Thermal Analysis

Description

Thermal Analysis deals with the theories of thermal analysis (thermodynamics, irreversible thermodynamics, and kinetics) as well as instrumentation and techniques (thermometry, differential thermal analysis, calorimetry, thermomechanical analysis and dilatometry, and thermogravimetry). Applications of thermal analysis are also described. This book consists of seven chapters and begins with a brief outline of the history and meaning of heat and temperature before listing the techniques of thermal analysis. The reader is then introduced to the basis of thermal analysis, paying particular attention to the macroscopic theories of matter, namely, equilibrium thermodynamics, irreversible thermodynamics, and kinetics. The next chapter discusses thermometry, focusing on the international temperature scale and the techniques of measuring temperature. Examples of heating and cooling curves are linked to the discussion of transitions. The groundwork for a detailed understanding of transition temperature is given. The chapters that follow explore the principles of differential thermal analysis, calorimetry, thermomechanical analysis and dilatometry, and thermogravimetry. This book is intended for the senior undergraduate or beginning graduate student, as well as for the researcher and teacher interested in thermal analysis. Cover Thernal Analysis Copyright Preface Acknowledgments 1. Introduction 1.1 Heat, Temperature, and Thermal Analysis 1.1.1 History 1.1.2 Thermodynamic Description of Heat 1.1.3 Temperature Scales 1.1.4 Techniques of Thermal Analysis 1.2 Microscopic and Macroscopic Description of Matter 1.2.1 Classification 1.2.2 Microscopic Structure 1.2.3 Link between the Microscopic and Macroscopic Descriptions Problems for Chapter 1 References for Chapter 1 2. The Basis of Thermal Analysis 2.1 Macroscopic Description of Matter 2.1.1 Equilibrium Thermodynamics 2.1.2 Irreversible Thermodynamics 2.1.3 Kinetics 2.2 Functions of State for Thermal Analysis 2.2.1 Thermometry 2.2.2 Calorimetry 2.2.3 Thermomechanical Analysis and Dilatometry 2.2.4 Thermogravimetry Problems for Chapter 2 References for Chapter 2 3. Thermometry 3.1 Introduction 3.2 International Temperature Scale 1990 3.3 Temperature Measurement and Thermometers 3.3.1 Liquid-in-Glass Thermometers 3.3.2 Resistance Thermometers 3.3.3 Thermocouples 3.3.4 Other Thermometers 3.4 Transitions in One-Component Systems 3.4.1 Thermodynamics of Transitions 3.4.2 Melting and Evaporation 3.4.3 Glass Transition 3.4.4 Cooling and Heating Curves 3.5 Transitions in Two-Component Systems 3.5.1 Thermodynamics of the Transition 3.5.2 Molecular Mass Determination 3.5.3 Ebulliometry 3.5.4 Cryoscopy Problems for Chapter 3 References for Chapter 3 4. Differential Thermal Analysis 4.1 Principles 4.2 History 4.3 Instrumentation 4.3.1 General Design 4.3.2 Modern Instruments 4.3.3 Standardization and Techniques 4.3.4 Extreme-Condition DTA 4.4 Mathematical Treatment of DTA 4.4.1 DTA with Temperature Gradient within the Sample 4.4.2 DTA without Temperature Gradient within the Sample 4.5 Qualitative DTA Applications 4.5.1 Phase Transitions 4.5.2 Chemical Reactions 4.6 Phase Diagrams 4.6.1 General Discussion 4.6.2 Theory 4.6.3 Phase Diagrams of Macromolecules 4.7 Time-Dependent Analysis 4.7.1 Irreversible Thermodynamics of Melting 4.7.2 Melting of Flexible, Linear Macromolecular Crystals 4.7.3 Glass Transition Analysis Problems for Chapter 4 References for Chapter 4 5. Calorimetry 5.1 Principles and History 5.2 Instrumentation 5.2.1 Isothermal and Isoperibol Calorimeters 5.2.2 Adiabatic Calorimeters 5.2.3 Compensating Calorimeters 5.2.4 Twin and Scanning Calorimeters 5.3 Description of Some Modern Instruments 5.4 Heat Capacity 5.4.1 Measurement 5.4.2 Theory 5.4.3 Heat Capacities of Solids 5.4.4 Heat Capacities of Linear Macromolecules (the Advanced THermal Analysis System, ATHAS) 5.5 Transitions and Reactions 5.5.1 Measurement of Enthalpies 5.5.2 Melting of Linear Macromolecules 5.5.3 Entropies of Fusion 5.5.4 Purity Analysis 5.6 Quantitative Analysis of the Glass Transition Problems for Chapter 5 References for Chapter 5 6. Thermomechanical Analysis and Dilatometry 6.1 Principles and History 6.1.1 Length and Volume Units 6.1.2 Length Measurement 6.1.3 Volume and Density Measurement 6.1.4 Stress and Pressure Measurement 6.2 Instrumentation for Thermomechanical Analysis 6.3 The p-V-T Diagrams 6.3.1 Phenomenological Description 6.3.2 Packing Fraction 6.3.3 The p-V-T Surface of Crystals, Liquids, and Glasses 6.3.4 Comparison of Expansivity and Specific Heat Capacity 6.4 Typical TMA Data 6.5 Melting and Crystallization 6.5.1 Equilibrium and Nonequilibrium 6.5.2 Homopolymer Equilibria 6.5.3 Equilibrium Extension 6.6 Dynamic Mechanical Analysis 6.6.1 Principles and Instrumentation 6.6.2 Data Treatment 6.6.3 Applications Problems for Chapter 6 References for Chapter 6 7. Thermogravimetry 7.1 Principles and History 7.2 Instrumentation 7.3 Standardization and Technique 7.4 Qualitative Thermogravimetry 7.4.1. Decomposition 7.4.2. Polymer Degradation 7.4.3. Thermogravimetry and DTA 7.5 Quantitative Thermogravimetry 7.5.1. Lithium Phosphate Polymerization 7.5.2. Calcium Oxalate/Carbonate Decomposition 7.5.3. Lifetime Prediction 7.6 Final Summary Problems for Chapter 7 References for Chapter 7 Appendix. Table of Thermal Properties of Linear Macromolecules Solutions to the Problems Index