PERGAMON MATERIALS SERIES

Multinuclear Solid-State NMR

of Inorganic Materials
by
Kenneth J.D. MacKenzie
School of Chemical and Physical Sciences,
Victoria University of Wellington, and
New Zealand Institute for Industrial Research and Development

Mark E. Smith
Department of Physics, University of Warwick, UK

2002

PERGAMON
An Imprint of Elsevier Science
Amsterdam - Boston - London - New York - Oxford - Paris
San Diego - San Francisco - Singapore - Sydney - Tokyo
Contents

Preface v

CHAPTER 1
INTRODUCTION
1.1. Methodology of Materials Characterisation by NMR 3
1.2. Historical Aspects of NMR Spectroscopy 6
1.3. Brief Description of the NMR Experiment 7
1.3.1 General Principles 7
1.3.2 Overcoming NMR Spectral Broadening in Solids by MAS 10
1.3.3 Other NMR Experiments used with Solids 11
1.3.3.1 Decoupling 12
1.3.3.2 Cross-Polarisation (CP) 12
1.3.3.3 Spin-Echo Experiments 12
1.3.3.4 Two-Dimensional Experiments 12
1.3.4 Nuclei Suitable for NMR Spectroscopy 13
1.4. Further Reading 17
References 18

CHAPTER 2
PHYSICAL BACKGROUND
2.1. Fundamental Interaction with External Magnetic Fields 23
2.1.1 A Quantum Mechanical Description of the Zeeman Interaction 25
2.1.2 Bulk Magnetisation 26
2.1.3 The Rotating Frame and the Application of RF Pulses 29
2.1.4 Observation of the NMR Signal 34
2.2. Internal Interactions 35
2.2.1 The Dipolar Interaction 37
2.2.2 Scalar Coupling 40
2.2.3 Paramagnetic Coupling 43
2.2.4 Chemical Shielding 44
2.2.5 Knight Shift 48
2.2.6 Quadrupole Interaction 50
2.2.7 Nature of Interactions 57
x Contents

2.3. One Dimensional Methods for Improving Resolution 58

2.3.1 Magic Angle Spinning and First-Order Effects 59
2.3.1.1 Physical Principles 59
2.3.1.2 Formation of Spinning Sidebands 61
2.3.2 Magic Angle Spinning and Higher-Order Effects 63
2.3.2.1 MAS of Second-Order Quadrupole Effects 64
2.3.2.2 Residual Coupling Effects due to Quadrupolar Nuclei
inMASSpectra 71
2.3.2.3 Nonequivalent Homonuclear Spins 74
2.3.3 Variable Angle Spinning 74
2.3.4 Double Angle Spinning 75
2.3.5 Multiple Quantum Transitions 77
2.3.6 Ultrasonically-Induced Narrowing 78
2.4. Dipolar Decoupling 78
2.4.1 Heteronuclear Dipolar Decoupling 78
2.4.2 Homonuclear Dipolar Decoupling 79
2.5. Spin-locking 83
2.6. Cross-Polarisation 85
2.7. Two-Dimensional Methods 90
2.7.1 Dynamic Angle Spinning 92
2.7.2 2D MQMAS 93
2.8. NMR Relaxation 98
2.8.1 Introduction to Relaxation 98
2.8.2 Mechanism for Relaxation Processes 101
References 105

CHAPTER 3
EXPERIMENTAL APPROACHES
3.1. Basic Experimental Principles of FT NMR 111
3.2. Instrumentation 112
3.2.1 Overview of a Pulsed FT NMR Spectrometer 112
3.2.2 Magnets 113
3.2.3 Shimming 115
3.2.4 Transmitters 116
3.2.5 Probes 120
3.2.6 Connection of the Probe 122
3.2.7 Signal Detection 124
3.2.8 Additional Equipment 127
 Contents XI

3.3. Practical Acquisition of NMR Spectra 127

3.3.1 Processing the FID to Produce a Spectrum 128
3.3.1.1 Window Functions 128
3.3.1.2 Shifting of the Time Origin and Linear Back
Prediction 129
3.3.1.3 ZeroFilling 129
3.3.1.4 Phase Correction 130
3.3.1.5 Baseline Correction 130
3.3.2 Complications in Recording Spectra 130
3.4. Static Broad Line Experiments 133
3.4.1 Pulsed Echo Experiments 133
3.4.2 Stepped Experiments 136
3.5. One-Dimensional High Resolution Techniques 138
3.5.1 Magic Angle Spinning (MAS) 138
3.5.2 Extraction of Parameters from MAS NMR Spectra 143
3.5.3 Suppression of Spinning Sidebands 143
3.5.4 Special Considerations for MAS of Quadrupolar Nuclei 144
3.5.5 Magic Angle Spinning Observation of Satellite Transitions 149
3.5.6 Double Angle Rotation of Quadrupolar Nuclei 150
3.5.7 Practical Implementation of CRAMPS 152
3.6. Two-Dimensional Experiments 153
3.6.1 NutationNMR 153
3.6.2 Off-Resonance Nutation 154
3.6.3 Order-Resolved Sideband Spectra 155
3.6.4 Dynamic Angle Spinning (DAS) 156
3.6.5 Two-Dimensional Sequences Developed from Solution NMR 157
3.6.6 Multiple Quantum Experiments in Dipolar Coupled Systems 160
3.6.7 Multiple Quantum NMR Experiments of Non-Integer 161
Spin Quadrupolar Nuclei
3.6.8 2D XY Correlation Methods 168
3.6.9 Correlation of Tensor Information - Separated Local 170
Field Experiments
3.7. Summary of Approaches for Examining Quadrupole Nuclei 172
3.8. Multiple Resonance 172
3.8.1 Cross-Polarisation (CP) 173
3.8.2 SEDOR, REDOR and TEDOR 178
3.8.3 TRAPDOR and REAPDOR 182
3.9. Techniques for Determining Relaxation Times and Motional 183
Parameters
3.9.1 MeasurementofTi 183
Xll Contents

3.9.2 Other Spin-Lattice Relaxation Times (T l p T 1D ) 184

3.9.3 Transverse Relaxation Times (T2) 185
3.9.4 Molecular Motion 186
3.9.5 Diffusion Measurements 187
3.10. NMR Under Varying Physical Conditions 187
3.10.1 Variable Temperature NMR 187
3.10.2 High Pressure Experiments 189
References 190

CHAPTER 4
29
SI NMR
4.1. General Considerations 201
4.1.1 Broadening Effects in 29 Si Spectra 201
4.1.2 Relaxation Effects in 29Si Spectra 202
4.1.3 Effect of Structure on 29Si Spectra 204
4.2. Si-0 Compounds 205
4.2.1 Relationships between 29Si NMR Spectra and 205
Structure/Bonding
4.2.2 Four-Coordinated Si-O-Compounds 205
4.2.3 Tetrahedral 29 Si Chemical Shifts in Silicates 205
4.2.4 29 Si Chemical Shifts in Aluminosilicates 206
4.2.5 Effects of Other Nearest Neighbours on the 29 Si Shift 208
4.3. Order-Disorder Effects in Minerals 208
4.4. Identification of Silicate Minerals 212
4.5. Thermal Decomposition of Silicate Minerals 214
4.6. Relationships between 29 Si Chemical Shift (d) and Structure 217
4.6.1 Relationships between 8 and the Si-O Bond Length 218
4.6.2 Relationships between 8 and the Si-O-Si Bond Angle 219
4.6.3 More Complex Relationships between 8 and the Structure 223
4.7. Five and Six-Coordinated Si-0 Compounds 225
4.8. Cross-Polarisation (CPMAS) Experiments 227
4.8.1 Cross-Polarisation between'H and 29 Si 227
4.8.2 Cross-Polarisation between l9 F and 29 Si 229
4.8.3 Other Cross-Polarisation Experiments with 29 Si 229
4.9. Glasses, Gels and Other Amorphous Materials 230
4.9.1 Silicate Glasses 231
4.9.2 Deconvolution of 29Si NMR Spectra 235
4.9.3 Connectivities in Glass 236
4.9.4 Chalcogenide Glasses 238
 Contents Xlll

4.9.5 Gels 240

4.9.6 Other Amorphous Materials 242
4.10. Si-N and Si-N-0 Compounds 244
4.11. Si-Al-O-N Compounds 247
4.11.1 /3-Sialon, Si6_zAlzOzN8_z 247
4.11.2 O-Sialon, Si 2 _ x Al x 0 1+x N 2 . x 250
4.11.3 X-Sialon, nominally Si 1 2 Al I 8 0 3 9 N 8 251
4.11.4 Polytypoid Sialons, (Si,Al)m(OJSf)m+] 253
4.11.5 a-Sialons, MxSii2.(m+n)Alm+nOnN16_n 253
4.12. Other Metal Silicon Nitrides and Oxynitrides 253
4.13. Si-C, Si-C-O and Si-C-N Compounds 255
4.13.1 Silicon Oxycarbide Species 256
4.13.2 Silicon Carbonitride Species 257
4.14. Other Materials 257
4.14.1 Biologically Compatible Glasses 257
4.14.2 Cements 257
4.14.3 Inorganic Polymers 259
References 260

CHAPTER 5
27
AL NMR
5.1. General Considerations 271
5.2. Chemical Shifts in 27A1 Spectra 272
5.2.1 27A1 Chemical Shifts in Al-O Environments 273
5.2.2 27A1 Chemical Shifts in Aluminosilicates 274
5.2.3 Relationships between 27A1 Chemical Shift (8jso) and Structure 279
5.3. Five-Coordinated Al-0 281
5.3.1 A1 (V) in Well-Defined (Crystalline) Environments 281
5.3.2 A1 (V) in Non-Crystalline Environments 283
5.3.3 A1 (V) in Zeolites 287
5.4. Aluminium Oxides 291
5.5. Amorphous Aluminium Compounds 294
5.5.1 Aluminate Gels 294
5.5.2 Glasses 299
5.5.3 Other Amorphous Systems 303
5.6. Aluminophosphates 304
5.7. Aluminium Borate and Molybdate 307
5.7.1 Aluminium Borate 307
5.7.2 Aluminium Molybdate 307
XIV Contents

5.8. Aluminium Fluorides 308

5.9. Thermal Decomposition Reactions 310
5.10. Cements 313
5.11. Nitride and Oxynitride Compounds 316
5.12. Sialon Compounds 317
5.12.1 Polytypoid Sialons 317
5.12.2 ß-Sialons 318
5.12.3 O-Sialons 320
5.12.4 X-Sialons 321
5.12.5 a-Sialons 322
5.12.6 Sialon Glasses 323
References 324

CHAPTER 6
l7
0 NMR
6.1. Introduction 333
6.2. Background 334
6.2.1 Enrichment Schemes 334
6.2.2 Experimental NMR Methodology 337
6.2.3 Relationships between NMR Parameters and Structure 346
6.3. Binary Oxides 349
6.3.1 Crystalline Materials 349
6.3.2 Sol-Gel Produced Samples 352
6.4. Crystalline Ternary Ionic Systems 355
6.5. Silicates and Germanates 359
6.5.1 Crystalline Materials 359
6.5.1.1 Silica and Germania 359
6.5.1.2 Ternary Silicates 361
6.5.1.3 Silicates and Germanates of Zirconium and Titanium 365
6.5.2 Amorphous Materials 366
6.5.2.1 Silica and Germania 366
6.5.2.2 Metal Silicate and Germanate Glasses 367
6.5.2.3 Gel-Based Silicates 369
6.6. Aluminium- and Gallium-Containing Systems 372
6.6.1 Alumina and Aluminates 372
6.6.2 Crystalline Alumino- and Gallosilicates 375
6.6.3 Amorphous Aluminosilicates 379
6.7. Boron-Containing Systems 381
6.7.1 Borates 381
 Contents xv

6.7.2 Ternary and Quaternary Systems 382

6.8. Other Systems 384
6.9. Hydrogen-Containing Samples 386
6.9.1 Crystalline Hydroxides and Other Hydrogen-Containing 386
Materials
6.9.2 Hydrous Gels and Glasses 387
6.10. High Temperature Ceramic Superconductors 388
References 390

CHAPTER 7
NMR OF OTHER COMMONLY STUDIED NUCLEI
7.1. 2 3 NaNMR 399
7.1.1 General Considerations 399
7.1.2 23 Na NMR Spectra of Sodium Compounds 399
7.1.3 Relationships between the 23 Na Chemical Shift and 403
Structural Parameters
23
7.1.4 Na NMR of Crystalline Materials 406
7.1.5 23 Na NMR Studies of Thermal Reactions 412
7.1.6 23 Na NMR of Glasses 413
7.1.6.1 Silicate and Aluminosilicate Glasses 413
7.1.6.2 Sodium Borosilicate Glasses 414
7.1.6.3 Sodium Borate, Germanate and Tellurite 415
Glasses and Melts
7.1.6.4 Phosphate Glasses 415
7.1.6.5 Miscellaneous Glass Studies 416
7.1.7 2 3 NaNMRofZeolites 418
7.2. " B N M R 420
7.2.1 General Considerations 420
7.2.2 " B NMR of Crystalline Compounds 421
7.2.3 ' 'B NMR of Glasses 424
7.2.4 ' 'B NMR of Zeolites 431
7.3. 3 1 PNMR 432
7.3.1 Relationships between 31 P NMR Parameters and Structure 438
7.3.2 31 P NMR of Glasses 441
7.3.2.1 Binary Phosphate Glasses 441
7.3.2.2 Phosphosilicate Glasses 443
7.3.2.3 Alkali Borophosphate Glasses 445
7.3.2.4 Borosilicophosphate Glasses 445
7.3.2.5 Phosphoaluminosilicate Glasses 446
7.3.2.6 Alkali Phosphoaluminoborosilicate Glasses 447
XV) Contents

7.3.2.7 Phosphorus Chalcogenide Glasses 447

31
7.3.3 P NMR of AlP0 4 Molecular Sieves 448
31
7.3.4 P NMR of Biomaterials 450
References 452

CHAPTER 8
NMR OF LOW--Y NUCLIDES
8.1. General Considerations 461
8.1.1 Problems Associated with Low-y Nuclei 461
8.2. NMR of Spin-'/ 2 Nuclei 462
9
8.2.1 " Y NMR 462
107
8.2.2 Ag and 109Ag NMR 469
8.2.3 ' " W N M R 473
8.3. Quadrupolar Nuclei 475
8.3.1 14 NNMR 475
8.3.2 25 Mg NMR 479
8.3.3 33 S NMR 488
8.3.4 35C1 and 37C1 NMR 491
8.3.5 39K NMR 495
8.3.6 43 Ca NMR 502
8.3.7 47Ti and 49 Ti NMR 505
8.3.8 67Zn NMR 511
8.3.9 91 Zr NMR 514
8.3.10 95 Mo and 97 Mo NMR 516
8.3.11 1 3 5 Baand 1 3 7 BaNMR 522
8.3.12 Other Miscellaneous Low-y Nuclei 525
References 526

CHAPTER 9
N M R OF OTHER SPIN-1/;, NUCLEI
9.1. Introduction 535
9.2. Abundant High-y Nuclei 536
9.2.1 'HNMR 536
9.2.1.1 Background to Proton Studies in Inorganic Materials 536
9.2.1.2 Studies of Stoichiometric Protons in
Crystalline Materials 539
9.2.1.3 Non-Stoichiometric Proton Environments in
Crystalline and Glassy Materials 542
 Contents xvn

9.2.1.4 'H NMR ofHydrous Glasses 545

9.2.1.5 Biomineral-Related Materials 550
9.2.2 19F NMR 550
9.2.2.1 Introduction 550
9.2.2.2 Simple Inorganic Fluorides 551
9.2.2.3 More Complex Fluorides 554
9.2.2.4 Applications to Fluoroapatite Studies 555
9.2.2.5 Fluorine in Aluminosilicate Minerals and
Related Materials 556
9.2.2.6 Surface Interaction of Fluorine with Silica- and
Alumina-Based Materials 557
9.2.2.7 Fluorine in Alumino- and Gallophosphates 559
9.2.2.8 Fluorine in Oxygen-Containing Glasses 559
9.2.2.9 Fluoride Glasses 560
9.2.2.10 Fluorine in Other Materials 562
9.2.2.11 Fluorine as a Source of Cross-Polarisation 562
9.2.2.12 Summary of 19F Shift Trends and Other
NMR Properties 562
9.3. Dilute or Medium-7 Nuclei 563
9.3.1 13C NMR 563
9.3.1.1 13C NMR of Elemental Carbon 563
9.3.1.2 Silicon Carbide 568
9.3.1.3 Other Binary Carbides 570
9.3.1.4 Ternary and Quaternary Carbides 572
9.3.1.5 Carbonates 572
9.3.2 15 NNMR 574
9.3.2.1 Nitrides 575
9.3.2.2 Silicon Aluminium Oxynitride Ceramics and Glasses 576
9.3.2.3 Nitride Ceramics from Polymerie Precursors 579
9.3.2.4 Nitrates and Nitrites 582
9.3.3 77 Se NMR 583
9.3.4 l u C d a n d 1 1 3 C d N M R 587
9.3.5 " 5 Sn, 1 1 7 Snand 1 1 9 SnNMR 591
9.3.5.1 Crystalline Oxygen-Containing Materials 591
9.3.5.2 Oxide Solid Solutions and Glasses 594
9.3.5.3 Non-oxide Materials 595
9.3.6 123 Teand 125 TeNMR 598
9.3.6.1 Crystalline Tellurides 598
9.3.6.2 Crystalline Tellurites and Tellurates 599
9.3.6.3 Glassy Tellurium-Containing Materials 601
xvin Contents
l29
9.3.7 XeNMR 601
195
9.3.8 Pt NMR 603
199
9.3.9 Hg NMR 604
203
9.3.10 T1 and 205T1 NMR 604
207
9.3.11 PbNMR 607
9.3.11.1 Correlations between 207 Pb Chemical Shifts
and Structure 607
207
9.3.11.2 Pb NMR of Crystalline Lead Compounds 609
9.3.11.3 2ü7 Pb NMR of Lead-Containing Glasses 613
9.3.11.4 2ü7 Pb in Sol-Gel Prepared Ceramics 615
References 616

CHAPTER 10
NMR OF OTHER QUADRUPOLAR NUCLEI
10.1. 6 Liand 7 LiNMR 629
10.1.1 General Considerations 629
10.1.2 6 J Li NMR of Crystalline Solids 630
10.1.3 Relation between 6Li Chemical Shifts and Structure 634
67
10.1.4 Li NMR of Fast Lithium Ion Conductors 636
10.1.5 6 J Li NMR of Glasses 638
10.2. 9 BeNMR 639
10.3. 5 I VNMR 642
10.3.1 General Considerations 642
10.3.2 51 V NMR of Vanadium Oxides and the Vanadates 642
10.3.3 5 1 VNMRofZeolitesandCatalysts 646
63
10.4. Cu and 65Cu NMR 649
10.4.1 63 Cu NMR of Superconductors and Superfast lonic Conductors
650
10.5. 6 9 Gaand 7 1 GaNMR 653
10.5.1 General Considerations 653
697l
10.5.2 Ga NMR of Crystalline Compounds 655
10.5.3 6 9 7 1 Ga NMR of Other Compounds 657
10.6. 87Rb NMR 658
10.6.1 General Considerations 658
87
10.6.2 Rb NMR of Crystalline Compounds 658
10.6.3 87 Rb NMR of Rubidium Fullerides 661
10.7. 93Nb NMR 662
10.8. l 3 3 CsNMR 665
10.8.1 General Considerations 665
 Contents xix
133
10.8.2 Cs NMR of Crystalline Caesium Compounds 666
l33
10.8.3 Cs NMR of Minerals and Zeolites 669
133
10.8.4 Cs NMR of Füllendes, Superionic Conductors 673
and Semiconductors
10.9. 139 LaNMR 674
References 678

CHAPTER 11
SOLID STATE NMR OF METALS AND ALLOYS
11.1. Introduction 687
11.2. Experimental Approaches 689
11.3. Metallic Elements 691
11.4. Intermetallic Alloys 693
11.5. Phase Transformations, Ordering and Defect Sites 696
11.6. Phase Composition and Precipitation 698
11.7. Atomic Motion 700
References 701

SUBJECT INDEX 703

MINERAL INDEX