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Principles of Inorganic
Materials Design
Principles of Inorganic Materials Design
Third Edition
John N. Lalena
Physical Scientist
David A. Cleary
Gonzaga University
Olivier B.M. Hardouin Duparc

École polytechnique Institut Polytechnique Paris
This edition first published 2020
© 2020 John Wiley & Sons Inc.
Edition history:
“John Wiley & Sons Inc. (1e, 2005)”
“John Wiley & Sons Inc. (2e, 2010)”
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The right of John N. Lalena, David A. Cleary, and Olivier B. M. Hardouin Duparc to be identified as the authors of this
work has been asserted in accordance with law.
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Library of Congress Cataloging-in-Publication Data
Names: Lalena, John N. author. | Cleary, David A., 1957– author. | Duparc,
Olivier B. M. Hardouin, author.
Title: Principles of inorganic materials design / John N. Lalena, U.S.
Department of Energy, David A. Cleary, Gonzaga University, Olivier B. M.
Hardouin Duparc, E’cole Polytechnique.
Description: Third edition. | Hoboken, NJ, USA : Wiley, 2020. | Includes
bibliographical references and index.
Identifiers: LCCN 2019051901 (print) | LCCN 2019051902 (ebook) | ISBN
9781119486831 (hardback) | ISBN 9781119486916 (adobe pdf) | ISBN
9781119486763 (epub)
Subjects: LCSH: Chemistry, Inorganic–Materials. | Chemistry,
Technical–Materials.
Classification: LCC QD151.3 .L35 2020 (print) | LCC QD151.3 (ebook) | DDC
546–dc23
LC record available at https://lccn.loc.gov/2019051901
LC ebook record available at https://lccn.loc.gov/2019051902
Cover Design: Wiley

Cover Images: Molecular model, illustration © VICTOR HABBICK VISIONS/SCIENCE PHOTO LIBRARY/Getty
Images, Blue crystals © assistantua/Getty Images
Set in 9.5/12.5pt STIXTwoText by SPi Global, Pondicherry, India
Printed in United States of America
10 9 8 7 6 5 4 3 2 1
v
Contents
Foreword to Second Edition xiii

Foreword to First Edition xv
Preface to Third Edition xix
Preface to Second Edition xx
Preface to First Edition xxi
Acronyms xxiii
1 Crystallographic Considerations 1
1.1 Degrees of Crystallinity 1
1.1.1 Monocrystalline Solids 2
1.1.2 Quasicrystalline Solids 3
1.1.3 Polycrystalline Solids 4
1.1.4 Semicrystalline Solids 5
1.1.5 Amorphous Solids 8
1.2 Basic Crystallography 8
1.2.1 Crystal Geometry 8
1.2.1.1 Types of Crystallographic Symmetry 12
1.2.1.2 Space Group Symmetry 17
1.2.1.3 Lattice Planes and Directions 27
1.3 Single-Crystal Morphology and Its Relationship to Lattice Symmetry 32
1.4 Twinned Crystals, Grain Boundaries, and Bicrystallography 37
1.4.1 Twinned Crystals and Twinning 37
1.4.2 Crystallographic Orientation Relationships in Bicrystals 39
1.4.2.1 The Coincidence Site Lattice 39
1.4.2.2 Equivalent Axis–Angle Pairs 44
1.5 Amorphous Solids and Glasses 46
1.5.1 Oxide Glasses 49
1.5.2 Metallic Glasses and Metal–Organic Framework Glasses 51
1.5.3 Aerogels 53
Practice Problems 53
References 55
2 Microstructural Considerations 57
2.1 Materials Length Scales 57
2.1.1 Experimental Resolution of Material Features 61
2.2 Grain Boundaries in Polycrystalline Materials 63
vi Contents
2.2.1 Grain Boundary Orientations 63

2.2.2 Dislocation Model of Low Angle Grain Boundaries 65
2.2.3 Grain Boundary Energy 66
2.2.4 Special Types of “Low-Energy” Boundaries 68
2.2.5 Grain Boundary Dynamics 69
2.2.6 Representing Orientation Distributions in Polycrystalline Aggregates 70
2.3 Materials Processing and Microstructure 72
2.3.1 Conventional Solidification 72
2.3.1.1 Grain Homogeneity 74
2.3.1.2 Grain Morphology 76
2.3.1.3 Zone Melting Techniques 78
2.3.2 Deformation Processing 79
2.3.3 Consolidation Processing 79
2.3.4 Thin-Film Formation 80
2.3.4.1 Epitaxy 81
2.3.4.2 Polycrystalline PVD Thin Films 81
2.3.4.3 Polycrystalline CVD Thin Films 83
2.4 Microstructure and Materials Properties 83
2.4.1 Mechanical Properties 83
2.4.2 Transport Properties 86
2.4.3 Magnetic and Dielectric Properties 90
2.4.4 Chemical Properties 92
2.5 Microstructure Control and Design 93
References 96
3 Crystal Structures and Binding Forces 99

3.1 Structure Description Methods 99
3.1.1 Close Packing 99
3.1.2 Polyhedra 103
3.1.3 The (Primitive) Unit Cell 103
3.1.4 Space Groups and Wyckoff Positions 104
3.1.5 Strukturbericht Symbols 104
3.1.6 Pearson Symbols 105
3.2 Cohesive Forces in Solids 106
3.2.1 Ionic Bonding 106
3.2.2 Covalent Bonding 108
3.2.3 Dative Bonds 110
3.2.4 Metallic Bonding 111
3.2.5 Atoms and Bonds as Electron Charge Density 112
3.3 Chemical Potential Energy 113
3.3.1 Lattice Energy for Ionic Crystals 114
3.3.2 The Born–Haber Cycle 119
3.3.3 Goldschmidt’s Rules and Pauling’s Rules 120
3.3.4 Total Energy 122
3.3.5 Electronic Origin of Coordination Polyhedra in Covalent Crystals 124
3.4 Common Structure Types 127
Contents vii
3.4.1 Iono-covalent Solids 128

3.4.1.1 AX Compounds 128
3.4.1.2 AX2 Compounds 130
3.4.1.3 AX6 Compounds 132
3.4.1.4 ABX2 Compounds 132
3.4.1.5 AB2X4 Compounds (Spinel and Olivine Structures) 134
3.4.1.6 ABX3 Compounds (Perovskite and Related Phases) 135
3.4.1.7 A2B2O5 (ABO2.5) Compounds (Oxygen-Deficient Perovskites) 137
3.4.1.8 AxByOz Compounds (Bronzes) 139
3.4.1.9 A2B2X7 Compounds (Pyrochlores) 139
3.4.1.10 Silicate Compounds 140
3.4.1.11 Porous Structures 141
3.4.2 Metal Carbides, Silicides, Borides, Hydrides, and Nitrides 144
3.4.3 Metallic Alloys and Intermetallic Compounds 144
3.4.3.1 Zintl Phases 147
3.4.3.2 Nonpolar Binary Intermetallic Phases 149
3.4.3.3 Ternary Intermetallic Phases 151
3.5 Structural Disturbances 153
3.5.1 Intrinsic Point Defects 154
3.5.2 Extrinsic Point Defects 155
3.5.3 Structural Distortions 156
3.5.4 Bond Valence Sum Calculations 158
3.6 Structure Control and Synthetic Strategies 162
References 167
4 The Electronic Level I: An Overview of Band Theory 171

4.1 The Many-Body Schrödinger Equation and Hartree–Fock 171
4.2 Choice of Boundary Conditions: Born’s Conditions 177
4.3 Free-Electron Model for Metals: From Drude (Classical) to Sommerfeld
(Fermi–Dirac) 179
4.4 Bloch’s Theorem, Bloch Waves, Energy Bands, and Fermi Energy 180
4.5 Reciprocal Space and Brillouin Zones 182
4.6 Choices of Basis Sets and Band Structure with Applicative Examples 188
4.6.1 From the Free-Electron Model to the Plane Wave Expansion 189
4.6.2 Fermi Surface, Brillouin Zone Boundaries, and Alkali Metals versus Copper 191
4.6.3 Understanding Metallic Phase Stability in Alloys 193
4.6.4 The Localized Orbital Basis Set Method 195
4.6.5 Understanding Band Structure Diagram with Rhenium Trioxide 196
4.6.6 Probing DOS Band Structure in Metallic Alloys 199
4.7 Breakdown of the Independent-Electron Approximation 200
4.8 Density Functional Theory: The Successor to the Hartree–Fock Approach in Materials
Science 202
4.9 The Continuous Quest for Better DFT XC Functionals 205
4.10 Van der Waals Forces and DFT 208
References 210
viii Contents
5 The Electronic Level II: The Tight-Binding Electronic Structure Approximation 213
5.1 The General LCAO Method 214
5.2 Extension of the LCAO Treatment to Crystalline Solids 219
5.3 Orbital Interactions in Monatomic Solids 221
5.3.1 σ-Bonding Interactions 221
5.3.2 π-Bonding Interactions 225
5.4 Tight-Binding Assumptions 229
5.5 Qualitative LCAO Band Structures 232
5.5.1 Illustration 1: Transition Metal Oxides with Vertex-Sharing Octahedra 236
5.5.2 Illustration 2: Reduced Dimensional Systems 238
5.5.3 Illustration 3: Transition Metal Monoxides with Edge-Sharing Octahedra 240
5.5.4 Corollary 243
5.6 Total Energy Tight-Binding Calculations 244
References 246
6 Transport Properties 249

6.1 An Introduction to Tensors 249
6.2 Microscopic Theory of Electrical Transport in Ceramics: The Role of Point Defects 254
6.2.1 Oxygen-Deficient/Metal Excess and Metal-Deficient/Oxygen Excess Oxides 256
6.2.2 Substitutions by Aliovalent Cations with Valence Isoelectronicity 261
6.2.3 Substitutions by Isovalent Cations That Are Not Valence Isoelectronic 263
6.2.4 Nitrogen Vacancies in Nitrides 266
6.3 Thermal Conductivity 268
6.3.1 The Free Electron Contribution 269
6.3.2 The Phonon Contribution 271
6.4 Electrical Conductivity 274
6.4.1 Band Structure Considerations 278
6.4.1.1 Conductors 278
6.4.1.2 Insulators 279
6.4.1.3 Semiconductors 281
6.4.1.4 Semimetals 290
6.4.2 Thermoelectric, Photovoltaic, and Magnetotransport Properties 292
6.4.2.1 Thermoelectrics 292
6.4.2.2 Photovoltaics 298
6.4.2.3 Galvanomagnetic Effects and Magnetotransport Properties 301
6.4.3 Superconductors 303
6.4.4 Improving Bulk Electrical Conduction in Polycrystalline, Multiphasic, and
Composite Materials 307
6.5 Mass Transport 308
6.5.1 Atomic Diffusion 309
6.5.2 Ionic Conduction 316
References 322
7 Hopping Conduction and Metal–Insulator Transitions 325

7.1 Correlated Systems 327
7.1.1 The Mott–Hubbard Insulating State 329
Contents ix
7.1.2 Charge-Transfer Insulators 334

7.1.3 Marginal Metals 334
7.2 Anderson Localization 336
7.3 Experimentally Distinguishing Disorder from Electron Correlation 340
7.4 Tuning the M–I Transition 343
7.5 Other Types of Electronic Transitions 345
References 347
8 Magnetic and Dielectric Properties 349

8.1 Phenomenological Description of Magnetic Behavior 351
8.1.1 Magnetization Curves 354
8.1.2 Susceptibility Curves 355
8.2 Atomic States and Term Symbols of Free Ions 359
8.3 Atomic Origin of Paramagnetism 365
8.3.1 Orbital Angular Momentum Contribution: The Free Ion Case 366
8.3.2 Spin Angular Momentum Contribution: The Free Ion Case 367
8.3.3 Total Magnetic Moment: The Free Ion Case 368
8.3.4 Spin–Orbit Coupling: The Free Ion Case 368
8.3.5 Single Ions in Crystals 371
8.3.5.1 Orbital Momentum Quenching 371
8.3.5.2 Spin Momentum Quenching 373
8.3.5.3 The Effect of JT Distortions 373
8.3.6 Solids 374
8.4 Diamagnetism 376
8.5 Spontaneous Magnetic Ordering 377
8.5.1 Exchange Interactions 379
8.5.1.1 Direct Exchange and Superexchange Interactions in Magnetic Insulators 382
8.5.1.2 Indirect Exchange Interactions 387
8.5.2 Itinerant Ferromagnetism 390
8.5.3 Noncollinear Spin Configurations and Magnetocrystalline Anisotropy 394
8.5.3.1 Geometric Frustration 394
8.5.3.2 Magnetic Anisotropy 397
8.5.3.3 Magnetic Domains 398
8.5.4 Ferromagnetic Properties of Amorphous Metals 401
8.6 Magnetotransport Properties 401
8.6.1 The Double Exchange Mechanism 402
8.6.2 The Half-Metallic Ferromagnet Model 403
8.7 Magnetostriction 404
8.8 Dielectric Properties 405
8.8.1 The Microscopic Equations 407
8.8.2 Piezoelectricity 408
8.8.3 Pyroelectricity 414
8.8.4 Ferroelectricity 416
References 422
x Contents
9 Optical Properties of Materials 425

9.1 Maxwell’s Equations 425
9.2 Refractive Index 428
9.3 Absorption 436
9.4 Nonlinear Effects 441
9.5 Summary 446
References 447
10 Mechanical Properties 449

10.1 Stress and Strain 449
10.2 Elasticity 452
10.2.1 The Elasticity Tensors 455
10.2.2 Elastically Isotropic and Anisotropic Solids 459
10.2.3 The Relation Between Elasticity and the Cohesive Forces in a Solid 465
10.2.3.1 Bulk Modulus 466
10.2.3.2 Rigidity (Shear) Modulus 467
10.2.3.3 Young’s Modulus 470
10.2.4 Superelasticity, Pseudoelasticity, and the Shape Memory Effect 473
10.3 Plasticity 475
10.3.1 The Dislocation-Based Mechanism to Plastic Deformation 481
10.3.2 Polycrystalline Metals 487
10.3.3 Brittle and Semi-brittle Solids 489
10.3.4 The Correlation Between the Electronic Structure and the Plasticity
of Materials 490
10.4 Fracture 491
References 495
11 Phase Equilibria, Phase Diagrams, and Phase Modeling 499

11.1 Thermodynamic Systems and Equilibrium 500
11.1.1 Equilibrium Thermodynamics 504
11.2 Thermodynamic Potentials and the Laws 507
11.3 Understanding Phase Diagrams 510
11.3.1 Unary Systems 510
11.3.2 Binary Systems 511
11.3.3 Ternary Systems 518
11.3.4 Metastable Equilibria 522
11.4 Experimental Phase Diagram Determinations 522
11.5 Phase Diagram Modeling 523
11.5.1 Gibbs Energy Expressions for Mixtures and Solid Solutions 524
11.5.2 Gibbs Energy Expressions for Phases with Long-Range Order 527
11.5.3 Other Contributions to the Gibbs Energy 530
11.5.4 Phase Diagram Extrapolations: The CALPHAD Method 531
References 535
12 Synthetic Strategies 537

12.1 Synthetic Strategies 538
12.1.1 Direct Combination 538
Contents xi
12.1.2 Low Temperature 540

12.1.2.1 Sol–Gel 540
12.1.2.2 Solvothermal 543
12.1.2.3 Intercalation 544
12.1.3 Defects 546
12.1.4 Combinatorial Synthesis 548
12.1.5 Spinodal Decomposition 548
12.1.6 Thin Films 550
12.1.7 Photonic Materials 552
12.1.8 Nanosynthesis 553
12.1.8.1 Liquid Phase Techniques 554
12.1.8.2 Vapor/Aerosol Methods 556
12.1.8.3 Combined Strategies 556
12.2 Summary 558
References 559
13 An Introduction to Nanomaterials 563

13.1 History of Nanotechnology 564
13.2 Nanomaterials Properties 565
13.2.1 Electrical Properties 566
13.2.2 Magnetic Properties 567
13.2.3 Optical Properties 567
13.2.4 Thermal Properties 568
13.2.5 Mechanical Properties 569
13.2.6 Chemical Reactivity 570
13.3 More on Nanomaterials Preparative Techniques 572
13.3.1 Top-Down Methods for the Fabrication of Nanocrystalline Materials 572
13.3.1.1 Nanostructured Thin Films 572
13.3.1.2 Nanocrystalline Bulk Phases 573
13.3.2 Bottom-Up Methods for the Synthesis of Nanostructured Solids 574
13.3.2.1 Precipitation 575
13.3.2.2 Hydrothermal Techniques 576
13.3.2.3 Micelle-Assisted Routes 577
13.3.2.4 Thermolysis, Photolysis, and Sonolysis 580
13.3.2.5 Sol–Gel Methods 581
13.3.2.6 Polyol Method 582
13.3.2.7 High-Temperature Organic Polyol Reactions (IBM Nanoparticle Synthesis) 584
13.3.2.8 Additive Manufacturing (3D Printing) 584
References 586
14 Introduction to Computational Materials Science 589

14.1 A Short History of Computational Materials Science 590
14.1.1 1945–1965: The Dawn of Computational Materials Science 591
14.1.2 1965–2000: Steady Progress Through Continued Advances in Hardware and
Software 595
14.1.3 2000–Present: High-Performance and Cloud Computing 598
14.2 Spatial and Temporal Scales, Computational Expense, and Reliability of Solid-State
Calculations 600
xii Contents
14.3 Illustrative Examples 604

14.3.1 Exploration of the Local Atomic Structure in Multi-principal Element Alloys by
Quantum Molecular Dynamics 604
14.3.2 Magnetic Properties of a Series of Double Perovskite Oxides A2BCO6 (A = Sr, Ca;
B = Cr; C = Mo, Re, W) by Monte Carlo Simulations in the Framework of the
Ising Model 606
14.3.3 Crystal Plasticity Finite Element Method (CPFEM) Analysis for Modeling Plasticity in
Polycrystalline Alloys 613
References 617
15 Case Study I: TiO2 619

15.1 Crystallography 619
15.2 Microstructure 623
15.3 Bonding 626
15.4 Electronic Structure 627
15.5 Transport 628
15.6 Metal–Insulator Transitions 632
15.7 Magnetic and Dielectric Properties 632
15.8 Optical Properties 634
15.9 Mechanical Properties 635
15.10 Phase Equilibria 636
15.11 Synthesis 638
15.12 Nanomaterial 639
Practice Questions 639
References 640
16 Case Study II: GaN 643

16.1 Crystallography 643
16.2 Microstructure 646
16.3 Bonding 647
16.4 Electronic Structure 647
16.5 Transport 648
16.6 Metal–Insulator Transitions 650
16.7 Magnetic and Dielectric Properties 652
16.8 Optical Properties 652
16.9 Mechanical Properties 653
16.10 Phase Equilibria 654
16.11 Synthesis 654
16.12 Nanomaterial 656
Practice Questions 657
References 658
Appendix A: List of the 230 Space Groups 659

Appendix B: The 32 Crystal Systems and the 47 Possible Forms 665
Appendix C: Principles of Tensors 667
Appendix D: Solutions to Practice Problems 679
Index 683
xiii
Foreword to Second Edition
Materials science is one of the broadest of the applied science and engineering fields since it uses
concepts from so many different subject areas. Chemistry is one of the key fields of study, and in
many materials science programs, students must take general chemistry as a prerequisite for all but
the most basic of survey courses. However, that is typically the last true chemistry course that they
take. The remainder of their chemistry training is accomplished in their materials classes. This has
served the field well for many years, but over the past couple of decades, new materials develop-
ment has become more heavily dependent upon synthetic chemistry. This second edition of
Principles of Inorganic Materials Design serves as a fine text to introduce the materials student
to the fundamentals of designing materials through synthetic chemistry and the chemist to some
of the issues involved in materials design.
When I obtained my BS in ceramic engineering in 1981, the primary fields of materials science –
ceramics, metals, polymers, and semiconductors – were generally taught in separate departments,
although there was frequently some overlap. This was particularly true at the undergraduate level,
although graduate programs frequently had more subject overlap. During the 1980s, many of these
departments merged to form materials science and engineering departments that began to take a
more integrated approach to the field, although chemical and electrical engineering programs
tended to cover polymers and semiconductors in more depth. This trend continued in the 1990s
and included the writing of texts such as The Production of Inorganic Materials by Evans and
De Jonghe (Prentice Hall College Division, 1991), which focused on traditional production meth-
ods. Synthetic chemical approaches became more important as the decade progressed and acade-
mia began to address this in the classroom, particularly at the graduate level. The first edition of
Principles of Inorganic Materials Design strove to make this material available to the upper division
undergraduate student.
The second edition of Principles of Inorganic Materials Design corrects several gaps in the first
edition to convert it from a very good compilation of the field into a text that is very usable in
the undergraduate classroom. Perhaps the biggest of these is the addition of practice problems
at the end of every chapter since the second best way to learn a subject is to apply it to problems
(the best is to teach it), and this removes the burden of creating the problems from the instructor.
Chapter 1, Crystallographic Considerations, is new and both reviews the basic information in most
introductory materials courses and clearly presents the more advanced concepts such as the math-
ematical description of crystal symmetry that are typically covered in courses on crystallography of
physical chemistry. Chapter 10, Mechanical Properties, has also been expanded significantly to
provide both the basic concepts needed by those approaching the topic for the first time and the
solid mathematical treatment needed to relate the mechanical properties to atomic bonding,
xiv Foreword to Second Edition
crystallography, and other material properties treated in previous chapters. This is particularly
important as devices use smaller active volumes of material, since this seldom results in the materi-
als being in a stress-free state.
In summary, the second edition of Principles of Inorganic Materials Design is a very good text for
several applications: a first materials course for chemistry and physics students, a consolidated
materials chemistry course for materials science students, and a second materials course for other
engineering and applied science students. It also serves as the background material to pursue the
chemical routes to make these new materials described in texts such as Inorganic Materials Syn-
thesis and Fabrication by Lalena and Cleary (Wiley, 2008). Such courses are critical to insure that
students from different disciplines can communicate as they move into industry and face the need
to design new materials or reduce costs through synthetic chemical routes.
Martin W. Weiser
Martin earned his BS in ceramic engineering from Ohio State University and MS and PhD in
Materials Science and Mineral Engineering from the University of California, Berkeley. At Berkeley
he conducted fundamental research on sintering of powder compacts and ceramic matrix compo-
sites. After graduation he joined the University of New Mexico (UNM) where he was a visiting assis-
tant professor in chemical engineering and then assistant professor in mechanical engineering. At
UNM he taught introductory and advanced materials science classes to students from all branches
of engineering. He continued his research in ceramic fabrication as part of the Center for Micro-
Engineered Ceramics and also branched out into solder metallurgy and biomechanics in collabo-
ration with colleagues from Sandia National Laboratories and the UNM School of Medicine,
respectively.
Martin joined Johnson Matthey Electronics in a technical service role supporting the Discrete
Power Products Group (DPPG). In this role he also initiated JME’s efforts to develop Pb-free solders
for power die attach that came to fruition in collaboration with John N. Lalena several years later
after JME was acquired by Honeywell. Martin spent several years as the product manager for the
DPPG and then joined the Six Sigma Plus organization after earning his Six Sigma Black Belt work-
ing on polymer/metal composite thermal interface materials (TIMs). He spent the last several years
in the R&D group as both a group manager and principle scientist where he lead the development of
improved Pb-free solders and new TIMs.
xv
Foreword to First Edition
Whereas solid-state physics is concerned with the mathematical description of the varied physical
phenomena that solids exhibit and the solid-state chemist is interested in probing the relationships
between structural chemistry and physical phenomena, the materials scientist has the task of using
these descriptions and relationships to design materials that will perform specified engineering
functions. However, the physicist and the chemist are often called upon to act as material designers,
and the practice of materials design commonly requires the exploration of novel chemistry that may
lead to the discovery of physical phenomena of fundamental importance for the body of solid-state
physics. I cite three illustrations where an engineering need has led to new physics and chemistry in
the course of materials design.
In 1952, I joined a group at the MIT Lincoln Laboratory that had been charged with the task of
developing a square B–H hysteresis loop in a ceramic ferrospinel that could have its magnetization
reversed in less than 1 μs by an applied magnetic field strength less than twice the coercive field
strength. At that time, the phenomenon of a square B–H loop had been obtained in a few iron alloys
by rolling them into tapes so as to align the grains, and hence the easy magnetization directions,
along the axis of the tape. The observation of a square B–H loop led Jay Forrester, an electrical
engineer, to invent the coincident-current, random-access magnetic memory for the digital com-
puter since, at that time, the only memory available was a 16 × 16 byte electrostatic storage tube.
Unfortunately, the alloy tapes gave too slow a switching speed. As an electrical engineer, Jay For-
rester assumed the problem was eddy-current losses in the tapes, so he had turned to the ferrimag-
netic ferrospinels that were known to be magnetic insulators. However, the polycrystalline
ferrospinels are ceramics that cannot be rolled! Nevertheless, the Air Force had financed the
MIT Lincoln Laboratory to develop an air defense system of which the digital computer was to
be a key component. Therefore, Jay Forrester was able to put together an interdisciplinary team
of electrical engineers, ceramists, and physicists to realize his random-access magnetic memory
with ceramic ferrospinels.
The magnetic memory was achieved by a combination of systematic empiricism, careful materi-
als characterization, theoretical analysis, and the emergence of an unanticipated phenomenon that
proved to be a stroke of good fortune. A systematic mapping of the structural, magnetic, and switch-
ing properties of the Mg–Mn–Fe ferrospinels as a function of their heat treatments revealed that the
spinels, in one part of the phase diagram, were tetragonal rather than cubic and that compositions,
just on the cubic side of the cubic–tetragonal phase boundary, yield sufficiently square B–H loops if
given a carefully controlled heat treatment. This observation led me to propose that the tetragonal
distortion was due to a cooperative orbital ordering on the Mn3+ ions that would lift the cubic-field
orbital degeneracy; cooperativity of the site distortions minimizes the cost in elastic energy and
leads to a distortion of the entire structure. This phenomenon is now known as a cooperative
xvi Foreword to First Edition
Jahn–Teller distortion since Jahn and Teller had earlier pointed out that a molecule or molecular
complex, having an orbital degeneracy, would lower its energy by deforming its configuration to a
lower symmetry that removed the degeneracy. Armed with this concept, I was able almost imme-
diately to apply it to interpret the structure and the anisotropic magnetic interactions that had been
found in the manganese–oxide perovskites since the orbital order revealed the basis for specifying
the rules for the sign of a magnetic interaction in terms of the occupancies of the overlapping orbi-
tals responsible for the interatomic interactions. These rules are now known as the Goodenough–
Kanamori rules for the sign of a superexchange interaction. Thus an engineering problem
prompted the discovery and description of two fundamental phenomena in solids that ever since
have been used by chemists and physicists to interpret structural and magnetic phenomena in tran-
sition metal compounds and to design new magnetic materials. Moreover, the discovery of coop-
erative orbital ordering fed back to an understanding of our empirical solution to the engineering
problem. By annealing at the optimum temperature for a specified time, the Mn3+ ions of a cubic
spinel would migrate to form Mn-rich regions where their energy is lowered through cooperative,
dynamic orbital ordering. The resulting chemical inhomogeneities acted as nucleating centers for
domains of reverse magnetization that, once nucleated, grew away from the nucleating center. We
also showed that eddy currents were not responsible for the slow switching of the tapes, but a small
coercive field strength and an intrinsic damping factor for spin rotation.
In the early 1970s, an oil shortage focused worldwide attention on the need to develop alternative
energy sources, and it soon became apparent that these sources would benefit from energy storage.
Moreover, replacing the internal combustion engine with electric-powered vehicles, or at least the
introduction of hybrid vehicles, would improve the air quality, particularly in big cities. Therefore, a
proposal by the Ford Motor Company to develop a sodium–sulfur battery operating at 3008 C with
molten electrodes and a ceramic Na+-ion electrolyte stimulated interest in the design of fast alkali
ion conductors. More significant was interest in a battery in which Li+ rather than H+ is the work-
ing ion, since the energy density that can be achieved with an aqueous electrolyte is lower than
what, in principle, can be obtained with a nonaqueous Li+-ion electrolyte. However, realization
of a Li+-ion rechargeable battery would require identification of a cathode material into/from
which Li+ ions can be inserted/extracted reversibly. Brian Steele of Imperial College, London, first
suggested the use of TiS2, which contains TiS2 layers held together only by van der Waals S2––S2–
bonding; lithium can be inserted reversibly between the TiS2 layers. M. Stanley Whittingham’s
demonstration was the first to reduce this suggestion to practice while he was at the Exxon Cor-
poration. Whittingham’s demonstration of a rechargeable Li–TiS2 battery was commercially non-
viable because the lithium anode proved unsafe. Nevertheless, his demonstration focused attention
on the work of the chemists Jean Rouxel of Nantes and R. Schöllhorn of Berlin on insertion com-
pounds that provide a convenient means of continuously changing the mixed valency of a fixed
transition metal array across a redox couple. Although work at Exxon was halted, their demonstra-
tion had shown that if an insertion compound, such as graphite, was used as the anode, a viable
lithium battery could be achieved, but the use of a less electropositive anode would require an alter-
native insertion-compound cathode material that provided a higher voltage versus a lithium anode
than TiS2. I was able to deduce that no sulfide would give a significantly higher voltage than that
obtained with TiS2 and therefore that it would be necessary to go to a transition metal oxide.
Although oxides other than V2O5 and MoO3, which contain vandyl or molybdyl ions, do not form
layered structures analogous to TiS2, I knew that LiMO2 compounds exist that have a layered struc-
ture similar to that of LiTiS2. It was only necessary to choose the correct M3+ cation and to deter-
mine how much Li could be extracted before the structure collapsed. That was how the Li1−xCoO2
cathode material was developed, which now powers the cell telephones and laptop computers. The
Foreword to First Edition xvii
choice of M = Co, Ni, or Ni0.5+δMn0.5−δ was dictated by the position of the redox energies and an
octahedral site preference energy strong enough to inhibit migration of the M atom to the Li layers
on the removal of Li. Electrochemical studies of these cathode materials, and particularly of Li1−x
Ni0.5+δMn0.5−δO2, have provided a demonstration of the pinning of a redox couple at the top of the
valence band. This is a concept of singular importance for interpretation of metallic oxides having
only M–O–M interactions, of the reason for oxygen evolution at critical Co(IV)/Co(III) or Ni(IV)/Ni
(III) ratios in Li1−xMO2 studies, and of why Cu(III) in an oxide has a low-spin configuration. More-
over, exploration of other oxide structures that can act as hosts for insertion of Li as a guest species
has provided a means of quantitatively determining the influence of a counter cation on the energy
of a transition metal redox couple. This determination allows tuning of the energy of a redox couple,
which may prove important for the design of heterogenous catalysts.
As a third example, I turn to the discovery of high-temperature superconductivity in the copper
oxides, first announced by Bednorz and Müller of IBM Zürich in the summer of 1986. Karl A.
Müller, the physicist of the pair, had been thinking that a dynamic Jahn–Teller ordering might pro-
vide an enhanced electron–phonon coupling that would raise the superconductive critical temper-
ature TC. He turned to his chemist colleague Bednorz to make a mixed-valence Cu3+/Cu2+
compound since Cu2+ has an orbital degeneracy in an octahedral site. This speculation led to
the discovery of the family of high-TC copper oxides; however, the enhanced electron–phonon cou-
pling is not due to a conventional dynamic Jahn–Teller orbital ordering, but rather to the first-order
character of the transition from localized to itinerant electronic behavior of σ-bonding Cu: 3d elec-
trons of (x2 − y2) symmetry in CuO2 planes. In this case, the search for an improved engineering
material has led to a demonstration that the celebrated Mott–Hubbard transition is generally
not as smooth as originally assumed, and it has introduced an unanticipated new physics associated
with bond length fluctuations and vibronic electronic properties. It has challenged the theorist to
develop new theories of the crossover regime that can describe the mechanism of superconductive
pair formation in the copper oxides, quantum critical-point behavior at low temperatures, and an
anomalous temperature dependence of the resistivity at higher temperatures as a result of strong
electron–phonon interactions.
These examples show how the challenge of materials design from the engineer may lead to new
physics as well as to new chemistry. Sorting out of the physical and chemical origins of the new
phenomena fed back to the range of concepts available to the designer of new engineering materi-
als. In recognition of the critical role in materials design of interdisciplinary cooperation between
physicists, chemists, ceramists, metallurgists, and engineers that is practiced in industry and gov-
ernment research laboratories, John N. Lalena and David A. Cleary have initiated, with their book,
what should prove to be a growing trend toward greater interdisciplinarity in the education of those
who will be engaged in the design and characterization of tomorrow’s engineering materials.
John B. Goodenough
John received the Nobel Prize in Chemistry in 2019. See his biography page 386.
xix
Preface to Third Edition
I contacted John Nick Lalena almost ten years ago, electronically by e-mail to inform him of my
enthusiasm for a review paper he had written on crystallography and share some comments. Nick
responded immediately, and we started an intense e-mail correspondence. I then discovered the
second edition of this book, and I loved it very much, as a kind of multifacetted diamond. Of course,
diamonds always have some defects, and I commented on them with Nick again, besides my admi-
ration for the broad scope of the book and its most pleasant style to my taste. Somewhat later, in
August 2018, Nick let me know about the preparation of a third edition and asked me if I would
accept to review some of the new and rewritten chapters. As I started the job, I naturally made
comments and even suggested new lines that could be added here and there – so much so that Nick
and Dave proposed me to become a third co-author for the third edition. Principles of Inorganic
Materials Design now has an added French touch in some places, even if science is naturally
universal.
The third edition is thicker than the second, which was thicker than the first. Quite a few sections
in existing chapters have been rewritten and/or expanded. Three chapters have been added, two of
them being case study chapters. Thanks to the skills of its three authors, PIMD3, as we like to call it,
is very versatile. It has fundamental aspects presented pedagogically as appropriate for a textbook,
with additional historical focus and biographical presentations of some of our heroes in crystallog-
raphy, solid-state physics, and materials science. It has some sections on rather recent develop-
ments in electron density functional theory as well as a new appendix presenting tensors from
different physical points of view. It also touches on a plethora of topics of relevance to the practi-
tioners of materials science such as mechanical engineers, including a new section about additive
manufacturing,
Diamonds must be sculpted so that they can shine from whatever angle they are looked at, just as
with the French Blue Diamond of the Crown now visible at the Smithsonian Institution. At the
same time the best natural diamonds contain defects, and, to quote a phrase attributed to Sir
Charles Frank, “crystals are like people: it is the defects in them that make them interesting.”
I thus believe that readers, either students, teachers, researchers or practitioners, will learn a lot
from this book and enjoy it even more than I enjoyed PIMD2, while, at the same time, they should
hopefully find it not absolutely perfect in places from their own point of view. Science is not a closed
book, and no science book should be a closed book either: a good science book should stay open and
be read and annotated.
Olivier B. M. Hardouin Duparc

xx
Preface to Second Edition
In our first attempt at writing a textbook on the highly interdisciplinary subject of inorganic mate-
rials design, we recognized the requirement that the book needed to appeal to a very broad-based
audience. Indeed, practitioners of materials science and engineering come from many different
educational backgrounds, each emphasizing different aspects. These include solid-state chemistry,
condensed-matter physics, metallurgy, ceramics, mechanical engineering, and materials science
and engineering (MS&E). Unfortunately, we did not adequately anticipate the level of difficulty
that would be associated with successfully implementing the task of attracting readers from so
many disciplines that, though distinct, possess the common threads of elucidating and utilizing
structure/property correlation in the design of new materials.
As a result, the first edition had a number of shortfalls. First and foremost, owing to a variety of
circumstances, there were many errors that, regrettably, made it into the printed book. Great care
has been taken to correct each of these. In addition to simply revising the first edition, however, the
content has been updated and expanded as well. As was true with the first edition, this book is con-
cerned, by and large, with theoretical structure/property correlation as it applies to materials
design. Nevertheless, a small amount of space is dedicated to the empirical practice of synthesis
and fabrication. Much more discussion is devoted to these specialized topics concerned with the
preparation of materials, as opposed to their design, in numerous other books, one of which is
our companion textbook, Inorganic Materials Synthesis and Fabrication.
Some features added to this second edition include an expanded number of worked examples and
an appendix containing solutions to selected end-of-chapter problems. The overall goal of our sec-
ond edition is, quite simply, to rectify the problems we encountered earlier, thereby producing a
work that is much better suited as a tool to the working professionals, educators, and students
of this fascinating field.
John N. Lalena and David A. Cleary

xxi
Preface to First Edition
Inorganic solid-state chemistry has matured into its own distinct subdiscipline. The reader may
wonder why we have decided to add another textbook to the plethora of books already published.
Our response is that we see a need for a single source presentation that recognizes the interdisci-
plinary nature of the field. Solid-state chemists typically receive a small amount of training in con-
densed-matter physics, and none in materials science or engineering, and yet all of these traditional
fields are inextricably part of inorganic solid-state chemistry.
Materials scientists and engineers have traditionally been primarily concerned with the fabrica-
tion and utilization of materials already synthesized by the chemist and identified by the physicist
as having the appropriate intrinsic properties for a particular engineering function. Although the
demarcation between the three disciplines remains in an academic sense, the separate job distinc-
tions for those working in the field is fading. This is especially obvious in the private sector where
one must ensure that materials used in real commercial devices not only perform their primary
function but also meet a variety of secondary requirements.
Individuals involved with these multidisciplinary and multitask projects must be prepared to
work independently or to collaborate with other specialists in facing design challenges. In the latter
case, communication is enhanced if each individual is able to speak the “language” of the other.
Therefore, in this book we introduce a number of concepts that are not usually covered in standard
solid-state chemistry textbooks. When this occurs, we try to follow the introduction of the concept
with an appropriate worked example to demonstrate its use. Two areas that have lacked thorough
coverage in most solid-state chemistry texts in the past, namely, microstructure and mechanical
properties, are treated extensively in this book.
We have kept the mathematics to a minimum – but adequate – level, suitable for a descriptive
treatment. Appropriate citations are included for those needing the quantitative details. It is
assumed that the reader has sufficient knowledge of calculus and elementary linear algebra, par-
ticularly matrix manipulations, and some prior exposure to thermodynamics, quantum theory, and
group theory. The book should be satisfactory for senior level undergraduate or beginning graduate
students in chemistry. One will recognize from the Table of Contents that the entire textbooks have
been devoted to each of the chapters in this book, and this limits the depth of coverage out of neces-
sity. Along with their chemistry colleagues, physics and engineering students should also find the
book to be informative and useful.
Every attempt has been made to extensively cite all the original and pertinent research in a fash-
ion similar to that found in a review article. Students are encouraged to seek out this work. We have
also included biographies of several individuals who have made significant fundamental contribu-
tions to inorganic materials science in the twentieth century. Limiting these to the small number we
have room for was, of course, difficult. The reader should be warned that some topics have been left
xxii Preface to First Edition
out. In this book, we only cover nonmolecular inorganic materials. Polymers and macromolecules
are not discussed. Nor are the other extreme, for example, molecular electronics. Also omitted are
coverages of surface science, self-assembly, and composite materials.
We are grateful to Professor John B. Wiley, Dr. Nancy F. Dean, Dr. Martin W. Weiser, Professor
Everett E. Carpenter, and Dr. Thomas K. Kodenkandath for reviewing various chapters in this book.
We are grateful to Professor John F. Nye, Professor John B. Goodenough, Dr. Frans Spaepen,
Dr. Larry Kaufman, and Dr. Bert Chamberland for providing biographical information. We would
also like to thank Professor Philip Anderson, Professor Mats H. Hillert, Professor Nye, Dr. Kaufman,
Dr. Terrell Vanderah, Dr. Barbara Sewall, and Mrs Jennifer Moss for allowing us to use photographs
from their personal collections. Finally, we acknowledge the inevitable neglect our families must
have felt during the period taken to write this book. We are grateful for their understanding and
tolerance.
John N. Lalena and David A. Cleary

xxiii
Acronyms
AC alternating current
AFMs antiferromagnets
AIMD Ab initio molecular dynamics
AOT aerosol OT (sodium dioctylsulfosuccinate)
APW augmented plane wave
BCC body-centered cubic
BM Bohr magneton
BMGs bulk metallic glasses
BOs Bloch orbitals - also referred as Bloch sums
BVS bond valence sums
BZ Brillouin zone
CA cellular automation
CALPHAD CALculation of PHAse Diagrams
CB carbazole-9-carbonyl chloride
CCP cubic-close package
CCSL constrained coincidence site lattice
CDW charge density wave
CFSE crystal field stabilization energy
CI configuration interaction
CMR colossal magnetoresistance
COs crystal orbitals
CRSS critical resolved shear stress
CSL coincidence site lattice
CTAB cetyltrimethylammonium bromide
CTE coefficient of thermal expansion
CVD chemical vapor deposition
CVM cluster variation method
DE double exchange
DFT density functional theory
DMFT dynamical mean field theory
DOS density-of-states
DR1 disperse red 1
DSC (lattice) displacement shift complete (lattice)
DSC differential scanning calorimetry
DTA differential thermal analysis
xxiv Acronyms
EAM embedded atom method

EBS electrostatic bond strength
EBSD electron backscatter diffraction
ECAE equal-channel angular extrusion
ECAP equal-channel angular pressing
EDTA ethylenediamine tetraacetate
EMF electromagnetic field
EOS equation of state
EPMA electron probe microanalysis
FC field cooled
FCC face-centered cubic
FDM finite difference method
FEM finite element method
FVM finite volume method
GB grain boundary
GGA generalized gradient approximation
GLAD glancing angle deposition
GMR giant magnetoresistance
GTOs Gaussian-type orbitals
HCP hexagonal close packed
HeIM helium ion microscope
HF Hartree Fock
HOMO highest occupied molecular orbital
HRTEM high-resolution transmission electron microscopy
IC integrated circuits
IR infrared radiation
JT Jahn–Teller
LCAO linear combination of atomic orbitals
LCAO-MO linear combination of atomic orbitals - molecular orbitals
LCOAO linear combination of orthogonalized atomic orbitals
LDA local density approximation
LHB lower Hubbard band
LRO long-range (translational) order
LSDA local spin-density approximation
LUMO lowest unoccupied molecular orbital
MC Monte Carlo
MCE magnetocaloric effect
MD molecular dynamics
M-I metal-insulator
MMC metal matrix composite
M–NM metallic–nonmetallic
MO molecular orbital
MOCVD metal–organic chemical vapor deposition
MP Møller–Plesset
MPB morphotropic phase boundary
MRO medium-range order
Acronyms xxv
MS&E materials science and engineering

MSD microstructure sensitive design
MWNT multiwalled carbon nanotubes
NA numerical aperture
ND normal directions
NFE nearly free electron
NMR nuclear magnetic resonance
ODF orientation distribution function
PFCM phase field crystal modeling
PFM phase field modeling
PIMD principles of inorganic materials design
PIMD path integral molecular dynamics
PCF (single-mode) photonic crystal fiber
PLD pulsed laser deposition
PV photovoltaic
PVD physical vapor deposition
PVP poly(vinylpyrrolidone)
PZT Pb(Zr,Ti)O3
QMC quantum Monte Carlo
QMD quantum molecular dynamics
RD radial directions
RKKY Rudderman–Kittel–Kasuya–Yoshida
RP Ruddlesden–Popper
RPA random-phase approximation
SALC symmetry-adapted linear combination
SANS small-angle Newton scattering
SAXS small-angle X-ray scattering
SC simple cubic
SCF self-consistent field
SDS sodium dodecylsulfate
SDW spin-density wave
SEM scanning electron microscope
SHS self-propagating high-temperature synthesis
SK Slater-Koster
SMA shape memory alloys
SP spin-polarized
SPD severe plastic deformation
SRO short-range order
STM scanning tunneling microscope
STOs Slater-type orbitals
SWNT single-walled carbon nanotubes
TB tight binding
TD transverse directions
TE thermoelectric
TEM transmission electron microscope
TEOS tetraethyl orthosilicate
xxvi Acronyms
TGG templated grain growth

TIM thermal interface material
TOPO trioctylphosphine oxide
TSSG top-seeded solution growth
UFG ultrafine-grained
UHB upper Hubbard band
UTS ultimate tensile strength
VEC valence electron concentration
VRH variable range hopping
VSEPR valence shell electron pair repulsion
XC exchange and correlation
XRD X-ray diffraction
ZFC zero-field cooled
1
Crystallographic Considerations
There are many possible classification schemes for solids that can be envisioned. We can categorize
a material based solely on its chemical composition (inorganic, organic, or hybrid), the primary
bonding type (ionic, covalent, metallic), its structure type (catenation polymer, extended three-
dimensional network), or its crystallinity (crystalline or noncrystalline). It is the latter scheme that
is the focus of this chapter. A crystalline material exhibits a large degree of structural order in the
arrangement of its constituent particles, be they atoms, ions, or molecules, over a large length scale
whereas a noncrystalline material exhibits structural order only over the very short-range length
scale corresponding to the first coordination sphere. It is structural order – the existence of a
methodical arrangement among the component particles – that makes the systematic study and
design of materials with prescribed properties possible.
A crystal may be explicitly defined as a homogeneous solid consisting of a periodically repeating
three-dimensional pattern of particles. There are three key structural features to crystals, between
physics and mathematics:
1) The motif, which is the group of atoms or molecules repeated at each lattice point.
2) Symmetry, the geometric arrangement of the lattice points, defined by a repeating unit cell.
3) Long-range (translational) order (LRO), referring to the periodicity, or regularity in the arrange-
ment of the material’s atomic or molecular constituents on a length scale at least a few times
larger than the size of the unit cell.
The presence of a long-range order allows crystals to scatter incoming waves, of appropriate wave-
lengths, so as to produce discrete diffraction patterns, which, in turn, ultimately enables ascertain-
ment of the actual atomic positions and, hence, crystalline structure. The periodic LRO can be
extended to quasiperiodic LRO to encompass quasicrystals; see Section 1.1.2.
1.1 Degrees of Crystallinity
Crystallinity, like most things, can vary in degree. Even single crystals (a.k.a. monocrystals) have
intrinsic point defects (e.g. lattice site vacancies) and extrinsic point defects (e.g. impurities), as well
as extended defects such as dislocations. Defects are critical to the physical properties of crystals
and will be extensively covered in later chapters. What we are referring to here with the degree
of crystallinity is not the simple proportion of defects present in the solid, but rather the spectrum
Principles of Inorganic Materials Design, Third Edition. John N. Lalena, David A. Cleary,
and Olivier B. M. Hardouin Duparc.
© 2020 John Wiley & Sons, Inc. Published 2020 by John Wiley & Sons, Inc.
2 1 Crystallographic Considerations
Table 1.1 Degrees of crystallinity.
Type Defining features
Monocrystalline LRO
Quasicrystalline Noncrystallographic rotational symmetry, no LRO
Polycrystalline Crystallites separated by grain boundaries
Semicrystalline Crystalline regions separated by amorphous regions
Amorphous and glassy state No LRO, no rotational symmetry, does possess short-range order
of crystallinity that encompasses the entire range from really crystalline to fully disordered amor-
phous solids. Table 1.1 lists the various classes. Let us take each of them in the order shown.
1.1.1 Monocrystalline Solids

At the top of the list is the single crystal, or monocrystal, which has the highest degree of order.
Several crystalline materials of enormous technological or commercial importance are used in
monocrystalline form. Figure 1.1a shows a drawing of a highly symmetrical quartz crystal, such
as might be grown freely suspended in a fluid. For a crystal, the entire macroscopic body can be
regarded as a monolithic three-dimensional space-filling repetition of the fundamental crystallo-
graphic unit cell. Typically, the external morphology of a single crystal is faceted (consisting of
faces), as in Figure 1.1a, although this need not be the case. The word habit is used to describe
the overall external shape of a crystal specimen. Habits, which can be polyhedral or non-polyhedral,
may be described as cubic, octahedral, fibrous, acicular, prismatic, dendritic (treelike), platy,
(a) (b) (c)
Figure 1.1 (a) A drawing of a quartz monocrystal. The morphology exhibits the true point symmetry of
the lattice. (b) A portion of a Penrose tiling with fivefold rotational symmetry based on two rhombuses.
A Penrose tiling is a nonperiodic tiling of the plane and is a two-dimensional analog of a quasicrystal.
(c) A micrograph of a polycrystalline sample of aluminum plastically deformed under uniaxial tension.
blocky, or bladelike, among many others. The point symmetry of the crystal’s morphological form
cannot exceed the point symmetry of the lattice.
In industry, exceedingly pure single crystals are typically grown with specific crystallographic
orientations and subsequently sliced or cut in a way that enables the maximum number of units
to be obtained of that particular orientation. This process is applied in the manufacturing of semi-
conductors (e.g. silicon), optical materials (e.g. potassium titanyl phosphate), and piezoelectric
materials (e.g. quartz). No other crystalline material manufactured today matches the very low
impurity and defect levels of silicon crystals produced for the microelectronics industry. Disloca-
tion-free silicon crystals were produced as far back as the early 1960s. However, the elimination
of these dislocations allowed intrinsic point defects to agglomerate into microdefect voids.
Although the voids were of a very low density (106 cm−3) and size (150 nm), the drive toward
increasingly higher density integrated circuits has made their further reduction the biggest chal-
lenge facing single-crystal silicon producers (Falster and Voronkov 2000).
1.1.2 Quasicrystalline Solids

It will be seen later in this chapter (Section 1.2.1.1.2) that a crystal may or may not possess non-
trivial rotational symmetry, but if it does, the rotational symmetry can only be of specific orders
(namely, 2, 3, 4, or 6, as n in rotational angle ϕ = 2π/n). By contrast, quasicrystals possess a non-
crystallographic rotational symmetry, and, as a result, they do not possess translational order, or
periodicity, in our pedestrian three-dimensional space. Hence, they are termed aperiodic or, pref-
erably, quasiperiodic. They own a quasi-order that is coherent enough to scatter incoming waves,
thereby producing sharp spots in a diffraction pattern, which may actually be a general definition
of crystals, periodic (the usual crystals) or quasiperiodic (quasicrystals). The most common qua-
sicrystals are ternary intermetallic phases. Like most other intermetallic phases, they are brittle,
yet hard, solids. Some are currently being investigated as candidates for surface coatings and as
nanoparticle reinforcements in alloys, owing to a variety of interesting properties, including
reduced wetting, low thermal and electrical conductivities, low friction coefficients, high hard-
ness, excellent, corrosion resistance, ductile–brittle transition, and high-temperature superplas-
ticity (Jazbec 2009).
Nonclassical crystallography rotational symmetry was observed in April 1982 by Daniel Shecht-
man (b. 1941) when he was at the National Bureau of Standard (NBS) (pre-NIST) at Gaithersburg,
Maryland, USA. Dan, or Danny, was a good electron microscopist, and his observation of an elec-
tron diffraction pattern exhibiting fivefold symmetry could not be wrong. The problem was that it
could be due to multiple twinning in the rapidly solidified Al–Mn alloy he was observing, following
a suggestion first made by David Brandon, rather than to a genuine, nonclassical, fivefold symmetry
obviously inconsistent with lattice translations. With his numerous microscopic observations at dif-
ferent scales, Danny had some arguments to think it was genuine and not due to multiple twinning.
The observation was first reported and cautiously argued in a well written paper in November 1984
by Shechtman, Ian Blech (b. 1936), Denis Gratias (b. 1947), and John Cahn (1928–2016) who
headed the NBS Center for Materials Research. Paul Steinhard (b. 1952) and his PhD student
Dov Levine (b. 1958) had a paper published the following month, where they baptized as “quasi-
crystals” a new class of ordered crystals including the Al–Mn observed by Shechtman. Apart for
Linus Pauling (1901–1994) who kept on arguing in favor of multiple twinning, sometimes in an
excessively ridiculing manner, together with some of his followers in the United States, the exist-
ence of quasicrystals easily became rather well accepted. The Nobel Prize in Chemistry was
awarded to Shechtman in 2011.
The first quasicrystals exhibited fivefold rotational symmetry. A Penrose tiling (a two-
dimensional tiling of the plane analogous to three-dimensional quasicrystals) with this order of
rotational symmetry is illustrated in Figure 1.1b. The initial discovery was followed by the discovery
of quasicrystals with 8-, 10-, and 12-fold rotational symmetry. All of these early samples were
obtained by rapidly solidifying liquid phases whose equilibrium crystal structures contained icosa-
hedrally packed groups of atoms. Sir Frederick Charles Frank (1911–1998) of the University of Bris-
tol and John S. Kasper (1915–2005) of the General Electric Research Laboratories showed in 1958
that icosahedral coordination (Z = 12), as well as other coordination polytetrahedra with coordi-
nation numbers Z = 14, 15, and 16, is a major structural component of some melts. Such tetrahed-
rally close-packed structures, in which atoms are located at the vertices and centers of various
space-filling arrangements of polytetrahedra, are now called Frank–Kasper phases (Frank and Kas-
per 1958a, b).
Quasicrystalline phases form at compositions close to the related crystalline phases. When soli-
dified, the resultant structure has icosahedra threaded by a network of wedge disclinations, having
resisted reconstruction into crystalline units with three-dimensional translational periodicity. The
most well-known examples of quasicrystals are inorganic phases from the ternary intermetallic sys-
tems: Al–Li–Cu, Al–Pd–Mn, Zn–Mg–Ln, Al–Ni–Co, Al–Cu–Co, and Al–Mn–Pd. In 2007, certain
blends of polyisoprene, polystyrene, and poly(2-vinylpyridine) were found to form star-shaped
copolymers that assemble into the first known organic quasicrystals (Hayashida et al. 2007).
As the first reported quasicrystals were metastable phases at room temperature produced by rapid
solidification, they were consequently of poor quality. Stable quasicrystals have since been discov-
ered that have revealed very high structural perfection and can form macroscopic crystals. This dis-
covery made it possible to apply conventional solidification techniques. The preferred method
appears to be system-specific, as it depends on the temperature stability of the quasicrystalline
phase. If the quasicrystal is only stable at elevated temperatures, for example, it can decompose into
a crystalline phase if the melt is solidified slowly. If the phase is thermodynamically stable down to
room temperature, as is the case for Al–Pd–Mn, quasicrystals can be grown with conventional cool-
ing rates (e.g. 10 C/h).
A relationship actually exists between periodic and quasiperiodic patterns such that any quasi-
lattice may be formed from a periodic lattice in some higher dimension (Cahn 2001; John Werner
Cahn 1928–2016). The points that are projected to the physical three-dimensional space are usually
selected by cutting out a slice from the higher-dimensional lattice. Therefore, this method of con-
structing a quasiperiodic lattice is known as the cut-and-project method. In fact, the pattern for any
three-dimensional quasilattice (e.g. icosahedral symmetry) can be obtained by a suitable projection
of points from some six-dimensional periodic space lattice into a three-dimensional subspace. The
idea is to project part of the lattice points of the higher-dimensional lattice to three-dimensional
space, choosing the projection such that one preserves the rotational symmetry. The set of points
so obtained are called a Meyer set after French mathematician Yves Meyer (b. 1939). The mathe-
matics of quasicrystals is too involved to be adequately described in this book.
1.1.3 Polycrystalline Solids

The vast majority of inorganic materials used in commerce fit into the third class of Table 1.1, the
polycrystalline form. A polycrystal may be a compacted and sintered (densified) powder, a solid-
ification product, or some other dense aggregate of small crystallites or grains. Figure 1.1c shows
the cross section of a polycrystalline aluminum sample, with a grain size of 90 μm, deformed under
uniaxial tension. The crystallites of a polycrystal are made from the same unit cell as a monocrystal
is, but the grains of a polycrystalline body are separated from one another by grain boundaries.
A polycrystal can be considered to consist of small crystalline regions separated by regions of
disorder, although it must be stressed that the grain boundaries are not totally incoherent or
amorphous. Three very important points should be remembered:
1) Depending on their size, the individual grains may or may not be visible to the unaided eye.
Grains can range in size from nanometers to centimeters.
2) The grain boundaries are solid–solid interfacial regions a few nanometers thick.
3) Rarely do all the grains comprising a polycrystal have the same size, orientation, or even
shape. In fact, polycrystalline grains are morphologically dissimilar to their monocrystalline
counterparts.
1.1.4 Semicrystalline Solids

Another category of inorganic solid is the inorganic polymer. All polymers – organic, inorganic, and
organometallic – are special types of covalently bonded substances in which the entire solid may be
considered a macromolecule composed of identical molecular units, called the monomer, which
are linked together. One-dimensional chains and two-dimensional layers of atoms are often found
in the structures of inorganic crystals. Therefore, any solid in which there exists extended covalent
bonding in one or more directions could be classified as polymeric. For example, α- and β-Si3N4, as
well as B2O3, contain layers of Si/N and B/O atoms, respectively, and could thus be considered two-
dimensional polymers, while ReO3, with its vertex-sharing network of ReO6 octahedra, might be
thought of as a three-dimensional polymer. The majority of chemists reserve the term polymer for
solids that retain their macromolecular structure and properties after a physical change (i.e. melting
or solution behavior). Such inorganic materials, which include the polysilanes, polygermanes, and
polystannanes, consist of a catenation (long chain) backbone made of one type of main group ele-
ment other than carbon (but usually with organic substituents) or, as in the case of silicones and
polyphosphazenes, a pseudo-catenation backbone made of two different non-carbon elements.
These are invariably one-dimensional polymers. Of course, these chains pack and fold together
to form three-dimensional solids.
As with organic polymers, inorganic polymers can be crystalline, amorphous, or glassy. The ease
with which macromolecules can pack together into a regular array will depend on the stereochem-
ical sequence of the backbone’s monomeric units. This is worth looking at a little more closely with
the more familiar organic polymers. In an organic molecule, a carbon–carbon single covalent bond
is cylindrically symmetrical and thus exhibits free rotation about the bond. The different spatial
arrangements of atoms attached to each of the carbons of the single bond are called conformations,
while two different configurations of the same molecule are called conformational isomers. The
most common method of illustrating the different possible arrangements is through Newman pro-
jections, named after Melvin S. Newman (1908–1993), an Ohio State University chemistry profes-
sor. An example using butane (CH3CH2CH2CH3) is pictured in Figure 1.2. In the figure, the circle
represents the third carbon atom in the chain, C3, which is behind the plane of the page, while the
second carbon atom in the chain, C2, is above the plane of the page, lying at the intersection of the
three lines representing the two C–H bonds and the C–C bond to the first carbon atom in the chain,
C1. The C2–C3 bond itself is in the plane of the page.
There are three types of conformations brought about by the rotation of the C2–C3 bond anti
(where the methyl groups are furthest apart), which is the lowest-energy conformation; eclipsed
(where the methyl groups are closest), which is the highest-energy conformation; and gauche,
A A A Figure 1.2 The possible conformations

A
A around adjacent carbon atoms in chain.
A
Anti Gauche Eclipsed
(a) (b) Figure 1.3 (a) Relative configurations at two contiguous carbon
atoms in a chain. (b) Relative configurations of consecutive, but
A A
not necessarily contiguous, constitutionally equivalent carbon
C–C C–C–C–C–C–C atoms in a chain.
A B B B
Erythro Meso
B A B
C–C C–C–C–C–C–C
A B A
Threo Racemo
which is the intermediate energy. Each C–C bond of a macromolecule can have its own conforma-
tion. The relative configurations at two contiguous carbon atoms in the main chain are designated
by the prefix erythro or threo, as illustrated in Figure 1.3a. Stereosequences within a polymeric chain
terminating in stereoisomeric centers at both ends of the segment, which comprise two, three, four,
or five consecutive (but not necessarily contiguous) centers of that type, called diads, triads, tetrads,
and pentads, respectively. Relative configurations of consecutive, but again not necessarily contig-
uous, constitutionally equivalent carbon atoms that have a symmetrically constituted connecting
group (if any) are designated meso. Opposite configurations are called racemo. These are illustrated
in Figure 1.3b. Polymers with long meso sequences are termed isotactic, while polymers with long
racemo sequences are syndiotactic.
The majority of C–C bonds in amorphous organic polymers, which are typically branched or con-
tain large pendant groups (not part of the main chain), are generally found with random conforma-
tions. As a result, the chains are arranged randomly throughout the material. Some polymers may
also form a brittle glass if rapidly cooled, particularly those containing chains that can easily
become tangled or viscous during cooling. Glassy polymers include polystyrene, e.g. Styrofoam®
(Tg = 100 C), and polyethylene terephthalate, e.g. Dacron® (Tg = 70 C). Unlike amorphous poly-
mers, the C–C bonds in crystalline polymers are predominantly in the all-anti conformation, and
the chains are arranged into lamellae (platelike configurations), but these well-packed regions can
be separated by amorphous regions where the chains are entangled. Hence, even a crystalline
polymer contains an amorphous fraction, as illustrated in the sketch of Figure 1.4. A percent
crystallinity can therefore be specified. This situation has given rise to the term semicrystalline.
In fact, most crystalline polymers are semicrystalline, the amorphous fraction typically accounting
Figure 1.4 A sketch depicting the semicrystalline nature

of a polymer. The lamellae are crystalline regions while
the entangled regions between them are amorphous.
for ~60 wt% of the total polymer (Cheremisinoff 2001). Semicrystalline polymers are also
sometimes referred to as polycrystalline polymers, even though they are really single crystalline
(they have no grain boundaries). The crystalline regions, or domains, may have differing texture
or crystallographic orientation. Monocrystalline polymers are transparent, whereas polycrystalline
polymers are translucent, and totally amorphous polymers are opaque. Likewise, crystalline
polymers are harder, stiffer, and denser than amorphous polymers.
With inorganic polymers, a similar situation is found. Both meso polymers and racemo polymers
are capable of crystallizing, but polymers in which meso and racemo placement occur randomly
along the backbone are amorphous. Other structural features that preclude crystallizability include
any defects that introduce chain irregularity. Even when the conditions conducive to crystallinity
are met, the resultant polymers still contain a significant fraction of amorphous material. This is
owing to the length of the polymer chain; different segments become incorporated into different
crystalline orientations (Mark et al. 2005).
A relatively new field called supramolecular chemistry has been developed and continuously
studied over the last four decades. Supramolecular assemblies and supramolecular polymers
differ from macromolecules, where the monomeric units are covalently linked. In a supramolecular
polymer, the monomeric units self-assemble via reversible, highly directional, noncovalent inter-
actions. These types of bonding forces are sometimes called secondary interactions. Hydrogen
bonding is the secondary force most utilized in supramolecular chemistry, but metal coordination
and aromatic π–π electronic interactions have also been used. From a materials standpoint, supra-
molecular assemblies are promising because of the reversibility stemming from the secondary inter-
actions. The goal is to build materials whose architectural and dynamical properties can respond
reversibly to external stimuli. Solid phases are prepared by self-assembly from solution. In the solid
state, supramolecular polymers can be either crystalline or amorphous.
1.1.5 Amorphous Solids

The final category in Table 1.1 is the amorphous solid, which includes, as a subset, the glassy or
vitreous state that is further discussed in Section 1.5. These phases are totally noncrystalline. All
glasses are monolithic and amorphous, but only amorphous materials prepared by rapidly cooling,
or quenching, a molten state through its glass transition temperature (Tg), are glasses. Both silica-
based glasses and metallic glasses have a variety of uses in commerce. Non-glassy amorphous solids
are normally prepared by severely mechanochemically damaging a crystalline starting material, for
example, via ion implantation or ball milling. Although amorphous and glassy substances do not
possess the long-range translational order characteristic of crystals, they do usually exhibit short-
range structural order, for example, the first coordination sphere about a cation.
1.2 Basic Crystallography
Geometric crystallography is the scientific field concerned with the different possible ways atoms,
or groups of atoms, which we term the structural motif, can fit together to form the periodic pat-
terns observed in crystalline substances. Through crystallography, we may establish the internal
arrangement of atoms within a crystal, as well as the possible types of morphological, or external,
symmetry that can be observed. Specific crystal structures are presented in Chapter 3. Additionally,
methods have been developed for ascertaining surface and interfacial configurations, for example,
at grain boundaries. There is a fundamental postulate that pervades modern crystalline physics, and
to which we can associate the names of Franz Ernst Neumann (1798–1895), Bernhard Minnigerode
(1837–1896), Woldemar Voigt (1850–1918), and Pierre Curie (1859–1906), which asserts that the
symmetries of the physical properties of crystals are related to the symmetries of their crystalline
form, the symmetry of the physical properties exhibited by a crystal is at least as high as the crys-
tallographic symmetry. It is apparent that crystallographic structure and symmetry are of great
importance in studying and designing solids at every length scale, which makes geometric crystal-
lography a fitting start for this book.
1.2.1 Crystal Geometry

A crystal is a physical object – it can be touched or at least physically observed. However, an abstract
construction in Euclidean space may be envisioned, known as a direct-space lattice (also referred to
as the real space lattice, space lattice, or just lattice for short), which is composed of equidistant
lattice points representing the geometric centers of the structural motifs. Any two of these lattice
points are connected by a primitive translation vector, R (which can also be noted T or t, but not τ),
given by
R = n1 a + n2 b 11
in two dimensions or, in three dimensions, by
R = n1 a + n2 b + n3 c 12
where n1, n2, n3 are integers that may be positive, negative, or equal to zero and a, b, c are the
basis vectors. It is also possible to write the lattice vector R in terms of the components of the
direction index, in which case n1, n2, and n3 are usually replaced by u, v, and w, respectively.
Whereas direction indices are written in square brackets without commas, that is, [u v w]
(note, however, that a family of directions is written as u v w , see Section 1.2.1.3), we shall convene
to note a vector R by separating its components by commas: [n1, n2, n3]. So that, normally, [1 1 1]
indicates a direction while [1, 1, 1] is a vector (which is in the [1 1 1] direction and can just as legit-
imately be expressed using the unit vectors as [1 i, 1 j, 1k]). A general spatial vector r = x a + y b + z
c will be noted [x, y, z].
In three-dimensional space, the parallelepiped defined by the lengths of the basis vectors and
the angles between them (α = angle between vectors b and c; β = angle between vectors a and
c; γ = angle between vectors a and b) contains the smallest volume that can be stacked repeat-
edly to produce the entire crystal. It is called a primitive unit cell of the lattice. Hence, the
lengths of the basis vectors are called unit cell parameters. Because the unit cell joins eight
lattice points, each one shared between eight neighboring cells, a primitive unit cell contains
exactly one lattice point 8 × 12 = 1 . In the crystal, associated with each lattice point is a copy of
an atomic motif, which may be a single atom, a collection of atoms, an entire molecule (in molec-
ular crystals, like fullerite made of C60 fullerenes), or an assembly of molecules. The atomic
motif (from Georges Friedel 1895) is also referred to as the atomic basis (from Max Born
1915), the lattice complex (from Paul Niggli 1919), or the asymmetric unit (from Patterson
1928), since it exhibits no symmetry of the crystal of its own. The atomic basis must not be confused
with the mathematical basis made of three vectors defining a unit cell as discussed above. The
chemical/electronic surroundings of each lattice point are identical with those of each and every
other lattice point. The crystal then looks the same when viewed from any of the lattice points.
For example, in the rock salt (halite when considered as a mineral) cubic cell shown in
Figure 1.5, the lattice points are on the edges of the cube and the centers of the faces (beware that
in diamond, by contrast, the asymmetric unit is made of two carbon atoms, which look symmetric
but are not because of their differently oriented neighborhoods). A sodium and chloride ion pair
constitutes the asymmetric unit in NaCl, the ion pair being systematically repeated, using point
symmetry and translational symmetry operations to form the crystal structure of the crystal.
The atomic motif is therefore the minimum unit from which the structure can be generated by
a combination of point symmetry and translational operations. In NaCl, the 1 : 1 stoichiometry
means that the cell will look the same regardless of whether we start with the anions or the cations
on the corner. For polyatomic motifs, in general, different but equivalent descriptions of the motif
can generate the same crystal.
Figure 1.5 The face-centered cubic unit cell (lattice

parameter a) of rock salt (halite) with a two-atom motif.
= Chloride
= Sodium
α
α
α
The motif may be an achiral molecule or a chiral molecule (non-superimposable on any of its
mirror images, like a hand), but as stated above the motif need not be a molecule. The motif of
trigonal α-quartz (a.k.a. low quartz) is a chiral motif made of three SiO2 chemical units. Chiral crys-
tals occur in left- and right-handed enantiomorphs (see Section 1.2.1.2). Like low quartz, hexagonal
β-quartz (a.k.a. high quartz) also occurs in left- and right-handed forms. There are 65 chiral, or
enantiomorphic, space groups.
Let us insist on vocabulary in order to avoid confusion: a crystal is a lattice plus an atomic motif. It
is a mathematical lattice, as defined by Eq. (1.2), plus a physical motif, made of atoms. The lattice
has its mathematical basis, a, b, c. The atomic motif is also many times simply called a basis since
the introduction by Max Born. Another usual confusion is to call a crystal a lattice. For instance,
diamond has the diamond structure that is not a lattice, the corresponding lattice being FCC.
Similarly, HCP is a structure, not a lattice. It is a hexagonal lattice with a two-atom motif. Yet,
in the phrases “lattice dynamics” and “lattice energy” (studied in Section 3.3.1), the word lattice
corresponds to a crystal structure, with atoms and interatomic interactions, not just abstract lattice
points. Due to historical developments of the word lattice in different languages (réseau, Gitter) and
different scientific communities (see Hardouin Duparc 2014), there is no way to do better than to
warn the reader to be especially careful that the meaning of words many times depends on their
context.
Example 1.1 How many atoms (ions) are shown in the cubic unit cell in Figure 1.5? How many
should really be counted per cubic cell?
Solution
There are 14 sodium cations and 13 chloride anions. Among the sodium ions, eight located at the
edges are each shared between eight cells so that they contribute for only 8 ⅛ = 1 sodium ion.
The six ion atoms in the face-centered positions are shared between two unit cells, contributing
6 ½ = 3 sodium ions. The 12 chloride ions at the midpoints of each edge are shared between 4
cells and thus contribute 12 ¼= 3 chloride ions, whereas the chloride anion located at the center
of the cell is wholly owned by it. The cubic cell thus actually owns four sodium cations and four
chloride anions that are grouped into four sodium/chloride ion pairs. These four pairs have an
absolutely equivalent environment, which means only one is necessary as primitive. Rock salt is a
face-centered cubic lattice with a two ion motif. The two ion motif can be chosen as {(0,0,0),
(0.5,0,0)} or {(0,0,0),(0,0.5,0)} or {(0,0,0),(0,0,0.5)}, which are equivalent with respect to the sym-
metry of the cubic cell. One can also choose the pair {(0,0,0),(0.5,0.5,0.5)}. The halite crystal can
also be considered as being composed of two interpenetrating face-centered cubic sublattices, one
of sodium ions and one of chloride ions. The two sublattices are displaced relative to one another
by a/2 along a cube edge direction where a is the unit cell dimension, i.e. by a vector [0.5, 0, 0]
or [0, 0.5, 0] or [0, 0, 0.5]. Still another pictured is proposed in Figure 3.3, with share NaCl6
octahedra.
Copper, diamond, and rock salt are all FCC and are usually represented by their cubic unit cells.
Yet, their primitive unit cell is not cubic. It is rhombohedral, so as to contain only one motif. A usual
choice of primitive vectors is [0, 0.5, 0.5], [0.5, 0, 0.5], and [0.5, 0.5, 0], which join a lattice point to its
three nearest neighbors (and see Table 4.1 in Section 4.5 for BCC). This rhombohedral unit cell is
harder to visualize and does not clearly exhibit the cubic symmetry, which is actually implied by the
fact that its rhombohedral angles are equal to 60 . This means that it is often convenient to choose a
unit cell larger than the primitive unit cell.
Non-primitive unit cells contain extra lattice points, not at the vertices. For example, in three
dimensions, non-primitive unit cells may be of three kinds:
1) Face centered, where a lattice point resides at the center of each face of the unit cell.
2) Body centered, where a lattice point resides at the center of the unit cell.
3) Side centered, where an extra lattice point resides at each of two opposing faces of the unit cell.
These are denoted as F, I, and A, B, or C, respectively, while primitive cells are denoted as P and
rhombohedral as R. The I stands for Innenzentriert in German (internally centered). Several sym-
metry-related copies of the asymmetric unit may be contained in the non-primitive unit cell (a.k.a.
conventional cell), which can also generate the entire crystal structure by means of translation in
three dimensions. Although primitive unit cells are smaller than non-primitive unit cells, the non-
primitive unit cell may be preferred if it possesses higher symmetry. In general, the unit cell used is
the smallest one with the highest symmetry.
In two dimensions, there are only five unique ways of choosing translation vectors for a plane
lattice, or net. These are called the 5 two-dimensional Bravais lattices (Figure 1.6a), after the French
physicist and mineralogist Auguste Bravais who derived them in 1850 (Bravais 1850). The unit cells
for each plane lattice may be described by three parameters: two translation vectors (a, b) and one
interaxial angle, usually symbolized as γ. The five lattices are oblique, rectangular, centered
(a) (b)
P
Triclinic P A
α α
γ γ Monoclinic
b b
α = b; γ = 90° α ≠ b; γ = 90°
γʹ
αʹ bʹ
P I F C
α
γ Orthorhombic
b
α ≠ b; γ = 90°
αʹ = bʹ; γʹ ≠ 90°
P R
P I
Tetragonal Hexagonal Rhombohedral
α α γ
b b
α = b; γ = 120° α ≠ b; γ ≠ 90°, 120°
P I F
Cubic
Figure 1.6 (a) The 5 two-dimensional Bravais lattices. Clockwise from upper left: square, rectangular,
oblique, hexagonal, and centered rectangular (center). (b) The 14 three-dimensional Bravais lattices.
Table 1.2 The volumes of the unit cells for each crystal system.
Cubic V = a3
Tetragonal V = a2c
Hexagonal V = a2c sin(60 )
Trigonal V = a2c sin(60 )
Orthorhombic V = abc
Monoclinic V = abc sin(β)
Triclinic V = abc{(1 − cos2 α − cos2 β − cos2 γ) + 2(cos α cos β cos γ)}0.5
rectangular, square, and hexagonal. In three dimensions, there are 14 unique ways of connecting
lattice points to define a unit cell. They are called the 14 three-dimensional Bravais lattices
(Figure 1.6b), which represent the possible types of crystal symmetry called crystal classes (also
called symmetry classes) based on their symmetry groups and the ways in which these groups
act on the lattice points. The unit cells may be described by the six parameters mentioned earlier:
the lengths of the three translation vectors (a, b, c) and the three interaxial angles (α, β, γ), from
which seven crystal systems may be differentiated such as cubic, tetragonal, hexagonal, trigonal,
orthorhombic, monoclinic, and triclinic. The volumes of each unit cell may be calculated from
their unit cell parameters, as shown in Table 1.2.
1.2.1.1 Types of Crystallographic Symmetry

The most succinct and mathematically precise way to discuss crystal geometry or symmetry is via
matrix algebra. Each point in a Euclidean space is uniquely described by a column of coordinates.
However, the coordinates of a point are meaningful only when referred to some other point, for
example, an arbitrarily chosen origin O with coordinates (0, 0, 0) and the choice of three basis
vectors. The distance between the origin and, for instance, any other lattice point, R, is given
by a primitive translation vector, such as Eq. (1.2). Hence, the numbers in the column of coordi-
nates may be either the coefficients of the vector R, [n1, n2, n3], or the coordinates of the point R,
(n1, n2, n3). It is customary to use boldface to represent vectors, as for a, b, c, R, r, V, etc. Once an
origin O has been chosen, there is a one-to-one correspondence between a point R and a vector R,
with R = OR, or.
The point space definition is pursued here. Reference is now taken as a Cartesian reference frame,
with three mutually orthogonal unitary axes, with basis vectors usually labeled i, j, k. A point x
corresponding to a vector x with respect to the origin O as x1 i + x2 j + x3 k will be noted (x1, x2,
x3) in the text or as a column in an equation:
x1
x= x2 13
x3
The right-hand side of Eq. (1.3) is a (3 × 1) column matrix. It is equivalent to a column vector x. The
choice of parentheses, (), to enclose a matrix in Eq. (1.3) and the followings complies with the choice
made by the International Tables for Crystallography (Hahn 2005 for vol. A).
Now, any type of motion or symmetry operation that leaves a lattice invariant may be written
in matrix notation. For example, if a lattice point is moved from point x in Euclidean space with
coordinates (x1, x2, x3) to point x with coordinates (x 1 , x 2 , x 3 ), this can be written as
x1 W 11 W 12 W 13 x1 w1
x2 = W 21 W 22 W 23 x2 + w2 14
x3 W 31 W 32 W 33 x3 w3
In this expression, the (3 × 3) square matrix W is a transformation matrix describing a rotation,

proper or improper (its determinant is equal to +1 or to −1; see below), while the lone (3 × 1) col-
umn matrix on the right-hand side is a vector, w, describing a translation part. Following the ITCs,
the operation at play in Eq. (1.4) is noted W or (W,w). Seitz’s original notation would be {W|w},
with {W|w} x = W x + w.
Equation (1.4) is valid for any lattice type or crystal system. Its form indicates that the elements of
the column vector x , representing the coordinates of point x , are given by
3
xi = W ij x j + wi , i = 1, 2, 3 15
k =1
It is also possible to construct a (4 × 4) square augmented matrix for the system, which has the
advantage that the motion is described by a single matrix W, rather than the pair (W,w). Successive
applications of motions are then described by the product of the augmented matrices. This product
is naturally non-commutative (non-Abelian), since already Wa Wb Wb Wa in general. It should
be stressed that each type of motion, or symmetry operation, has corresponding values for the
matrix elements in W and w, which are summarized in Table 1.3. The elements of W depend
on our choice for the coordinate system. Conventionally, the symmetry directions are chosen as
coordinate axes, along with the shortest compatible basis vectors, which will be explained shortly
for each type of symmetry operation. In this way, W will be in the simplest possible form, six or
five of the nine matrix elements being zeros and the remaining elements consisting of the integers
+1 and/or −1.
When the translation vector, w, is equal to zero (i.e. if the column consists entirely of zeros), the
symmetry operation is reduced to W and has at least one fixed point. It is called a point symmetry
Table 1.3 Types of symmetry operations based on the values of the translation
vector w, the transformation matrix W, and its determinant. I is the identity matrix.
w W det(W) Symmetry
0 W +1 Rotation
0 I +1 Identity
0 W −1 Rotoinversion
0 −I −1 Inversion
0 W2 = I −1 Reflection
T I +1 Translation
τ W +1 Screw rotation
τ W −1 Glide reflection
operation. If its determinant, det(W) (given by W11W22W33 + W12W23W31 + W13W21W32 −

W31W22W13 − W32W23W11 − W33W21W12), is equal to +1, it is called a proper rotation. If the rota-
tion angle ϕ is null, it is simply the neutral transformation or identity operation, I. If det(W) is
equal to −1, the motion is called an improper rotation, or rotoinversion, which is equivalent to
the combination of a rotation about an axis and an inversion through a point on that axis (these
operations commute). If the rotation part of the rotoinversion is null, then the rotoinversion is
termed an inversion, W itself is equal to −I. If W2 = I, the improper motion is termed a reflec-
tion, and if W −I, the improper motion is a rotoinversion. If w 0 and W = I, the motion is a
translation, the translation vector being w. If w 0 and det(W) = +1, the motion is termed a
screw rotation. It is the combination of a rotation and a translation (the type of motion you do
when you use a cork-screw). If w 0 and det(W) = −1, the motion is termed a glide reflection.
For screw rotations and glide reflections, the exact value of w depends on the choice of the ori-
gin for the application of the corresponding W rotation. In any case, w should be smaller than a
unit cell dimension, hence the choice of the symbol τ rather than T or t or R as used in Eq. (1.2).
Note that only glide reflections can occur in two-dimensional space and neither glide nor screw
motions are possible in one-dimensional space.
1.2.1.1.1 Inversion
An inversion center, also called a center of symmetry, is a point such that inversion through
the point produces an identical arrangement. In a lattice, all lattice points are centers of sym-
metry of the lattice. Inversion moves a point from a position with coordinates (x, y, z) to the
position (−x, −y, −z). The corresponding Seitz operator is (−I,0) where −I is the negative unit
matrix:
−1 0 0
0 −1 0 16
0 0 −1
With a chiral molecule (i.e. a molecule that is non-superimposable on its mirror image), the oper-
ation of inversion produces an enantiomer, or molecule with a reversal of sense. Pairs of chiral
molecules (e.g. sodium ammonium tartrate), or of nonmolecular structural motifs (e.g. the helical
arrangement of SiO4 tetrahedra in quartz), may crystallize as separate enantiomorphs, which are
pairs of chiral crystals. These are left-handed and right-handed crystals, consisting exclusively of
left- and right-handed units, respectively. This situation is actually quite rare. Morphologically,
an enantiomorph exhibits hemihedry or mirror-image hemihedral faces. The adjective hemihedral
refers to the fact that only half of the symmetry-related facets are modified (e.g. inclined) simulta-
neously and in the same manner. Hemihedral faces should not be confused with the term hemi-
hedral crystal, which refers to a form exhibiting only half the number of faces of the holohedral
form (those point groups with the highest possible symmetry of the crystal class). By far, the com-
monest situation is that pairs of chiral partners crystallize in an orthomorphic form or a racemic
monocrystal with equally many left- and right-handed molecules in the fundamental body and
hence in the macroscopic volume unit. In other words, pairs of enantiomers usually produce a crys-
tal with holohedral morphology even though the molecules themselves possess chiral centers.
It should be noted that some achiral molecules in solution (e.g. the aqueous solution of Na+
and [ClO3]−) can crystallize into enantiomorphic crystals (NaClO3, sodium chlorate, a strong
herbicide).
1.2.1.1.2 Rotational Symmetry

A crystal possesses an n-fold rotation axis if it coincides with itself upon rotation about the axes
by 360 /n. Unlike inversion, rotation leaves handedness unchanged, that is, det(W) = +1. For
any geometric rotation of a Cartesian coordinate or vector about a fixed origin in three-
dimensional Euclidean space, a matrix describing the rotation can be written. The rotation
matrix is an n × n square matrix for which the transpose is its inverse and for which the deter-
minant is +1. In general, a rotation need not be along a coordinate axis. If the rotation axis is
given by the unit vector u = [ux, uy, uz], then a rotation by an angle ϕ about that fixed axis is
given by the following expression Ru(ϕ) (Rodrigues 1840) that we provide here without dem-
onstration (note that we follow the standard convention that a clockwise rotation by a vector
in a fixed coordinate system makes a negative angle and a counterclockwise rotation, a posi-
tive angle):
cos ϕ + u2x 1 − cos ϕ ux uy 1 − cos ϕ − uz sin ϕ ux uz 1 − cos ϕ + uy sin ϕ

ux uy 1 − cos ϕ + uz sin ϕ cos ϕ + u2y 1 − cos ϕ uy uz 1 − cos ϕ − ux sin ϕ
ux uz 1 − cos ϕ − uy sin ϕ uy uz 1 − cos ϕ + ux sin ϕ cos ϕ + u2z 1 − cos ϕ
17
The columns of the matrix Eq. (1.7) form a right-handed orthonormal set: if one choses to call
them vectors, then v1, v2, v3, one has vi vj = δij (tedious to check but true), and “right-handed”
because they correspond to the final rotated values of our standard “right-handed” basis vectors
[1, 0, 0], [0, 1, 0], and [0, 0, 1], in that order. This rotation matrix is also called a special orthogonal
matrix.
The components ux, uy, and uz in Eq. (1.7) correspond to a unit vector u. They directly correspond
to the directions cosines of u (the cosines of the angles formed by u with the respective Cartesian
basis vectors i, j, and k). If the rotation axis were indicated by a larger vector, l, one simply has
u=l l =l l2x + l2y + l2z 18
For example, for a rotation about the body diagonal [1, 1, 1] of a cube, u = [1, 1, 1]/ 3, and the
values to be used in Eq. (1.7) are ux = uy = uz = 1/ 3.
Let us give a very simple example of a rotation Ru(ϕ). We recall that the direction indices of the
Cartesian coordinate axes are the x-axis = [1 0 0], the y-axis = [0 1 0], and the z-axis = [0 0 1]. These
indices are identical with the i, j, and k unit vectors that are codirectional with the x-, y-, and z-axes,
respectively. For example, if the rotation axis is the z-axis, described by the direction indices
[u v w] = [0 0 1], these indices are numerically equivalent to the direction cosines: cos α = ux = 0,
cos β = uy = 0, and cos γ = uz = 1. Therefore, with a counterclockwise rotation of angle ϕ about
the vector u = [0, 0, 1], the z-axis, Eq. (1.7) reduces to
cos ϕ − sin ϕ 0
Rz ϕ = sin ϕ cos ϕ 0 19
0 0 1
Similar expressions are found to represent counterclockwise rotations about the x-axis and
y-axis. These are left as an exercise for the reader. In a crystal lattice, with bases vectors a,
b, and c, the rotation described above by Eq. (1.9) corresponds to a counterclockwise rotation
around the c coordinate axis. As indicated in Eq. (1.9), the c coordinate will be unchanged by
any rotation about c. Consider a fourfold counterclockwise rotation around the c-axis. Here,
ϕ = −90 and Rc(ϕ) takes the form:
0 1 0
Rc −90 = −1 0 0 1 10
0 0 1
The lattice structure of a crystal, however, restricts the possible values for ϕ. In a symmetry oper-
ation, the lattice is mapped onto itself. Hence, each matrix element – and thus the trace of W (W11
+ W22 + W33) – must be an integer. From matrix theory, we know that the trace of a matrix, as well
as its determinant, is an invariant. Hence, the trace of a rotation matrix is, from Eq. (1.9), equal to (1
+ 2 cos ϕ). It is then obvious that for a lattice symmetry rotation, 2 cos ϕ must be an integer. Thus,
only onefold (360 ), twofold (180 ), threefold (120 ), fourfold (90 ), and sixfold (60 ) rotational sym-
metry are allowed. The corresponding axes are termed, respectively, monad, diad, triad, tetrad, and
hexad. The onefold, 360 or 2π, case is actually trivial and corresponds to ϕ = 0 modulo 2π. Only
triclinic crystals are in this case. A famous example is the gemstone turquoise.
The limitation on the types of n-fold rotational axes can be easily visualized by considering the
analogous task of completely tiling a two-dimensional plane with polygon tiles, a process called
tessellation. Congruent regular polygons (equilateral and equiangular polygons) such as squares,
equilateral triangles, and hexagons can be used, as can irregular polygons like simple quadrilaterals
(e.g. isosceles trapezoids, rhombuses, rectangles, parallelograms) and even herringbones. In fact,
a trip to the garden/tile shop will reveal that it is possible to produce a tessellation using plane
figures with curved boundaries, as well. However, a tessellation of the plane cannot be produced
with pentagons, heptagons, or higher regular polygons. In three dimensions, space-filling polyhe-
dra include the cube, the rhombic dodecahedron, and the truncated octahedron. However, combi-
nations of tetrahedra and octahedra, as well as of octahedra, truncated octahedra, and cubes, also
fill space.
Example 1.2 Derive the rotation matrix for a clockwise rotation about the z-axis, given by the
vector u = [0, 0, 1]. Derive the matrix for the counterclockwise rotoinversion about the z-axis.
Solution
Our convention is that a clockwise rotation is given by a negative angle. From trigonometry, we
know that cos(−ϕ) = cos(ϕ) and that sin(−ϕ) = −sin(ϕ). Hence, our matrix must be
cos ϕ sin ϕ 0
Rz −ϕ = − sin ϕ cos ϕ 0
0 0 1
In the conventional counterclockwise sense for ϕ but for a rotoinversion, which is a rotation
followed by an inversion, the product −I Rz(ϕ) gives (see Eqs. 1.6 and 1.9)
− cos ϕ − sin ϕ 0
Wz ϕ = sin ϕ − cos ϕ 0
0 0 −1
It is easy to check that its determinant is equal to −1 (see Table 1.3). Note that since −I is purely
diagonal, the product −I Rz(ϕ) is commutative: −I Rz(ϕ) = Rz(ϕ) (−I). The reader should check
that, in general, Rz(ϕa) Rx(ϕb) Rx(ϕb) Rz(ϕa) (see Pratice Problem 9).
1.2.1.1.3 Reflection
Reflection is also called mirror symmetry since the operation is that of a mirror plane in three
dimensions, or an axis in two-dimensions, which reflects an object into another indistinguishable
one. Consider a reflection in a plane parallel to b and c. The reflection essentially changes the alge-
braic sign of the coordinate measured perpendicular to the plane while leaving the two coordinates
whose axes define the plane unchanged. Hence, W for a mirror reflection in the bc (yz) plane takes
the form
−1 0 0
0 1 0 1 11
0 0 1
Like inversion through a center of symmetry, the operation of reflection produces a right-handed
object from a left-handed one.
1.2.1.1.4 Fixed-Point-Free Motions

These include translations, screw rotations, and glide reflections. Because the primitive translation
vector (Eq. 1.2) joins any two lattice points, an equivalent statement is that Eq. (1.2) represents the
operation of translational symmetry bringing one lattice point into coincidence with another. How-
ever, we must choose the basis vectors (a, b, c) so as to include all lattice points, thus defining a
primitive unit cell of the lattice containing only one lattice point. The basis vectors are then lattice
translation vectors. The operation of translation requires that W in Eq. (1.4) be equal to the identity
matrix and that the translation vector, w, be nonzero. If w 0 and det(W) = +1, the motion is
termed a screw rotation. If w 0 and det(W) = −1, the motion is termed a glide reflection, which
moves every lattice point and changes the handedness.
1.2.1.2 Space Group Symmetry

If one replaces each face of a crystal by its face normal (a vector), the point symmetry group of a
macroscopic crystal is seen to be determined by the group of linear mappings of this vector space.
Although morphological symmetry is determined by this group of linear mappings in vector
space, the possible types of morphological symmetry are one and the same with a specific group
of motions in direct space, which is the physical three-dimensional space in which we live. These
types of point symmetries are known as the crystallographic point groups. They are the point
groups that map a space lattice onto itself or the sets of point symmetry operations (i.e. rotations
and reflections, but not translations) that may be performed on a crystal, which leave at least one
point fixed in space while moving each atom in the crystal to a position of an atom of the same
kind. It has been seen previously that the lattice structure of a crystal restricts the types of rota-
tional symmetry. Only onefold (360 ), twofold (180 ), threefold (120 ), fourfold (90 ), and sixfold
(60 ) rotational symmetry are allowed. If reflections are included as well as the different possible
types of rotations, it is found that there are, in totality, two crystallographic point groups for
one dimension, 10 for two dimensions, and 32 for three dimensions. These latter are listed in
Table 1.4. By contrast, there are an infinite number of noncrystallographic point groups for
dimensions greater than or equal to 2.
When the 32 crystallographic point groups are arranged in the patterns allowed by the 14 three-
dimensional Bravais lattices, it is found that there exist only 230 three-dimensional space groups.
These are listed in Appendix A, subdivided into the 32 crystallographic point groups. The notation
system developed by Schoenflies for designating point group symmetry is still widely used for space
Table 1.4 The 32 crystallographic point groups and their symmetry elements.
Point group Symmetry operations and/or elementsa
Triclinic
1 E
1 E, i
Monoclinic
2 E, C2
m E, σ h
2/m E, C2, i, σ h
Orthorhombic
222 E, C2, C 2 , C 2
mmm E, C2, C 2 , C 2 , i, σ h, σ v, σ v
mm2 E, C2, σ v, σ v
Tetragonal
4 E, 2C4, C2
4 E, 2S4, C2
4/m E, 2C4, C2, i, 2S4, σ h
4mm E, 2C4, C2, 2σ v, 2σ d
422 E, 2C4, C2, 2C2 , 2C2
4/mmm E, 2C4, C2, 2C2 , 2C2 , i, 2S4, σ h, 2σ v, 2σ d
42m E, C2, 2C2 , 2σ d, 2S4
Trigonal
3 E, 2C3
3 E, 2C3, i, 2S6
32 E, 2C3, 3C 2
3m E, 2C3, 3σ v
3m E, 2C3, 3C 2 , i, 2S6, 3σ v
Hexagonal
6 E, 2C6, 2C3, C2
6 E, 2C3, σ h, 2S3
6/m E, 2C6, 2C3, C2, i, 2S3, 2S6, σ h
622 E, 2C6, 2C3, C2, 3C 2 , 3C2
6mm E, 2C6, 2C3, C2, 3σ v, 3σ d
62m E, 2C6, 3C 2 , σ h, 2S3, 3σ v
6/mmm E, 2C6, 2C3, C2, 3C 2 , 3C2 , i, 2S3, 2S6, σ h, 3σ v, 3σ d
Cubic
23 E, 8C3, 3C2
m3 E, 8C3, 3C2, i, 8S6, 3σ h
432 E, 8C3, 3C2, 6C2, 6C4
43m E, 8C3, 3C2, 6σ d, 6S4
m3m E, 8C3, 3C2, 6C2, 6C4, i, 8S6, 3σ h, 6σ d, 6S4
a
E = identity operation, Cn = n-fold proper rotation, Sn = n-fold improper rotation,
σ h = horizontal plane reflection, σ v = vertical plane reflection, σ d = dihedral plane reflection,
i = inversion.
group symmetry by spectroscopists. However, crystallographers use the Hermann–Mauguin, or

“International,” notation. This system was developed by Carl Hermann (1898–1961) and Charles
Mauguin (1878–1958) (Hermann 1931; Mauguin 1931). Each space group is isogonal with one of
the 32 crystallographic point groups. However, space group symbols reveal the presence of
two additional symmetry elements, formed by the combination of point group symmetry (proper
rotations, improper rotations, and reflection), with the translational symmetries of the Bravais
lattices. The two types of combinational symmetry are the glide plane and screw axis. No glide
planes or screw axes are necessary to describe 73 of the space groups. These are called symmorphic
space groups. The others are called non-symmorphic space groups.
The first character of an international space group symbol is a capital letter designating the
Bravais lattice centering type (primitive = P; all-face-centered = F; body-centered = I; side-
centered = C, A; rhombohedral = R). This is followed by a modified point group symbol giving
the symmetry elements (axes and planes) that occur for each of the lattice symmetry directions
for the space group. The following symbols are used: m (reflection plane); a, b, c (axial glide planes);
d (diamond glide plane); e (double glide plane for centered cells); g (glide line in two dimensions),
n (diagonal glide line); 1 (inversion center); 2, 3, 4, 5 (rotoinversion axes); 2, 3, 4, 6 (n-fold rotation
axes); and 2p, 3p, 4p, 6p (n-fold screw axes, np).
Both short and full symbols are used for the space groups. In the latter, both symmetry axes and
symmetry planes for each symmetry direction are explicitly designated, whereas in the former sym-
metry axes are suppressed. For example, the short symbol I4/mmm designates a body-centered
tetragonal space lattice with three perpendicular mirror planes. One of these mirror planes is also
perpendicular to the rotation axis, which is denoted by the slash between the 4 and the first m, while
the other two mirror planes are parallel with, or contain, the rotation axis. The full symbol for this
space group is I4/m 2/m 2/m 42/n 21/n 21/c, which reveals the additional presence of screw axes and
a diagonal glide line.
By convention, the coordinates of points giving the locations of atoms or molecules inside the
unit cell are given by (x, y, z) relative to the origin (0, 0, 0), where x is a fraction of the a unit cell
parameter, y is a fraction of b unit cell parameter, and z is a fraction of the c unit cell parameter (see
Example 1.3). The selection of the origin depends on the symmetry of the space lattice. For centro-
symmetric space groups, the inversion center is chosen as the origin. For noncentrosymmetric
space groups, the point with the highest site symmetry and lowest multiplicity is chosen as the
origin. If no site symmetry higher than 1 (no point symmetry) is present, a screw axis or glide
plane is chosen as the origin. The site symmetry of the origin is often, but not always, identical with
the short space group symbol.
In contrast to a special position, a general position is left invariant only by the identity operation.
Each space group has only one general position, but the position may have multiple equivalent
coordinates. If an atom resides at a general position, it resides at all the equivalent coordinates.
For example, for a phase crystallizing in the space group Im3m, an atom located in the general posi-
tion (x, y, z) will, by symmetry, also be found at 96 other coordinates. In Im3m, the general position
has a multiplicity of 96. In any space group, the general position always has the highest multiplicity
of all the positions in the group. For primitive cells, the multiplicity of the general position is
equal to the order of the point group of the space group; for centered cells, the multiplicity is equal
to the product of the order of the point group and the number of lattice points per cell.
Example 1.3 List the point coordinates, relative to the origin (0, 0, 0), for all the atoms of the cubic
unit cell of a pure metal with the body-centered cubic (BCC) structure (space group Im3m).
Solution
This is the case of, for instance, alpha iron. By convention, we take the origin to be at the center
of the (centrosymmetric) cube. The point coordinates for each of the nine atoms are then the
origin (0, 0, 0) and the eight cube corners (±0.5, ±0.5, ±0.5) that each count for one eighth of the
cube, being shared between eight equivalent cubes. The cubic unit cell really contains only two
atoms. However, all the lattice points in any type of lattice are equivalent since they are related
by simple translation. Therefore, any one of these nine equivalent atomic sites in the BCC struc-
ture could be chosen as the origin. They are all said to be the same “position” and that is (0,
0, 0). The primitive unit cell contains only one site and one atom in the pure metal case with
BCC structure (such as iron and the VB and VIB periodic elements, for instance, at room pres-
sure and temperature).
Compounds, with forced fully polyatomic motifs, provide a wealth of structures, some of which
will be presented in Section 3.4. We already introduced rock salt, NaCl, in Figure 1.5 and Exam-
ple 1.1. Perovskite, with its CaTiO3, is analyzed in Example 1.4. The crystallographer will wonder at
the fact not only that different chemical ABO3 compounds crystallize in the perovskite structure
(see Section 3.4.1.6) but also that some others, which chemically look similar, crystallize in different
structures, less symmetric. CaCO3, for instance, crystallizes as calcite in normal temperature and
pressure conditions. Its crystal system is trigonal, its crystal class is hexagonal scalenohedral, 3m,
and its space group R3c (#167), with a double chemical formula per primitive (rhombohedral) unit
cell, is Ca2C2O6. Its rhombohedral cell angle is 46 6 , far from the 60 that would give it a cubic
symmetry. Magnesite MgCO3, rhodochrosite MnCO3, sidérite (chalybite) FeCO3, and smithsonite
(calamine) ZnCO3 also crystallize like calcite, with rather similar rhombohedral cell angles. This is
a case of isomorphism, a notion due to the German chemist Eilhard Mitscherlich (1794–1863). But
dolomite, Ca0.5Mg0.5CO3, is rhombohedral 3, with the R3 space group (#148). Even more surprising
is CaSiO3, where C is just replaced by its chemical analog Si in the CaCO3: it crystallizes as wol-
lastonite, which is only triclinic, in the pinacoidal, 1, crystal class with the P1 space group and
six chemical formulae per primitive unit cell.
As far as sodium chlorate NaClO3, already alluded to at the end of Section 1.2.1.1.1, is concerned,
it crystallizes in the P212121 space group (#19), a chiral compatible non-enantiomorphous space
group. René-Just Haüy (1743–1822) disagreed with Mitscherlich about the possibility of isomor-
phism. Haüy was wrong. Yet, Mitscherlich was certainly far from realizing all the possibilities just
described. Mitscherlich was also puzzled by the properties of sodium ammonium salt of tartaric and
paratartaric acids. A solution of tartrate rotates polarized light, while a solution of paratartrate has
no effect. Mitscherlich, however, could not see any differences in the external form of their crystal
salts, and he transmitted the puzzle to the French physicist Jean-Baptiste Biot (1774–1862), a spe-
cialist in the study of optical activity, as a note to be published by the French Academy of Science.
The young Louis Pasteur (1822–1895), then a student in chemistry and optical crystallography,
solved the enigma in the first months of 1848. Convinced that the paratartrate sodium ammonium
salt had to be a mixture of two dissymmetric (we now say chiral) crystal forms with right- or left-
leaning hemihedral facets, respectively, he proved able, thanks to his good eyes (and good temper-
ature conditions for crystallization of these salts), to see the two forms and manually separate them,
finding that in solution the two salts had opposite rotations, as did the liberated acids. Pasteur thus
identified, for the first time, the two enantiomers of a chiral substance and recognized the existence
of molecular chirality. Pasteur later beautifully illustrated the difference between the chirality of
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from his horse, on his unlucky expedition to Mándará, remained
without a weapon in his hand. However, he was of opinion that at
present, with such a large army, no danger of this kind was to be
feared. He showed me also, in the most flattering manner, that he
had imitated my example of having my chronometer continually
girded around my waist; and he assured me that he found it very
convenient.
The troop was here proceeding in stately order, and a broad line of
battle deployed, one officer, with the title of jérma, riding in advance,
and being followed by the four fan-bearers of the sheikh, in full array;
but a little further on, a small tract of underwood compelled them to
change their order of march, and proceed in one long line. The vizier
was kind enough to send me a message to the effect that I had
better get in front, so as not to be in the midst of the confusion. The
place of encampment was chosen on the north-west side of the town
of Márte; and when the sheikh had dismounted, in order to take
possession of the mat house which had been prepared for him, the
whole host of cavalry galloped up in the fiercest manner, before I
was able to get out of their way, so that I received a very severe
shock from a horseman, who struck against me with great violence.
In the afternoon my friend and companion on my journey to
Ádamáwa, Kashélla Bíllama, called on me; and we mounted on
horseback, in order to pay a visit to the market, which is held every
Friday outside the western gate of the town, where an open area
surrounded by several wells spreads out. But the market, at least
that day, was very insignificant: it was not furnished with a single
shed or stall, and not a single article of manufacture was exposed,
Negro millet, butter, and wooden bowls being almost the only articles
offered for sale; and sellers, as well as buyers, were very few in
number. The town contains about four thousand inhabitants, and,
taking into account the strategical art of this country, possesses
proper defences, the clay wall being in a good state of repair, and
having a gate on each side excepting the side of the market, where
there are two. Towards the east there is a little cultivated ground, and
on the north a small suburb, consisting of large, conical, thatched
huts, where, besides Kanúri, several Fúlbe or Felláta families are
living. The interior of the town consists of narrow lanes; and most of
the houses are clay buildings. There was nothing interesting to be
seen; but I was agreeably surprised when my companion, who was a
native of this place, took me to pay my compliments to his mother,
who kept a small shed, or rather, as we should say, a shop, in the
little market-place inside the town. It was certainly a trait of a good-
natured and friendly disposition.
We remained here the following day; but our stay was not at all
pleasant, there being very little shade near the encampment, while
our tents were so worn that they scarcely afforded any protection
against the sun. Owing to the smallness of my means, I had been
obliged to leave my large tent in Kúkawa.
Sunday, Nov. 30.—The following morning I was obliged to remain
behind the army a considerable time, in order to allow the air to
acquire a more genial temperature. I enjoyed the more the beautiful
morning, although the country did not possess many attractions.
Here, also, it exhibited that black boggy soil, called “fírki,” which is
peculiar to the southern parts of Bórnu, though near the village of
Little Márte, or “Márte ghaná,” some slight variation was seen, in a
crop of Indian corn or “holcus” still standing in the fields; the ears,
however, were quickly plucked off by the undisciplined army. Further
on I reached a group of villages ornamented by a cluster of beautiful
tamarind-trees, and here lay down awhile to enjoy the delicious
shade. Numbers of people were resting here and there, in order to
partake of the hospitality of the villagers; for, to the ruin of the
country there is no commissariat in these armies to provide for the
wants of the private individual, and every one must supply himself
with food in the best manner he can.
Our march, however, was very short, the encampment having
been chosen on the west side of the town of Alá. This town also is of
some importance, and surrounded by a wall in good repair, with two
gates on the north and west sides and only one on the south and
east. The interior is enlivened by large trees, consisting of chédia
(elastic gum), and kúrna-trees, while the huts are remarkable for
their high conical roof, the thatch of which, in a great many
instances, is interlaced by the clasps of the Cucurbita lagenaria, the
whole looking very cheerful. The sheikh having requested me
repeatedly to give my compass up to him, as he imagined it would
be sufficient for one of us to possess such an instrument, I thought it
prudent to offer him my musical box as a present, remarking that I
would willingly give away such articles, but not scientific instruments.
Several hares had been caught in the course of the day; and in the
evening we had some of them very palatably dressed by the
experienced female slave of Lamíno.
Monday, Dec. 1.—Soon after starting, early in the morning we had
to traverse some underwood, which caused a great rush and much
confusion among the undisciplined army, so that two or three
horsemen were seriously injured. On such occasions, as well as in
the thick covert of the forest, I had a full opportunity of testing the
valuable properties of the Arab stirrups, which protect the whole leg,
and, if skilfully managed, keep every obtruder at a respectful
distance; indeed I am almost sure that if, on these my African
wanderings, I had made use of English stirrups I should have lost
both my legs. Our way afterwards led over monotonous fírki ground,
where we were cheered by the sight of some fine crops of sorghum.
Detached hamlets were seen in every direction, even where the
country did not present any traces of cultivation; but with the
exception of the Shúwa villages, this province does not contain many
small hamlets, the population being concentrated in larger places.
Underwood succeeded to the fírki ground, and extended to the very
walls of the large town of Díkowa.
The sight of this town, with its walls over-towered by the regularly
shaped crowns of magnificent fig-trees, was very imposing. The
western wall, along which our road lay, was covered with women and
children, and we met a numerous procession of females in their best
attire, who were going to salute their sovereign upon his arrival at the
encampment; and coming from the capital, which is distinguished by
the ugliness of its female inhabitants, I was agreeably surprised at
their superior countenance and figure. But though the observer might
be gratified with the personal appearance of the natives, their
industry was questionable; for only a small tract of cultivated ground
was to be seen on this side of the town, girt by a forest of mighty
trees.
The encampment, or “ngáufate,” began to form close to the
southern wall of the town, amidst sandy ground free from trees, and
completely surrounded by a thick covert. Although it was December,
the sun was very powerful; and, until the camels arrived, I sat down
in the shade of a “bíto,” or Balanites, while the encampment was
spreading out in all directions, and approached the edge of the
covert. I then gave up my shady place to Kashélla Játo, an officer of
the musketeers, who, in acknowledgment, offered me a clear piece
of delicious gum, just taken from the tree and full of sweet fluid; in
which state it is certainly a delicacy, and is so esteemed here as well
as in Western Negroland. The encampment springing up gradually
from the ground, with its variety of light dwellings built only for the
moment—the multifarious appearance of armed people—the number
of horses of all colours, some of the most exquisite beauty—the
uninterrupted train of beasts of burden, camels, and pack-oxen,
laden with the tents, furniture, and provisions, and mounted by the
wives and concubines of the different chiefs, well dressed and
veiled,—altogether presented a most interesting picture; for now
almost the whole host or “kebú,” had collected, and twenty thousand
men, with ten thousand horses, and at least as many beasts of
burden, were no doubt assembled on this spot. At length our two
tents also were pitched, and we could make ourselves as
comfortable as the scanty shade which they afforded allowed us.
In the evening, our conversation with the vizier turning upon the
means which remained for Bórnu to attain once more to her former
greatness, these devastating expeditions and slave-hunts fell under
discussion; and I took the liberty to indicate, in opposition to such a
system, the necessity of a well-established government, with a
strong military force capable of extending their dominion. I also
called the attention of the vizier to the point, that, as they could never
rely upon the Turks, who might easily cut off all supplies of foreign
merchandize, it was greatly to their interest to keep open to
themselves that large river which passed a short distance to the
south of their dominions, and which would enable them to supply
themselves with every kind of European manufacture at a much
cheaper rate than they were able to obtain them by the northern
route. He did not hesitate to throw the whole blame upon the former
sultans; but those poor men, when they possessed the dominion of
the Kwána tribe, probably had no idea that the river which ran
through their territory joined the sea; and even if they had, the
relation between Islam and Christianity at that period was of so
hostile a character, that, for the very reason that this stream might
open to the Christians a more easy access to their country, they
shunned any nearer connection with it as dangerous. However,
under the present entirely altered state of affairs, there is no question
that an energetic native chief, basing his power on a supply of
European merchandize, as facilitated by the river Bénuwé, might
easily dominate a great part of Central Africa; but energy is just the
very thing these people are wanting in.
From this point of our discourse there was an easy transition to
that of the abolition of slavery; and here my late lamented friend Mr.
Overweg made a most eloquent speech on this important question.
The vizier could not bring forward any other argument in his defence,
than that the slave-trade furnished them with the means of buying
muskets; and, lamentable as it is, this is certainly the correct view of
the subject, for even on the west coast the slave-trade originated in
the cupidity of the natives in purchasing the arms of Europeans.
Such is the history of civilization! If the poor natives of Africa had
never become acquainted with this destructive implement of
European ingenuity, the slave-trade would never have reached those
gigantic proportions which it has attained. For at first the natives of
Africa wanted firearms as the surest means of securing their
independence of, and superiority over, their neighbours; but in the
further course of affairs, these instruments of destruction became
necessary, because they enabled them to hunt down less favoured
tribes, and, with a supply of slaves so obtained, to procure for
themselves those luxuries of European civilization with which they
had likewise become acquainted. This is the great debt which the
European owes to the poor African, that, after having caused, or at
least increased, this nefarious system on his first bringing the natives
of those regions into contact with his state of civilization, which has
had scarcely any but a demoralizing effect, he ought now also to
make them acquainted with the beneficial effects of that state of
society. Entering, therefore, into the views of our hosts, I told them
that their country produced many other things which they might
exchange for firearms, without being forced to lay waste the whole of
the neighbouring countries, and to bring misery and distress upon so
many thousands.
I informed them of the last negotiations of Her Britannic Majesty’s
messengers with the King of Dahomé, when our friend, listening with
the greatest interest to the account of these noble endeavours of Her
Majesty’s Government, which he could not but admire, declared, in
the most distinct manner, that, if the British Government were able to
furnish them with a thousand muskets and four cannons, they would
be willing to subscribe any obligatory article for abolishing the slave-
trade in their country—of course not including, all at once, domestic
slavery; for such a measure would scarcely be feasible in a country
where all the relations of domestic life are based upon this system.
But the abolition of the foreign slave-trade would be the beginning of
a better system. However, I told them that, supposing Government
were to entertain such a proposal, the first thing for them to do was
to open themselves a road to the river Bénuwé, as it would be
difficult, not only with respect to the state of the country to be
traversed, but also on account of the suspicions of the Turks, to
provide them with such a military store by way of the desert. But at
present this whole question has been superseded; the vizier himself
has succumbed, and his master, the Sheikh ʿOmár, although he has
been fortunate enough once more to usurp the sovereign authority,
seems scarcely sufficient to hold out any guarantee of the stability of
his dynasty. Moreover, the slave-trade at present is, in fact,
abolished on the north coast; and this circumstance must eventually
exercise a great influence over the destinies of Bórnu, on account of
its central situation, especially if at length a regular intercourse be
established on the river Bénuwé.
It was our lot to remain here several days; for while the Kanúri
people, who were expected to join the expedition, had already
assembled in sufficient numbers, only a very small portion of the
indigenous Arab or Shúwa population had as yet come up; for
almost all of them live in the south-eastern parts of the country,
where they have taken possession of the deserted seats of former
tribes, which were annihilated or weakened in the relentless wars
between Islamism and Paganism. On the first day of our arrival, our
encampment was very comfortable; but every day that we stayed
here it became more confined, owing principally to the numerous
cavalry of these Arab tribes, almost all of whom are mounted; and
many a newcomer was seen hurrying about without being able to
find a spot to lie down, or to meet with friends to treat him. I myself
had to entertain a respectable man among these Shúwa, of the
name of Háj Hamadán, belonging to the tribe of the Hasúnna.
This man, who generally had his settlement far to the east, in the
Wady Guskáb, had come some time previously to Logón in order to
pay a visit to some relations of his, and had now joined this
expedition. But one must be very careful with these Shúwa; for, to
use a common expression, if you give them an inch, they are wont to
take an ell. But for their Jewish character, I should have liked to enter
into more intimate relations with them than I actually did.
Their emigration into these regions, at least several centuries ago,
is certainly not without interest; and, as I have already had occasion
to observe in another place, they preserve the characteristic type of
their race very distinctly—a middle-sized, slender figure (which,
however, is apt to become fuller as they advance in years), small
pleasing features, and a dark olive complexion. Their dialect is very
peculiar; and while it lays claim to a far greater purity than belongs to
the dialects of the coast, by the profusion of vowels which it has
preserved, its character is deteriorated, and becomes nearly
ridiculous, by the continued repetition and insertion of certain words.
A Shúwa is not able to say three words without inserting his favourite
term “kúch, kúch,” which corresponds to the English word
“thorough,” but which is not Arabic at all. When they omit the word
“kúch,” they make use of another term, “bérketek,” “your worship,”
which at once bears testimony to the servile and degraded position
which they occupy in Negroland, although in Bórnu they are still
treated with some indulgence and lenity, especially since the time
when Mohammed Tiráb, the father of the present vizier, who
belonged to the tribe of the Sálamát, attained the highest degree of
power and influence in the country. In Wádáy again, even at the
present time, they are treated very badly.
Of Kanúri people, besides a few smaller bodies of troops, only two
officers, or kashéllas, ʿAlí Marghí and Jérma, were wanting. All the
officers and bodies of troops on this side of the komádugu of Bórnu,
the so-called Yeou, were collected together, the only exception being
Kashélla Mánzo, my hospitable host in Zurríkulo, whose presence at
his post was required on account of the Tuarek; for, as regards the
officers and chiefs of the provinces on the other side of the
komádugu, nobody is required to take part in these expeditions of
the sheikh, every officer remaining at his post, except when his
master enters upon a war in his own quarters.
While the encampment itself presented considerable interest, as
being the temporary abode of so many people, the town of Díkowa,
near which we were encamped, seemed well deserving some
attention, as having been repeatedly the residence of the rulers of
the country, and being still one of the largest towns in the kingdom. I
therefore paid a visit to it in the afternoon of the second day of our
stay, being accompanied by my friend Bíllama. We entered the town
by the western gate; and I saw that the walls were about thirty feet
high, and terraced on the inside like those of the capital, and of
considerable breadth at the base: they were in a state of good repair.
I was struck by the height and round shape of the huts, which
entirely wanted the characteristic top, or, as the Kanúri people call it,
kógi ngímbe, and were of the same kind as I had observed in the
other towns of this southern province. Every hut had its little
courtyard, in some of which vegetation was seen, mostly karás.
The further we proceeded, the more I was pleased with the
general appearance of the town, the exterior of which had made a
favourable impression upon me on our first arrival. Large, beautiful,
wide-spreading fig-trees, ngábore, chédia or elastic gum-trees, and
kórna-trees, spread their shade all around, and two or three isolated
papaw-trees, or as the Kanúri call them, bambús-másarbe, with their
remarkable feathery crowns and their smooth virgin-like stems,
formed a lively contrast to the broad-leafed canopy of the other
trees, while the hedges and fences of the courtyards were partly
enlivened by a luxurious creeper called “dagdágel” by the natives.
The real nucleus of the town seemed to consist entirely of clay
houses.
After a very pleasant ride, we reached the house of the “maínta,”
or governor, who still enjoys a certain degree of independence. The
chief ornament of the place in front of his house was the most
splendid caoutchouc-tree I have ever seen; indeed I can scarcely
imagine that the diameter of its crown, which was so regularly and
symmetrically shaped that it appeared as if effected by art,
measured less than from seventy to eighty feet. It really formed a
beautiful fáge, or, as the Háusa people call it, íchenbatú, or open
council-hall, such as are common in these places; but at present no
political business of any importance was transacted here, and it
formed a favourite lounge for idle people, amongst whom there was
a troop of musicians, playing lustily upon their instruments to console
the petty chief for the loss of his former power, which had dwindled
away to a mere shadow. I would gladly have paid him a visit; but,
poor as I was at the time, and without a single article worthy of
acceptance, I was rather glad that I was under no obligation to him.
The interruption in the daily course of life of the inhabitants, by the
presence of the army, was the more to be lamented, as it prevented
me from becoming an eyewitness to the chief industry of the natives,
which consists in weaving, and manufacturing into shirts, the cotton
which they grow; for they are almost exclusively cotton-growers, and
have very little corn. But, although they are able to produce a fine
sort of texture, they are very badly off for dyeing, and in this respect
are far outstripped by the inhabitants of Ujé and Mákari. Instead of
the beating of shirts, which forms so pleasant a sound in many other
industrial towns of Negroland, there was nothing to be heard but the
sound which proceeded from the powder-mill, if I may be allowed to
give this grand name to a yard in which eight slaves were employed
in pounding powder in large wooden mortars; for this is the way in
which powder is prepared in Negroland, and during my stay in
Bagírmi every time I had my coffee pounded (as I did not possess a
coffee-mill), I excited the suspicion that I was preparing powder. Of
course the presence of the army was the reason why so little activity
was to be seen at present, and the little market, or durríya, which is
held in the afternoon, was very badly attended; but the size and
populousness of the town made such an impression upon me, that I
thought myself justified in rating the number of inhabitants at about
twenty-five thousand.
Altogether I was so much pleased with the character of the place,
that on expressing my satisfaction to one of the inhabitants who
came to salute my companion, with the words, “Átema bílla ngílla”
(“This is a fine town”), he replied, with conscious pride, “Áte bílla
déka gení; áte bílla maíwa” (“This is not a country town; this is a
royal residence”). We reached the gate on the north-west side of the
town, just at the moment when ʿAbd eʾ Rahmán, the eldest brother
of the Sheikh ʿOmár, arrived with a party of horsemen. What his
business was I do not know; but before the expedition left the town,
there had been a great many unfavourable rumours concerning his
ambitious designs, and the malcontents expected that he would avail
himself of this opportunity for striking a blow at the vizier, in order to
prevent the expedition from proceeding against Mándará, as he
himself was supposed to be on friendly terms with the chief of that
country. But whatever may have been his intentions, he found his
rival still too strong; and, after a friendly parting from his brother, he
retraced his steps.
The view over the encampment, which presented itself when from
the north I turned to the south-west side of the town, was extremely
interesting; and I kept along the higher ground formed by the rubbish
which had accumulated at the foot of the wall. Tents of every
description and size—light sheds constructed with the long stalks of
Indian corn, supported by four poles, and connected lightly at the top
and forming high-topped gables—horses and men, all in the greatest
confusion, presented a busy scene of animated life; but the place
where our tents were pitched had become so confined, that I was
glad to avail myself of any opportunity which presented itself of
roving about in the neighbourhood.
The most attractive place was the komádugu, or watercourse,
which passes at some distance to the south of the town, and is
distinguished by the special name of Yálowe. It was a very charming
spot, winding along through a rich and varied forest, bordered by an
uninterrupted line of the finest fig-trees, principally of the kind called
“ngábore.” The channel itself was only about forty yards wide,
encompassed by banks of from twelve to fifteen feet in height, and at
present it was not enlivened by a continuous stream, but contained
several detached pools of stagnant water. Although the water was
cool, and not disagreeable to the taste, still it was not very pure, and
could not but contain the germs of much disease. This is the same
komádugu with which, in its upper course in the territory of Ujé, I had
become acquainted on my journey to Ádamáwa. The banks all
around were enlivened by horses and pack-oxen, who were enjoying
the rich verdure; and there was not a shady tree but had been taken
possession of by a troop of Kánembú or Kanúri, in order to find that
comfortable repose which the noisy encampment could not afford.
Having heard that the wealth of the inhabitants of Díkowa
consisted of cotton, I expected to find extensive well-kept cotton-
plantations; but, although the article was cultivated to a great extent,
I was astonished at the neglected appearance which it exhibited, the
cotton-fields being almost buried beneath the thicket, and overgrown
not only with rank grass, but even with trees and bushes, so that
scarcely any space was left for the plants to spread out;
nevertheless their luxuriant growth bore ample testimony to the rich
nature of the soil, and gave an idea of the wealth that lies buried in
these regions. I have already observed, on another occasion, that
the natives of Negroland take very little care of their cotton-
plantations; and there is no doubt that, if sufficient care was
bestowed, quite a different quality might be produced.
I roved about in this wild and fertile region till I was entirely
hemmed in by an impenetrable thicket. While returning hence to our
encampment by a more westerly path, I was ruminating in my mind
how the former rulers of this country had evinced so much more
feeling for the bounty and beauty of nature than its present
possessors; for, while these have chosen for their residence the
most monotonous district of the empire, the former selected those
parts which nature itself had embellished—the shores of the so-
called Yeou, or the komádugu Wáube, and this fine watercourse of
Díkowa; and they not only chose the most interesting spots, but they
even embellished them by art, as the large artificial basins in the
neighbourhood of Ghasréggomo, Ghámbarú, and Dámasak amply
testify. In this respect it is not uninteresting that we are informed by
the Imám Áhmed, the historian of the King Edrís Alawóma, that his
master, when he visited the town of Fíka, could not forego the
pleasure of paying a visit to the famous little alpine lake which lies at
some distance from that town. Although the country of Bórnu is far
from being the most favoured part of Negroland, yet the shores of
these watercourses are very rich indeed, and capable of maintaining
a numerous population.
In returning to our encampment, I passed the market, or durríya,
which was held every afternoon on the west side of the
encampment. It was really a busy scene, not yielding in importance
to the little daily market of the capital; and this was not at all
marvellous, as a greater crowd of people, and a far greater number
of horses, were gathered here than the average population of
Kúkawa. Not only were provisions, such as meat, grain, beans,
ground-nuts, and other articles of a like description, offered for sale,
but even small luxuries; and there was a good deal of bartering, as
the buyers were destitute of currency—kúngona, or cowries, as well
as gábagá, or cotton strips. I also observed that the encampment,
especially on this side, where it was skirted by a thick covert of trees,
was encircled by a living wall of light Kánembú spearmen, who were
keeping watch; for although the army was still in its own territory, yet,
in the weak state of the government, a certain degree of insecurity
already commences here; and the very first evening of our being
encamped on this spot, the ngáufate was roused by the gangéma, or
announcement by beat of drum, to the effect that everybody should
be on his guard against horse-stealers.
While the country around presented interesting features, and the
encampment itself exhibited a scene of great variety, the time we
spent here passed away comfortably and agreeably, with the sole
exception that the space allotted to us was too confined to be
comfortable. We were on the most friendly terms with the sheikh as
well as with his vizier; and all court etiquette was dispensed with.
This went so far that I and my companion accommodated our noble
and princely friends with our woollen jackets and drawers; for they
began to feel the cold at night very severely, and on these occasions
the very respectable Háj Edrís had to play the part of a royal
laundress.
Already, during our hibernal stay in the country of Aír, we had been
obliged to accommodate our old and austere friend Ánnur and his
numerous relatives with our Turkish waistcoats: but we had not yet
condescended to give away our under-clothing; and being ourselves
extremely poor and destitute in every respect, it was certainly not a
little privation we imposed upon ourselves. The clothes of the sheikh
and his vizier were all very wide, and not fit for keeping out the cold. I
have repeatedly had occasion to mention how sensitive the Africans
are to cold; and I am persuaded that, in the burning regions of
Central Africa, a good cargo of warm under-clothing would find a
ready sale, especially if it should arrive in the months of December
and January. But neither did our noble hosts, on their part, fail to do
everything in their power to render our situation as comfortable as
possible; and it was very satisfactory to see how anxious the vizier
was to supply us with all desirable information.
One evening, at a late hour, when I was reposing in my tent and
about to go to bed, he sent for me in the greatest hurry, as if my life
or death were at stake; and upon hastening thither, anxious to hear
what was the matter, I was told that the vizier had been informed of a
person being in the encampment who, like my old friend the mállem
Katúri, had accompanied the memorable expedition of Ámba
Sámbo, the warlike chief of Chámba, towards the country of Ígbo on
the sea-coast. But while the latter had gone to Mbáfu with the main
body of the army, the adventurous proceedings of that person had
not even been limited by the boundaries of the sea; and he informed
me, in the most positive and conclusive manner, that the body of
troops which he accompanied had sailed along a rocky coast for
fifteen days, when they unexpectedly met with an island, where they
took possession of a number of muskets; their owners, who were all
dressed in jackets, having taken refuge in their large vessel.
He did not doubt that these people were Christians, and according
to the description which he gave me of the vessel, there can scarcely
be any doubt that it was a European one; but I did not feel quite
certain as to the point whether he had navigated a large river, or the
open sea, though I think it probable they went down the Niger, and
surprised one of the European traders at the mouth of the river. At
any rate, however, this is an extremely interesting circumstance. I
apprehend that the chiefs of Ádamáwa will hesitate in future to
extend their expeditions so far, after an English steamer has gone up
the river to the very heart of their own country. It was this same
Bórnu horseman who informed me that, on that expedition, all the
horses had died from a disease proceeding from worms.
While chatting together upon these subjects till after midnight, I
had an opportunity of giving the vizier some little information
regarding the peculiar character of the maritime power of the Imám
of Maskat, of which he had never heard before, and which interested
him exceedingly. With the Arabs of Timbúktu, also, this subject
formed a topic of the highest interest, as they had no idea that there
were people of the same faith living on the eastern shores of this
continent; and they delighted in the thought, that even in those
regions there were Moslems, who were not quite destitute of political
power. For, although the famous traveller Ebn Batúta has given to
his countrymen an account of these regions, it was only in Sókoto
that I met with a man, the learned Káderi dan Táffa, who knew
Sofála by name.
My friend Bíllama also frequently called on me, and furnished me
with a variety of information, while I applied myself strenuously to the
study of the Kanúri language, which had discouraged me at first,
owing to the difficulties of its grammatical structure: and I could
scarcely have had a better teacher than our friend Háj Edrís; for,
being of Kanúri origin, he had lived a great many years in the east,
especially in Medína, and had become almost an Arab. He was
certainly an intelligent and honest man; and in the course of our stay
we became indebted to him in many respects. Of course we could
not expect him to render his service gratuitously, as he himself was
not in affluent circumstances, though as a courtier he had to keep up
a good appearance; but being myself very poor at the time, I could
do nothing but place him upon a needle-pension, the needles being
very useful in the encampment for buying provisions.
CHAPTER XLIII.
THE BORDER-REGION OF THE SHÚWA.
Saturday, Dec. 6.—At length, after a protracted stay, we left our

encampment at Díkowa, though still in complete uncertainty whether
the expedition was directed against Mándará or not; for as yet the
chief of that little country (which, through the adventures of Major
Denham, has obtained in Europe a greater share of attention than it
really deserves), relying upon the natural strength of his mountains,
had not yet made his submission. The rumours which we heard from
thence were of the most contradictory nature; and it seemed as if
Abú Bakr, which is the name of the present chief, had made up his
mind to a determined resistance, having retired into his mountain
fastnesses, to the great disappointment of the vizier, who repeatedly
asked me and my companion, with great anxiety, what was to be
done, and how it was possible for the cavalry to attack the enemy in
his mountainous retreat: for, whatever military strength the Kanúri
may still possess, it is almost solely to be looked for in their cavalry.
The former excellence of the Kánembú spearmen, resulting from
their enthusiastic devotion to their leader, has disappeared long ago,
at least since the overthrow of the old dynasty; and the vizier had to
expect very little sympathy from this body, as most of them were
decidedly favourable to the interest of his adversary, ʿAbd eʾ
Rahmán. As far as I had been able to learn the nature of those rocky
mountains on my journey to Yóla, I could not but think that not only
the cavalry of Bórnu, but even the Kánembú spearmen, accustomed
as they were to the level plains of their country, would be incapable
of climbing those rocky cliffs.
The whole country was enveloped in a thick fog when we started
in the morning; so that the passage of the komádugu, with its steep
banks, caused a considerable crowding and pushing, which was far
from agreeable. When we had got safely over, we had to pass a
thick forest, consisting of “bíto” and “kindín,” or talha-trees; and on
our left appeared the large walled place of Áfagé, a considerable
town, but not so large as Díkowa. After only a short interval, we saw
another town on our right, called Kodége, the walls of which were in
an advanced state of decay, but were at present adorned with living
battlements of male and female spectators.
Proceeding a short distance onward, we encamped at an early
hour to the westward of another walled town, called Zógoma. The
whole of this district, favoured as it is by nature, seems to have been
once in a very flourishing condition. It was, however, rather odd that
we should have encamped here, as the horses had to be led back to
Áfagé for water.
I had scarcely pitched my tent, when that cruel minister of police,
Lamíno, a man whose character my friend Háj Edrís used
significantly to describe in the few words, “Kárgo díbbi, kíndi díbbi”
(“Bad in heart, and bad in deed”), brought into my presence a
famous cut-throat of the name of Barka-ngólo, whose neck was
secured in a large machine called “bégo,” consisting of two pieces of
wood from four to five feet in length, and very heavy, so that every
movement was accompanied with the greatest pain. Nevertheless
my mischievous friend persuaded himself that it would gratify me to
see this miserable wretch fight with another culprit secured in the
same manner, by giving to each of them a long whip of
hippopotamus-hide, and forcing them by threats to flog each other. It
was a horrible sight; and I had great difficulty in convincing my cruel
friend that such a scene was far from being agreeable to me. In
order to get rid of him, I presented him with a quantity of cloves to
give to his beloved ʿAáisha, of whose culinary powers we had
already had several proofs. He was greatly pleased with my present;
and with an amorous smile he described to me how deeply he was in
love with his darling, saying that he loved her, and she loved him
also: “and,” added he, in a very sentimental way, “such a mutual love
is the greatest bliss on earth.” Europeans must not fancy that there is
no such feeling among these Africans as love, although it is not quite
so ethereal as it sometimes seems to be with us. Notwithstanding
these amorous declarations, which sounded very ridiculous coming
from such a mass of flesh as he was, I was glad when he was gone.
We were now approaching hostile territory, and in the evening a
“gangéma,” or proclamation accompanied by beat of drum, was
made throughout the whole encampment, to the effect that the train
of camels and pack-oxen, which previously had greatly hemmed in
the cavalry, should not start until after the former had moved on.
Zógoma is the farthest town of the Bórnu territory in this direction;
and the following day we encamped in a district of the name of
Mása, close to a swamp, thickly covered with water-plants,
principally the Pistia stratiotes. Several Shúwa villages were lying
about at short distances from each other.
On the road we passed some cotton-plantations and stubble-
fields. The chief agricultural produce of Mása consisted of “sábade,”
the sweet sorghum or Sorghum saccharatum. This sort of grain I had
not yet seen in the course of my journey; but in Díkowa my friend
Malá Ibrám had sent me a large quantity of it, in order that I might
indulge in this African luxury. At that period I was surprised at the
great length of these stalks, some of which measured fourteen feet;
but how astonished was I afterwards, when, in the course of my
travels in the luxuriant valleys of Kebbi, I found specimens of twice
that length! This evening the vizier treated us with the marrow of the
“sábade,” which, in snow-white pieces of about eight inches in
length, were neatly placed upon a straw cover or “féfe,” such as are
used in the country. While indulging in this simple African dainty, our
conversation, very naturally, turned upon the cultivation as well as
the preparation of sugar, which is one of those articles of European
industry that most excites the admiration of the natives of this
country. But when they learn in what a filthy manner it is refined, they
become horrified, and hesitate whether they shall say farewell to this
indulgence, or overcome the scruples and prejudices of their creed.
There is no doubt that the “sábade” would yield a rich produce of
sugar; but it is not necessary to have recourse to this expedient, as
the sugar-cane itself grows wild in several regions of Negroland, and
we shall actually find a small plantation of it, and boiling-houses, on
a small scale, carried on by a native in the neighbourhood of Sókoto.
Our conversation at these African soirées with the vizier became
sometimes so learned, that even Ptolemy with his “Mandros oros”
was quoted. But, sad as it must seem to all who, like myself, delight
in going back into remote antiquity, this famous mountain, which at
the first sight seems to be an ancient memorial of the Mándará
mountains of some seventeen hundred years standing, appears to
belong entirely to Western Africa. Our kind host always found great
delight in every kind of information; it was only a pity he was wanting
in manly energy to carry out his good projects.
Monday, Dec. 8.—Woe to those regions through which an army
takes its march in these parts of the world, were it even their own
country. We passed this morning some very extensive cornfields, the
crops of which were of the most luxuriant growth; but
notwithstanding the piteous clamours, and even the threats of the
slaves who were watching on the highly raised platforms in order to
keep away the birds from the corn, the rich ears fell a prey to the
hungry horsemen, for their own sustenance and that of their animals.
These raised platforms are here called “górgo”; and the ropes which
were fastened between them and the trees were provided with small
hollow gourds, “káre,” filled with stones, which, when set in motion,
were intended to frighten away the birds. After a tolerable march, we
took up our encampment near the straggling hamlet Delhé, a locality
touched at by Major Denham, on his unfortunate expedition to
Mándará, but placed by him much too far southward.
All the cottages in these Shúwa villages have a conical roof rising
to a great elevation, and tapering like a sugar-loaf,—the thatch being
put on in a very irregular way, and fastened with ropes, though it is
pleasantly and cheerfully adorned by the climbers of the “ságade” or
“kubéwa,” a species of the Cucurbita melopepo (squash gourd), if
not identical with it, the fruit of which, when boiled, has a very
pleasant taste, and in some regions of Negroland, as far as
Timbúktu, forms the principal vegetable for seasoning food.
The long duration of the rainy season here, as well as in
Ádamáwa, renders sheds for the cattle necessary; and these consist
of huts constructed similarly to the dwellings of man, but more
spacious, with the exception that the walls consist merely of trunks of
trees. The Shúwa of this village, as well as those of a neighbouring
one, which after the name of a chief is called Háj Amaka, belong to
the tribe of the Bulgówa, or ʿAwisíya. The place where we encamped
was full of brushwood; and it took us a long time to pitch our tents.
The variation of the temperature was so great, that I caught a severe
cold; it was therefore agreeable to me that we remained here the
following day: for while, during the greatest heat, at two o’clock p.m.,
the thermometer in the ventilated tent showed often from 93° to 96°
Fahr., during the night it generally fell to between 50° and 53°. The
vizier was kind enough, when I did not come to his soirée, to send
one of his young slaves with a censer; but I was so unfortunate as to
excite the anger of the little tyrannical messenger, who wanted me to
imitate their own custom, which is, to place the censer under their
wide shirt, and, by drawing the opening close over the head, to
concentrate the fumes arising from the incense under their shirt, and
receive it into the face, while I, thinking this rather too much, was
satisfied with holding my face over it.
Wednesday, Dec. 10.—We made a short march in advance, and
transferred our encampment to Díggera, through a country where
wilderness and cultivated ground alternated. Here we remained the
five following days; and I had sufficient leisure to regret that I was not
better provided with books. Anxious to employ my time usefully, I
began, with the assistance of two Mándará, or rather Wándalá
slaves, to write down a vocabulary of the language of that country,
which by the natives themselves is called “Ára-Wándalá,” as they
call their country “Khakh-Wándalá,” or “Khákh-Úndalá.”
The cold which we experienced during our stay here we
considered very severe—at least from an African point of view and
feeling; for in Europe it would have been thought very moderate.
Fortunately our encampment was more comfortable than it had been
at Delhé, and presented features of considerable interest; for here
we saw the first complete example of those shallow stagnant
watercourses which are so highly characteristic of the equatorial
regions of this continent, and explain at the same time the conflicting
statements with regard to the direction of so many watercourses in
these regions. However, there are two different kinds of these

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Principles of Inorganic Materials Design

3rd Edition John N. Lalena

Fundamentals of Inorganic Glasses 3rd Edition Mauro

Database Principles: Fundamentals of Design,

eTextbook 978-0134454177 Building Construction:

Principles of Microeconomics 8th Edition N. Gregory

The Principles of Constitutionalism N W Barber

Materials for Biomedical Engineering: Inorganic Micro-

Materials for Biomedical Engineering - Inorganic Micro-

Principles of Microeconomics, Asia-Pacific Edition N.

Olivier B.M. Hardouin Duparc

Limit of Liability/Disclaimer of Warranty

Cover Design: Wiley

Set in 9.5/12.5pt STIXTwoText by SPi Global, Pondicherry, India

Printed in United States of America

Foreword to Second Edition xiii

2.2.1 Grain Boundary Orientations 63

3 Crystal Structures and Binding Forces 99

3.4.1 Iono-covalent Solids 128

4 The Electronic Level I: An Overview of Band Theory 171

6 Transport Properties 249

7 Hopping Conduction and Metal–Insulator Transitions 325

7.1.2 Charge-Transfer Insulators 334

8 Magnetic and Dielectric Properties 349

9 Optical Properties of Materials 425

10 Mechanical Properties 449

11 Phase Equilibria, Phase Diagrams, and Phase Modeling 499

12 Synthetic Strategies 537

12.1.2 Low Temperature 540

13 An Introduction to Nanomaterials 563

14 Introduction to Computational Materials Science 589

14.3 Illustrative Examples 604

15 Case Study I: TiO2 619

16 Case Study II: GaN 643

Appendix A: List of the 230 Space Groups 659

Foreword to Second Edition

Foreword to First Edition

Preface to Third Edition

Olivier B. M. Hardouin Duparc

Preface to Second Edition

John N. Lalena and David A. Cleary

Preface to First Edition

John N. Lalena and David A. Cleary

EAM embedded atom method

MS&E materials science and engineering

TGG templated grain growth

1.1 Degrees of Crystallinity

Table 1.1 Degrees of crystallinity.

Type Defining features

1.1.1 Monocrystalline Solids

(a) (b) (c)

1.1.2 Quasicrystalline Solids

1.1.3 Polycrystalline Solids

1.1.4 Semicrystalline Solids

A A A Figure 1.2 The possible conformations

Figure 1.4 A sketch depicting the semicrystalline nature

1.1.5 Amorphous Solids

1.2 Basic Crystallography

1.2.1 Crystal Geometry

Figure 1.5 The face-centered cubic unit cell (lattice

1.2.1.1 Types of Crystallographic Symmetry

In this expression, the (3 × 3) square matrix W is a transformation matrix describing a rotation,

operation. If its determinant, det(W) (given by W11W22W33 + W12W23W31 + W13W21W32 −