Hermann Schmalzried Chemical Kinetics of Solids vel na w York Basel - Cambridge « TokyoPreface Chemistry is concerned with reactions, structures, and properties of matter. ‘The scope of this is immense, Alone the chemistry of the solid state cannot be treated in a single monograph to any depth. The course of processes in space and time, and their rates in terms of state variables is the field of kineties, The understanding of kinetics in the solid state is the aim of this book. In contrast to fluids, crystals have a greater number of control parameters: “crystal structure, strain and stress, grain boundaries, line defects (dislocations), and the size and shape of crystallites, ete, These are all relevant to kinetics “Treatments that go beyond transport and diffusion in this important field of physical chemistry are scarce In the previous monograph Solid State Reactions (Verlag Chemie, 1975), | attempted to base the understanding of solid state kinetics on point defect thermodynamics and transport theory. tn the meantime, spectacular progress in experimental ((n-situ) methodology, the growth of materials science (in which practical needs predominate), and a closer acquaintance of chemists with formal theories of non-equilibrium systems have been observed. The question thus arose: Should there be yet another revision of Solid State Reactions following those of 1978 and 1981, or should a new and more comprehensive monograph be written? The answer is this new book. It stresses a deeper con- ceptual framework on the one side and the unifying aspects of solid state Kinetics, despite their multitude and diversity, on the other side, ‘The growing diversity is reflected in fields such as radiation chemistry and mechanochemis- try (tribochemistey), for example. In order to systematize the multitude of solid state processes and their inter- actions, it seems more important to shape the physico-chemical concepts for relevant limiting cases than to report on many complex reactions in a qualita- tive manner, This is also reflected in the preponderance of inonganic systems Chemical Kinetics of Solids covers a special part of solid state chemistry and physical chemistry. It has been written for graduate students and researchers who want to understand the physical chemistry of solid state processes in fair depth and to be able to apply the basic ideas to new (practical) situations. Ghemical Kinetics of Solids requires the sisndard knowledge of kinetic text- books and a sufficient chemical thermodynamics background. The fundamental statistical theory underlying the more or less phezomenological approach of this monograph can be found in a recent book by A.R. Allnatt and A.B. Lidierd: Atomic Transport in Solids. which complements and deepens the theo: retical sections, A latge part of Chemical Kinetics of Solids was written while 1 enjoyed the hespitalities of the Theoretical Chemistry Department at Oxford University.Vi Preface the CNRS Bellevue Laboratoire Physique des Materiaux (Meudon, France), and the Department of Physical Chemistry at the Polish Academy of Science (Warsaw). The Volkswagenstiftung made the sabbatical leave possible by a generous stipend. Also, the help of the Fonds der Chemischen Industrie has to be mentioned here with gratitude, Criticisms, encouragement, and the sharing of ideas and time by many coworkers and friends are gratefully acknowledged. The great influence of the late C, Wagner, and in particular of A.B. Lidiard (Oxford) is. profoundly appreciated. B, Baranowski (Warsaw), K.D. Becker (Hannover), P. Haasen (Gottingen), M. Martin (Hannover), and Z. Munir (Davis, Cal.) read parts of the manuscript and gave generous advice and suggestions. The graphic work benefited from the skills of C. Majoni. Last but not least, the book would not have been written without the invaluable help of A. Kiihn. Buntenbock, December 1994 H. SchmalzriedTable of Contents Preface V Symbols and Definitions XIII 1 Introduction 1 Scope 1 Historical Remarks 6 Four Basic Kinetic Situations 10 1 Homogeneous Reactions: Point Defect Relaxation 10 2 Steady State Flux of Point Defects in a Binary Compound 12 3 The Kinetics of an Interface Reaction 14 4 Kineties of Compound Formation: A +B = AB 16 References 18 of Point Defects 19 1 Introduction 19 2 ‘Thermodynamics of Crystals 21 2.1 Phenomenological Approach 21 2.2 Remarks on Statistical Thermodynamics of Point Defects 27 3 Some Practical Aspects of Point Defect Thermodynamics 31 4 Point Defects in Solid Solutions 38 Conclusions 40 References 41 3. One. and Two-Dimensional Defects in Crystals 43 1 Introduction 43 2 Dislocations 43 2.1 Strain, Stress, and Energy 43 2.2 Kinetic Effects Due to Dislocations 48 3 Grain Boundaries 50 3.1 Structure and Energy of Grain Boundaries 50 3.2 Phase Boundaries in Solids 54 4 Mobility of Dislocations, Grain Boundaries, and Phase Boundaries $7 References 60 4. Basic Kinetic Concepts and Situations 61 41 Introduction 61 4.1.1 Systematics of Solid State Chemical Processes 61var 42 42.1 43 43.1 43.2 433 44 441 44.2 45 45.1 45.2 46.1 5.2. 53 53 5.3.2 533 s4 Sad SA2 S43 548 ‘Table of Contents The Concepts of Irreversible Thermodynamics 63 Structure Element Fluxes 66 Diffusion 68 Introduction 68 Fickian Transpo. 70 Chemical Diffusion 71 ‘Transport in Tonic Solids 75 Introduction 75 ‘Transport ir Binary lonic Crystals AX 78 ‘Transport Across Phase Boundaries 82 Introduction. Equilibrium Phase Boundaries 82 Non-Equilibrium Phase Boundaries 84 ‘Transport in Semiconductors; Junctions 85 Introduction 85 ‘The ip-n) Junction 86 Basic Rate Equations for Homogeneous Reactions 88 Introduction 88 Rate Equations 89 References 95 jes and Dynamics, Local Equilibrium 95 Introduction 95 Linear Response 99) Transition State 101 Brownian Motion 103 Kinetic Parameters and Dynamics 107 Phenomenological Coefficients and Kinetic Theory 107 Correlation of Atomic Jumps 109 Conductivity of lonic Crystals: Frequeney Dependence 112 Diffusive Motion and Phonons 116 Relaxation of Irregular Structure Elements 117 Introduction 117 Relaxation of Structure Elements in Nonstoichiometric Compounds AO U8 Relaxation of Intrinsic Disorder 119 Defect Equilibration During Interdiffusion 123 ‘The Atomistics of Interdiffusion 123 ‘The Kirkendall Effect 125 Local Defect Equilibration During Interdiffusion 127 Interdiffusion of Heterovalent Compounds 133 References 135 6 Heterogeneous Solid State Reactions 137 61 Introduction 13762 62.1 622 6.23 63 63.1 63.2 64 65 65.1 65.2 66 67 Table of Contenss 1X Nucleation and Initial Growth 138 Introductory Remarks 138 Nucleation Kinetics 140 Early Growth 143 Compound Formation 146 Formation Kinetics of Double Salts 146 Formation of Multiphase Prosvets 153 Displacement Reactions 155 Powder Reactions 157 General 157 Self-Propagating Exothermic Powder Reactions 158 Interface Rate Control 160 ‘Thermal Decomposition of Solids 162 References 163 7 Onidation of Metals 165 uM 72 13 1 TAA 1S Introduction 165 Wagner's Theory of Metal Oxidation 166 Non-Parabolic Rate Laws 171 Alley Oxidation 175 ‘The Morphological Stability of Boundaries During Metal Oxidation 176 Some Practical Aspects of High Temperature Corrosion 179 References 181 8. Solids in Thermodynamic Potential Gradients 183 8a 82 83 84 85 86 87 88 Introduction 183 Multicomponent Solids in Chemical Potential Gradients 184 Kinetic Decomposition of Compounds in Chemical Potential Gradients 189 Cross Effects 191 Demixing Under Non-Hydrostatic Stress 198 Demixing in Temperature Gradients (Ludwig-Soret Effect) 200 Dewixing in Multiphase Systems 202 Multiphase Systems in Electric Fields 204 References 207 9 Internal Reactions 209 9. 9.2 93 931 932, Introduction 209 Internal Oxidation of Metals 211 Internal Reactions in Nonmetallic Systems 213 Internal Oxidation in Nonmetallic Solid Solutions 213, Internal Reduction in Nonmetallic Solutions 217x 98 9.48 9.42 9.43 9.5 951 96 Table of Contents Internal Reactions Driven by Other than Chemical Potential Gradients 220 Internal Reactions in Heterophase Assemblages 221 Internal Reactions in Inhomogeneous Systems with Varying Disorder ‘Types 222 Formal Treatment of Electrochemical Internal Reactions 226 Internal Reactions A +B = AB in Crystal C as Solvent 229 ‘The Internal Reaction AO + BO, = ABO, 229 Internal Reactions During Interdiffusion 231 References 233 10 Reactions At and Across Interfaces 235 10.1 10.2 10.3 10.4 10.4.1 10.4.2 10.4.3, 10.4.4 10.4.5 10.5 10.6 Introduction 235 Some Fundamental Aspects of Interface Thermodynamics 236 Static Interfaces 244 Moving Interfaces 250 General Remarks 250 Interface Motion During Phase Transformation 252 Interface Movement During the Heterogeneous Reaction A+B=AB 257 ‘The Dragged Boundary (Generalized Solute Drag) 258 Diffusion Induced Grain Boundary Motion 260 Morphological Questions 261 ‘The Atomic Structure of Moving Interfaces 262 References 264 11 Morphology 265 ia 2 M21 11.2.2 11.2.3 1124 1.2.5 3 1a Introduction 265 Interface Stability 267 Qualitative Discussion 267 Examples of Unstable Moving Interfaces 273 Formal Stability Analysis 277 Stabilizing Factors 282 Stability and the Reaction Path 282 Moving Boundaries in Other ‘Than Chemical Fields 285 Non-Monotonous Behavior in Time 288 References 290 12 Phase Transformations 291 12.1 122 12.24 12.2.2 Introduction 291 Nondiffusive Transformations 296 Martensitic Transformations 296 Second-Order Transformations 298123 123.1 12.3.2 Table of Contos XT Diffusive Transformations 304 First-Order Transformation with Sraall Composition Changes 305 Spinodal Decomposition 308 References 312 13 Reactions in Solids Under Irradiation 315, 13 13.2 13.2.1 13.2.2 B23 133 133.1 13.3.2 133.3 Introduction 315 Particle Irradiation 317 Basic Concepts 317 Radiation Effects in Halides (Radiolysis) 320 Radiation Effects in Metals 321 Photon Irradiation 324 Basic Concepts 324 Radiation Ettects in Halides (Photolysis) 326 ‘Ag Based Photography 327 References 328 14 Influence of Mechanical Stress 331 14 14.2 121 4.22 14.3 143.1 32 33 4a 14.41 14.4.2 443 1444 145 15. Transport and Reactions in Special Systems 15.1 15.2 15.2.1 15.2.2 15.2. 18.24 15.2.3 Introduction 331 ‘Thermodynamic Considerations 332 ‘Thermodynamics of Stressed Solids 332 ‘Thermodynamics of Stressed Solids with Only Immobile Components 335 ‘Transport in Stressed Solids 336 Introductory Remarks 336 ‘The Influence of Stress on Heterogeneous Reactions A+B = AB 337 ‘Transport in Inhomogencously Stressed Crystals 338 Creep and Fracture 342 Introductory Remarks 642 Creep 342 Fracture 347 ‘Toughening of Crystals by Phase Transformations 349 Tribochemistry 351 References 353 Introduction 355 Silicates 356 Introductory Remarks 356 Transport in Silicates 357 Order-Disorder Reactions 363 The Role of Hydrogen in Silicates 364 Silicate Glasses 365Table of Consens Fast lon Conductors 368 Introductory Remarks 368 Halides 370 AgsS (Ag:Se, AgsTe) 372 Oxides: Stabilized Zirconia 374 B-Alumina 377 Proton Conductors 379 Hydrides 380 Introduetory Remarks 380 Phase Equilibria 382 Kinetics of Hydride Formation and Decomposition 383, Molecular (Organic) Crystals 386 Introductory Remarks 386 Diffusion in Molecular Crystals 388 Conducting Polymers 389 References 391 16 Appendix: Experimental Methods for In-situ Investigations 393 16.1 16.2 16.2.4 16.2.2 16.2.3 16.3 16.3.1 16.3.2 16.4 16.4.1 16.4.2 16.4.3 16.5 16.5.1 16.5.2 16.5.3 16.6 16.6.1 16.6.2 16.6.3 Introduetion 393 ‘Thermogravimetry, -manometry, -volumetry, -analysis 395 ‘Thermogravimetry 395 ‘Thermomanometry, Thermovolumetry 396 ‘Thermal Analysis 397 Electrochemical Measurements 398 Introductory Remarks 398. Chemical Potential Sensors 399 Spectroscopic Methods: Nuclear Spectroscopy 402 Introduction 402 Physical Background 404 In-situ Application, Examples 408 Spectroscopic Methods: Electromagnetic Spectroscopy (IR, VIS, UV. X-ray) 412 Introduction 412 Physical Background 412 In-situ Application, Examples 413 Particle Spectroscopy 415 Introduction 415 Physical Background 416 Examples 417 References 419 Epilogue 421 Subject Index 423 Author Index 431‘The following list is meant to 1) compile frequently used symbols and 2) define frequently used quantities. If the same symbol has different meanings, it is stated in the text. If the vector character of a quantity is stressed, the corresponding symbol is set boldface. If only the absolute value matters, the boldface is omitted, ‘The symbol * over a letter designates a tensor (e.g., B). A basic concept is the struc ture element (= SE). A crystal is composed of SE's which are characterized by their chemical identity, their sublattice site, and their electric charge, Regular SE's define the perfect crystal. Irregular SE's are point defects in imperfect crystals and include vacancies or interstitials. The general symbol of a SE is 52: S denotes the chemical unit (element or molecule), q the electric charge, and x the sublattice. V denotes a vacant site, Often the electric charge g is referred to the perfect erystal (excess quantity, - — positive, ‘= negative, x = neutral) ‘The corresponding SE notation is called the Kroeger-Vink notation. When useful. the IUPAC manual Quantities, Units and Symbols in Physical Chemistry was used with respect to the notation. Discrepancies in some instances stem from the fact that different symbols are used in different subject fields A area [em*] 4, activity of chemical component i (= e!™"-#2)"#7) b, mobility of particles of sort i (= /K,) 6 concentration of component / (= m/V [moliem’]) D, _(self)iffusion coefficient of particles of component i Dj tracer diffusion coefficient of particles of component i B (chemical) interdiffusion coefficient € charge of electron (= 1.610" ©) e' electron in crystal fe. electron in a conduction band state £ modulus of elasticity, Young’s coefficient [Pa] electric field vector (= -Ve) fi activity coefficient of component i (= a, /'N,)xv ‘Symbols and Definitions correlation factor, jump efficiency in non-random walk motion Faraday constant (= 96485 Coulombs per equivalent) Helmholtz energy (UTS) Gibbs energy (H-TS) partial molar Gibbs energy of component i (= 14) standard Gibbs energy change of reaction shear modulus (sometimes G, to distinguish it from Gibbs energy) [Pa] Gibbs energy per particle 1 (= G; Np) Planck constant (= fi» 2 = 6.626- 10 [Js] electron hole in crystal hole in a valence band state enthalpy electric current density fa-F) flux density of particles of sort é [mol/em’ s} Boltamann constant (= 1.38 10 JK") {reaction) rate constant in kinetic rate equations L)2x wave vector, or k force vector uansport coefficient, generalized conductance of component i Debye-Hilckel screening length mass of particle # amount of substance (number of moles) [mol] number of moles of component i fraction (mole, site, number of state) of component i Loschmid (Avogadro) number (= 6.02 10 mot!) partial pressure of component i (= N,+ P in ideal gas) pressure (= Ep) (excess) electric charge, characterizing a SE Nok = 8.314 (JK mol”]) molar gas constant entropySymbols and Definivons XV structure element time transport number of component i (= o)/ 0) temperature [K] electrochemical mobility of 7 (= 9/E) energy, internal energy voltage (difference, change) (= g:-91) velocity (average drift) of particles i (y= velocity vector) volume (V,, = molar volume) partial molar volume of component i vacancy with charge q on sublattice x (= SE) thermodynamic force on species i number (z, = number of particles /) valence nutsber of particles partition function phase denotation surface energy, interface energy deviation from reference value, normally from stoichiometric composition relative permittivity (dielectric constant) absolute permittivity of vacuum (dielectric constant) (= 8.854 10" [as/Vem) space coordinate (&1, & &) thickness order parameter electrochemical potential (= y+z,-F-g) wave length chemical potential of particles (GOPNJary¢n, = WRT ING) standard value of 4;, usually referred to pure substance i with a = 1 frequency, transition rate [s"], sometimes denoted w/2:r Poisson ratio in theory of elasticityXVI Symbols and Definitions density of mass, charge, partictes, etc., specific quantity, 6 electrical conductivity (= E 0) @ entropy production rate r _ time interval, especially relaxation time B) @ — electric potential (Yop «7 angular frequency1 Introduction In this first chapter, we will outline the scope of this book on the kineties of chemical processes in the solid state. They are often different from the kinetics of processes in fluids because of structural constraints. After a brief historical introduction, typical situations of non-equilibrium crystals will be described. These will illustrate: some basic concepts and our approach 10 understanding solid state kinetics. 1.1 Scope ‘Chemical reactions are processes in which atoms change positions while their outer electrons rearrange. If two aloms are going to react, they have first to meet each other. This means that they have to come close enough that forces between their ‘outer electrons become operative. The prerequisite for the meeting of different in- dividual atomic particles in an assemblage is their mixing on an atomic scale Although this mixing can easily be visualized in gases or liquids, the mixing of solids (for example of erystals) at atomic dimensions is less obvious. There was even a say- ing long ago that solids do not react with each other. Such a statement, however, con- tradicts our experience since the arts of ceramics and metallugy, in which reacting solids were involved, have been cultivated for thousands of years Normally, crystals do not exhibit convective flow and, therefore, mixing by convee tion at atomic dimensions is not possible. AS a consequence, diffusive transport and heterogeneous reactions are the only processes which can be anticipated at this point. The amazing evolution of solid state physics and chemistry over the last 30 years induced an intensive study of various solid state processes, particularly in the context of materials science, Materials have always been an important feature of civilization and ate the basis of our modern technical society. Their preparation is often due solely to reactions between solids, Solid state reactions are also often responsible for the materials’ adaptarion to a specific technical purpose, or for the degradation of a material. In retrospect, one can understand why solid state chemists, whe were familiar with ‘rystallographic concepts, found it so difficult to imagine and visualize the mobility of the atomic structure elements of a crystal. Indeed, there is no mobility of these particles in a perfect crystal, just as there is no mobility of an individual car on a densely packed parking lot. It was only after the emergence of the concept of disorder and point defects in erystals atthe turn of this century, and later in the twen- ties and thirties when the thermodynamics of defects was understood, that the idea