landau Levels in Two-Dimensional Graphite. 168 8. Electronic and Magnetic Properties. . . . . . . . 172 8.1 Diamagnetism . . . . . . . . . . . . . . . . . 172 8.1.1 Diamagnetism in Two-Dimensional Graphite. 175 8.1.2 Magnetic Susceptibility of Carbon Fibers 176 8.2 Electron Spin Resonance. . . 179 8.2.1 The g-Shift in Graphite . . . . . . . . 182 8.2.2 Anisotropy Effects . . . . . . . . . . 184 8.2.3 Application of ESR to Vapor-Grown Carbon Fibers. 187 8.3 Electrical Resistivity . . . . . 188 8.3.1 Experimental Techniques 188 8.3.2 Electrical Resistivity Data 189 8.3.3 Simple Two-Band Model 195 8.3.4 Size Effects in the Resistivity of Vapor-Grown Fibers 198 8.4 Magnetoresistance . . . . . . . . . . . . . . . . .. 202 8.4.1 Positive Magnetoresistance ........... 204 8.4.2 Negative Magnetoresistance in Pregraphitic Carbons and Fibers. . . . . . . . . . . . . . . . .. 207 8.5 Hall Effect . . . . . . . . . . . . . . . . . . . .. 216 8.6 Thermoelectric Power of Benzene-Derived Carbon Fibers 217 8.7 Piezoresistance and the Effect of Hydrostatic Pressure 221 8.7.1 Effect of Pressure on Resistance . . . . . 226 8.7.2 Effect of Pressure on the Magnetoresistance 227 8.8 Non-ohmic Behavior .... 228 8.9 Electrical Noise. . . . . . . . . . . 228 9. High Temperature Properties . . . . . 230 9.1 High Temperature Thermal Properties 230 9.1.1 Thermal Conductivity 230 9.1.2 Thermal Expansion Coefficient 232 9.1.3 Specific Heats . . . . . . . 232 9.2 High Temperature Resistivity 233 9.3 High Temperature Mechanical Properties 236 9.4 Oxidation Resistance . . . . . . . 238 9.4.1 Experimental Results . . . . 239 9.4.2 Oxidation-Resistant Coatings 242 10. Intercalation of Graphite Fibers and Filaments 10.1 Structural Order and Intercalation 10.2 Structure and Staging . . . . 10.3 Lattice Properties ..... 10.4 Electrical Transport Properties 10.4.1 Electrical Conductivity 10.4.2 Magnetoresistance 10.4.3 Weak Localization . . 10.5 Thermal Transport Properties 10.6 Thermopower 10.7 Mechanical Properties 10.8 Exfoliation. . . . . 11. Ion Implantation of Graphite Fibers and Filaments 292 11.1 The Ion Implantation Process . . . . . . . 293 11.2 Application to Carbon Fibers ....... 295 11.3 Implantation-Induced Structural Modifications 296 11.3.1 Characterization of Samples 302 11.3.2 Regrowth . . . . . . . . . . . . . 303 12. Applications of Graphite Fibers and Filaments 304 12.1 Economic Considerations ....... 304 12.2 Structural Applications of Composites. . 307 12.2.1 Carbon Fiber-Polymer Composites 307 12.2.2 Carbon-Carbon Composites . . . 317 12.3 Electrical Applications for Carbon Fibers 318 12.3.1 Electromagnetic Interference Shielding 318 12.3.2 Antistatic Coatings . . . . . . . . . 321 12.3.3 Electrical Devices Based on Carbon-Resin Composites Near the Percolation Threshold 322 12.3.4 Fibers with Super conducting Coatings 324 12.3.5 CCVD Carbon on Ex-polymer Fibers 325 12.4 Thermal Applications . . . . 326 12.5 Nuclear Reactor Applications ...... 327 12.6 Optical Applications " . . . . . . . . 329 12.6.1 Application of Carbon Filaments as Obscurants 329 12.6.2 Low-Reflectivity Surfaces . . . . . . . . 332 12.7 Applications for Intercalated Carbon Fibers . . . 334 12.8 Batteries and Other Electrochemical Applications . 335 12.9 Medical Applications 339 References . . 341 Subject Index 361 390P ISBN-13:978-3-642-83381-6 e-ISBN-13:978-3-642-83379-3 DOl: 10.1007/978-3-642-83379-3 |
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