1 Mechanochemistry and Nanoscience ............................. I
1.1 Mechanochemistry of Solids .............................. 1
1.1.1 History of Mechanochemistry ...................... 1
1.1.2 Theories and Models in Mechanochemistry .......... 8
1.1.3 Mechanical Activation ........................... 14
1.1.4 Thermodynamics in Mechanochemistry .............. 16
1.1.5 Kinetics of Mechanochemical Reactions ........... 19
1.2 Introduction to Nanoscience ............................ 29
1.2.1 Historical Outline .............................. 31
1.2.2 Classification of Nanostructures ................ 32
1.2.3 Theoretical Fundamentals ........................ 34
1.2.4 Synthesis Routes (with the Exception of
Mechanochemical Approach) ....................... 39
1.2.5 Mechanochemical Approach ........................ 44
1.2.6 Properties ...................................... 69
1.3 Nanogeoscience ......................................... 76
1.3.1 Mineral Nanoparticle Surfaces ................... 77
1.3.2 Nano- Versus Mechano-Approach: Analogy .......... 78
1.3.3 Clusters and Aggregates Formation ............... 80
1.4 Nanoparticles in Medicine .............................. 82
1.4.1 Size of Biological Objects ...................... 82
1.4.2 Nanomaterials for Cancer Therapy and
Diagnosis ....................................... 83
1.5 Opportunities and Other Challenges ..................... 90
1.6 Conclusion ............................................. 91
References .................................................. 92
2 High-Energy Milling ........................................ 103
2.1 Introduction .......................................... 103
2.2 Basic Phenomena ....................................... 103
2.3 Energy Requirement .................................... 105
2.4 Milling Equipments .................................... 107
2.4.1 Vibration Mills ................................ 107
2.4.2 Planetary Mills ................................ 111
2.4.3 Mixer Mills .................................... 113
2.4.4 Attritors (Stirred Ball Mills) ................. 114
2.4.5 New Mill Design ................................ 116
2.4.6 Process Variables .............................. 117
2.5 Accompanying Phenomena ................................ 119
2.5.1 Temperature Effects ............................ 119
2.5.2 Contamination .................................. 121
2.5.3 Amorphization .................................. 121
2.5.4 Mechanochemical Equilibrium .................... 121
2.5.5 Agglomeration and Aggregation .................. 122
2.6 Surfactants ........................................... 126
References ............................................ 129
3 Selected Identification Methods ............................ 133
3.1 Introduction .......................................... 133
3.2 Infrared Spectroscopy ................................. 133
3.3 X-Ray Photoelectron Spectroscopy ...................... 138
3.4 Scanning Electron Microscopy .......................... 143
3.5 Scanning Tunnelling Microscopy ........................ 146
3.6 Atomic Force Microscopy ............................... 148
3.7 Transmission Electron Microscopy ...................... 150
3.8 X-Ray Diffraction ..................................... 152
3.9 Mossbauer Spectroscopy ................................ 162
3.10 Electron Paramagnetic Resonance ....................... 167
3.11 Conclusion ............................................ 171
References ................................................. 172
4 From Minerals to Nanoparticles ............................. 177
4.1 Introduction .......................................... 177
4.2 Solid Gas Reactions Stimulated by Mechanical
Activation ............................................ 177
4.2.1 Stibnite Sb2S3 ................................. 179
4.2.2 Cinnabar HgS ................................... 180
4.2.3 Galena PbS ..................................... 181
4.2.4 Sphalerite ZnS ................................. 182
4.3 Mechanochemical Reduction via Solid-Solid Reactions ... 186
4.3.1 Redox Reactions ................................ 187
4.3.2 Nanocomposites ................................. 188
4.3.3 Oxides ......................................... 190
4.3.4 Wolframates .................................... 209
4.3.5 Titanates ...................................... 212
4.3.6 Sulphides ...................................... 216
4.3.7 Other Minerals ................................. 245
References ............................................ 249
5 Mechanochemistry in Minerals Engineering ................... 257
5.1 Introduction .......................................... 257
5.2 Mechanochemical Solid Solid Processing ................ 259
5.2.1 Mechanochemical Reduction ...................... 259
5.3 Mechanochemical Solid-Liquid Processing ............... 263
5.3.1 Milling and Leaching as Separated Processes .... 263
5.3.2 Oxidative Leaching ............................. 264
5.3.3 Acidic Leaching ................................ 266
5.3.4 Alkaline Leaching .............................. 268
5.3.5 Selective Leaching of Bismuth .................. 273
5.3.6 Non-Cyanide Leaching of Precious Metals ........ 276
5.3.7 Simultaneous Milling and Leaching
(Mechanochemical Leaching) ..................... 283
5.4 Sorption .............................................. 288
5.4.1 Zinc Sorption on Calcite ....................... 288
5.4.2 Sulphides ...................................... 290
References ............................................ 292
6 Applied Mechanochemistry ................................... 297
6.1 Introduction .......................................... 297
6.2 Mineral Processing .................................... 297
6.2.1 Sulphides ...................................... 298
6.2.2 Other Minerals ................................. 300
6.3 Extractive Metallurgy ................................. 302
6.3.1 Mechanical Activation as Pretreatment Step
for Leaching ................................... 303
6.3.2 Attritors in Hydrometallurgy ................... 318
6.3.3 Mechanochemical Processes for Ore Treatment .... 321
6.4 Chemical Engineering .................................. 341
6.4.1 Crystal Engineering ............................ 341
6.4.2 Heterogeneous Catalysis ........................ 345
6.5 Materials Engineering ................................. 352
6.5.1 Thermoelectric Power Generator Materials ....... 354
6.5.2 Room Temperature Solders ....................... 354
6.5.3 Bearings ....................................... 355
6.6 Coal Industry ......................................... 355
6.6.1 Humic Acids .................................... 355
6.7 Building Industry ..................................... 358
6.7.1 Mechanical Activation of Quartz SiO2 ........... 359
6.7.2 Mechanical Activation of Cement ................ 360
6.7.3 Solidification of Silicate Concretes with
Mechanically Activated Precursors .............. 363
6.7.4 Modification of Concrete Properties by
Application of Waste Materials After Milling ... 363
6.7.5 Manufacture of Exterior Wall Panels with
Intervention of Mechanical Activation .......... 364
6.8 Agriculture ........................................... 365
6.9 Pharmacy .............................................. 370
6.9.1 Solubility of Drugs ............................ 370
6.9.2 Polymorphism and Amorphization ................. 373
6.9.3 Biological Activity of Drugs ................... 375
6.9.4 Mechanochemical Synthesis of Drugs ............. 377
6.10 Waste Treatment ....................................... 380
6.10.1 Mineral Waste .................................. 380
6.10.2 Materials Waste ................................ 387
6.10.3 Organic Waste .................................. 389
References ................................................. 392
Author Index .................................................. 407
Subject Index ................................................. 409
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