Principles of Inorganic Materials Design

ISBN-13: 9781119486831 / Angielski / Twarda / 2020 / 720 str.

John N. Lalena; David A. Cleary; Everett Carpenter

Spis treści

Foreword to Second Edition xiiiForeword to First Edition xvPreface to Third Edition xixPreface to Second Edition xxPreface to First Edition xxiAcronyms xxiii1 Crystallographic Considerations 11.1 Degrees of Crystallinity 11.1.1 Monocrystalline Solids 21.1.2 Quasicrystalline Solids 31.1.3 Polycrystalline Solids 41.1.4 Semicrystalline Solids 51.1.5 Amorphous Solids 81.2 Basic Crystallography 81.2.1 Crystal Geometry 81.2.1.1 Types of Crystallographic Symmetry 121.2.1.2 Space Group Symmetry 171.2.1.3 Lattice Planes and Directions 271.3 Single-Crystal Morphology and Its Relationship to Lattice Symmetry 321.4 Twinned Crystals, Grain Boundaries, and Bicrystallography 371.4.1 Twinned Crystals and Twinning 371.4.2 Crystallographic Orientation Relationships in Bicrystals 391.4.2.1 The Coincidence Site Lattice 391.4.2.2 Equivalent Axis-Angle Pairs 441.5 Amorphous Solids and Glasses 461.5.1 Oxide Glasses 491.5.2 Metallic Glasses and Metal-Organic Framework Glasses 511.5.3 Aerogels 53Practice Problems 53References 552 Microstructural Considerations 572.1 Materials Length Scales 572.1.1 Experimental Resolution of Material Features 612.2 Grain Boundaries in Polycrystalline Materials 632.2.1 Grain Boundary Orientations 632.2.2 Dislocation Model of Low Angle Grain Boundaries 652.2.3 Grain Boundary Energy 662.2.4 Special Types of "Low-Energy" Boundaries 682.2.5 Grain Boundary Dynamics 692.2.6 Representing Orientation Distributions in Polycrystalline Aggregates 702.3 Materials Processing and Microstructure 722.3.1 Conventional Solidification 722.3.1.1 Grain Homogeneity 742.3.1.2 Grain Morphology 762.3.1.3 Zone Melting Techniques 782.3.2 Deformation Processing 792.3.3 Consolidation Processing 792.3.4 Thin-Film Formation 802.3.4.1 Epitaxy 812.3.4.2 Polycrystalline PVD Thin Films 812.3.4.3 Polycrystalline CVD Thin Films 832.4 Microstructure and Materials Properties 832.4.1 Mechanical Properties 832.4.2 Transport Properties 862.4.3 Magnetic and Dielectric Properties 902.4.4 Chemical Properties 922.5 Microstructure Control and Design 93Practice Problems 96References 963 Crystal Structures and Binding Forces 993.1 Structure Description Methods 993.1.1 Close Packing 993.1.2 Polyhedra 1033.1.3 The (Primitive) Unit Cell 1033.1.4 Space Groups and Wyckoff Positions 1043.1.5 Strukturbericht Symbols 1043.1.6 Pearson Symbols 1053.2 Cohesive Forces in Solids 1063.2.1 Ionic Bonding 1063.2.2 Covalent Bonding 1083.2.3 Dative Bonds 1103.2.4 Metallic Bonding 1113.2.5 Atoms and Bonds as Electron Charge Density 1123.3 Chemical Potential Energy 1133.3.1 Lattice Energy for Ionic Crystals 1143.3.2 The Born-Haber Cycle 1193.3.3 Goldschmidt's Rules and Pauling's Rules 1203.3.4 Total Energy 1223.3.5 Electronic Origin of Coordination Polyhedra in Covalent Crystals 1243.4 Common Structure Types 1273.4.1 Iono-covalent Solids 1283.4.1.1 AX Compounds 1283.4.1.2 AX2 Compounds 1303.4.1.3 AX6 Compounds 1323.4.1.4 ABX2 Compounds 1323.4.1.5 AB2X4 Compounds (Spinel and Olivine Structures) 1343.4.1.6 ABX3 Compounds (Perovskite and Related Phases) 1353.4.1.7 A2B2O5(ABO2.5) Compounds (Oxygen-Deficient Perovskites) 1373.4.1.8 AxByOz Compounds (Bronzes) 1393.4.1.9 A2B2X7 Compounds (Pyrochlores) 1393.4.1.10 Silicate Compounds 1403.4.1.11 Porous Structures 1413.4.2 Metal Carbides, Silicides, Borides, Hydrides, and Nitrides 1443.4.3 Metallic Alloys and Intermetallic Compounds 1443.4.3.1 Zintl Phases 1473.4.3.2 Nonpolar Binary Intermetallic Phases 1493.4.3.3 Ternary Intermetallic Phases 1513.5 Structural Disturbances 1533.5.1 Intrinsic Point Defects 1543.5.2 Extrinsic Point Defects 1553.5.3 Structural Distortions 1563.5.4 Bond Valence Sum Calculations 1583.6 Structure Control and Synthetic Strategies 162Practice Problems 165References 1674 The Electronic Level I: An Overview of Band Theory 1714.1 The Many-Body Schrödinger Equation and Hartree-Fock 1714.2 Choice of Boundary Conditions: Born's Conditions 1774.3 Free-Electron Model for Metals: From Drude (Classical) to Sommerfeld (Fermi-Dirac) 1794.4 Bloch's Theorem, Bloch Waves, Energy Bands, and Fermi Energy 1804.5 Reciprocal Space and Brillouin Zones 1824.6 Choices of Basis Sets and Band Structure with Applicative Examples 1884.6.1 From the Free-Electron Model to the Plane Wave Expansion 1894.6.2 Fermi Surface, Brillouin Zone Boundaries, and Alkali Metals versus Copper 1914.6.3 Understanding Metallic Phase Stability in Alloys 1934.6.4 The Localized Orbital Basis Set Method 1954.6.5 Understanding Band Structure Diagram with Rhenium Trioxide 1964.6.6 Probing DOS Band Structure in Metallic Alloys 1994.7 Breakdown of the Independent-Electron Approximation 2004.8 Density Functional Theory: The Successor to the Hartree-Fock Approach in Materials Science 2024.9 The Continuous Quest for Better DFT XC Functionals 2054.10 Van der Waals Forces and DFT 208Practice Problems 210References 2105 The Electronic Level II: The Tight-Binding Electronic Structure Approximation 2135.1 The General LCAO Method 2145.2 Extension of the LCAO Treatment to Crystalline Solids 2195.3 Orbital Interactions in Monatomic Solids 2215.3.1 sigma-Bonding Interactions 2215.3.2 pi-Bonding Interactions 2255.4 Tight-Binding Assumptions 2295.5 Qualitative LCAO Band Structures 2325.5.1 Illustration 1: Transition Metal Oxides with Vertex-Sharing Octahedra 2365.5.2 Illustration 2: Reduced Dimensional Systems 2385.5.3 Illustration 3: Transition Metal Monoxides with Edge-Sharing Octahedra 2405.5.4 Corollary 2435.6 Total Energy Tight-Binding Calculations 244Practice Problems 246References 2466 Transport Properties 2496.1 An Introduction to Tensors 2496.2 Microscopic Theory of Electrical Transport in Ceramics: The Role of Point Defects 2546.2.1 Oxygen-Deficient/Metal Excess and Metal-Deficient/Oxygen Excess Oxides 2566.2.2 Substitutions by Aliovalent Cations with Valence Isoelectronicity 2616.2.3 Substitutions by Isovalent Cations That are Not Valence Isoelectronic 2636.2.4 Nitrogen Vacancies in Nitrides 2666.3 Thermal Conductivity 2686.3.1 The Free Electron Contribution 2696.3.2 The Phonon Contribution 2716.4 Electrical Conductivity 2746.4.1 Band Structure Considerations 2786.4.1.1 Conductors 2786.4.1.2 Insulators 2796.4.1.3 Semiconductors 2816.4.1.4 Semimetals 2906.4.2 Thermoelectric, Photovoltaic, and Magnetotransport Properties 2926.4.2.1 Thermoelectrics 2926.4.2.2 Photovoltaics 2986.4.2.3 Galvanomagnetic Effects and Magnetotransport Properties 3016.4.3 Superconductors 3036.4.4 Improving Bulk Electrical Conduction in Polycrystalline, Multiphasic, and Composite Materials 3076.5 Mass Transport 3086.5.1 Atomic Diffusion 3096.5.2 Ionic Conduction 316Practice Problems 321References 3227 Hopping Conduction and Metal-Insulator Transitions 3257.1 Correlated Systems 3277.1.1 The Mott-Hubbard Insulating State 3297.1.2 Charge-Transfer Insulators 3347.1.3 Marginal Metals 3347.2 Anderson Localization 3367.3 Experimentally Distinguishing Disorder from Electron Correlation 3407.4 Tuning the M-I Transition 3437.5 Other Types of Electronic Transitions 345Practice Problems 347References 3478 Magnetic and Dielectric Properties 3498.1 Phenomenological Description of Magnetic Behavior 3518.1.1 Magnetization Curves 3548.1.2 Susceptibility Curves 3558.2 Atomic States and Term Symbols of Free Ions 3598.3 Atomic Origin of Paramagnetism 3658.3.1 Orbital Angular Momentum Contribution: The Free Ion Case 3668.3.2 Spin Angular Momentum Contribution: The Free Ion Case 3678.3.3 Total Magnetic Moment: The Free Ion Case 3688.3.4 Spin-Orbit Coupling: The Free Ion Case 3688.3.5 Single Ions in Crystals 3718.3.5.1 Orbital Momentum Quenching 3718.3.5.2 Spin Momentum Quenching 3738.3.5.3 The Effect of JT Distortions 3738.3.6 Solids 3748.4 Diamagnetism 3768.5 Spontaneous Magnetic Ordering 3778.5.1 Exchange Interactions 3798.5.1.1 Direct Exchange and Superexchange Interactions in Magnetic Insulators 3828.5.1.2 Indirect Exchange Interactions 3878.5.2 Itinerant Ferromagnetism 3908.5.3 Noncollinear Spin Configurations and Magnetocrystalline Anisotropy 3948.5.3.1 Geometric Frustration 3948.5.3.2 Magnetic Anisotropy 3978.5.3.3 Magnetic Domains 3988.5.4 Ferromagnetic Properties of Amorphous Metals 4018.6 Magnetotransport Properties 4018.6.1 The Double Exchange Mechanism 4028.6.2 The Half-Metallic Ferromagnet Model 4038.7 Magnetostriction 4048.8 Dielectric Properties 4058.8.1 The Microscopic Equations 4078.8.2 Piezoelectricity 4088.8.3 Pyroelectricity 4148.8.4 Ferroelectricity 416Practice Problems 421References 4229 Optical Properties of Materials 4259.1 Maxwell's Equations 4259.2 Refractive Index 4289.3 Absorption 4369.4 Nonlinear Effects 4419.5 Summary 446Practice Problems 446References 44710 Mechanical Properties 44910.1 Stress and Strain 44910.2 Elasticity 45210.2.1 The Elasticity Tensors 45510.2.2 Elastically Isotropic and Anisotropic Solids 45910.2.3 The Relation Between Elasticity and the Cohesive Forces in a Solid 46510.2.3.1 Bulk Modulus 46610.2.3.2 Rigidity (Shear) Modulus 46710.2.3.3 Young's Modulus 47010.2.4 Superelasticity, Pseudoelasticity, and the Shape Memory Effect 47310.3 Plasticity 47510.3.1 The Dislocation-Based Mechanism to Plastic Deformation 48110.3.2 Polycrystalline Metals 48710.3.3 Brittle and Semi-brittle Solids 48910.3.4 The Correlation Between the Electronic Structure and the Plasticity of Materials 49010.4 Fracture 491Practice Problems 494References 49511 Phase Equilibria, Phase Diagrams, and Phase Modeling 49911.1 Thermodynamic Systems and Equilibrium 50011.1.1 Equilibrium Thermodynamics 50411.2 Thermodynamic Potentials and the Laws 50711.3 Understanding Phase Diagrams 51011.3.1 Unary Systems 51011.3.2 Binary Systems 51111.3.3 Ternary Systems 51811.3.4 Metastable Equilibria 52211.4 Experimental Phase Diagram Determinations 52211.5 Phase Diagram Modeling 52311.5.1 Gibbs Energy Expressions for Mixtures and Solid Solutions 52411.5.2 Gibbs Energy Expressions for Phases with Long-Range Order 52711.5.3 Other Contributions to the Gibbs Energy 53011.5.4 Phase Diagram Extrapolations: The CALPHAD Method 531Practice Problems 534References 53512 Synthetic Strategies 53712.1 Synthetic Strategies 53812.1.1 Direct Combination 53812.1.2 Low Temperature 54012.1.2.1 Sol-Gel 54012.1.2.2 Solvothermal 54312.1.2.3 Intercalation 54412.1.3 Defects 54612.1.4 Combinatorial Synthesis 54812.1.5 Spinodal Decomposition 54812.1.6 Thin Films 55012.1.7 Photonic Materials 55212.1.8 Nanosynthesis 55312.1.8.1 Liquid Phase Techniques 55412.1.8.2 Vapor/Aerosol Methods 55612.1.8.3 Combined Strategies 55612.2 Summary 558Practice Problems 559References 55913 An Introduction to Nanomaterials 56313.1 History of Nanotechnology 56413.2 Nanomaterials Properties 56513.2.1 Electrical Properties 56613.2.2 Magnetic Properties 56713.2.3 Optical Properties 56713.2.4 Thermal Properties 56813.2.5 Mechanical Properties 56913.2.6 Chemical Reactivity 57013.3 More on Nanomaterials Preparative Techniques 57213.3.1 Top-Down Methods for the Fabrication of Nanocrystalline Materials 57213.3.1.1 Nanostructured Thin Films 57213.3.1.2 Nanocrystalline Bulk Phases 57313.3.2 Bottom-Up Methods for the Synthesis of Nanostructured Solids 57413.3.2.1 Precipitation 57513.3.2.2 Hydrothermal Techniques 57613.3.2.3 Micelle-Assisted Routes 57713.3.2.4 Thermolysis, Photolysis, and Sonolysis 58013.3.2.5 Sol-Gel Methods 58113.3.2.6 Polyol Method 58213.3.2.7 High-Temperature Organic Polyol Reactions (IBM Nanoparticle Synthesis) 58413.3.2.8 Additive Manufacturing (3D Printing) 584References 58614 Introduction to Computational Materials Science 58914.1 A Short History of Computational Materials Science 59014.1.1 1945-1965: The Dawn of Computational Materials Science 59114.1.2 1965-2000: Steady Progress Through Continued Advances in Hardware and Software 59514.1.3 2000-Present: High-Performance and Cloud Computing 59814.2 Spatial and Temporal Scales, Computational Expense, and Reliability of Solid-State Calculations 60014.3 Illustrative Examples 60414.3.1 Exploration of the Local Atomic Structure in Multi-principal Element Alloys by Quantum Molecular Dynamics 60414.3.2 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 60614.3.3 Crystal Plasticity Finite Element Method (CPFEM) Analysis for Modeling Plasticity in Polycrystalline Alloys 613References 61715 Case Study I: TiO2 61915.1 Crystallography 61915.2 Microstructure 62315.3 Bonding 62615.4 Electronic Structure 62715.5 Transport 62815.6 Metal-Insulator Transitions 63215.7 Magnetic and Dielectric Properties 63215.8 Optical Properties 63415.9 Mechanical Properties 63515.10 Phase Equilibria 63615.11 Synthesis 63815.12 Nanomaterial 639Practice Questions 639References 64016 Case Study II: GaN 64316.1 Crystallography 64316.2 Microstructure 64616.3 Bonding 64716.4 Electronic Structure 64716.5 Transport 64816.6 Metal-Insulator Transitions 65016.7 Magnetic and Dielectric Properties 65216.8 Optical Properties 65216.9 Mechanical Properties 65316.10 Phase Equilibria 65416.11 Synthesis 65416.12 Nanomaterial 656Practice Questions 657References 658Appendix A: List of the 230 Space Groups 659Appendix B: The 32 Crystal Systems and the 47 Possible Forms 665Appendix C: Principles of Tensors 667Appendix D: Solutions to Practice Problems 679Index 683

O autorze

JOHN N. LALENA primarily focuses on the research of materials behavior and structure/property correlations across multiple length scales. He has over 25 years of experience in the private sector, including time spent at Honeywell Electronic Materials and Texas Instruments. He currently serves as a Physical Scientist in the Advanced Manufacturing Office at the U.S. Department of Energy.DAVID A. CLEARY is a Professor in the Department of Chemistry at Gonzaga University in Washington, USA. His research interests are in synthesis and characterization of ternary semiconductors for applications in chemical sensors and energy storage and in testing metal oxides for photoelectrolysis of water.OLIVIER B.M. HARDOUIN DUPARC is a researcher at the École Polytechnique Paris. His research primarily focuses on ab initio modeling of materials to unravel their atomic structure and mechanical properties.