Introduction ................................................. xiii
Part 1 Carbon Phases, Precursors and Parent Compounds .......... 1
Chapter 1 A Historical Overview ................................ 3
1.1 The alchemy of carbon ...................................... 3
1.2 Elemental carbon and its allotropic varieties .............. 5
1.3 Novel molecular varieties .................................. 7
1.4 Natural forms .............................................. 9
1.4.1 Carbon: witness of the evolution of the universe .... 9
1.4.2 Natural carbons from Earth ......................... 10
1.4.3 Comparison between natural and artificial
carbons ............................................ 13
1.5 Contribution from quantum mechanics ....................... 14
1.5.1 Homonuclear diatomic molecules ..................... 14
1.5.2 Curved surfaces: the rehybridization phenomena ..... 16
1.5.3 Presentation of the crystalline forms .............. 17
1.5.4 The isotopes of the carbon atom .................... 19
1.6 Conclusion ................................................ 21
1.7 Bibliography .............................................. 21
Chapter 2 Polymorphism of Crystalline Phases .................. 25
2.1 Thermodynamic stability and phase diagram ................. 25
2.1.1 Stable and metastable phases ....................... 27
2.1.2 The phase diagram of carbon ........................ 28
2.1.3 С ase of the molecular phases ...................... 32
2.1.4 Crystallographic presentation of usual phases ...... 34
2.2 Classical forms of carbon ................................. 37
2.2.1 Cohesive energy and equation of state for solids ... 37
2.2.2 Structures with a fixed coordination number ........ 39
2.3 Molecular and exotic forms ................................ 43
2.3.1 Tri-coordinated structures on curved surfaces ...... 43
2.3.2 Exotic structures with mixed coordination
numbers ............................................ 51
2.4 State of the art and conclusion ........................... 53
2.5 Bibliography .............................................. 54
Chapter 3 Non-Crystalline Carbons ............................. 61
3.1 Reminder about defects and imperfections in networks ...... 62
3.1.1 Ideal single crystals .............................. 62
3.1.2 Crystalline imperfections .......................... 62
3.1.3 Non-crystalline solids ............................. 63
3.1.4 Homogenity of a solid .............................. 65
3.2 Thermodynamic approach and the classification of solids ... 70
3.2.1 Generalities ....................................... 70
3.2.2 Classification of carbon-based materials ........... 72
3.3 Fabrication and characterization techniques ............... 81
3.3.1 Thin-film coating techniques ....................... 81
3.3.2 Deposition mechanisms .............................. 84
3.3.3 The role of catalysts .............................. 89
3.3.4 Characterizations at different scales .............. 91
3.4 Conclusion ................................................ 92
3.5 Bibliography .............................................. 93
Chapter 4 Derivative Compounds and Analogs .................... 97
4.1 Doping carbons and solid solutions ........................ 98
4.1.1 Doped diamonds ..................................... 98
4.1.2 Doped graphitic phases ............................ 103
4.1.3 Fullerenes and nanotubes doping ................... 108
4.2 2D and 3D analog compounds ............................... 1ll
4.2.1 Boron nitride ..................................... 111
4.2.2 Boron carbides .................................... 113
4.2.3 Carbon nitrides ................................... 113
4.2.4 Carbon-boron nitrides ............................. 115
4.3 Similar materials ........................................ 116
4.3.1 Aggregates and inorganic nanotubes ................ 116
4.3.2 Bulk compounds .................................... 117
4.4 Conclusion ............................................... 118
4.5 Bibliography ............................................. 118
Chapter 5 From Aromatic Precursors to the Graphene Plane ..... 127
5.1 Condensed polyaromatic systems ........................... 128
5.1.1 Presentation of condensed aromatic molecules ...... 128
5.1.2 Thermochemical evolution of organic precursors .... 136
5.1.3 Association of aromatic molecules and
supramolecular organization ....................... 141
5.1.4 Structural and physico-chemical characteristics
of low temperature carbons ........................ 146
5.2 The graphene plane ....................................... 151
5.2.1 Characteristics and properties .................... 152
5.2.2 Growth in the vapor phase and thermodynamic
stability ......................................... 154
5.2.3 Intercalation and exfoliation processes ........... 155
5.3 Current situation and conclusion ......................... 160
5.4 Bibliography ............................................. 160
Part 2 Physical Properties of Solid Carbons .................. 169
Chapter 6 General Structural Properties ...................... 171
6.1 Elastic and mechanic properties .......................... 172
6.1.1 Reminder of the main definitions .................. 172
6.1.2 Elasticity modulus of crystalline phases .......... 175
6.1.3 Behavior laws relative to bulk polycrystalline
graphites ......................................... 179
6.1.4 Behavior laws for carbon filaments ................ 183
6.2 Thermal properties ....................................... 188
6.2.1 Thermodynamic definitions ......................... 188
6.2.2 Specific heat ..................................... 192
6.2.3 Thermal dilatation ................................ 197
6.2.4 Thermal conductivity .............................. 200
6.3 Conclusion ............................................... 207
6.4 Bibliography ............................................. 208
Chapter 7 Electronic Structures and Magnetic Properties ...... 217
7.1 Electronic band structures ............................... 218
7.1.1 Band structure of hexagonal graphite single
crystals .......................................... 218
7.1.2 Experimental evaluations of energy parameters ..... 220
7.1.3 Models for graphitic carbons ...................... 223
7.1.4 Electronic dimensionality of n solids ............. 225
7.2 Static magnetic properties ............................... 227
7.2.1 General presentation of diamagnetism .............. 231
7.2.2 Graphite single crystal and graphene plane ........ 235
7.2.3 Different varieties of graphitic carbons .......... 238
7.2.4 Quantum phenomena on carbon nanotubes ............. 240
7.3 Electron spin (or paramagnetic) resonance ................ 240
7.3.1. General characteristics of ESR/EPR ................ 241
7.3.2 The Pauli paramagnetism of graphites .............. 244
7.3.3 EPR of various carbon varieties ................... 248
7.3.4 Magnetic interactions ............................. 251
7.4 NMR ...................................................... 252
7.4.1 Non-crystalline carbons and precursors ............ 253
7.4.2 Case of graphite and related compounds ............ 254
7.5 Conclusion ............................................... 255
7.6 Bibliography ............................................. 256
Chapter 8 Electronic Transport Properties .................... 265
8.1 Electrical conductivity .................................. 270
8.1.1 Different conduction mechanisms ................... 270
8.1.2 Transport in the ballistic regime ................. 282
8.1.3 Non-ohmic transport and applications .............. 286
8.1.4 Electromechanical properties ...................... 292
8.2 Galvanomagnetic properties ............................... 293
8.2.1 Evolution of graphitic carbons in classical
regime ............................................ 293
8.2.2 Quantum phenomena in crystalline phases ........... 298
8.2.3 Comparison between different types of graphitic
compounds ......................................... 302
8.3 Thermoelectric properties ................................ 305
8.3.1 Graphites and bulk carbons ........................ 305
8.3.2 Carbon filaments .................................. 307
8.3.3 Thermomagnetic effects ............................ 308
8.3.4 Remark on electronic thermal conductivity ......... 309
8.4 Conclusion ............................................... 310
8.5 Bibliography ............................................. 310
Chapter 9 Optical Properties and their Applications .......... 321
9.1 Properties in linear optics .............................. 325
9.1.1 Experimental techniques and general
presentation ...................................... 325
9.1.2 Single crystal of graphite ........................ 329
9.1.3 Graphitic carbons ................................. 331
9.1.4 Fullerenes and nanotubes .......................... 335
9.1.5 The diamond crystals .............................. 338
9.1.6 Adamantine carbons ................................ 339
9.2 Nonlinear and photo-induced properties ................... 344
9.2.1 Luminescence in diamond-type phases ............... 345
9.2.2 Photo-induced and nonlinear effects in
fullerenes ........................................ 348
9.2.3 Photo-induced and nonlinear effects in
nanotubes ......................................... 349
9.3 Analysis methods and applications ........................ 351
9.3.1 Overview of the relevant techniques ............... 352
9.3.2 Applications in optics and optoelectronics ........ 356
9.4 Conclusion ............................................... 358
9.5 Bibliography ............................................. 358
Chapter 10 Vibrational Properties ............................. 369
10.1 Phonon spectra in crystalline phases ..................... 370
10.1.1 Diamonds .......................................... 373
10.1.2 Graphite and graphene ............................. 374
10.1.3 Nanotubes ......................................... 378
10.1.4 Carbynes and fullerenes ........................... 380
10.1.5 Comparison between elongation modes ............... 381
10.2 Specific characteristics of Raman scattering ............. 383
10.2.1 Raman resonance of graphite ....................... 386
10.2.2 Raman resonance of к systems and electron-phonon
interactions ...................................... 387
10.2.3 Influence of structural disorder .................. 389
10.2.4 Characterization of non-crystalline carbons ....... 391
10.3 Data from infrared spectroscopy .......................... 394
10.3.1 Thermochemical evolution of carbon-based
precursors ........................................ 396
10.3.2 Analysis of surface functions ..................... 398
10.4 Conclusion ............................................... 399
10.5 Bibliography ............................................. 400
Part 3. Carbon Materials and Uses ............................. 409
Chapter 11 Surface and Interface Phenomena .................... 411
11.1 Physical-chemistry characteristics ....................... 412
11.1.1 Surface properties in diamonds and graphites ...... 417
11.1.2 Case of graphitic-type phases ..................... 421
11.1.3 Adsorption mechanisms ............................. 425
11.2 Electric and electrochemical aspects ..................... 429
11.2.1 Double layer model and electrokinetic potential ... 429
11.2.2 Electronic transfers .............................. 432
11.3 Solid interfaces, tribology and mechano-chemical
effects .................................................. 439
11.3.1 Interactions between solid surfaces in motion ..... 440
11.3.2 Grinding of graphitic powder ...................... 444
11.3.3 Friction coefficients of diamond phases ........... 445
11.3.4 Friction coefficients of graphitic phases ......... 447
11.3.5 Wear and lubrication .............................. 449
11.4 Conclusion ............................................... 449
11.5 Bibliography ............................................. 450
Chapter 12 Chemical Reactivity and Surface Treatment .......... 461
12.1 Oxidation reactions ...................................... 463
12.1.1 Review of the reactions with molecular oxygen ..... 464
12.1.2 Combustion mechanism of various carbons ........... 465
12.1.3 Selectivity between different phases .............. 467
12.1.4 Other gaseous oxidants ............................ 468
12.1.5 Oxidation in the liquid phase ..................... 471
12.1.6 Oxidations in the solid phase ..................... 473
12.1.7 Technical analysis relevant to surface
functions ......................................... 475
12.2 Hydrogenation and halogenation reactions ................. 480
12.2.1 Reactions with hydrogen ........................... 480
12.2.2 Reactions with halogens ........................... 482
12.3 Surface treatment and heterogenous catalysis ............. 486
12.3.1 Surface modifications ............................. 486
12.3.2 Catalytic effects ................................. 489
12.4 Conclusion ............................................... 492
12.5 Bibliography ............................................. 492
Chapter 13 Divided and Porous Carbons ......................... 503
13.1 General presentation of heterogenous carbons ............. 504
13.1.1 Basic classification .............................. 504
13.1.2 Carbons from a solid phase ........................ 505
13.1.3 Carbons from a liquid phase ....................... 510
13.1.4 Porous carbons with a gas phase ................... 511
13.2 Properties of porous carbons ............................. 516
13.2.1 Porous textures and surface characteristics ....... 519
13.2.2 Dynamic properties ................................ 524
13.3 Competition between chemical reactions and diffusion ..... 533
13.3.1 The Thiele model and its ramifications ............ 533
13.3.2 Chemical deposition in the vapor phase ............ 536
13.3.3 Formation from energetic processes ................ 538
13.4 Conclusion ............................................... 540
13.5 Bibliography ............................................. 541
Chapter 14 Carbon Filaments, Composites and Heterogenous
Media .............................................. 553
14.1 Carbon filaments ......................................... 554
14.1.1 History of nanofilaments .......................... 554
14.1.2 Evolution of carbon fibers ........................ 559
14.1.3 Main physical characteristics of carbon
filaments ......................................... 562
14.2 Role in composite materials .............................. 563
14.2.1. Multidimensional and multiscale systems .......... 564
14.2.2 Fiber-matrix interactions ......................... 566
14.2.3 Classes of composites and nanocomposites .......... 570
14.3 Random heterogenous media ................................ 572
14.3.1 Electrical conductivity and percolation models .... 575
14.3.2 Role of interfacial properties and influence of
the matrix ........................................ 577
14.3.3 Consequences of the percolation phenomenon ........ 579
14.4 Conclusion ............................................... 581
14.5 Bibliography ............................................. 581
Chapter 15 Use of Carbon Materials ............................ 591
15.1 Sensing applications and nanoelectronics ................. 592
15.1.1 Sensors and actuators ............................. 593
15.1.2 Nanoelectronic .................................... 595
15.2 Carbon for energy ........................................ 596
15.2.1 Solar radiations, conversion, and heat storage .... 596
15.2.2 Gas storage ....................................... 598
15.2.3 Electrochemical storage ........................... 599
15.2.4 Carbons in nuclear energy ......................... 605
15.3 Thermostractural composites and transport ................ 610
15.3.1 Space applications ................................ 611
15.3.2 Braking disks ..................................... 613
15.4 Carbons for chemistry and environmental problems ......... 615
15.4.1 Applications in industrial chemistry .............. 615
15.4.2 Carbon and environment ............................ 617
15.5 Biocarbons ............................................... 618
15.5.1 Prosthesis and medical implants ................... 618
15.5.2 Biological fluids and hemocompatibility ........... 619
15.5.3 Nanotoxicology .................................... 619
15.5.4 Application trends ................................ 620
15.6 General conclusion ....................................... 621
15.7 Bibliography ............................................. 621
Main Signs and Symbols ........................................ 631
List of Basic Boxes ........................................... 634
Index ......................................................... 635
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