Ultrananocrystalline Diamond: Synthesis, Properties, and Applications

Table of Contents......Page 0
Front Matter......Page 1
Contributors......Page 3
Preface......Page 6
Table of Contents......Page 8
Introduction......Page 18
1.1 Historical Overview......Page 19
1.2 Nanocarbon Classification......Page 23
1.3 Exotic Nanocarbons......Page 27
References......Page 31
Introduction......Page 38
2.1 Stellar Nucleosynthesis and Presolar Stardust......Page 39
2.2 Discovery and Identification of Presolar Minerals......Page 41
2.3 Origins of Meteoritic Nanodiamonds......Page 42
2.4 Isotopic Compositions of Meteoritic Nanodiamonds: Stellar Sources......Page 43
2.4.1 Primary C, Surface Bound H, and Trapped N......Page 45
2.4.2 Trapped Noble Gases......Page 48
2.4.3 Trapped Te, Pd, Ba, and Sr......Page 61
2.4.4 Inferred Stellar Sources......Page 63
2.5.1 Twin Microstructure......Page 65
2.5.2 Dislocation Microstructure......Page 69
2.5.3 Polytypes......Page 70
2.5.4 Inferred Mechanisms of Formation......Page 71
2.6 Noble Gas and N Content in Meteoritic Nanodiamonds: Nebular Processes......Page 73
2.7 Nanodiamonds in Interplanetary Dust Particles: Insights on Solar Nebula Evolution......Page 80
2.8 Summary of Experimental Data......Page 82
2.9 The New Astronomy......Page 83
References......Page 84
Introduction......Page 94
3.1 Nanodiamonds: Shapes......Page 96
3.2 Types of Nanodiamond and Methods of Their Synthesis......Page 97
3.2.1 Zero-dimensional Nanodiamond Structures......Page 99
3.2.2 One-dimensional ND Structures......Page 110
3.2.3 Two-dimensional ND Structures......Page 117
3.2.4 Three-dimensional ND Structures......Page 119
3.3 Conclusion......Page 123
References......Page 124
Introduction: Nanocarbon Phase Stability......Page 131
4.1 Nanocarbon Phase Diagrams......Page 132
4.2 Theoretical Studies of the Relative Phase Stability of Nanocarbons......Page 137
4.2.1 Stability of Large Nanocarbon Particles......Page 138
4.2.2 Stability of Small Nanocarbon Particles......Page 143
4.2.3 Coexistence of Bucky-diamond and Other Nanocarbon Phases......Page 144
4.2.4 Stability of Quasi One-dimensional Nanocarbon......Page 146
4.3.1 Morphology of Nanodiamond Particles......Page 148
4.3.2 Morphology of Diamond Nanorods and Nanowires......Page 155
4.3.3 Hybrid Nanocarbon Materials......Page 160
4.4 Conclusions......Page 161
References......Page 163
Introduction......Page 170
5.1 Characterization of n-type Conductivity in UNCD Films......Page 172
5.2 Applications of n-type UNCD Films......Page 178
5.2.1 Field Electron Emission......Page 180
5.2.2 Electrodes for Electrochemistry and Biosensing......Page 181
5.2.3 High-temperature n-type UNCD/p-type All-diamond Heterostructure Diode......Page 182
5.3 Electronic Structure of UNCD Grain Boundaries......Page 183
5.4 UNCD and Carbon Nanotube/UNCD Composites as Potential High-efficiency, High-temperature Thermoelectric Materials......Page 186
5.5 Summary......Page 191
Acknowledgments......Page 192
References......Page 193
Introduction......Page 198
6.1.1 MPACVD Reactor and Process Parameters......Page 201
6.1.2 Arrangements for Spectroscopic Diagnostics......Page 203
6.2.1 Optical Emission and Broadband Absorption Spectroscopy......Page 204
6.2.2 Plasma Modeling......Page 212
6.3.1 Deposition and Characterization of NCD Films......Page 215
6.3.2 Plasma Diagnostics......Page 220
6.4.1 Parametric Studies......Page 224
6.4.2 Mechanisms of C_2 Formation......Page 233
6.4.3 Conclusion on Plasma Modeling......Page 235
6.5 General Conclusion......Page 236
References......Page 237
Introduction......Page 242
7.1 The Deposition System and Deposition Parameters......Page 244
7.2 Evolution and Properties of the Films Studied by NEXAFS: Coordination and Orientation......Page 248
7.3 Phase Composition of the Films as Reflected by Raman Spectroscopy......Page 253
7.4 Crystalline Structure of the Films by XRD......Page 259
7.6 Surface and Grain Boundary Phase Composition Studied by EELS......Page 261
7.7 Hydrogen Content in the Films by SIMS and ERD......Page 264
7.8 Hydrogen Bonding Configuration in the Nanodiamond Films Studied by HREELS......Page 265
7.10 Visualization and Evolution of the Films Studied by HR TEM......Page 270
7.11 Formation Mechanism of the Nanodiamond Film Deposited from Energetic Species......Page 273
7.12 Summary......Page 279
References......Page 280
Introduction......Page 286
8.1 Computational Methodologies......Page 287
8.2.1 The (110) 1 x 1:H Surfaces......Page 288
8.2.2 Clean (110) Diamond Surface......Page 291
8.3 Carbon Dimer Growth Mechanisms on the (100) Surface of Diamond......Page 292
8.3.1 The (100) 2 x 1:H Diamond Surface......Page 293
8.3.2 The (100) 2 x 1 Diamond Surface......Page 294
8.3.3 Nitrogen Addition to (100) 2 x 1 Surface......Page 297
8.3.4 A Model for UNCD Growth Kinetics......Page 298
8.4.1 Grain Boundaries in UNCD......Page 300
8.4.2 Structure of High-angle Twist GBs in Diamond......Page 301
8.4.3 Electronic Structure of GBs with pi Bonding in UNCD......Page 303
8.5.1 Nitrogen in Diamond and Amorphous Carbon......Page 306
8.5.2 Nitrogen Impurities in the UNCD GBs......Page 307
8.5.3 Other Impurities in the UNCD GBs......Page 311
References......Page 312
Introduction......Page 316
9.1 The Material......Page 318
9.2.1 Elasticity and Strength Experiments......Page 321
9.2.2 Fracture Toughness Experiments......Page 323
9.3.1 Stress-strain Curves......Page 327
9.3.2 Size Effect and Weibull Analysis......Page 329
9.3.3 Toughness Measurements......Page 332
9.4 Fractographic Analysis......Page 338
9.5 Theoretical Strength......Page 340
9.6 Conclusions......Page 341
References......Page 342
10. On the Discovery of Detonation Nanodiamond......Page 346
References......Page 355
Introduction......Page 357
11.1 Industrial Technologies of Detonation Synthesis of UNCD......Page 359
11.2.1 Chemical Purification......Page 364
11.2.2 UNCD Modification......Page 381
References......Page 385
Introduction......Page 388
12.1.2 X-ray Diffraction......Page 389
12.1.3 Small-angle X-ray Scattering......Page 391
12.1.4 Raman Scattering......Page 392
12.1.5 HRTEM and SEM Studies......Page 395
12.1.6 STM and AFM Studies......Page 396
12.1.7 Visible and Far-infrared Spectroscopic Studies......Page 398
12.1.8 NMR and EPR Studies......Page 399
12.2 The Structure of UNCD Clusters and the Aggregation Problem......Page 400
12.3 Mechanical Properties......Page 405
12.5 Electronic Properties......Page 406
Acknowledgments......Page 407
References......Page 408
Introduction......Page 414
13.1 Stability of Nanocarbons......Page 417
13.2.1 Surface Groups of NDs......Page 420
13.2.2 Thermal Stability of ND Surface Groups......Page 422
13.2.3 Critical View of the Formation of sp^2-bonded Carbon in Pristine NDs......Page 427
13.2.4 The Onset Temperature of ND Graphitization......Page 429
13.3 Kinetics of Diamond Graphitization......Page 431
13.3.1 Experimental Approaches for the Study of ND Graphitization......Page 432
13.3.2 Kinetic Parameters of ND Graphitization for the Temperature Range of 1370-1860 K......Page 434
13.4.1 Diamond Surface Reconstruction......Page 440
13.4.2 Cleavage Energies of Diamond Planes......Page 442
13.4.3 Shape of Diamond Particles......Page 443
13.4.4 Graphite/Diamond Interfaces......Page 445
13.4.5 Formation of Nanocarbon Species via "Low"-temperature Diamond Graphitization......Page 448
13.4.6 The Formation of the Closed Curved Graphitic Structure on the Surface of Micron-size Diamond......Page 454
13.5 Catalytic Graphitization of NDs in the Presence of Metal Clusters......Page 459
13.6 Graphitization of NDs in the Presence of Oxygen- and Hydrogen-containing Gases......Page 463
13.7 Properties of ND Annealing Products: OLC, sp^2/sp^3 Nanocomposites......Page 466
13.8 Conclusion......Page 470
References......Page 472
14.1.1 Chrome Plating......Page 485
14.1.2 Copper Plating......Page 488
14.1.3 Zinc Plating......Page 489
14.1.5 Silvering......Page 490
14.1.6 Gold Plating......Page 491
14.1.8 Anode Oxidation......Page 492
14.1.9 The Deposition of Alloys along with UNCD......Page 493
14.2 Polymer Compositions and Antifriction Coatings......Page 494
14.2.1 The Polyisoprene and Butadiene-Styrene Copolymer......Page 496
14.2.2 The Polysiloxane Polyblock Cyclolinear Copolymer......Page 499
14.2.3 Polyurethane Foam......Page 500
14.2.4 Frost-resistant Butadiene-Nitrile Rubber......Page 501
14.2.5 Rubbers Stable to Explosive Decompression......Page 502
14.2.6 Gas-flame Deposition of Polymer Coatings......Page 503
14.3 Polishing......Page 504
14.4 Oils and Lubricants......Page 512
14.5 Diamond Sinters and Compacts......Page 516
14.6 Bioactivity of UNCD Particles......Page 521
14.7 Other Technological Applications of UNCD Particles......Page 528
References......Page 529
Introduction......Page 536
15.1 Functionalization of ND with Heteroatoms and Chemical Groups......Page 538
15.2 Modification with Nucleic Acids......Page 543
15.3 Interaction with Proteins......Page 547
15.4 Application in Biosensors and Medicine......Page 548
15.5 Biocompatibility of ND......Page 554
15.6 Conclusion......Page 556
References......Page 557
Introduction......Page 565
16.1 Patents on Methods of DND Synthesis......Page 566
16.2 Patents on Post-synthesis Treatments......Page 569
16.3 Patents on Composition of Matter......Page 576
16.4 Patents on Applications......Page 579
16.5 Conclusion......Page 586
References......Page 587
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N......Page 606
O......Page 608
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U......Page 615
Z......Page 616