Contributors ................................................... xv
Preface ....................................................... xix
PART 1 OVERVIEW: NATURALLY OCCURRING UNCD AND ITS
LABORATORY SYNTHESIS .................................... 1
1 Carbon Family at the Nanoscale ............................... 3
O.A. Shenderova, A.S. Barnard, and D.M. Gruen
Introduction ................................................. 3
1.1 Historical Overview ..................................... 4
1.2 Nanocarbon Classification ............................... 8
1.3 Exotic Nanocarbons ..................................... 12
1.4 Conclusion ............................................. 16
References .................................................. 16
2 Extraterrestrial Nanodiamonds in the Cosmos ................. 23
T.L. Daulton
Introduction ................................................ 23
2.1 Stellar Nucleosynthesis and Presolar Stardust .......... 24
2.2 Discovery and Identification of Presolar Minerals ...... 26
2.3 Origins of Meteoritic Nanodiamonds ..................... 27
2.4 Isotopic Compositions of Meteoritic Nanodiamonds:
Stellar Sources ........................................ 28
2.4.1 Primary C, Surface Bound H, and Trapped N ....... 30
2.4.2 Trapped Noble Gases ............................. 33
2.4.3 Trapped Те, Pd, Ba, and Sr ...................... 46
2.4.4 Inferred Stellar Sources ........................ 48
2.5 Microstructure of Meteoritic Nanodiamonds: Formation
Mechanisms ............................................. 50
2.5.1 Twin Microstructure ............................. 50
2.5.2 Dislocation Microstructure ...................... 54
2.5.3 Polytypes ....................................... 55
2.5.4 Inferred Mechanisms of Formation ................ 56
2.6 Noble Gas and N Content in Meteoritic Nanodiamonds:
Nebular Processes ...................................... 58
2.7 Nanodiamonds in Interplanetary Dust Particles:
Insights on Solar Nebula Evolution ..................... 65
2.8 Summary of Experimental Data ........................... 67
2.9 The New Astronomy ...................................... 68
Acknowledgments ............................................. 69
References .................................................. 69
3 Types of Nanocrystalline Diamond ............................ 79
O.A. Shenderova and G. McGuire
Introduction ................................................ 79
3.1 Nanodiamonds: Shapes ................................... 81
3.2 Types of Nanodiamond and Methods of Their Synthesis .... 82
3.2.1 Zero-Dimensional Nanodiamond Structures ......... 84
3.2.2 One-Dimensional ND Structures ................... 95
3.2.3 Two-Dimensional ND Structures .................. 102
3.2.4 Three-Dimensional ND Structures ................ 104
3.3 Conclusion ............................................ 108
Acknowledgments ............................................ 109
References ................................................. 109
PART 2 STABILITY OF NANODIAMOND .............................. 115
4 Stability of Nanodiamond ................................... 117
A.S. Barnard
Introduction: Nanocarbon Phase Stability ................... 117
4.1 Nanocarbon Phase Diagrams ............................. 118
4.2 Theoretical Studies of the Relative Phase Stability
of Nanocarbons ........................................ 123
4.2.1 Stability of Large Nanocarbon Particles ........ 124
4.2.2 Stability of Small Nanocarbon Particles ........ 129
4.2.3 Coexistence of Bucky-diamond and Other
Nanocarbon Phases .............................. 130
4.2.4 Stability of Quasi One-Dimensional
Nanocarbon ..................................... 132
4.2.5 Summary ........................................ 134
4.3 Morphologies .......................................... 134
4.3.1 Morphology of Nanodiamond Particles ............ 134
4.3.2 Morphology of Diamond Nanorods and Nanowires ... 141
4.3.3 Hybrid Nanocarbon Materials .................... 146
4.4 Conclusions ........................................... 147
Acknowledgments ............................................ 149
References ................................................. 149
PART 3 UNCD FILMS AND RELATED MATERIALS ...................... 155
5 Electron Transport and the Potential of
Ultrananocrystalline Diamond as a Thermoelectric
Material ................................................... 157
D.M. Gruen
Introduction ............................................... 157
5.1 Characterization of n-type Conductivity in UNCD
Films ................................................. 159
5.2 Applications of n-type UNCD Films ..................... 165
5.2.1 Field Electron Emission ........................ 167
5.2.2 Electrodes for Electrochemistry and
Biosensing ..................................... 168
5.2.3 High-Temperature n-type UNCD/p-type
All-Diamond Heterostructure Diode .............. 169
5.3 Electronic Structure of UNCD Grain Boundaries ......... 170
5.4 UNCD and Carbon Nanotube/UNCD Composites as
Potential High-Efficiency, High-Temperature
Thermoelectric Materials .............................. 173
5.5 Summary ............................................... 178
Acknowledgments ............................................ 179
References ................................................. 180
6 Plasma-Assisted Synthesis: Plasma Experimental
Diagnostics and Modeling ................................... 185
E. Bénédic, G. Lombardi, K. Hassouni, E Mohasseb,
and A. Gicquel
Introduction ............................................... 185
6.1 Experimental Details .................................. 188
6.1.1 MPACVD Reactor and Process Parameters .......... 188
6.1.2 Arrangements for Spectroscopic Diagnostics ..... 190
6.2 Fundamentals of Plasma Diagnostics .................... 191
6.2.1 Optical Emission and Broadband Absorption
Spectroscopy ................................... 191
6.2.2 Plasma Modeling ................................ 199
6.3 Investigations of Typical NCD Deposition
Conditions ............................................ 202
6.3.1 Deposition and Characterization of NCD
Films .......................................... 202
6.3.2 Plasma Diagnostics ............................. 207
6.3.3 Conclusion on Plasma Characterization .......... 211
6.4 Investigations of Ar/H2/CH4 Microwave Discharges
with the Plasma Thermochemical Model .................. 211
6.4.1 Parametric Studies ............................. 211
6.4.2 Mechanisms of C2 Formation ..................... 220
6.4.3 Conclusion on Plasma Modeling .................. 222
6.5 General Conclusion .................................... 223
References ................................................. 224
7 Nanodiamond Films Deposited from Energetic Species:
Material Characterization and Mechanism of Formation ....... 229
I. Gouzman, Sh. Michaelson, and A. Hoffman
Introduction ............................................... 229
7.1 The Deposition System and Deposition Parameters ....... 231
7.2 Evolution and Properties of the Films Studied by
NEXAFS: Coordination and Orientation .................. 235
7.3 Phase Composition of the Films as Reflected by
Raman Spectroscopy .................................... 240
7.4 Crystalline Structure of the Films by XRD ............. 246
7.5 Morphological Evolution of the Films by AFM ........... 248
7.6 Surface and Grain Boundary Phase Composition
Studied by EELS ....................................... 248
7.7 Hydrogen Content in the Films by SIMS and ERD ......... 251
7.8 Hydrogen Bonding Configuration in the Nanodiamond
Films Studied by HREELS ............................... 252
7.9 Density Evolution of the Films Examined by XRR ........ 257
7.10 Visualization and Evolution of the Films Studied by
HR ТЕМ ................................................ 257
7.11 Formation Mechanism of the Nanodiamond Film
Deposited from Energetic Species ...................... 260
7.12 Summary ............................................... 266
Acknowledgments ............................................ 267
References ................................................. 267
8 Theoretical Studies of UNCD Synthesis and Properties ....... 273
P. Zapol, M. Sternberg, and L.A. Curtiss
Introduction ............................................... 273
8.1 Computational Methodologies ........................... 274
8.2 Carbon Dimer Growth Mechanisms on the (110)
Face of Diamond ....................................... 275
8.2.1 The (110) 1 x 1:H Surfaces ..................... 275
8.2.2 Clean (110) Diamond Surface .................... 278
8.3 Carbon Dimer Growth Mechanisms on the (100) Surface
of Diamond ............................................ 279
8.3.1 The (100) 2 x 1:H Diamond Surface .............. 280
8.3.2 The (100) 2 x 1 Diamond Surface ................ 281
8.3.3 Nitrogen Addition to (100) 2 x 1 Surface ....... 284
8.3.4 A Model for UNCD Growth Kinetics ............... 285
8.4 Electronic Structure of UNCD .......................... 287
8.4.1 Grain Boundaries in UNCD ....................... 287
8.4.2 Structure of High-Angle Twist GBs in
Diamond ........................................ 288
8.4.3 Electronic Structure of GBs with к bonding
in UNCD ........................................ 290
8.5 Electronic Structure of Doped UNCD .................... 293
8.5.1 Nitrogen in Diamond and Amorphous Carbon ....... 293
8.5.2 Nitrogen Impurities in the UNCD GBs ............ 294
8.5.3 Other Impurities in the UNCD GBs ............... 298
Acknowledgments ............................................ 299
References ................................................. 299
9 Mechanical Properties of Undoped and Doped
Ultrananocrystalline Diamond: Elasticity, Strength,
and Toughness .............................................. 303
H.D. Espinosa, B. Peng, N. Moldovan, X. Xiao,
O. Auciello, and J. Carlisle
Introduction ............................................... 303
9.1 The Material .......................................... 305
9.2 Experimental Technique ................................ 308
9.2.1 Elasticity and Strength Experiments ............ 308
9.2.2 Fracture Toughness Experiments ................. 310
9.3 Experimental Results .................................. 314
9.3.1 Stress-Strain Curves ........................... 314
9.3.2 Size Effect and Weibull Analysis ............... 316
9.3.3 Toughness Measurements ......................... 319
9.4 Fractographic Analysis ................................ 325
9.5 Theoretical Strength .................................. 327
9.6 Conclusions ........................................... 328
Acknowledgments ............................................ 329
References ................................................. 329
PART 4 UNCD PARTICLES OF DETONATION ORIGIN ................... 333
10 On the Discovery of Detonation Nanodiamond ................. 335
V.V. Danilenko
References ................................................. 344
11 Synthesis and Post-Synthesis Treatment of Detonation
Nanodiamonds ............................................... 347
V.Yu. Dolmatov
Introduction ............................................... 347
11.1 Industrial Technologies of Detonation Synthesis
of UNCD ............................................... 349
11.2 Post-Synthesis Purification and Modification .......... 354
11.2.1 Chemical Purification .......................... 354
11.2.2 UNCD Modification .............................. 371
References ................................................. 375
12 Characterization and Physical Properties of UNCD
Particles .................................................. 379
A.Ya. Vul'
Introduction ............................................... 379
12.1 Methods for Characterization of UNCD Particles ........ 380
12.1.1 General Remarks ................................ 380
12.1.2 X-ray Diffraction .............................. 380
12.1.3 Small-Angle X-ray Scattering ................... 382
12.1.4 Raman Scattering ............................... 383
12.1.5 HRTEM and SEM Studies .......................... 386
12.1.6 STM and AFM Studies ............................ 387
12.1.7 Visible and Far-Infrared Spectroscopic
Studies ........................................ 389
12.1.8 NMR and EPR Studies ............................ 390
12.1.9 EELS Characterization of UNCD Powders .......... 391
12.2 The Structure of UNCD Clusters and the Aggregation
Problem ............................................... 391
12.3 Mechanical Properties ................................. 396
12.4 Optical Properties .................................... 397
12.5 Electronic Properties ................................. 397
Summary .................................................... 398
Acknowledgments ............................................ 398
References ................................................. 399
13 Diamond Phase Transitions at Nanoscale ..................... 405
V.L. Kuznetsov and Yu.V. Butenko
Introduction ............................................... 405
13.1 Stability of Nanocarbons .............................. 408
13.2 Surface Chemistry: Stability of Surface Species ....... 411
13.2.1 Surface Groups of NDs .......................... 411
13.2.2 Thermal Stability of ND Surface Groups ......... 413
13.2.3 Critical View of the Formation of
sp2-Bonded Carbon in Pristine NDs ............. 418
13.2.4 The Onset Temperature of ND Graphitization ..... 420
13.3 Kinetics of Diamond Graphitization .................... 422
13.3.1 Experimental Approaches for the Study of
ND Graphitization .............................. 423
13.3.2 Kinetic Parameters of ND Graphitization
for the Temperature Range of 1370-1860 К ....... 425
13.4 Mechanism of Diamond Graphitization ................... 431
13.4.1 Diamond Surface Reconstruction ................. 431
13.4.2 Cleavage Energies of Diamond Planes ............ 433
13.4.3 Shape of Diamond Particles ..................... 434
13.4.4 Graphite/Diamond Interfaces .................... 436
13.4.5 Formation of Nanocarbon Species via "Low"-
Temperature Diamond Graphitization ............. 439
13.4.6 The Formation of the Closed Curved Graphitic
Structure on the Surface of Micron-Size
Diamond ........................................ 445
13.5 Catalytic Graphitization of NDs in the Presence of
Metal Clusters ........................................ 450
13.6 Graphitization of NDs in the Presence of Oxygen-
and Hydrogen-Containing Gases ......................... 454
13.7 Properties of ND Annealing Products: OLC, spVsp3
Nanocomposites ........................................ 457
13.8 Conclusion ............................................ 461
Acknowledgments ............................................ 463
References ................................................. 463
14 Applications of Detonation Nanodiamond ..................... 477
V.Yu. Dolmatov
14.1 Electrochemical Coatings .............................. 477
14.1.1 Chrome Plating ................................. 477
14.1.2 Copper Plating ................................. 480
14.1.3 Zinc Plating ................................... 481
14.1.4 Tin Plating .................................... 482
14.1.5 Silvering ...................................... 482
14.1.6 Gold Plating ................................... 483
14.1.7 Nickel Plating ................................. 484
14.1.8 Anode Oxidation ................................ 484
14.1.9 The Deposition of Alloys along with UNCD ....... 485
14.2 Polymer Compositions and Antifriction Coatings ........ 486
14.2.1 The Polyisoprene and Butadiene-Styrene
Copolymer ...................................... 488
14.2.2 The Polysiloxane Polyblock Cyclolinear
Copolymer ...................................... 491
14.2.3 Polyurethane Foam .............................. 492
14.2.4 Frost-Resistant Butadiene-Nitrile Rubber ....... 493
14.2.5 Rubbers Stable to Explosive Decompression ...... 494
14.2.6 Gas-flame Deposition of Polymer Coatings ....... 495
14.3 Polishing ............................................. 496
14.4 Oils and Lubricants ................................... 504
14.5 Diamond Sinters and Compacts .......................... 508
14.6 Bioactivity of UNCD Particles ......................... 513
14.7 Other Technological Applications of UNCD Particles .... 520
References ................................................. 521
15 Nanodiamond: Designing the Bio-Platform .................... 529
V.P. Grichko and O.A. Shenderova
Introduction ............................................... 529
15.1 Functionalization of ND with Heteroatoms and
Chemical Groups ....................................... 531
15.2 Modification with Nucleic Acids ....................... 536
15.3 Interaction with Proteins ............................. 540
15.4 Application in Biosensors and Medicine ................ 541
15.5 Biocompatibility of ND ................................ 547
15.6 Conclusion ............................................ 549
References ................................................. 550
16 History of Russian Patents on Detonation Nanodiamonds ...... 559
I.L. Petrov and O.A. Shenderova
Introduction ............................................... 559
16.1 Patents on Methods of DND Synthesis ................... 560
16.2 Patents on Post-Synthesis Treatments .................. 563
16.3 Patents on Composition of Matter ...................... 570
16.4 Patents on Applications ............................... 573
16.5 Conclusion ............................................ 580
Acknowledgments ............................................... 581
References .................................................... 581
Index ......................................................... 589
|
