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