Preface ....................................................... iii
Contributors to Volume 29 ....................................... v
Contents of Other Volumes ...................................... xi
1. Exfoliation of Graphite via Intercalation Compounds .......... 1
1.1. Introduction ............................................... 1
1.1.1. Reversible and Irreversible Exfoliation ............. 2
1.1.2. Terminology ......................................... 4
1.1.3. Objective of the Present Chapter .................... 4
1.2. Exfoliation of Graphite .................................... 5
1.2.1. Processes and Controlling Factors ................... 5
1.2.2. Effect of Exfoliation Conditions .................... 7
1.2.3. Effect of Intercalates ............................. 10
1.2.4. Effect of Host Graphite ............................ 15
1.2.5. Characterization of Exfoliated Graphite ............ 17
1.3. Exfoliation of Carbon Fibers .............................. 23
1.3.1. Exfoliation of VGCFs ............................... 24
1.3.2. Exfoliation of Mesophase-Pilch-Based and
PAN-Based Carbon Fibers ............................ 26
1.4. Mechanism of Exfoliation .................................. 37
1.5. Formation into Flexible Graphite Sheets ................... 43
1.5.1. Formation Process and Controlling Factors .......... 44
1.5.2. Properties of Flexible Graphite Sheets ............. 46
1.6. Applications of Exfoliated Graphite and Flexible
Graphite Sheets ........................................... 52
1.6.1. Sorption and Recovery of Spilled Heavy Oils ........ 53
1.6.2. Other Applications of Exfoliated Graphite .......... 57
1.6.3. Applications of Flexible Graphite Sheets ........... 62
1.6.4. Applications of Exfoliative Graphite ............... 63
1.7. Concluding Remarks ........................................ 64
References ..................................................... 65
2. Diamond Synthesized at Low Pressure ......................... 71
2.1. Introduction ............................................. 71
2.1.1. Scope of the Chapter ............................. 71
2.1.2. Phase Diagram of Carbon .......................... 74
2.1.3. Chemical Bonds and Structures of Diamond and
Graphite ......................................... 76
2.1.4. Natural and Synthetic Diamonds ................... 78
2.1.5. Brief History of Research on CVD Diamond
Synthesis ........................................ 80
2.1.6. Overview of the Chapter .......................... 82
2.2. Processes in the Gas Phase ............................... 83
2.2.1. Growth from Hydrocarbon/H2 Gas Mixtures .......... 84
2.2.2. Growth from C/H/O Gas Mixtures ................... 90
2.2.3. Growth from other Gas Mixtures ................... 93
2.3. Nucleation of Diamond .................................... 94
2.3.1. Homogeneous Nucleation ........................... 95
2.3.2. Surface Nucleation ............................... 95
2.4. Mechanism of Diamond Growth ............................. 116
2.4.1. Surface Boundary Layer .......................... 118
2.4.2. Model of Diamond Growth ......................... 123
2.5. Diamond Growth at Low Substrate Temperature ............. 126
2.5.1. Attainment of Necessary Substrate Temperature
and Its Measurement ............................. 127
2.5.2. Methods of Diamond Deposition at Low
Temperatures .................................... 128
2.5.3. Nucleation and Growth of Diamond at Low
Temperature ..................................... 129
2.5.4. Diamond Film Properties ......................... 133
2.5.5. Deposition of Diamond on Polymer Substrates ..... 134
2.5.6. Future Prospects ................................ 135
2.6. Epitaxial Diamond Growth ................................ 135
2.6.1. Homoepitaxial Diamond Growth from Active Vapor
Phase ........................................... 136
2.6.2. Heteroepilaxial Growth of Diamond ............... 139
2.7. Oriented Growth and Morphology of Diamond Coatings ...... 144
2.7.1. Stimulation of Oriented Growth by Substrate
Orientation ..................................... 144
2.7.2. Oriented Growth as a Consequence of Different
Growth Rates of Differently Oriented Crystals ... 145
2.7.3. Defects and Morphology .......................... 150
2.8. Doping of Diamond ....................................... 151
2.8.1. Introduction .................................... 151
2.8.2. Basics of Diamond Doping ........................ 152
2.8.3. Doping by Boron ................................. 153
2.8.4. Doping by Phosphorus ............................ 157
2.8.5. Doping by Other Elements ........................ 158
2.8.6. Other Diamond-Doping-Related Studies ............ 158
2.8.7. Conclusion ...................................... 159
2.9. Methods of CVD of Diamond ............................... 160
2.9.1. Introduction .................................... 160
2.9.2. Hot-Filament (HF) CVD ........................... 161
2.9.3. Microwave (MW) Plasma ........................... 164
2.9.4. DC Arc Jet ...................................... 168
2.9.5. Radio-Frequency (RF) Plasma ..................... 174
2.9.6. Oxygen-Acetylene Flame .......................... 178
2.10. Applications of CVD Diamond ............................. 188
2.10.1. Introduction .................................... 188
2.10.2. Mechanical Applications ......................... 188
2.10.3. Thermal Management .............................. 190
2.10.4. Applications in Electronics ..................... 191
2.10.5. Optical Applications ............................ 194
2.10.6. Electrochemical Applications .................... 195
2.10.7. Composite Reinforcement ......................... 197
2.10.8. Detectors for Radiation and Particles ........... 198
2.10.9. Conclusion ...................................... 199
2.11. Summary and Conclusions ................................. 200
References .................................................... 203
3. Energetics of Physical Adsorption of Gases and Vapors on
Carbons .................................................... 209
3.1. Introduction ............................................. 209
3.2. Thermodynamic Aspects of Gas Physisorption ............... 214
3.2.1. Classical Thermodynamics .......................... 214
3.2.2. Statistical Mechanics ............................. 227
3.2.3. Thermodynamic Quantities and Experimental
Results ........................................... 237
3.3. Methods and Techniques of Analysis ....................... 243
3.3.1. Direct Methods .................................... 243
3.3.2. Indirect Methods .................................. 261
3.3.3. Theoretical Methods ............................... 293
3.4. Summary and Conclusions .................................. 393
References .................................................... 397
Index ......................................................... 425
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