Hot Topics in Thermal Analysis and Calorimetry – serie

to Thermal Analysis Techniques and Applications Edited by Michael E. Brown Chemistry Department, Rhodes University, Grahamstown, South Africa KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN: 0-306-48404-8 Print ISBN: 1-4020-0472-9 ©2004 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©2001 Kluwer Academic Publishers Dordrecht All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: http://kluweronline. com and Kluwer's eBookstore at: http://ebooks. kluweronline. com CONTENTS Preface to the First Edition, Chapman & Hall, London, 1988 ix About the First Edition of this Book x Preface to the Second Edition xi 1. INTRODUCTION 1. 1 Definition and History 1 1. 2 Thermal Analysis Instruments 4 References 11 2. THERMAL EVENTS 2. 1 Introduction 13 2. 2 The Solid State 13 2. 3 Reactions of Solids 14 2. 4 Decomposition of Solids 15 2. 5 Reaction with the Surrounding Atmosphere 16 2. 6 Solid-Solid Interactions 16 References 17 3. THERMOGRAVIMETRY (TG) Introduction 3. 1 19 3. 2 The Balance 19 3. 3 Heating the Sample 21 3. 4 The Atmosphere 24 3. 5 The Sample 26 3. 6 Temperature Measurement 26 3. 7 Temperature Control 28 Sample Controlled Thermal Analysis (SCTA) 29 3. 8 3. 9 Calibration 36 3. 10 Presentation of TG Data 37 3.

to Thermal Analysis Techniques and Applications Edited by Michael E. Brown Chemistry Department, Rhodes University, Grahamstown, South Africa KLUWER ACADEMIC PUBLISHERS NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN: 0-306-48404-8 Print ISBN: 1-4020-0472-9 ©2004 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©2001 Kluwer Academic Publishers Dordrecht All rights reserved No part of this eBook may be reproduced or transmitted in any form or by any means, electronic, mechanical, recording, or otherwise, without written consent from the Publisher Created in the United States of America Visit Kluwer Online at: http://kluweronline. com and Kluwer's eBookstore at: http://ebooks. kluweronline. com CONTENTS Preface to the First Edition, Chapman & Hall, London, 1988 ix About the First Edition of this Book x Preface to the Second Edition xi 1. INTRODUCTION 1. 1 Definition and History 1 1. 2 Thermal Analysis Instruments 4 References 11 2. THERMAL EVENTS 2. 1 Introduction 13 2. 2 The Solid State 13 2. 3 Reactions of Solids 14 2. 4 Decomposition of Solids 15 2. 5 Reaction with the Surrounding Atmosphere 16 2. 6 Solid-Solid Interactions 16 References 17 3. THERMOGRAVIMETRY (TG) Introduction 3. 1 19 3. 2 The Balance 19 3. 3 Heating the Sample 21 3. 4 The Atmosphere 24 3. 5 The Sample 26 3. 6 Temperature Measurement 26 3. 7 Temperature Control 28 Sample Controlled Thermal Analysis (SCTA) 29 3. 8 3. 9 Calibration 36 3. 10 Presentation of TG Data 37 3.

Calorimetry is one of the oldest areas of physical chemistry. The date on which calorimetry came into being may be taken as 13 June 1783, the day on which Lavoisier and Laplace presented a contribution entitled ,,Memoire de la Chaleur“ at a session of the Academie Française. Throughout the existence of calorimetry, many new methods have been developed and the measuring techniques have been improved. At p- sent, numerous laboratories worldwide continue to focus attention on the development and applications of calorimetry, and a number of com- nies specialize in the production of calorimeters. The calorimeter is an instrument that allows heat effects in it to be determined by directly measurement of temperature. Accordingly, to determine a heat effect, it is necessary to establish the relationship - tween the heat effect generated and the quantity measured in the ca- rimeter. It is this relationship that unambiguously determines the mathematical model of the calorimeter. Depending on the type of ca- rimeter applied, the accuracy required, and the conditions of heat and mass transfer that prevail in the device, the relationship between the measured and generated quantities can assume different mathematical forms.

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.

Environmentally compatible polymers (green polymers) are the key to sustainable developments for our rich and convenient life. In order to develop green polymers, it is essential to understand that nature constructs a variety of materials that can be used. Plant materials such as cellulose, hemicellulose and lignin are the largest organic resources. Thermal Properties of Green Polymers and Biocomposites is unique in that it introduces thermal analysis applicable to green polymers and provides fundamental thermal properties of cellulose, polysaccharides and lignin. The book includes over 370 figures concerning thermal properties of green polymers with detailed experimental conditions. It also introduces newly patented environmentally compatible green polymers. Thermal properties provided include: thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermomechanometry (TMA) and dynamic mechanical analysis (DMA).This book covers two domains: This book is aimed at advanced users and specialists who are interested in green polymers and who utilize thermal analyses for the above polymers, especially in research laboratories, both academic and industrial.

Af ter a kind mo ti va tion by Judit Si mon (Ed i tor-in-Chief of the Jour nal of Ther mal Anal y s is and Cal o ri m e t r y , Kluwe r Ac a dem ic Pub lis her) and ne go ti a tions with po- si ble con tri bu tors - lasting for m ore than one year - it was de cided to write a book about the ap pli ca tion of ther mal meth ods in bi ol ogy. Its aim was to be a guide how to per form ex per i ments and what kind of in for mation m ight be gained by them. We tried to col lect in for mation tha t could be achieved only dur ing a long per sonal pra- tice. In this way sci en tists from bi ol ogy and med i cine , e. g. , who are not so skilled in phys ics and math e mat ics may re al ize very soon the beauty and power of this tool at one hand. On the other hand, those sci en tists with better back ground in nat u ral sc- ences can be more sensitive to find out exciting biological problems.

The Nature of Biological Systems as Revealed by Thermal Methods is a guide for experiments using thermal methods. The Editor has used his many years of experience to create a unique resource that will enable others with a less mathematical background, to realize the beauty and power of this tool and to gain a better understanding of biological problems. Biological calorimetry (and of course thermal analysis) is of increasing interest and is not covered thoroughly in other resources. The methods presented are macroscopic, for the rather inhomogeneous material (micromethods are often not possible or not pertinent). This book will help beginners in the field of thermal analysis or calorimetry understand the principles of thermodynamics being applied to biological systems. Biological systems are highly organized and very complex. The water and the different types of weak interactions among the macromolecules make the interpretation of thermal events very difficult. This book includes examples how to handle such problems.The Nature of Biological Systems as Revealed by Thermal Methods is unique in that it: The book is an invaluable resource for anyone interested in thermodynamics, including practising professionals applying thermal methods to biological problems; researchers and graduate students beginning work using thermal methods; and specialists of thermal analysis starting work on biological problems. In addition, this book will be a useful resource for libraries and institutes as the only book covering quantitative thermal analysis of biological systems.

Environmentally compatible polymers (green polymers) are the key to sustainable developments for our rich and convenient life. In order to develop green polymers, it is essential to understand that nature constructs a variety of materials that can be used. Plant materials such as cellulose, hemicellulose and lignin are the largest organic resources. Thermal Properties of Green Polymers and Biocomposites is unique in that it introduces thermal analysis applicable to green polymers and provides fundamental thermal properties of cellulose, polysaccharides and lignin. The book includes over 370 figures concerning thermal properties of green polymers with detailed experimental conditions. It also introduces newly patented environmentally compatible green polymers. Thermal properties provided include: thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermomechanometry (TMA) and dynamic mechanical analysis (DMA).This book covers two domains: This book is aimed at advanced users and specialists who are interested in green polymers and who utilize thermal analyses for the above polymers, especially in research laboratories, both academic and industrial.

MTDSC provides a step-change increase in the power of calorimetry to characterize virtually all polymer systems including curing systems, blends and semicrystalline polymers. It enables hidden transitions to be revealed, miscibility to be accurately assessed, and phases and interfaces in complex blends to be quantified. It also enables crystallinity in complex systems to be measured and provides new insights into melting behaviour. All of this is achieved by a simple modification of conventional DSC.In 1992 a new calorimetric technique was introduced that superimposed a small modulation on top of the conventional linear temperature program typically used in differential scanning calorimetry. This was combined with a method of data analysis that enabled the sample’s response to the linear component of the temperature program to be separated from its response to the periodic component. In this way, for the first time, a signal equivalent to that of conventional DSC was obtained simultaneously with a measure of the sample’s heat capacity from the modulation. The new information this provided sparked a revolution in scanning calorimetry by enabling new insights to be gained into almost all aspects of polymer characteristics.This book provides both a basic and advanced treatment of the theory of the technique followed by a detailed exposition of its application to reacting systems, blends and semicrystalline polymers by the leaders in all of these fields. It is an essential text for anybody interested in calorimetry or polymer characterization, especially if they have found that conventional DSC cannot help them with their problems.

The appearance of this English edition of my book, ?rst published in Russian in mid-2006, is related to the help and support of two prominent scientists: Professor Michael Brown (Rhodes University Grahamstown, South Africa) and Dr. Judit Simon (Budapest University of Technology and Economics, Hungary). The story is as follows. In the winter of 2006, in the process of exchange of views by email with Michael on some problems of decomposition kinetics, I asked him about the possibility of publishing my book in English. He s- gestedthatIshouldcontactJudit,theSeriesEditorof“HotTopicsinThermal Analysis and Calorimetry”. My application was kindly accepted, considered, and approved. As a result, Judit strongly recommended this book to Springer for publication, and Michael kindly agreed to help me with linguistic impro- ments of my hurriedly translated book. In the process of editing, he made some critical comments and questions, which stimulated me to improve and clarify the text, but we did have to agree to put our di?erences of scienti?c opinions aside so as not to delay the process. Without this invaluable help, this book would not be as “readable” as I hope it is now. The author uses this opportunity to express his sincere thanks to Michael and Judit for their signi?cant help and support. Although only about a year has gone after the preparation of the original edition of the book (in Russian), this English version of the manuscript has undergone considerable revision. These changes refer to Sections2. 2, 2.

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.

This is an expanded and revised second edition,  presenting accurate and comprehensive information about our leading thermal scientists to current and future generations. In our globalized world, most researchers in thermal analysis do not know each other in person and are not familiar with each other’s achievements. This volume provides the reader with an up-to-date list of the prominent members in this community. The publication contains only living scientists. The selection is based partly on several decades of the editors' personal professional experience and also partly on the opinion of the Regional Editors of the Journal of Thermal Analysis and Calorimetry.

This is an expanded and revised second edition,  presenting accurate and comprehensive information about our leading thermal scientists to current and future generations. In our globalized world, most researchers in thermal analysis do not know each other in person and are not familiar with each other’s achievements. This volume provides the reader with an up-to-date list of the prominent members in this community. The publication contains only living scientists. The selection is based partly on several decades of the editors' personal professional experience and also partly on the opinion of the Regional Editors of the Journal of Thermal Analysis and Calorimetry.

Features twenty-five chapter contributions from an international array of distinguished academics based in Asia, Eastern and Western Europe, Russia, and the USA. This multi-author contributed volume provides an up-to-date and authoritative overview of cutting-edge themes involving the thermal analysis, applied solid-state physics, micro- and nano-crystallinity of selected solids and their macro- and microscopic thermal properties. Distinctive chapters featured in the book include, among others, calorimetry time scales from days to microseconds, glass transition phenomena, kinetics of non-isothermal processes, thermal inertia and temperature gradients, thermodynamics of nanomaterials, self-organization, significance of temperature and entropy. Advanced undergraduates, postgraduates and researchers working in the field of thermal analysis, thermophysical measurements and calorimetry will find this contributed volume invaluable. This is the third volume of the triptych volumes on thermal behaviour of materials; the previous two receiving thousand of downloads guaranteeing their worldwide impact.

Features twenty-five chapter contributions from an international array of distinguished academics based in Asia, Eastern and Western Europe, Russia, and the USA. This multi-author contributed volume provides an up-to-date and authoritative overview of cutting-edge themes involving the thermal analysis, applied solid-state physics, micro- and nano-crystallinity of selected solids and their macro- and microscopic thermal properties. Distinctive chapters featured in the book include, among others, calorimetry time scales from days to microseconds, glass transition phenomena, kinetics of non-isothermal processes, thermal inertia and temperature gradients, thermodynamics of nanomaterials, self-organization, significance of temperature and entropy. Advanced undergraduates, postgraduates and researchers working in the field of thermal analysis, thermophysical measurements and calorimetry will find this contributed volume invaluable. This is the third volume of the triptych volumes on thermal behaviour of materials; the previous two receiving thousand of downloads guaranteeing their worldwide impact.

Provides a summary of non-equilibrium glassy and amorphous structures and their macro- and microscopic thermal properties.The book contains a carefully selected works of fourteen internationally recognized scientists involving the advances of the physics and chemistry of the glassy and amorphous states.

Thermal Analysis of Micro-, Nano- and Non-Crystalline Materials: Transformation, Crystallization, Kinetics, and Thermodynamics complements and adds to volume 8 Glassy, Amorphous and Nano-Crystalline Materials by providing a coherent and authoritative overview of cutting-edge themes in this field. In particular, the book focuses on reaction thermodynamics and kinetics applied to solid-state chemistry and thermal physics of various states of materials.Written by an international array of distinguished academics, the book deals with fundamental and historical aspects of phenomenological kinetics, equilibrium background of processes, crystal defects, non-stoichiometry and nano-crystallinity, reduced glass-transition temperatures and glass-forming coefficients, determination of the glass transition by DSC, the role of heat transfer and phase transition in DTA experiments, explanation of DTA/DSC methods used for the estimation of crystal nucleation, structural relaxation and viscosity behaviour in glass and associated relaxation kinetics, influence of preliminary nucleation and coupled phenomenological kinetics, nucleation on both the strongly curved surfaces and nano-particles, crystallization of glassy and amorphous materials including oxides, chalcogenides and metals, non-parametric and fractal description of kinetics, disorder and dimensionality in nano-crystalline diamond, thermal analysis of waste glass batches, amorphous inorganic polysialates and bioactivity of hydroxyl groups as well as reaction kinetics and unconventional glass formability of oxide superconductors.Thermal Analysis of Micro-, Nano- and Non-Crystalline Materials: Transformation, Crystallization, Kinetics, and Thermodynamics is a valuable resource to advanced undergraduates, postgraduates, and researches working in the application fields of material thermodynamics, thermal analysis, thermophysical measurements, and calorimetry.

Calorimetry is one of the oldest areas of physical chemistry. The date on which calorimetry came into being may be taken as 13 June 1783, the day on which Lavoisier and Laplace presented a contribution entitled ,,Memoire de la Chaleur“ at a session of the Academie Française. Throughout the existence of calorimetry, many new methods have been developed and the measuring techniques have been improved. At p- sent, numerous laboratories worldwide continue to focus attention on the development and applications of calorimetry, and a number of com- nies specialize in the production of calorimeters. The calorimeter is an instrument that allows heat effects in it to be determined by directly measurement of temperature. Accordingly, to determine a heat effect, it is necessary to establish the relationship - tween the heat effect generated and the quantity measured in the ca- rimeter. It is this relationship that unambiguously determines the mathematical model of the calorimeter. Depending on the type of ca- rimeter applied, the accuracy required, and the conditions of heat and mass transfer that prevail in the device, the relationship between the measured and generated quantities can assume different mathematical forms.

Environmentally compatible polymers (green polymers) are the key to sustainable developments for our rich and convenient life. In order to develop green polymers, it is essential to understand that nature constructs a variety of materials that can be used. Plant materials such as cellulose, hemicellulose and lignin are the largest organic resources. Thermal Properties of Green Polymers and Biocomposites is unique in that it introduces thermal analysis applicable to green polymers and provides fundamental thermal properties of cellulose, polysaccharides and lignin. The book includes over 370 figures concerning thermal properties of green polymers with detailed experimental conditions. It also introduces newly patented environmentally compatible green polymers. Thermal properties provided include: thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), thermomechanometry (TMA) and dynamic mechanical analysis (DMA). This book covers two domains: -Fundamentals of thermal properties of cellulose, polysaccharides and lignin (Chapters 3 to 5); -Developments of new biocompatible polymers derived from plant materials (Chapters 6 to 8). This book is aimed at advanced users and specialists who are interested in green polymers and who utilize thermal analyses for the above polymers, especially in research laboratories, both academic and industrial.

Af ter a kind mo ti va tion by Judit Si mon (Ed i tor-in-Chief of the Jour nal of Ther mal Anal y s is and Cal o ri m e t r y , Kluwe r Ac a dem ic Pub lis her) and ne go ti a tions with po- si ble con tri bu tors - lasting for m ore than one year - it was de cided to write a book about the ap pli ca tion of ther mal meth ods in bi ol ogy. Its aim was to be a guide how to per form ex per i ments and what kind of in for mation m ight be gained by them. We tried to col lect in for mation tha t could be achieved only dur ing a long per sonal pra- tice. In this way sci en tists from bi ol ogy and med i cine , e. g. , who are not so skilled in phys ics and math e mat ics may re al ize very soon the beauty and power of this tool at one hand. On the other hand, those sci en tists with better back ground in nat u ral sc- ences can be more sensitive to find out exciting biological problems.

MTDSC provides a step-change increase in the power of calorimetry to characterize virtually all polymer systems including curing systems, blends and semicrystalline polymers. It enables hidden transitions to be revealed, miscibility to be accurately assessed, and phases and interfaces in complex blends to be quantified. It also enables crystallinity in complex systems to be measured and provides new insights into melting behaviour. All of this is achieved by a simple modification of conventional DSC.In 1992 a new calorimetric technique was introduced that superimposed a small modulation on top of the conventional linear temperature program typically used in differential scanning calorimetry. This was combined with a method of data analysis that enabled the sample’s response to the linear component of the temperature program to be separated from its response to the periodic component. In this way, for the first time, a signal equivalent to that of conventional DSC was obtained simultaneously with a measure of the sample’s heat capacity from the modulation. The new information this provided sparked a revolution in scanning calorimetry by enabling new insights to be gained into almost all aspects of polymer characteristics.This book provides both a basic and advanced treatment of the theory of the technique followed by a detailed exposition of its application to reacting systems, blends and semicrystalline polymers by the leaders in all of these fields. It is an essential text for anybody interested in calorimetry or polymer characterization, especially if they have found that conventional DSC cannot help them with their problems.

The appearance of this English edition of my book, ?rst published in Russian in mid-2006, is related to the help and support of two prominent scientists: Professor Michael Brown (Rhodes University Grahamstown, South Africa) and Dr. Judit Simon (Budapest University of Technology and Economics, Hungary). The story is as follows. In the winter of 2006, in the process of exchange of views by email with Michael on some problems of decomposition kinetics, I asked him about the possibility of publishing my book in English. He s- gestedthatIshouldcontactJudit,theSeriesEditorof“HotTopicsinThermal Analysis and Calorimetry”. My application was kindly accepted, considered, and approved. As a result, Judit strongly recommended this book to Springer for publication, and Michael kindly agreed to help me with linguistic impro- ments of my hurriedly translated book. In the process of editing, he made some critical comments and questions, which stimulated me to improve and clarify the text, but we did have to agree to put our di?erences of scienti?c opinions aside so as not to delay the process. Without this invaluable help, this book would not be as “readable” as I hope it is now. The author uses this opportunity to express his sincere thanks to Michael and Judit for their signi?cant help and support. Although only about a year has gone after the preparation of the original edition of the book (in Russian), this English version of the manuscript has undergone considerable revision. These changes refer to Sections2. 2, 2.

Provides a summary of non-equilibrium glassy and amorphous structures and their macro- and microscopic thermal properties.The book contains a carefully selected works of fourteen internationally recognized scientists involving the advances of the physics and chemistry of the glassy and amorphous states.