Glass

1 - Foreword [Seite 5]
2 - Preface [Seite 15]
3 - List of contributing authorst [Seite 21]
4 - 1 Influence of Thermal Prehistory on Crystal Nucleation and Growth in Polymers [Seite 23]
4.1 - 1.1 Introduction [Seite 23]
4.2 - 1.2 State of the Art [Seite 24]
4.2.1 - 1.2.1 Dependence of the Properties of Glass-forming Melts on Melt History [Seite 24]
4.2.2 - 1.2.2 Polymer Crystallization [Seite 28]
4.2.3 - 1.2.3 Differential Fast Scanning Calorimetry [Seite 31]
4.3 - 1.3 Experimental [Seite 36]
4.3.1 - 1.3.1 Samples [Seite 36]
4.3.2 - 1.3.2 Suppression of Homogeneous Nucleation at Fast Cooling [Seite 38]
4.3.3 - 1.3.3 Non-isothermal Ordering Kinetics [Seite 50]
4.3.4 - 1.3.4 Isothermal Ordering Kinetics [Seite 58]
4.3.5 - 1.3.5 Identification of Different Nuclei Populations [Seite 70]
4.3.6 - 1.3.6 Enthalpy Relaxation and Crystal Nucleation in the Glassy State [Seite 74]
4.3.7 - 1.3.7 Summary of Experimental Results and Conclusions [Seite 94]
4.4 - 1.4 Illumination of the Nucleation and Growth Mechanism [Seite 96]
4.4.1 - 1.4.1 Low-temperature Endotherms and Homogeneous Nucleation [Seite 96]
4.4.2 - 1.4.2 Some Brief Theoretical Considerations [Seite 100]
4.5 - 1.5 Conclusions and Outlook [Seite 102]
5 - 2 Early Stages of Crystal Formation in Glass-forming Metallic Alloys [Seite 117]
5.1 - 2.1 Introduction [Seite 117]
5.2 - 2.2 Marginal Glass-formers [Seite 120]
5.2.1 - 2.2.1 Nucleation versus Growth Control [Seite 120]
5.2.2 - 2.2.2 Processing Pathway Modifications [Seite 123]
5.2.3 - 2.2.3 Nucleation and Growth Kinetics [Seite 127]
5.2.4 - 2.2.4 Characterization of the Amorphous Phase [Seite 131]
5.2.5 - 2.2.5 Nanocrystal Formation at Temperatures Well Below Tg [Seite 137]
5.3 - 2.3 Deformation-induced Nanocrystal Formation [Seite 146]
5.4 - 2.4 Bulk Metallic Glasses [Seite 149]
5.5 - 2.5 Conclusions and Hypotheses [Seite 153]
6 - 3 Crystalline and Amorphous Modifications of Silica: Structure, Thermodynamic Properties, Solubility, and Synthesis [Seite 159]
6.1 - 3.1 Introduction [Seite 159]
6.2 - 3.2 Properties of Silica Modifications: Literature Search [Seite 162]
6.2.1 - 3.2.1 Classical SiO2-literature [Seite 163]
6.2.2 - 3.2.2 Original Literature Sources on the Different Silica Modifications [Seite 163]
6.2.3 - 3.2.3 Internet Search [Seite 164]
6.3 - 3.3 Phase Diagram of SiO2 [Seite 164]
6.3.1 - 3.3.1 Fenner's Classical Diagram [Seite 164]
6.3.2 - 3.3.2 Flörke's Diagram [Seite 165]
6.3.3 - 3.3.3 Contemporary (p - T )-phase Diagrams of SiO2 [Seite 166]
6.4 - 3.4 Modifications of SiO2 and Their Synthesis [Seite 170]
6.4.1 - 3.4.1 Mineralogical Characteristics of the SiO2-modifications [Seite 170]
6.4.2 - 3.4.2 Synthesis of Quartz [Seite 170]
6.4.3 - 3.4.3 Synthesis and Stabilization of ß -cristobalite [Seite 173]
6.4.4 - 3.4.4 Synthesis of Keatite: Classical Aspects [Seite 181]
6.4.5 - 3.4.5 Synthesis of Coesite [Seite 182]
6.4.6 - 3.4.6 Stishovite: Synthesis and Thermal Stability [Seite 182]
6.4.7 - 3.4.7 Synthesis of Amorphous Modifications of Silica [Seite 185]
6.5 - 3.5 Structure and Thermodynamic Properties of the SiO2-modifications [Seite 186]
6.6 - 3.6 Solubility of the Different SiO2-modifications [Seite 192]
6.6.1 - 3.6.1 General Thermodynamic Dependencies [Seite 192]
6.6.2 - 3.6.2 Solubility Diagram of SiO2. Ostwald's Rule of Stages [Seite 197]
6.6.3 - 3.6.3 Solubility of SiO2: Size Effects [Seite 203]
6.6.4 - 3.6.4 Different SiO2-modifications at Hydrothermal Conditions: Technological Aspects [Seite 205]
6.7 - 3.7 Resources of the Silica Modifications [Seite 208]
6.7.1 - 3.7.1 Mineral Resources of Quartz [Seite 208]
6.7.2 - 3.7.2 Plant Resources of Silica [Seite 209]
6.7.3 - 3.7.3 Industrial Waste as Sources of Silica [Seite 210]
6.7.4 - 3.7.4 Coesite and Stishovite as Impactite Remnants [Seite 210]
6.8 - 3.8 Some Particularly Interesting Properties of Silica [Seite 211]
6.9 - 3.9 General Discussion: Technical Perspectives [Seite 212]
7 - 4 The Main Silica Phases and Some of Their Properties [Seite 219]
7.1 - 4.1 Introduction [Seite 219]
7.2 - 4.2 Specific Properties of Silica Resulting from the Electronic Structure of Silicon [Seite 220]
7.2.1 - 4.2.1 Specific Properties of Silica Compounds and Differences as Compared to Chemical Analogs: Silicon and Carbon [Seite 220]
7.2.2 - 4.2.2 Electron Structure of the Silicon Atom and its Interaction with Oxygen [Seite 223]
7.2.3 - 4.2.3 Consequences of p-Bonding in Silica [Seite 224]
7.2.4 - 4.2.4 Increase in Silicon Coordination Number as a Result of s-p-d-hybridization [Seite 225]
7.2.5 - 4.2.5 Implication of s-p-d-hybridization for Chemical Reactions and Physical Transformations of Silica [Seite 227]
7.3 - 4.3 Phases of Silica and Their Properties [Seite 229]
7.3.1 - 4.3.1 Dense Octahedral Silicas: High Pressure Phases [Seite 231]
7.3.2 - 4.3.2 Clathrasils: Friable Silica Phases [Seite 232]
7.3.3 - 4.3.3 Exception: Fibrous Silica [Seite 233]
7.3.4 - 4.3.4 Proper Silicas [Seite 233]
7.3.5 - 4.3.5 Main Crystalline Tetrahedral Silicas [Seite 235]
7.3.6 - 4.3.6 Amorphous Silica [Seite 245]
7.3.7 - 4.3.7 Polyamorphism [Seite 247]
7.4 - 4.4 Quartz and Some of Its Properties [Seite 250]
7.4.1 - 4.4.1 Enantiomorphism of Quartz [Seite 250]
7.4.2 - 4.4.2 Twins (Zwillinge) in Quartz [Seite 251]
7.4.3 - 4.4.3 Anisotropy of Quartz [Seite 254]
7.4.4 - 4.4.4 Thermal Expansion of Quartz [Seite 255]
7.4.5 - 4.4.5 High-Low or (a - ß )-Transformation in Quartz [Seite 263]
7.4.6 - 4.4.6 Pressure-induced Amorphization of Crystalline Silica [Seite 267]
7.5 - 4.5 Hydrothermal Synthesis of Quartz [Seite 267]
7.5.1 - 4.5.1 Brief History [Seite 268]
7.5.2 - 4.5.2 Temperature Drop Method [Seite 269]
7.5.3 - 4.5.3 Main Problems of Hydrothermal Synthesis of Quartz [Seite 272]
7.6 - 4.6 Concluding Remarks [Seite 283]
7.7 - 4.7 Appendix: The Crystal Skulls [Seite 283]
8 - 5 Chemical Structure of Oxide Glasses: A Concept for Establishing Structure-Property Relationships [Seite 291]
8.1 - 5.1 Introduction [Seite 291]
8.2 - 5.2 Structural Models [Seite 292]
8.3 - 5.3 Thermodynamic Approach [Seite 296]
8.4 - 5.4 Concept of Chemical Structure [Seite 299]
8.5 - 5.5 Short-range Order [Seite 303]
8.5.1 - 5.5.1 Na2O-B2O3 Glasses [Seite 303]
8.5.2 - 5.5.2 Li2O-B2O3 Glasses andMelts [Seite 305]
8.5.3 - 5.5.3 Na2O-SiO2 Glasses [Seite 309]
8.5.4 - 5.5.4 Na2O-B2O3-SiO2 Glasses [Seite 311]
8.6 - 5.6 Intermediate-Range Order [Seite 311]
8.7 - 5.7 Structure-Property Relationships [Seite 315]
8.8 - 5.8 Summary and Conclusions [Seite 318]
9 - 6 Bubbles in Silica Melts: Formation, Evolution, and Methods of Removal [Seite 323]
9.1 - Part I: Experimental Data and Basic Mechanisms [Seite 323]
9.1.1 - 6.1 Introduction [Seite 323]
9.1.2 - 6.2 Sources of Bubbles in Silica Melt and Glass [Seite 324]
9.1.2.1 - 6.2.1 Brief Account of the Technology of Silica Glass Production [Seite 324]
9.1.2.2 - 6.2.2 Raw Materials as a Source of Bubbles [Seite 325]
9.1.2.3 - 6.2.3 Furnace Atmosphere as a Source of Bubbles [Seite 327]
9.1.2.4 - 6.2.4 Interaction of Heaters and Form-shaping Equipment with the Melt as Source of Bubbles [Seite 330]
9.1.2.5 - 6.2.5 Concentrations of Impurities, Including Dissolved Gases, in Commercial Silica Glasses [Seite 330]
9.1.2.6 - 6.2.6 Experimental Study of Formation and Evolution of Bubbles in Silica Melts [Seite 331]
9.1.3 - 6.3 Physico-chemical Properties of Silica Melts Influencing the Formation and Evolution of Gas Bubbles [Seite 334]
9.1.3.1 - 6.3.1 Surface Tension [Seite 334]
9.1.3.2 - 6.3.2 Density [Seite 334]
9.1.3.3 - 6.3.3 Viscosity [Seite 335]
9.1.3.4 - 6.3.4 Solubility and Diffusion of Gases [Seite 337]
9.1.4 - 6.4 Summary to Part I [Seite 346]
9.2 - Part II: Theoretical Analysis and Computer Simulation of the Process [Seite 347]
9.2.1 - 6.5 Introduction to Part II [Seite 347]
9.2.1.1 - 6.5.1 Main Stages of Fusion of Powdered Silica under Heating and Evolution of Bubble Structure [Seite 347]
9.2.1.2 - 6.5.2 Selection of Parameters for the Temperature Dependence Equations that describe the Properties of the Silica Melt Affecting the Kinetics of the Process [Seite 348]
9.2.2 - 6.6 Micro-rheological Model and Computer Simulation of the Process [Seite 349]
9.2.2.1 - 6.6.1 The Micro-rheological Model of Powder Sintering and Structuring of a Porous Body [Seite 350]
9.2.2.2 - 6.6.2 Influence of Some Technological Factors on Formation of Bubble Structure under Heating of Powdered Silica Glass: Computer Simulation of the Process [Seite 357]
9.2.3 - 6.7 Summary to Part II [Seite 365]
9.3 - Part III: Mathematical Modeling and Computer Simulation of the Behavior of Gas-Filled Bubbles in Silica Melts [Seite 367]
9.3.1 - 6.8 Introduction [Seite 367]
9.3.2 - 6.9 Behavior of Isolated Bubbles [Seite 369]
9.3.3 - 6.10 Behavior of Solitary Gas-filled Bubbles under Mass Exchange with the Melt [Seite 370]
9.3.4 - 6.11 Two-phase Approach to the Description of Mono-disperse Ensembles of Bubbles [Seite 373]
9.3.5 - 6.12 Two-phase Approach to the Description of Poly-disperse Ensembles of Bubbles [Seite 378]
9.3.6 - 6.13 Diffusion of the Dissolved Gas in the Melt [Seite 382]
9.3.7 - 6.14 Relative Motion of Bubbles in the Melt: Modification of the Mathematical Model [Seite 386]
9.3.8 - 6.15 Flow of the Melt Governed by the Motion of the Bubbles: Complete System of Equations for Modeling of the Behavior of Gas-filled Bubble Ensembles in the Melt [Seite 391]
9.3.9 - 6.16 Summary to Part III [Seite 394]
10 - 7 Regularities and Peculiarities in the Crystallization Kinetics of Silica Glass [Seite 399]
10.1 - 7.1 Introduction [Seite 399]
10.2 - 7.2 Literature Review [Seite 403]
10.3 - 7.3 Development of Experimental Techniques [Seite 413]
10.4 - 7.4 Basic Phenomenological Features of the Crystallization Processes [Seite 416]
10.5 - 7.5 Influence of the Degree of Silica Reduction [Seite 420]
10.6 - 7.6 Influence of Concentration of "Structural Water" [Seite 424]
10.7 - 7.7 Influence of the Degree of Fusion Penetration of Quartz or Cristobalite Particles on Crystallization of Quartz Glasses [Seite 427]
10.8 - 7.8 Influence of Surface Contamination on Crystallization Kinetics [Seite 430]
10.9 - 7.9 Influence of the Composition of the Gas Medium on Crystallization of Quartz Glass [Seite 433]
10.9.1 - 7.9.1 Introductory Comments [Seite 433]
10.9.2 - 7.9.2 On Crystallization in Dry Gas Media [Seite 433]
10.9.3 - 7.9.3 Experiments on Crystallization in an Atmosphere Containing Water Vapor [Seite 435]
10.9.4 - 7.9.4 Crystallization of Quartz Glass in the Atmosphere of Gases in Equilibrium with the Melt [Seite 436]
10.10 - 7.10 Influence of the Drawing Process on the Crystallization Kinetics of Tubes of Quartz Glasses [Seite 439]
10.11 - 7.11 Summary of Results and Discussion [Seite 444]
10.11.1 - 7.11.1 Introductory Remarks [Seite 444]
10.11.2 - 7.11.2 Influence of Surface Reactions on Crystallization [Seite 445]
10.11.3 - 7.11.3 Relation Between Crystallization Rate and Viscosity [Seite 449]
10.12 - 7.12 Conclusions [Seite 457]
11 - 8 Stress-induced Pore Formation and Phase Selection in a Crystallizing Stretched Glass [Seite 463]
11.1 - 8.1 Introduction [Seite 463]
11.2 - 8.2 Stress Induced Pore Formation and Phase Selection in a Crystallizing Stretched Glass of Regular Shape [Seite 465]
11.2.1 - 8.2.1 The Model [Seite 465]
11.2.2 - 8.2.2 Experiments [Seite 467]
11.2.3 - 8.2.3 Theoretical Interpretation: Classical Nucleation Theory [Seite 474]
11.2.4 - 8.2.4 Theoretical Interpretation: Generalized Gibbs Approach [Seite 482]
11.3 - 8.3 Sintered Diopside-albite Glass-ceramics Forming Crystallization-induced Porosity [Seite 489]
11.3.1 - 8.3.1 Introduction [Seite 489]
11.3.2 - 8.3.2 Experimental [Seite 490]
11.3.3 - 8.3.3 Results and Discussion [Seite 492]
12 - 9 Crystallization of Undercooled Liquids: Results of Molecular Dynamics Simulations [Seite 503]
12.1 - 9.1 Introduction [Seite 503]
12.2 - 9.2 Thermodynamics and Kinetics of Crystal Formation [Seite 506]
12.3 - 9.3 Description of the Systems under Investigation in the Present Study [Seite 509]
12.3.1 - 9.3.1 Models [Seite 509]
12.3.2 - 9.3.2 Phase Diagram [Seite 510]
12.4 - 9.4 Methods of Modeling of Spontaneous Crystallization [Seite 511]
12.4.1 - 9.4.1 Mean Life-time Method [Seite 511]
12.4.2 - 9.4.2 Mean First-passage Time Method [Seite 515]
12.4.3 - 9.4.3 Transition Interface Sampling [Seite 518]
12.5 - 9.5 Temperature Dependence of the Interfacial Free Energy Density Crystal-liquid for Planar Interfaces [Seite 520]
12.5.1 - 9.5.1 Triple Point [Seite 520]
12.5.2 - 9.5.2 Melting Line [Seite 521]
12.6 - 9.6 Kinetics of Crystallization in a cLJ-system [Seite 525]
12.6.1 - 9.6.1 Crystallization Parameters [Seite 525]
12.6.2 - 9.6.2 Nucleation Rate [Seite 529]
12.6.3 - 9.6.3 Comparison of Homogeneous Nucleation Theory with Computer Simulation [Seite 530]
12.6.4 - 9.6.4 Nucleation in the Region Below the Endpoint of the Melting Line [Seite 531]
12.7 - 9.7 Kinetics of Crystallization in the mLJ-system and Free Energy of the Clusters of the Crystalline State [Seite 534]
12.7.1 - 9.7.1 Pressure Dependence of the Nucleation Rate [Seite 534]
12.7.2 - 9.7.2 Temperature Dependence of the Nucleation Rate [Seite 535]
12.8 - 9.8 Discussion and Conclusions [Seite 539]
13 - 10 Crystal Nucleation and Growth in Glass-forming Systems: Some New Results and Open Problems [Seite 543]
13.1 - 10.1 Introduction [Seite 544]
13.2 - 10.2 Consequences of Stochastic Structural Fluctuations in Ultraviscous Melts [Seite 549]
13.2.1 - 10.2.1 Structure Fluctuations, Nucleation and Distribution of Relaxation Times [Seite 549]
13.2.2 - 10.2.2 Structure Fluctuations and the Notion of Disordered Cluster Formation [Seite 550]
13.3 - 10.3 A Case Study: Crystallization Kinetics of a Typical Metal Alloy Melt [Seite 557]
13.3.1 - 10.3.1 General Considerations [Seite 557]
13.3.2 - 10.3.2 One Experimental Example [Seite 559]
13.3.3 - 10.3.3 Theoretical Interpretation in Terms of the KJMA-approach [Seite 562]
13.3.4 - 10.3.4 Crystallization on Rate Heating [Seite 565]
13.3.5 - 10.3.5 Differences Between Isothermal and Rate-heating Crystallization [Seite 568]
13.3.6 - 10.3.6 Origin of the Second Peak for Crystallization on Rate-heating [Seite 570]
13.4 - 10.4 Thermal Effects of Crystallization on Its Kinetics [Seite 572]
13.4.1 - 10.4.1 General Remarks [Seite 572]
13.4.2 - 10.4.2 Rayleigh-Bénard Convection Effects [Seite 573]
13.4.3 - 10.4.3 Marangoni or Thermo-capillarity Convection Effect [Seite 575]
13.5 - 10.5 Classical and Generalized Gibbs' Approaches to Cluster Formation and Growth [Seite 576]
13.5.1 - 10.5.1 Basic Ideas [Seite 576]
13.5.2 - 10.5.2 Application to Nucleation [Seite 578]
13.5.3 - 10.5.3 Application to Cluster Growth Processes [Seite 584]
13.5.4 - 10.5.4 Thermodynamics versus Kinetics: Ridge Crossing [Seite 585]
13.6 - 10.6 Specific Interfacial Energy and the Skapski-Turnbull Relation [Seite 590]
13.6.1 - 10.6.1 General Approach to the Determination of the Specific Interfacial Energy: Taylor Expansion [Seite 590]
13.6.2 - 10.6.2 Stefan's Rule and Skapski-Turnbull Relation: Some Interpretation and Extension to Thermodynamic Non-equilibrium States [Seite 592]
13.7 - 10.7 Dependence of Crystal Nucleation and Growth Processes on Pre-history [Seite 595]
13.7.1 - 10.7.1 Introductory Comments [Seite 595]
13.7.2 - 10.7.2 Kinetic Criteria for Glass-formation [Seite 596]
13.7.3 - 10.7.3 On the Dependence of the State of the Melt on Cooling and Heating Rates and Its Relevance for Crystal Nucleus Formation and Growth [Seite 600]
13.8 - 10.8 Conclusions [Seite 601]
14 - Index [Seite 609]