Handbook of Thermal Analysis and Calorimetry: Recent Advances, Techniques and Applications

Description

Handbook of Thermal Analysis and Calorimetry: Recent Advances, Techniques and Applications, Volume Six, Second Edition, presents the latest in a series that has been well received by the thermal analysis and calorimetry community. This volume covers recent advances in techniques and applications that complement the earlier volumes. There has been tremendous progress in the field in recent years, and this book puts together the most high-impact topics selected for their popularity by new editors Sergey Vyazovkin, Nobuyoshi Koga and Christoph Schick—all editors of Thermochimica Acta. Among the important new techniques covered are biomass conversion; sustainable polymers; polymer nanocompsoties; nonmetallic glasses; phase change materials; propellants and explosives; applications to pharmaceuticals; processes in ceramics, metals, and alloys; ionic liquids; fast-scanning calorimetry, and more. Features 19 all-new chapters to bring readers up to date on the current status of the field Provides a broad overview of recent progress in the most popular techniques and applications Includes chapters authored by a recognized leader in each field and compiled by a new team of editors, each with at least 20 years of experience in the field of thermal analysis and calorimetry Enables applications across a wide range of modern materials, including polymers, metals, alloys, ceramics, energetics and pharmaceutics Overviews the current status of the field and summarizes recent progress in the most popular techniques and applications Cover Contents Contributors Foreword 1. Development of Direct and Indirect Methods for the Determination of Vaporization Enthalpies of Extremely Low-V ... 1.1. Introduction 1.2. Kinetic Methods of Thermal Analysis (Vaporization) of Low-Volatile Compounds 1.3. Temperature Programed Desorption Combined With LOSMS 1.4. Thermogravimetric Methods for the Determination of Vapor Pressures and Thermal Stability of High Boiling Substances 1.5. Absolute Vapor Pressures of Extremely Low-Volatile Compounds From FSC 1.6. Differential Scanning Calorimetry (DSC) 1.7. Static Vapor Pressure Measurements 1.8. Calvet Vaporization Drop Microcalorimetry 1.9. Transpiration Method 1.10. UV Spectroscopy for Vaporization Studies of Low-Volatile Compounds 1.11. Correlation Gas Chromatography 1.12. How to Adjust DeltalgHmo(T) Values to the Reference Temperature 298.15K Properly? 1.13. Indirect Determination of Molar Enthalpies of Vaporization of ILs from Calorimetric Results 1.14. Conclusions and Outlook 1.15. References 2. Fast Scanning Chip Calorimetry 2.1. Introduction 2.2. FSC Instrumentation 2.2.1. Fast Scanning Sensors 2.2.2. Temperature Calibration 2.2.2.1. The Thermometer and Thermal Lag 2.2.2.2. Static Temperature Gradients 2.2.2.3. Lateral Temperature Profile in Membrane Based Calorimeters 2.2.3. Heat Capacity Determination 2.2.4. The Sample 2.3. Selected Applications of FSC 2.3.1. Polymer Crystallization 2.3.2. Crystal Nucleation in Polymers by Tammann's Nuclei Development Method 2.3.3. Enthalpy Relaxation and Homogeneous Crystal Nucleation in Polymer Glasses 2.3.4. Polymer Crystal Reorganization 2.3.5. Polymer Melting 2.3.6. Analysis of Chemically Unstable Materials 2.3.7. Analysis of Phase Transitions in Metals 2.3.8. Glass Transition 2.3.9. Combination of FSC With Other Analytical Techniques 2.4. Outlook 2.5. Acknowledgments 2.6. References 3. Dilatometry 3.1. Introduction 3.1.1. Thermal Strain and Phase Transitions in General 3.1.2. Methodology of Dilatometric Assessment of Phase Transformation 3.1.3. Dilatometry Applications in the Field of Materials 3.2. Measuring System 3.3. Analysis of Dilatometer Curves 3.4. Some Examples 3.4.1. Thermal Expansion Coefficient of an Austenitic Steel 3.4.2. Continuous Cooling Behavior of a Steel With Different Carbon Contents 3.4.3. Effect of Segregation on Isothermal Transformation Kinetics of Lower Bainite 3.5. Summary 3.6. Future Trends in Dilatometry 3.7. References 4. Modern Isoconversional Kinetics: From Misconceptions to Advances 4.1. Introduction 4.2. Misconceptions 4.2.1. Preexponential Factor and Reaction Model 4.2.2. Single-Step Approximation 4.2.3. Meaning of Isoconversional Activation Energy 4.2.4. Application to Processes on Cooling 4.3. Advances 4.3.1. Crystallization and Melting of Polymers 4.3.2. Solid-Solid Transition 4.3.3. Crystallization From Solution 4.3.4. Thermal Decomposition During Continuous Cooling 4.3.5. Other Processes 4.3.6. Deconvolution of Overlapped Processes 4.4. Conclusions 4.5. Acknowledgments 4.6. References 5. Kinetics and Mechanisms of Solid-Gas Reactions 5.1. Abbreviations 5.2. State of the Art 5.3. Kinetic Concepts and Background 5.3.1. Pseudo-Steady-State Approximation 5.3.2. Fundamental Processes 5.3.3. Rate-Determining Step Approximation 5.3.4. General Rate Equation 5.4. Experimental Methods 5.4.1. Isothermal and Isobaric TG 5.4.2. Conditions for Collecting Reliable Kinetic Data 5.4.3. Sudden Jump Method 5.4.4. Hyphenated Techniques 5.5. Kinetic Geometrical Models and Elementary Mechanisms 5.5.1. Kinetic Geometrical Models 5.5.1.1. One-Process Models 5.5.1.2. Two-Process Models 5.5.1.3. Validation Tests 5.5.1.3.1. Pseudo-Steady-State Assumption 5.5.1.3.2. Rate-Determining Step of Growth Assumption 5.5.1.3.3. f(α) Test 5.5.2. Elementary Mechanisms 5.5.2.1. Nucleation Elementary Mechanisms 5.5.2.2. Growth Elementary Mechanisms 5.6. Other Applications of the Jump Method 5.6.1. Study of phi(T,Pi) 5.6.2. No-Reproducible Experiments 5.6.3. Validation of the Geometrical Model 5.7. Nonisothermal, Nonisobaric Conditions (Case of a Reacting Bed): CIN4 Approach 5.8. Conclusions 5.9. References 6. Physico-Geometric Approach to the Kinetics of Overlapping Solid-State Reactions 6.1. Introduction 6.2. Phenomenology of Overlapping Reactions in the Solid State 6.2.1. Overlapping Processes of a Mixture of Different Substances and a Substance With Different Reactivities 6.2.2. Overlapping Processes Controlled by Physico-Geometric Events 6.2.3. Consecutive and Concurrent Chemical Processes 6.3. Experimental Approach to Overlapping Processes 6.3.1. Characterization of Sample and Tracking of Reaction Process 6.3.2. Experimental Separation of Overlapping TA Peaks 6.4. Kinetic Approach to Overlapping Processes 6.4.1. Kinetic Data of Overlapping Processes 6.4.2. Preliminary Kinetic Approach to Overlapping Processes 6.4.3. Kinetic Deconvolution Analysis 6.4.4. Kinetic Modeling of the Overlapping Processes in the Solid State 6.5. Conclusion 6.6. References 7. Analysis of Polymer Crystallization by Calorimetry 7.1. Introduction 7.2. General Aspects of Polymer Crystallization 7.3. Analysis of Polymer Crystallization by Differential Scanning Calorimetry 7.3.1. Isothermal Crystallization 7.3.2. Critical Issues in DSC Analysis of Isothermal Polymer Crystallization 7.3.3. Nonisothermal Crystallization by DSC 7.4. Analysis of Polymer Crystallization by Fast Scanning Calorimetry 7.4.1. Nonisothermal Crystallization 7.4.2. Nonisothermal Crystal Nuclei Formation 7.4.3. Nonisothermal Cold-Crystallization 7.4.4. Isothermal Crystallization 7.4.5. Crystal Nucleation in Glassy Polymers 7.5. Analysis of Polymer Crystallization by Temperature-Modulated Calorimetry 7.5.1. Quasi-isothermal Crystallization of Polymers Investigated by TMDSC 7.5.2. Nonisothermal Crystallization of Polymers Investigated by TMDSC 7.6. Flow-Induced Crystallization 7.7. Combined Calorimetric+Complementary Analytical Techniques 7.7.1. In Situ WAXD/FSC 7.7.2. In Situ Imaging and DSC 7.7.3. In Situ Rheology and DSC 7.8. Conclusions 7.9. References 8. Glass Transition and Physical Aging of Confined Polymers Investigated by Calorimetric Techniques 8.1. Introduction 8.2. Equilibrium vs. Nonequilibrium Dynamics 8.3. The Glass Transition 8.4. Recent Developments in Thermodynamic and Dynamic Aspects of Glasses Below Tg 8.4.1. Thermodynamics Below Tg 8.4.2. Dynamics Below Tg 8.5. Glass Dynamics in Confinement 8.5.1. Nonequilibrium Dynamics: Tg and Physical Aging 8.5.2. Relation to the Rate of Spontaneous Fluctuations 8.5.3. Factors Affecting Tg Depression: Free Interface and Adsorption 8.5.4. Theoretical Description 8.6. Accessing Low-Energy Glassy States by Aging Nanostructured Glasses 8.7. Conclusions 8.8. Acknowledgments 8.9. References 9. Decomposition of Organic Wastes: Thermal Analysis and Evolution of Volatiles 9.1. Introduction 9.2. Thermal Analysis 9.3. Uses of TG/DTG 9.4. Analysis of the Volatiles Evolved and Kinetics 9.5. Evolution of Compounds 9.6. Thermal Effects 9.7. Acknowledgments 9.8. References 10. Thermal Analysis of Biobased Polymers and Composites 10.1. Introduction 10.1.1. Thermal Analysis and Calorimetry 10.2. Application Fields 10.2.1. Protein Denaturation and Gelation 10.2.2. Polymerization and Curing of Biobased Thermosets 10.2.2.1. Polycondensation of FA 10.2.2.2. Polyepoxides-Based Thermosets 10.2.3. Crystallization of Biobased Polyesters 10.2.4. Nucleation 10.2.5. Glass Transition 10.2.6. Relaxation Process of Lignin 10.2.7. Degradation, Thermal, and Thermo-Oxidative Degradation 10.3. Conclusion 10.4. References 11. Polymer Nanocomposites 11.1. Abbreviations 11.2. Introduction 11.3. PNCs 11.4. Nano-Effects in PNCs 11.4.1. Confinement Effects 11.4.2. Entanglement Effects 11.4.3. The Influence of Nanoparticles on Glass Transition 11.4.4. The Influence of Nanoparticles on Polymer Melting and Crystallization 11.5. Thermal Analysis Methods in PNCs Characterization 11.5.1. DSC 11.5.1.1. Melting and Crystallization 11.5.1.2. Exfoliation and Intercalation 11.5.1.3. Glass Transition, Relaxation, and Fictive Temperature 11.5.1.4. Kinetics 11.5.1.5. Crystalline Fraction (CF), Rigid Amorphous Fraction (RAF), and Mobile Amorphous Fraction (MAF) 11.5.2. TMDSC 11.5.2.1. Glass Transition 11.5.2.2. Confinement Effect 11.5.2.3. Activation Energy of Glass Transition 11.5.3. Fast Scanning Calorimetry 11.5.4. LTA Micro-TA 11.5.5. Thermogravimetry (TG) 11.5.5.1. Thermal Stability 11.5.5.2. Thermal Degradation Kinetics 11.5.6. Thermoanalytical Methods (TG/MS, TG/FTIR) 11.5.7. DMA and TMA 11.5.8. Laser Flash Analysis (LFA) 11.5.9. DETA 11.6. Conclusions 11.7. Acknowledgments 11.8. References 12. Thermal Behavior of Chalcogenide Glasses 12.1. Introduction 12.2. Glass Transition Behavior 12.2.1. Enthalpy Relaxation Studied by DSC/DTA 12.2.2. Volume Relaxation Studied by TMA/DIL 12.2.3. Viscosity Measurements 12.2.4. Example Studies 12.3. Crystallization Behavior 12.3.1. Crystallization Studied by DSC/DTA 12.3.2. Crystallization Studied by TMA 12.3.3. Crystal Growth Rate Studied by Microscopy 12.3.4. Example Studies 12.4. Acknowledgment 12.5. References 13. Applications of Thermal Analysis to the Study of Phase-Change Materials 13.1. Introduction 13.2. Types of PCM and Their Applications 13.2.1. Latent Thermal Energy Storage Using PCMs 13.2.2. Classifications of PCMs and Their Applications 13.3. Thermal Analysis Methods on PCMs 13.3.1. Differential Scanning Calorimetry (DSC) 13.3.2. DSC-Dynamic Method 13.3.3. DSC-Step Method 13.3.4. T-History Method 13.3.5. Specific Heat Measurement Using the DSC 13.3.6. Thermogravimetric Analysis (TGA) 13.4. DSC Applications on PCMs 13.5. TGA Applications on PCMs 13.6. TGA Applications on Nanomaterial-Based PCMs 13.7. Merits and Challenges 13.8. Conclusions 13.9. Thermal Properties of Various Heat Storage Materials 13.10. References 14. Characteristics of Thermal Decomposition of Energetic Materials in a Study of Their Initiation Reactivity 14.1. Introduction 14.2. The Main Sources of Thermal Decomposition Data 14.3. Strategy and Reasons for the Various Approaches 14.3.1. Approach Based on Primary Fission Similarity 14.3.1.1. Detonation 14.3.1.1.1. Generalization of Validity of the Relationships Found 14.3.1.1.2. Thermal Reactivity as a Kissinger Slope Relationship 14.3.1.2. Impact Reactivity (Sensitivity) 14.3.1.3. Friction Reactivity (Sensitivity) 14.3.1.4. Sensitivity to Electric Spark 14.3.1.5. Note Concerning the Use of the Czech Vacuum Stability Test 14.3.2. Approach on the Basis of Electron Structure in the Reaction Center 14.3.2.1. NMR Chemical Shifts-Specification of the Reaction Center in the Molecule 14.3.2.2. Correlation of Reaction Characteristics With Electron Charges 14.4. Comment 14.4.1. Why Are Low-Temperature Thermal Decomposition Data Important? 14.4.2. Primary Fission-Reaction Center of the Molecule 14.4.3. Relationships Between Decomposition Activation Energies and Performance of EMs 14.4.4. Mechanical and Electric Spark Sensitivities in Connection With Thermal Decomposition 14.4.4.1. Toward the Initiation Reactivity of 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-Hexaazaisowurtzitane (HNIW) 14.5. Conclusion 14.6. Acknowledgments 14.7. References 14.8. Further Reading 15. Pharmaceutical Applications of Thermal Analysis 15.1. Introduction 15.2. Physical Characterization of Crystalline Drugs 15.2.1. Polymorphism 15.2.2. Solid-Solid Transition Temperature 15.2.3. Hydrates 15.2.4. Cocrystals 15.2.5. Unusual Melting Behavior 15.3. Evaluation of Amorphous Properties 15.3.1. Glass Transition and Relaxation 15.3.2. Specific Heat Capacity 15.3.3. Fragility 15.3.4. Crystallization Tendency 15.3.5. Crystallinity 15.3.6. Coamorphous 15.4. High-Speed DSC 15.5. Conclusions 15.6. Acknowledgment 15.7. References 16. Thermoanalytical Characterization Techniques for Multiferroic Materials 16.1. Introduction 16.1.1. Multiferroic Materials 16.1.2. Perovskite Oxide BiFeO3 16.1.2.1. Crystal Structure and Multiferroism in BiFeO3 16.1.2.2. Challenges of Bulk BiFeO3 Preparation 16.2. Thermoanalytic Characterization Techniques in BiFeO3 and Related Materials 16.2.1. Differential Scanning Calorimetry (DSC) and Differential Thermal Analysis (DTA) 16.2.2. Thermomechanical Analysis (TMA) and Thermodilatometry (TD) 16.2.3. Temperature-Dependent Structural Characterization Techniques (Thermodiffraction): X-Ray, Synchrotron, Neutron, an ... 16.2.4. Raman Thermospectroscopy 16.2.5. Impedance Thermospectroscopy 16.2.6. Dielectric Thermal Analysis (DEA) 16.3. Conclusions 16.4. Acknowledgments 16.5. References 17. Chalcogenides for Phase-Change Memory 17.1. Introduction 17.2. Glass-Forming Ability 17.3. Crystallization in Phase-Change Chalcogenides 17.3.1. Nucleation 17.3.2. Crystal Growth 17.3.3. Size-Dependent Crystallization 17.3.4. Uncertainty Over Tg in Fast Phase-Change Chalcogenides 17.3.5. Measurements of Crystal Growth Rate 17.3.6. Ultrafast DSC Measurements on Phase-Change Chalcogenides 17.3.6.1. The Kissinger Analysis 17.3.6.2. Johnson-Mehl-Avrami Kinetics 17.3.6.3. Regimes Revealed by Ultrafast DSC and the Influence of Mobility 17.3.7. Fragile-to-Strong Crossover 17.3.7.1. Effect of FSC on Crystallization Kinetics 17.4. Conclusions 17.5. Acknowledgment 17.6. References 17.7. Further Reading 18. Recent Advances in Thermal Analysis and Calorimetry of Aluminum Alloys 18.1. Introduction 18.1.1. Application of Aluminum Alloys for Structural Components 18.1.2. Heat Treatment Precipitation Hardening 18.1.3. Kinetics of Solid-Solid Phase Transformations and Its Measurement 18.2. Analysis of Solid-Solid Phase Transformations Kinetics in Metallic Alloys in a Wide Dynamic Range 18.2.1. Aluminum Alloys 18.2.2. Basics for Calorimetric Measurements of Solid-Solid Phase Transitions in (Al-) Alloys 18.2.3. Basics for Dilatometric Measurement of Solid-Solid Phase Transitions in (Al-) Alloys 18.2.4. Possible Reasons for the Remaining Zero-Level Curvature and its Elimination 18.2.5. Physical, Alloy-Specific Requirements on the Scanning Rate Range 18.2.6. DSC Devices, Quenching Dilatometer, and Sample Geometries Utilized to Achieve Nine Orders of Magnitude in Cooling ... 18.2.7. Some Peculiarities of Cooling Experiments-Temperature Control Limitations and Determination of the uCCR 18.3. Recent Developments 18.3.1. Brief Review on Sophisticated and Established DSC Methods-Their Field of Action and Limitations 18.3.2. Dilatometric Measurements of Solid-Solid Phase Transformations in Al Alloys 18.3.3. Analysis of Solid-Solid Phase Transformations at Fast Cooling Rates by FSC 18.4. Outlook and Future Prospective 18.5. Acknowledgment 18.6. References 19. Metals and Alloys 19.1. Introduction 19.1.1. DTA 19.1.1.1. Initial Metallurgical State of Alloy Samples 19.1.1.2. Temperature Calibration: Choice of Onset Temperature 19.1.1.3. Quantitative Enthalpy and Heat Capacity Calibration 19.1.1.4. Determination of Liquidus Temperature 19.1.2. DSC 19.1.3. TGA 19.1.4. Flash DSC 19.1.5. Dynamic Mechanical Analysis (DMA) 19.2. Phase Diagram Characterization 19.2.1. Binary Alloys 19.2.1.1. Determination of Type of Reaction 19.2.1.2. Li-Sb-Potential Anode Material in Li-Ion Batteries 19.2.2. Thermal Analysis of Ternary Alloys 19.2.2.1. Ternary Systems-Validation of Model Predictions 19.3. Metallic Glasses 19.3.1. Metrics for GFA 19.3.2. Stability of Metallic Glass-Isothermal Annealing 19.3.3. Structural Relaxation of BMGs 19.4. Oxidation of Alloys 19.4.1. Determining Rate Laws for High-Temperature Kinetics 19.4.2. Active/Passive Oxidation 19.5. Transient Liquid-Phase Bonding 19.5.1. Background 19.5.2. DSC Analysis of TLPB 19.6. Shape Memory Alloys (SMAs) 19.7. Kinetic Studies of Melting, Crystallization, and Glass Formation by Fast Scanning Calorimetry 19.7.1. Nonequilibrium Melting of Binary Alloys 19.7.2. Kinetic Competition in a Au55Pb22.5Sb22.5 Metallic Glass [148] 19.8. Conclusion 19.9. Acknowledgment 19.10. Appendix 19.10.1. Relevant Standards 19.10.2. Terms and Definitions 19.10.3. Calibration and Sensitivity 19.10.4. Analysis of Data 19.11. References Index A B C D E F G H I J K L M N O P Q R S T U V W X Y Z