RSC PAPERBACKS RS.C PRINCIPLES OF Thermal Analysis AND Calorimetry edited by P.J.HAINES
Foreword The Thermal Methods Group of the Royal Society of Chemistry,which was founded in95,has a tradition of education in thermal analysis dating back to its first residential thermal analysis school held at the Cement and Concrete Research Association in 1968.The Group has continued to be at the forefront of thermal education through the or- ganisation of schools,specialist meetings and both national and interna tional con erenc es Over the past twenty years,thermal methods have seen a rapid growth in their use in an increasingly wide range of applications.In addition,a number of powerful new techniques have been developed recently.It is thereoretimely that a groupofUKtiss have pood their specialist expertise to produce this w ide-ranging ho ok which should be f con to thos re new to th or who are coming to a particular technique for the first time.The broad range of techniques and applications covered means that there is also much to interest the more experienced thermal analyst. Throughout most of its long life the Thermal Methods Group has been fortunate in having an outstandin ontribution from three of its Pr r David Dol (Hon.Secretary)and 09 1a1r1 n1969-1971 Mackenzie(Chairman 1965-1967).These scientists throughout their long and distinguished careers were unstinting in helping young workers and those new to the field to develop their thermal analysis expertise.It is a most fitting tribute that this book is dedicated to their me nory and to their invalua ble contribution to the development of thermal analysis. Edward L.Charsley Past President of the International Confederation for Thermal Analysis and Calorimetry,(ICTAC) Centre for Thermal Studies,University of Huddersfield,UK
Foreword The Thermal Methods Group of the Royal Society of Chemistry, which was founded in 1965, has a tradition of education in thermal analysis dating back to its first residential thermal analysis school held at the Cement and Concrete Research Association in 1968. The Group has continued to be at the forefront of thermal education through the organisation of schools, specialist meetings and both national and international conferences. Over the past twenty years, thermal methods have seen a rapid growth in their use in an increasingly wide range of applications. In addition, a number of powerful new techniques have been developed recently. It is therefore timely that a group of UK scientists have pooled their specialist expertise to produce this wide-ranging book, which should be of considerable value to those who are new to the field or who are coming to a particular technique for the first time. The broad range of techniques and applications covered means that there is also much to interest the more experienced thermal analyst. Throughout most of its long life the Thermal Methods Group has been fortunate in having an outstanding contribution from three of its members, namely Professor David Dollimore (Chairman 1969-1 97 l), Dr Cyril J. Keattch (Hon. Secretary 1965-1998) and Dr Robert C. Mackenzie (Chairman 1965-1967). These scientists throughout their long and distinguished careers were unstinting in helping young workers and those new to the field to develop their thermal analysis expertise. It is a most fitting tribute that this book is dedicated to their memory and to their invaluable contribution to the development of thermal analysis. Edward L. Charsley Pust President of the International Confederation for Thermal Analysis and Calorimetry, (ICTAC) Centre for Thermal Studies, University of Huddersfield, UK V
Dedicated to the memory of Dr Cyril Jack Keattch, 1928-1999 Honorary Secretary of the Thermal Methods Group for its first 33 years Dr Robert Cameron Mackenzie 19202000 Founder Member of the TMG(Chairman 1965-1967)and ICTAC Professor David Dollimore 1927-2000 Chairman of the TMG 1969-1971 C.J.Keattch R.C.Mackenzie D.Dollimore
Dedicated to the memory of Dr Cyril Jack Keattch, 1928-1999 Honorary Secretary of the Thermal Methods Group for its first 33 years Dr Robert Cameron Mackenzie 1920-2000 Founder Member of the TNIG (Chairman 1965-1967) and ICTAC Professor David Dollimore Chairman of the TMG 1969-1971 1927-2000 C. J. Keattch R. C. Mackenzie D. Dollimore
Contents Chapter 1 Introduction 1 P.J.Haines Materials,Heat and Changes 1 Definitions of Thermal and Calorimetric Methods The Family of Thermal Methods Instrumentation for Thermal Analysis and Calorimetry 44 The Reasons for Using Thermal and Calorimetric Methods 6 The Need for Proper Practice Further Reading References Chapter 2 Ther imeiry and Derivative Therogravmery 10 Introduction and Definitions Instrumentation Balance 1022 Furnace Atmosphere Control Crucibles Thermocouples Temperature Control 16167 Data collection Isothermal Experiments 19 Reporting Thermogravimetry Results 24 A.Properties of the Sample B.Experimental Conditions 2424
Contents Chapter I Introduction P. J. Haines Materials, Heat and Changes Definitions of Thermal and Calorimetric Methods The Family of Thermal Methods Instrumentation for Thermal Analysis and Calorimetry The Reasons for Using Thermal and Calorimetric Methods The Need for Proper Practice Further Reading References Chapter 2 Thermogravimetry and Derivative Thermogravimetry G. R. Heal Introduction and Definitions Instrumentation Balance Furnace Atmosphere Control Crucibles Thermocouples Temperature Control Data Collection Isothermal Experiments Calibration for Mass and Temperature Effect of Experimental Variables Reporting Thermogravimetry Results A. Properties of the Sample B. Experimental Conditions 1 10 10 12 12 14 15 15 16 16 17 18 19 20 24 24 24 vii
viⅷ Contents C.Data Acquisition and Manipulation Methods 24 D.Results 25 Preliminary Steps Zero Setting Adding the Sample 28 Starting the run Ending the Run Example Experiment Results 2899 Applications 31 Oxysalt Decomposition Polymer Stability and Charcoal Production 33 Metal oxidation 3 Compos itional Analysis Glass-making Reactions 840 kinetics of solid-state reactions 42 Ancillary Techniques Residue analysis 50 51 High Thermogravimetry Further Reading 123 References Chapter 3 Differential Thermal Analysis and Differential Scanning Calorimetry 55 P.G.Laye Introduction 5 Definitions and Nomenclature 7 Applications 60 Theoretical Considerations Instrum entation Specification 5 Temperature Sensors 69 Crucibles Temperature and Atmosphere Control 70 Cooling Systems and Ac cessories 71 Calvet-type E u nen Experimental Considerations Variables
. Vlll Contents C. Data Acquisition and Manipulation Methods D. Results Preliminary Steps Crucible Treatment Zero Setting Adding the Sample Starting the Run Ending the Run Example Experiment Results Applications Oxysalt Decomposition Polymer Stability and Charcoal Production Metal Oxidation Compositional Analysis Glass-making Reactions Kinetics of Solid-state Reactions Ancillary Techniques Residue Analysis Other Temperature Regimes High Resolution Thermogravimetry A Typical Thermogravimetric Experiment Further Reading References 24 25 26 26 26 27 28 28 28 29 29 31 31 33 37 38 40 42 50 50 51 51 52 53 Chapter 3 Differential Thermal Analysis and Differential Scanning Calorimetry 55 P. G. Laye Introduction Definitions and Nomenclature Applications Theoretical Considerations Instrumentation Specification Temperature Sensors Crucibles Temperature and Atmosphere Control Cooling Systems and Accessories Calvet-type Equipment Experimental Considerations Variables 55 57 60 65 69 69 69 70 70 71 71 72 72
Contents ix Do's and Do not's Reterence Calibration Preliminaries 313667 Temperature Calibration Energy Calibration M Measurement of Heat Capacity Measurement of Energy Measurement of Purity Kinetics Final Thoughts on Measurement 9 Further Re References Chapter 4 Thermomechanical,Dynamic Mechanical and Dielectric Methods 9 D.M.Price Introduction and Principles Thermomechanical Analysis and Thermodilatometry 44 Dynamic Mechanical Analysis Dielectric Techniques 96 Instrumentation 101 echanical Analysis Dielectric Techniques 8 Typical Experiments Thermomechanical analysis 107 Dynamic Mechanical Analysis 109 Dielectric Techniques 113 Thermomechanical Analysis Dynamic Mechanical Analysis Dielectric Thermal Analysis 123 Modulated Temperature Thermomechanical and Dielectric Techniques Conclud Remarks Acknowledgements Further Reading References
Contents 1x Do’s and Do not’s Reference Calibration Preliminaries Temperature Calibration Energy Calibration Measurement of Heat Capacity Measurement of Energy Measurement of Purity Kinetics Final Thoughts on Measurement Measurements Further Reading References 73 75 76 76 77 79 82 82 85 87 89 91 91 92 Chapter 4 Thermomechanical, Dynamic Mechanical and Dielectric Methods D. M. Price 94 Introduction and Principles Thermomechanical Analysis and Thermodilatometry Dynamic Mechanical Analysis Dielectric Techniques Thermomechanical Analysis Dynamic Mechanical Analysis Dielectric Techniques Thermomechanical Analysis Dynamic Mechanical Analysis Dielectric Techniques Thermomechanical Analysis Dynamic Mechanical Analysis Dielectric Thermal Analysis Instrumentation Typical Experiments Applications Modulated Temperature Thermomechanical and Dielectric Techniques Concluding Remarks Acknowledgements Further Reading References 94 94 96 99 101 101 103 105 106 107 109 113 117 117 120 123 126 126 127 127 127
Contents Calorimetry 129 R.J.Willson Introduction 129 Definition of Calorimetry 130 The emistry and Thermodynamics 131 The First law of Thermodynamics 137 TThe Second Law of Thermodynamics The Third Law of Thermodynamics Calorimeters 136 Classification of Calorimeters 137 138 Instrumentation:Calorimeters for Special Purposes 1 Solution Calorimeters 139 Combustion Calorimeters 14 Reaction hazard calorimeters 144 Isothermal Calorimeters 145 Applications of Isothermal Calorimetry 146 Calorimetric Information The Calorimetric Signal 148 Reaction Mechanism Kinetic Information 152 Exa 153 hemical Reactions 153 Physical Changes Summary 8 Acknowledgements 161 References 161 Chapter 6 Simultaneous Thermal Analysis Techniques 166 S.B.Warrington Introduction:The Rationale behind the Simultaneous Approach 166 Simultaneous Thermogravimetry-Differential Thermal Analysis (TG-DTA) 167 Instrumentation Applications of TG-DTA Simultaneous Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) 172 Instrumentation 172
X Chapter 5 Calorimetry R. J. WiEEson Introduction Definition of Calorimetry Thermochemistry and Thermodynamics The First law of Thermodynamics The Second Law of Thermodynamics The Third Law of Thermodynamics Classification of Calorimeters Calibration Solution Calorimeters Combustion Calorimeters Reaction Hazard Calorimeters Isothermal Calorimeters Calorimeters Instrumentation: Calorimeters for Special Purposes Applications of Isothermal Calorimetry Calorimetric Information The Calorimetric Signal Reaction Mechanism Kinetic Information Chemical Reactions Physical Changes Summary Acknowledgements References Examples of Calorimetric Applications Chapter 6 Simultaneous Thermal Analysis Techniques S. B. Warrington Contents 129 129 130 131 132 133 133 136 137 138 139 139 141 144 145 146 148 148 150 152 153 153 156 160 161 161 166 Introduction: The Rationale behind the Simultaneous Approach 166 Simultaneous Thermogravimetry-Differential Thermal Analysis (TG-DTA) 167 Instrumentation 167 Applications of TG-DTA 170 172 Instrumentation 172 Simultaneous Thermogravimetry-Differential Scanning C a1 o rim e t r y (T G - D S C)
Contents Introduction Instrumentation for EGA Applications of EGA Less Common Techniques e Optical Techn X-Ray Techniques DTA-Rheometry Micro-thermal Analysis (u-TA) Summary 187 References 187 Appendices 190 1.A Symbols for Physical Quantities and Units 190 Nomenclature for Thermal Analysis and Calorimetry 191 1.B ces of Inforn 191 1.B.2 Major Textbooks on Thermal Analysis and Calorimetry 192 1 B 3 Videos CD-Roms etc. 197 1.B.4 Conference Proceedings 197 ICTAC and Its Affiliated So cieties in Europe and the USA 199 American and Other Standard Test Meth 200 3.1 American Society for Testing and Materials (ASTM)Methods 201 3.2 British Standards 205 4 Manufacturers,Consultants and Other Suppliers 207 5 Consultancies and Groups 214 Subject Index 216
Contents Applications of TG-DSC Evolved Gas Analysis (EGA) Introduction Instrumentation for EGA Applications of EGA Less Common Techniques Optical Techniques Spectroscopic Techniques X-Ray Techniques DTA-Rheometry Micro-thermal Analysis (p-TA) Summary References Appendices 1 .A 1 .B 2 3 4 5 Symbols for Physical Quantities and Units Nomenclature for Thermal Analysis and Calorimetry Sources of Information 1 .B. 1 Journals l.B.2 Major Textbooks on Thermal Analysis and l.B.3 Videos, CD-Roms etc. 1 .B.4 Conference Proceedings ICTAC and Its Affiliated Societies in Europe and the USA American and Other Standard Test Methods 3.1 American Society for Testing and Materials (ASTM) Methods 3.2 British Standards Manufacturers, Consultants and Other Suppliers Consultancies and Other Groups Calorimetry Subject Index xi 173 174 174 175 177 181 181 183 183 185 185 187 187 190 190 191 191 191 192 197 197 199 200 201 205 207 214 216
Acknowledgements The authors of this text acknowledge their debt to Cyril Keattch,Robert zie and David Dollimore. It is also a pleasure to acknowledge the contribution made by the instrument manufacturers over many years.They are listed in the Appen- dices,and the brochures,application notes and personal help which they have given,and continue to give,plays a vital part in the use of thermal ndmnaydes theirper sion to use The Thermal Methods Group maintains a web site,through the Royal Society of Chemistry at http://thermalmethodsgroup.org.uk and a list server whereby requests for information and queries about techniques may be exchanged.If you wish to join the TMG Internet Newsgroup, please follow the intructions on the TMG web site Than due to many people,particularly Dr Trevor Lever and Dr Michael Richardson for their help in preparing this book Peter J.Haines(Editor)
Acknowledgements The authors of this text acknowledge their debt to Cyril Keattch, Robert Mackenzie and David Dollimore. It is also a pleasure to acknowledge the contribution made by the instrument manufacturers over many years. They are listed in the Appendices, and the brochures, application notes and personal help which they have given, and continue to give, plays a vital part in the use of thermal and calorimetric analysis. The Group gratefully acknowledges their permission to use several of the diagrams in this text. The Thermal Methods Group maintains a web site, through the Royal Society of Chemistry at http://thermalmethodsgroup.org.uk and a list server whereby requests for information and queries about techniques may be exchanged. If you wish to join the TMG Internet Newsgroup, please follow the intructions on the TMG web site. Thanks are due to many people, particularly Dr Trevor Lever and Dr Michael Richardson for their help in preparing this book. Peter J. Haines (Editor) xii
Contributors P.J.Haines,Oakland Analytical Services,38 Oakland Avenue,Farnham, Surrey GU9 9DX.UK G.R.Heal,Deparment of Chemistry and Applied Chemistry.Universityof Salford,Salford M5 4WT.UK P.G.Laye.Cenire for Thermal Studies,Unieersity of Huddersfield. Queensgate,Huddersfield HDI 3DH,UK D.M.Price,Institute of Polymer Technology and Materials Engineering, Loughborough University,Loughborough LE11 3TU,UK S.B.Warri gton,Institute of Polyme hb Technology and Materials Engin ugh U ersity,Loughborough LEII 3TU,UK Harlow,Essex CM19 5AW,UK
Contributors P. J. Haines, Oakland Analytical Services, 38 Oakland Avenue, Farnham, Surrey GU9 9DX, UK G. R. Heal, Department of Chemistry and Applied Chemistry, University of SaEford, SaEford M5 4 WT, UK P. G. Laye, Centre for Thermal Studies, University of Huddersjield, Queensgate, Huddersjield HDl 3DH, UK D. M. Price, Institute of Polymer Technology and Materials Engineering, Loughborough University, Loughborough LEI 1 3TU, UK S. B. Warrington, Institute of Polymer Technology and Materials Engineering, Loughborough University, Loughborough LEI 1 3TU, UK R. J. Willson, GEaxoSmithKline, New Frontiers Science Park (South), Harlow, Essex CM19 5AW, UK . XI11