Sample Controlled Thermal Analysis

"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.

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

What is included with this book?

The New copy of this book will include any supplemental materials advertised. Please check the title of the book to determine if it should include any access cards, study guides, lab manuals, CDs, etc.

The Used, Rental and eBook copies of this book are not guaranteed to include any supplemental materials. Typically, only the book itself is included. This is true even if the title states it includes any access cards, study guides, lab manuals, CDs, etc.