Acknowledgments 9
1. Introduction 11
1.1. Modern ceramics 11
1.2. The essence of the ceramics technology 13
1.3. Technology design 14
1.3.1. Economic aspect of the technological processes 14
1.3.2. Development of the material microstructure during the heat treatment 17
1.3.3. Selection of technology and the present book structure 19
2. Thermodynamic aspects of the high-temperature technologies used in ceramic industry 23
2.1. General notes 23
2.2. Classification and characteristics of ceramic reactions in aspect of thermodynamic function changes 25
2.2.1. Classification 25
2.2.2. Exothermic reactions developed in result of the entropy increase 27
2.2.3. Chemical reactions between solids 27
2.2.4. Exothermic reactions, developed in result of the enthalpy reduction 28
2.2.5. Endothermic reactions 29
2.3. Examples of the prediction of high temperature reaction course direction on the basis of thermo-dynamic data 31
2.3.1. Removal of the carbon from copper layered elements in subassemblies of micro-electronic systems 31
2.3.2. Behaviour of calcium chloride in fired ceramic material 33
2.3.3. Synthesis and decomposition of the zirconium (ZrSiO4) 36
2.3.4. Thick-layered metallization of aluminum nitride bases for needs of microelectronics 37
2.3.5. Celsian synthesis 39
2.3.6. Reactions of MgO with carbonate in brickwork working zones of the oxygen converters 40
2.3.7. Mullite decomposition into corundum and SiO 42
2.4. Some reflections aimed at the entropy changes accompanying human activities (entropy concept according to Görlich’s definition) 43
2.5. Additional technological interpretation 45
3. Phase systems 47
3.1. Phases in ceramic materials 47
3.1.1. General notes 47
3.1.2. Condensed phases 48
3.1.3. Role of gaseous phase in firing processes 50
3.2. Some aspects of the phase diagrams interpretation 52
3.2.1. Single and two-component systems  52
3.2.2. Three-component systems 55
3.2.3. Multi-component systems 59
3.3. Phase composition of the clayey raw materials (aluminosilicate) 60
3.3.1. Assessment of the role of admixtures 60
3.3.2. Phase composition changes due to temperature increase and interpretation 61
3.3.3. Calculation cumulated content of the liquid phase and mullite 65
3.4. Examples of technical solutions based on the composition triangles of three-component systems 67
3.4.1. Free lime in ceramic materials 67
3.4.2. Firing synthesis of minerals, which have low coefficient of thermal expansion 70
3.4.3. Phase composition of the self-disintegrating sinters in production of aluminum oxide and cement from non-bauxite raw materials 71
3.4.4. Phases formed during zirconium sand – lime high temperature reaction 72
3.5. Examples of technological problems solution on the basis of the liquid phase characteristics within two and three-component systems 73
3.5.1. Lead-sodium flux in enamel composition and Pb slag 73
3.5.2. Glassy phase in porcelain materials 74
3.5.3. Phase composition of the refractory aluminosilicate products 77
3.5.4. Phase composition and easy-melting eutectics of the basic-type refractory materials 77
3.5.5. Corrosion of aluminosilicate refractory materials – influence of sodium-calcium glass 82
3.6. Supplementary technological interpretation 83
4. Kinetic aspects of the high-temperature ceramic transformations 85
4.1. Use of the kinetic data in ceramic technologies – general notes 85
4.1.1. Character of reactions in ceramic materials 85
4.1.2. Relation between constant reaction speed and temperature 86
4.1.3. Linear kinetics 88
4.1.4. Kinetics of the diffusion controlled reactions in solid phase and with liquid phase presence 89
4.1.5. Kinetics of the reaction of the first order and fractional order reactions 91
4.1.6. Kinetics of the reactions controlled by nucleation 91
4.1.7. Selected examples 92
4.2. Kinetics and mechanism of chosen reactions between solid and gaseous phases 93
4.2.1. Graphite oxidation mechanism 93
4.2.2. Oxidation of organic admixtures in products made from clay materials 94
4.2.3. Thermal treatment of cupric thin-layer elements: kinetic aspect and mass balance 99
4.2.4. Oxidation of heating rods made of molybdenum disilicide 101
4.2.5. Oxidation of products made of silicon carbide 104
4.2.6. Nitriding of highly pure silicon 107
4.3. Kinetics and mechanism of the interactions during crystallization of the reaction product from gaseous phase 109
4.3.1. Obtaining of the layers using method of chemical deposition of the gaseous phase (CVD)  109
4.3.2. High-temperature reactions MgO + C and precipitation of solid periclase layer 114
4.4. Kinetics and mechanism of certain high-temperature transformations and oxide mineral syntheses 116
4.4.1. Transition phase of quartz-cristobalite polymorphous transformation 116
4.4.2. Gamma – alfa Al2O3 transformation 119
4.4.3. High-temperature transformations of anhydrous aluminum silicates 120
4.4.4. Zirconium orthosilicate synthesis 121
4.4.5. Calcium zirconate synthesis 123
4.4.6. Alite synthesis in Portland cement-like compositions 126
4.5. Kinetics and mechanism of some processes occurring on a contact between molten glassy phases and solid phases 129
4.5.1. Dissolution of silica from glass-making batch in alkaline-siliceous alloys 129
4.5.2. Devitrification of silica glasses 133
4.5.3. Characteristics of the kinetics of refractory material corrosion caused by the molten glass 136
4.6. Supplementary technological interpretation 137
4.6.1. Possibility of kinetic process control by suitable selection of temperature and firing time (firing curve) 137
4.6.2. Process course and mechanism versus heat treatment 138
4.6.3. Possibilities of the process kinetics process control by the selection of right fired material properties, and/or the proper selection of the gaseous reagents composition 139
4.6.4. Some notes on technologically disadvantageous reactions 141
5. Dynamic aspect of the ceramic material microstructure formation 143
5.1. Introduction 143
5.2. Transitory and spontaneous reactions of the phase composition transformations 144
5.2.1. Typical constitutive phases occurring in various microstructure formation stages 144
5.2.2. Mullitization of clay raw materials 146
5.2.2.1. Kaolinite transformations in firing initial stage 146
5.2.2.2. Mechanism and kinetics of the mullite phase formation 147
5.2.2.3. Microstructure evolution during high temperatures heating 152
5.2.2.4. Metastable equilibrium states in the Al2O3-SiO2 system 153
5.2.3. Sodium-calcium glass melting and homogenization and a role of sodium sulfate being the initial material component 154
5.2.4. Synthesis of barium titanate from powdered substrates 155
5.3. Effects related with pore systems transformation 158
5.3.1. General notes 158
5.3.2. Hot pressing 160
5.3.2.1. Introduction 160
5.3.2.2. Use of the Hedvall’s effect in clay raw materials hot pressing 160
5.3.2.3. Hot pressing of face bricks made of dusty shales 162
5.3.3. Material porosity and cohesion changes resulting from the material components interaction 163
5.3.3.1. Influence of the raw material composition and type onto building brick microstructure 163
5.3.3.2. Some aspects of the whiteware ceramics fast firing 166
5.3.4. Gaseous bubbles in ceramic materials 167
5.4. Growth of layers deposed on brickworks and refractory elements operational surfaces 171
5.5. Notes on the behavior of some ceramic materials during exploitation in both room and high-temperature conditions 173
5.6. Supplementary technological interpretation 175
6. Structural aspects of the high-temperature reactions and general characteristics of sintering processes  177
6.1. Introduction 177
6.2. Examples of the network structure influence onto technological effects 178
6.2.1. Stabilization of the Ca2SiO4 polymorphous transition 178
6.2.2. High-temperature reactions between ZrSiO4 and CaO and role of the baghdadite phase 180
6.2.2.1. General characteristics of the reaction 180
6.2.2.2. Model of the reaction zone 181
6.2.2.3. Assumptions 185
6.2.3. Phases formed in refractory concretes in the MgO-Al2O3-SiO2 system 186
6.2.4. Ternary Si-C-O phase in process of SiC oxidation  187
6.3. Characteristics of the sintering processes  189
6.3.1. Spontaneous process 189
6.3.1.1. Free enthalpy drop during solid phase sintering 190
6.3.2. Mass transfer processes during solid phase sintering 192
6.3.2.1. Grains rearrangement 192
6.3.2.2. Volume diffusion and diffusion on inter-granular boundaries 194
6.3.2.3. Diffusion on free surfaces and diffusion via gaseous phase 195
6.3.2.4. Other mechanisms 197
6.3.3. Growth of grains during solid phase sintering 197
6.3.3.1. Thermodynamic aspect 197
6.3.3.2. Grain growth mechanism and kinetics 199
6.3.4. Solid phase sintering model (Coble-Kuczyński’s model) 203
6.3.5. Solid phase sintering kinetics 206
6.3.5.1. Measures of sintering advance 206
6.3.5.2. Solid phase sintering kinetics – model of spherical grains 210
6.3.5.3. Sintering kinetics – phenomenological approach 212
6.3.5.4. Kinetic effects in sintering process 213
6.3.6. Solid phase sintering of ceramic powders 216
6.3.7. Sintering with participation of liquid phase – specific sintering 219
6.3.7.1. Introduction 219
6.3.7.2. Rewetting 219
6.3.7.3. Liquid amount and viscosity 222
6.3.7.4. Sintering in conditions of perfect rewetting of the solid body with liquid phase 222
6.3.7.5. Sintering at the presence of liquid, which rewets the solid body imperfectly or poorly 232
6.3.8. Chemical sintering 234
6.4. Supplementary technological interpretation  236
7. Examples of innovative ceramic technology designs 238
7.1. Introduction 238
7.2. Examples of commonly known innovations  239
7.2.1. Low-cement refractory concretes 239
7.2.2. Magnesia – graphite refractory shapes 240
7.2.3. Self-propagating high-temperature synthesis 244
7.2.4. Aluminum nitride-based microelectronics 245
7.2.5. Chemical Vapour Deposition (CVD) 248
7.3. Examples of regional-spread and special innovations 252
7.3.1. Corrosion-resistant slag-alkaline binders 252
7.3.2. Complex conversion of poor aluminum-bearing raw materials into aluminum oxide and cement (J. Grzymek’s method) 255
7.3.3. Calcia refractory obtained with semi-hot consolidation method 255
7.3.4. Immobilization of nuclear wastes with use of ceramic materials 257
7.3.5. Hydroxyapatite bio-ceramics 258
7.3.6. Modification of rice hulls into silicone carbide and silicone nitrides 260
7.3.7. New solutions of the heat resistant materials engineering 262
7.3.8. Composites based on poly-crystalline tetragonal zirconium dioxide (TZP) with granulated wolfram carbide addition 263
References 267