Modern Luminescence Spectroscopy of Minerals and Materials (eBook)

Preface 6
Contents 10
CHAPTER 1 Introduction 20
CHAPTER 2 Theoretical Background 28
2.1 The s, p, d, f Atomic Orbitals 28
2.2 Point Group Symmetry 29
2.3 Absorption of the Excitation Energy 30
2.3.1 Optical Absorption Spectroscopy 30
2.3.2 Luminescence Excitation Spectroscopy 33
2.4 Radiative Return to the Ground State – Luminescence 37
2.4.1 Ligand Field Theory 37
2.4.2 Configurational Coordinate Diagram 42
2.4.3 Molecular Orbital Theory 45
2.4.4 Discrete Variational Multi Electron Technique 46
2.4.5 Luminescence Decay 46
2.4.6 Luminescence in the Band Scheme 49
CHAPTER 3 Experimental Techniques 52
3.1 Lasers 52
3.1.1 The Basic Theory of Laser Action 52
3.1.2 Short Description of the Lasers Used for Luminescence of Minerals Excitation 53
3.2 Steady-State Luminescence Spectroscopy 54
3.2.1 Experimental Apparatus 54
3.2.2 Spectral Deconvolution 55
3.3 Time-Resolved Luminescence Spectroscopy 56
3.4 Other Laser Based Spectroscopic Techniques 61
CHAPTER 4 Luminescent Minerals 62
4.1 Calcium (Ca2+) Bearing Minerals 67
4.1.1 Apatite Ca5(PO4)3(F, Cl, O, OH) 67
4.1.2 Scheelite CaWO4 72
4.1.3 Fluorite CaF2 75
4.1.4 Calcite and Aragonite CaCO3 75
4.1.5 Danburite CaB2(SiO4)2 80
4.1.6 Datolite CaB(SiO4)(OH) 81
4.1.7 Anhydrite CaSO4 81
4.1.8 Apophyllite Ca4KF(Si8O20)x8H2O 82
4.1.9 Hardystonite Ca2ZnSi2O7 83
4.1.10 Esperite Ca3PbZn4(SiO4)4 84
4.1.11 Charoite K2NaCa5(Si12O30)Fx3H2O 86
4.1.12 Prehnite Ca2Al2Si3O10(OH)2 86
4.1.13 Pectolite NaCa2Si3O8(OH) 87
4.1.14 Pyrochlore (Ca,Na)2Nb2O6(OH,F) 87
4.1.15 Leucophane NaCaBe(Si2O6)F 88
4.2 Lead (Pb2+) bearing minerals 88
4.2.1 Pyromorphite Pb5(PO4)3Cl 89
4.3 Tin (Sn4+) Bearing Minerals 90
4.3.1 Cassiterite SnO2 90
4.4 Barium (Ba2+) Bearing Minerals 92
4.4.1 Barite BaSO4 92
4.5 Strontium (Sr2+) Bearing Minerals 93
4.5.1 Celestine SrSO4 94
4.6 Titanium (Ti4+) Bearing Minerals 95
4.6.1 Titanite CaTiSiO5 95
4.6.2 Benitoite BaTiSi3O9 97
4.6.3 Other Titanium Bearing Minerals 99
4.7 Zinc (Zn2+) Bearing Minerals 99
4.7.1 Hydrozincite Zn5(CO3)2(OH)6 99
4.7.2 Willemite Zn2SiO4 99
4.8 Zirconium (Zr4+) Bearing Minerals 100
4.8.1 Zircon ZrSiO4 100
4.8.2 Baddeleyite ZrO2 103
4.9 Silicon (Si4+) Bearing Minerals 105
4.9.1 Wollastonite CaSiO3 105
4.9.2 Feldspars 106
4.9.3 Obsidian SiO2 109
4.10 Aluminum (Al3+) Bearing Minerals 109
4.10.1 Kyanite and Sillimanite Al2O[SiO4] 109
4.10.2 Topaz Al2SiO4F2 111
4.10.3 Corundum Al2O3 112
4.10.4 Spinel MgAl2O4 113
4.10.5 Beryl and Emerald Be3Al2Si6O18 114
4.10.6 Chrysoberyl and Alexandrite BeAl2O4 116
4.10.7 Garnet: Pyrope Mg3Al2(SiO4)3 and Grossular Ca3Al2(SiO4)3 119
4.10.8 Tourmaline (Na,Ca)(Mg,Al,Li)3Al6x(BO3)3Si6O18OH 121
4.10.9 Epidote (Zoisite) Ca2AlAl2O(OH)(Si2O7)(SiO4) 121
4.10.10 Eosphorite AlPO4Mn(OH)2H2O 122
4.10.11 Spodumen LiAlSi2O6 124
4.10.12 Boehmite and Diaspor AlOOH 125
4.10.13 Chlorite (Mg,Al,Fe)12[(Si,Al)8O20](OH)16 125
4.11 Sodium (Na+) Bearing Minerals 127
4.11.1 Sodalite Na8[Al6Si6O24]Cl2 127
4.12 Silver (Ag+)Minerals 128
4.12.1 Chlorargyrite AgCl and Embolite Ag(Cl,Br) 128
4.13 Manganese (Mn2+) Bearing Minerals 128
4.13.1 Rhodonite CaMn4Si5O15 and Rhodochrosite MnCO3 128
4.14 Uranium (U6+) Bearing Minerals 129
4.15 Magnesium (Mg2+) Bearing Minerals 130
4.15.1 Forsterite Mg2SiO4 131
4.16 Rare-Earth Bearing Minerals 131
4.16.1 Monazite (Ce,La)PO4 132
4.16.2 Thorite ThSiO4 132
4.17 Carbon Bearing Minerals 133
4.17.1 Diamond C 133
CHAPTER 5 Interpretation of Luminescence Centers 136
5.1 Rare-Earth Elements (REE) 136
5.1.1 The Classical Treatment of Optical Properties of Trivalent REE 136
5.1.2 Theory of Optical Transitions in Trivalent REE 138
5.1.3 Relaxation Processes in Trivalent REE 140
5.1.4 Energy Transfer to the Trivalent REE 141
5.1.5 The Treatment of Optical Properties of Divalent REE 143
5.2 Rare-Earth Elements Luminescence in Minerals 146
5.2.1 Ce3+ 146
5.2.2 Pr3 150
5.2.3 Nd3+ 156
5.2.4 Sm3+, Sm2+ 159
5.2.5 Eu3+, Eu2+ 161
5.2.6 Gd3+ 177
5.2.7 Tb3+ 177
5.2.8 Dy3+ 179
5.2.9 Er3+ 180
5.2.10 Ho3+ 182
5.2.11 Tm3+ 183
5.2.12 Yb3+, Yb2+ 184
5.3 Transition Metal Elements 185
5.3.1 3d3 Elements 186
5.3.2 3d2 Elements 205
5.3.3 3d1 Elements 210
5.3.4 3d8 Elements 216
5.3.5 3d6 Elements 217
5.3.6 3d5 Elements 217
5.4 s2 Ions 226
5.4.1 Bi3+, Bi2+ 226
5.4.2 Pb2+ 229
5.4.3 Pb+ 234
5.4.4 Tl+ 234
5.4.5 Sn2+ 234
5.4.6 Sb3+ 236
5.5 d10-Ions 237
5.5.1 Ag+ 237
5.5.2 Cu+ 240
5.6 d0 Complex Ions 240
5.6.1 Scheelite – WO4 241
5.6.2 Pyromorphite – VO4 242
5.6.3 Beryl – VO4 243
5.6.4 Benitoite – TiO6 243
5.7 Molecular Centers 246
5.7.1 Uranyl (UO2)2+ 246
5.7.2 O–2, S–2 and F-Centers 250
5.8 Radiation-Induced Centers 250
5.8.1 Zircon 250
5.8.2 Calcite 253
5.8.3 Topaz 254
5.8.4 Interstellar Matter 254
5.9 Reabsorption Lines of Oxygen andWater 254
5.9.1 Apatite-Luminescence Spectroscopy 254
5.9.2 Apatite – Photoacoustic Spectrophotometry 257
5.9.3 Diamond 258
5.10 Luminescence Centers in Diamonds 259
5.10.1 N3 259
5.10.2 H3, H4, S2, S1 and S3 261
5.10.3 A-Band 262
5.11 Unidentified Luminescence Centers 262
5.11.1 Apatite 262
5.11.2 Zircon 264
5.11.3 Barite 265
5.11.4 Calcite 267
CHAPTER 6 Applications of Laser-Induced Time-Resolved Spectroscopic Techniques 270
6.1 Time-Resolved Laser-Induced Breakdown Spectroscopy (LIBS) 270
6.1.1 Theory and Technique 270
6.1.2 Quantitative Elemental Analysis 273
6.1.3 LIBS in Geosciences 274
6.2 Gated Raman Spectroscopy 275
6.2.1 Theory and Technique 275
6.2.2 Raman and Luminescence 280
6.2.3 Raman in Geosciences 281
6.3 Second Harmonic Generation (SHG) 282
CHAPTER 7 Minerals Prospecting 288
7.1 Earth Surface 288
7.1.1 Geology Applications 288
7.1.2 Anti-Terror Applications 292
7.2 Earth Subsurface 293
7.3 Other Planets 294
7.3.1 LIBS System 294
7.3.2 Raman System 295
7.3.3 Combination of LIBS and Raman Systems 295
CHAPTER 8 Minerals Radiometric Sorting 298
8.1 Laseroluminescent Sorting 301
8.2 LIBS Sorting 302
8.3 Combination of Sorting Techniques 305
8.3.1 Diamonds 305
8.3.2 Industrial Minerals 307
8.3.3 Base Metals 323
8.3.4 Non-Ferrous Metals 325
8.3.5 Precious Metals 327
8.3.6 Fuel Minerals 330
CHAPTER 9 Identification of Minerals 332
9.1 Luminescent Minerals 332
9.2 Gemology 334
9.3 Micro Photoluminescence 339
CHAPTER 10 Waste Storage Geomaterials 340
CHAPTER 11 Luminescent Bio-Minerals 344
Conclusions 346
References 350
Index 362