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.

Thermal analysis comprises a group of techniques used to determine the physical or chemical properties of a substance as it is heated, cooled, or held at constant temperature. It is particularly important for polymer characterization, but also has major application in analysis of pharmaceuticals and foodstuffs. This comprehensive handbook presents practical and theoretical aspects of the key techniques of DSC, TGA, TMA, DMA, and related methods. It also includes separate chapters on the glass transition, polymers, polymorphism, purity determination, and method development. The large number of practical examples included should inspire readers toward new ideas for applications in their own fields of work. The chapters are independent of one another and can be read individually in any desired order. Based on years of experience in thermal analysis of users, application specialists, consultants, and course instructors, this book provides practical help to newcomers, inexperienced users, and anyone else interested in the practical aspects of thermal analysis.

Thermal Analysis: From Introductory Fundamentals to Advanced Applications presents an easy-to-understand introduction to Thermal Analysis (TA) principles alongside in-depth coverage of the wide variety of techniques currently in use across several industries. It covers differential scanning calorimetry (DSC), temperature modulated DSC (TMDSC), differential thermal analysis (DTA), thermogravimetry (TG) or thermogravimetric analysis (TGA), thermomechanical analysis (TMA), differential photo-calorimetry (DPC), dynamic mechanical analysis (DMA), thermodilatometry (TD), dielectric thermal analysis (DEA), thermally-stimulated current (TSC), emanation thermal analysis (ETA), thermoluminescence (TL), fast scanning calorimetry (FSC), and microcalorimetry. Chapters define the various TA techniques, report the Temperature-Modulated DSC (TMDSC) method and its applications, especially its use for studying the thermodynamic properties of polymers and pharmaceuticals, focus on the potential of TA in materials science with applications in chemistry and engineering, demonstrate, in detail, the various applications of TA in food, electronic industries, solid-state reactions, chemistry of polymers and large directing agents, kinetic studies, demonstrate the crystal structure and phase changes occurring upon heating by TA, and the potential of TA in recycling and waste management. - Gives a solid introduction to the scientific principles of TA for those who are new to these techniques or need a deeper understanding - Illustrates concepts with more than 100 schematic and analysis curves, several flow charts, process diagrams and photographs - Contains chapters that cover the user of TA in materials science and crystal structures

Thermal Analysis techniques are used in a wide range of disciplines, from pharmacy and foods to polymer science, materials and glasses; in fact any field where changes in sample behaviour are observed under controlled heating or controlled cooling conditions. The wide range of measurements possible provide fundamental information on the material properties of the system under test, so thermal analysis has found increasing use both in basic characterisation of materials and in a wide range of applications in research, development and quality control in industry and academia. Principles and Applications of Thermal Analysis is written by manufacturers and experienced users of thermal techniques. It provides the reader with sound practical instruction on how to use the techniques and gives an up to date account of the principle industrial applications. By covering basic thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) including the new approach of Fast Scanning DSC, together with dynamic mechanical analysis (DMA /TMA) methods, then developing the discussion to encompass industrial applications, the book serves as an ideal introduction to the technology for new users. With a strong focus on practical issues and relating the measurements to the physical behaviour of the materials under test, the book will also serve as an important reference for experienced analysts.

The wide range of applications of thermal methods of analysis in measuring physical properties, studying chemical reactions and determining the thermal behaviour of samples is of interest to academics and to industry. These applications prompted the writing of this book, in the hope that the descriptions, explanations and examples given would be of help to the analyst and would stimulate the investigation of other thermal techniques. Thermal studies are a fascinating means of examining the samples and the problems brought to us by colleagues, students and clients. If time allows, watching crystals change on a hot-stage microscope, or measuring the properties and changes on a DSC or TG or any thermal instrument can be a rewarding activity, besides providing valuable analytical information. This book started from a series of lectures delivered at Kingston University and at meetings of the Thermal Methods Group of the United Kingdom. The collaboration and information supplied to all the contribu tors by colleagues and instrument manufacturers is most gratefully ack nowledged, as are the valuable contributions made at meetings of the International Confederation for Thermal Analysis and Calorimetry (ICT AC) and at the European Symposia on Thermal Analysis and Calorimetry (ESTAC).

Presents a solid introduction to thermal analysis, methods, instrumentation, calibration, and application along with the necessary theoretical background. Useful to chemists, physicists, materials scientists, and engineers who are new to thermal analysis techniques, and to existing users of thermal analysis who wish expand their experience to new techniques and applications Topics covered include Differential Scanning Calorimetry and Differential Thermal Analysis (DSC/DTA), Thermogravimetry, Thermomechanical Analysis and Dilatometry, Dynamic Mechanical Analysis, Micro-Thermal Analysis, Hot Stage Microscopy, and Instrumentation. Written by experts in the various areas of thermal analysis Relevant and detailed experiments and examples follow each chapter.

Thermal Analysis deals with the theories of thermal analysis (thermodynamics, irreversible thermodynamics, and kinetics) as well as instrumentation and techniques (thermometry, differential thermal analysis, calorimetry, thermomechanical analysis and dilatometry, and thermogravimetry). Applications of thermal analysis are also described. This book consists of seven chapters and begins with a brief outline of the history and meaning of heat and temperature before listing the techniques of thermal analysis. The reader is then introduced to the basis of thermal analysis, paying particular attention to the macroscopic theories of matter, namely, equilibrium thermodynamics, irreversible thermodynamics, and kinetics. The next chapter discusses thermometry, focusing on the international temperature scale and the techniques of measuring temperature. Examples of heating and cooling curves are linked to the discussion of transitions. The groundwork for a detailed understanding of transition temperature is given. The chapters that follow explore the principles of differential thermal analysis, calorimetry, thermomechanical analysis and dilatometry, and thermogravimetry. This book is intended for the senior undergraduate or beginning graduate student, as well as for the researcher and teacher interested in thermal analysis.