Sample Controlled Thermal Analysis

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Format: Hardcover
Pub. Date: 2003-11-01
Publisher(s): Kluwer Academic Pub
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Summary

"Sample Controlled Thermal Analysis" (SCTA) defines the branch of thermal analysis in which a feedback from the sample is used to control its heating or cooling. It is therefore the sample itself which determines its own heating and cooling conditions, as the name implies. This approach is a real breakthrough in the field of thermal analysis. It has the advantage, compared with conventional thermal analysis, of eliminating uncertainties due to thermal effects in the sample container, improving resolution, and accurately determining reaction temperatures and accurate kinetic data. SCTA has, since its introduction in the early 1970's, been used in many studies both on inorganic and to a certain extent organic (polymers) compounds with the aim of studying the temperature, type and kinetics of reactions taking place during heating and cooling; in the case of ceramics and adsorbents SCTA has even been used in the synthesis of materials with specific properties. These techniques are now also available in commercial thermal analysis instruments. Sample Controlled Thermal Analysis gives a short presentation of the spirit and history of SCTA and then focuses on: basic SCTA techniques, applications of SCTA in kinetic studies and applications in the study of ceramics, adsorbents and catalysts. Finally the expected future development of SCTA is discussed. This book is an invaluable reference for materials scientists, chemists, geologists, and engineers involved in the development of new materials, the manufacturing processes and quality control. It is also useful for research in solid state chemistry, materials science, materials in general, and analytical chemistry. Producers of thermoanalytical equipment and manufacturers of catalysts, technological ceramics and adsorbents for industrial or environment applications will find this an important resource.

Table of Contents

List of Contributing Authors and Laboratories ix
Preface xi
Chapter 1: GENERAL INTRODUCTION TO SAMPLE-CONTROLLED THERMAL ANALYSIS (SCTA)
J. Rouquerol and O. Toft Sorensen
1.1. Spirit and Definition of SCTA
1(2)
1.2. History of SCTA
3(3)
References
6(2)
Chapter 2: A FRAMEWORK FOR THE SCTA FAMILY
J. Rouquerol and O. Toft Sorensen
2.1. Representing the Specificity of SCTA
8(3)
2.2. Simple Distinction Between the Various Forms of SCTA
11(3)
2.3. Concluding Remarks
14(1)
References
14(2)
Chapter 3: BASIC SCTA TECHNIQUES
J. Rouquerol and O. Toft Sorensen
3.1. Introduction
16(1)
3.2. Constant Rate Thermal Analysis
17(11)
3.2.1. Constant Heat-Flow Thermal Analysis or Constant rate DTA
17(2)
3.2.2. Constant Rate Evolved Gas Detection (CR-EGD)
19(7)
3.2.3. Constant Rate Thermogravimetry (CR-TG)
26(2)
3.2.4. Constant Rate Thermodilatometry(CR-TD)
28(1)
3.3. Varying Rate Thermal Analysis
28(6)
3.3.1. Rate-Jump EGD and Rate-Jump TG
28(3)
3.3.2. Controlled Rate Evolved Gas Analysis (CR-EGA)
31(2)
3.3.3. Increasing Rate Thermal Analysis
33(1)
3.3.4. Modulated Rate EGD and Modulated Rate TG
34(1)
3.4. Alternate Rate- and Temperature-Controlled Thermal Analysis
34(15)
3.4.1. Stepwise Isothermal Analysis (SIA)
35(2)
3.4.2. Forced Stepwise Isothermal Analysis (FSIA)
37(1)
3.4.3. Stepwise Temperature Modulated DSC (MTDSC) (M. Reading)
37(7)
3.4.4. The Proportional Heating Rate TA (PHTA) (P. Barnes, E. Fesenko, G.M.B. Parkes)
44(2)
3.4.5. The "Max Res" Technique (M. Reading)
46(2)
3.4.6. The Dynamic Heating Technique (M. Reading)
48(1)
3.5. Combined Rate and Temperature-Controlled Thermal Analysis
49(3)
3.5.1. High Resolution Thermogravimetry (M. Reading)
49(3)
3.6. Sample Controlled Thermomicroscopy (E.L. Charsley, C. Stewart)
52(4)
3.6.1. Experimental
53(1)
3.6.2. Results and Discussion
54(2)
3.7. Sample Controlled Reaction Rate by Gas Blending Techniques (P. Barnes, E. Fesenko, G.M.B. Parkes)
56(3)
References
59(3)
Chapter 4: SCTA AND KINETICS
J.M. Criado and L.A. Pérez-Maqueda
4.1. Introduction
62(1)
4.2. The Fundamental Problem with the Kinetics of Heterogeneous Reactions
62(1)
4.3. The Fundamental Problem with Non-Isothermal Kinetics
63(6)
4.4. Advantages of SCTA
69(4)
4.5. Kinetic Analysis of CRTA Curves
73(1)
4.6. The Shape of CRTA Curves
73(5)
4.7. Master plots
78(4)
4.8. Rate-Jump and Related Methods
82(4)
4.9. Relationship between CRTA and other SCTA Methods
86(4)
4.10. Unified Theory for Kinetic Analysis of Solid State Reactions
90(3)
4.11. Comparison of Resolution Power of CRTA and Conventional Non-Isothermal Methods: A Kinetic Approach
93(2)
4.12. Conclusions
95(1)
References
96(6)
Chapter 5: SCTA AND CERAMICS
O. Toft Sorensen
5.1. Introduction
102(1)
5.2. Sample Controlled Thermogravimetry
102(12)
5.2.1. Stepwise Isothermal analysis of Ba-oxalate
102(5)
5.2.2. Stepwise Isothermal analysis of Pure and Doped Ce-carbonates
107(4)
5.2.3. Forced Stepwise Isothermal Analysis of Ce-carbonates
111(2)
5.2.4. Binder Removal Studied by SCTA
113(1)
5.3. Dilatometric SCTA Measurements
114(11)
5.3.1. Introduction
114(2)
5.3.2. Sintering Kinetics
116(9)
5.4. SCTA and Material Synthesis (J.M. Criado)
125(6)
References
131(4)
Chapter 6: SCTA AND ADSORBENTS
P. Llewellyn, F. Rouquerol and J. Rouquerol
6.1. Introduction
135(1)
6.2. SCTA and Adsorbents Preparation
136(22)
6.2.1. Activated Alumina
137(12)
6.2.2. Activated Carbon
149(2)
6.2.3. Zeolites
151(4)
6.2.4. Ordered Mesoporous Materials
155(3)
6.3. SCTA and Adsorbents Characterization
158(9)
6.3.1. Introduction
158(1)
6.3.2. Quasi-Isothermal Thermodesorption
158(5)
6.3.3. Constant Rate Thermodesorption
163(4)
6.4. SCTA and Adsorbent Outgassing
167(3)
6.5. Conclusions
170(1)
References
171(3)
Chapter 7: SCTA AND CATALYSIS
E.A. Fesenko, P.A. Barnes and G.M.B. Parkes
7.1. Sample Controlled Thermolysis
174(20)
7.1.1. Decomposition of Complex Precursors
174(7)
7.1.2. Variation in Reaction Pathway during CRTA preparation of catalysts
181(4)
7.1.3. Texture and Structure of catalysts prepared using CRTA
185(4)
7.1.4. Effects of Self generated atmospheres on Catalysts Preparation
189(5)
7.2. Redox Reactions Using Temperature and Concentration Control
194(17)
7.2.1. SCTA Reduction
195(12)
7.2.2. SCTA Oxidation
207(4)
7.3. SCTA and Catalysis
211(11)
7.3.1. Surface-Catalysed Reactions in a Controlled Environment
212(6)
7.3.2. Energetics of Surface Elimination Processes
218(4)
References
222(4)
Chapter 8: SCTA IN THE FUTURE
M. Reading
8.1. Introduction
226(1)
8.2. New Sensors
226(4)
8.2.1. Macro Scale Sensors
226(1)
8.2.2. Nano Scale Sensors
227(3)
8.3. New Types of Measurements for SCTA
230(3)
8.4. Optimising Resolution and The Parameter Space Problem
233(1)
8.5. Peak Shape Recognition
233(7)
8.6. Which Algorithm for Best Resolution
240(1)
8.7. SCTA when Dealing with Multiple Parameters
241(3)
8.8. Overview
244(1)
References
245(2)
Subject Index 247

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