Developments in Polymer Characterisation—1 PDF
Preview Developments in Polymer Characterisation—1
DEVELOPMENTS IN POLYMER CHARACfERISATION-l DEVELOPMENTS IN POLYMER CHARACTERISATION-l Edited by 1. V. DAWKINS Chemistry Department, Loughborough University of Technology, UK APPLIED SCIENCE PUBLISHERS LTD LONDON APPLIED SCIENCE PUBLISHERS LTD RIPPLE ROAD, BARKING, ESSEX, ENGLAND British Library Cataloguing in Publication Data Developments in polymer characterisation. I. I. Polymers and polymerization-Analysis I. Dawkins, J V 547'.84 QD139.P6 ISBN -13: 978-94-009-9648-9 e-ISBN-13: 978-94-009-9646-5 DOl: 10.1007/ 978-94-009-9646-5 WITH 21 TABLES AND 86 ILLUSTRATIONS © APPLIED SCIENCE PUBLISHERS LTD 1978 Softcover reprint of the hardcover I st edition 1978 All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publishers, Applied Science Publishers Ltd, Ripple Road, Barking, Essex, England PREFACE Over two decades ago, !he term characterisation covered just those techniques which measured the properties of polymers in solution in order to determine molecular weight and size. The discoveries of stereoregular polymers and polymer crystals created the need for new and advanced techniques for characterising chain structures and bulk properties. Further demands for new and improved characterisation methods for bulk polymers have resulted from the recent development and exploitation of multi phase polymeric systems, such as polymer blends, block and graft copolymers, and polymer composites. Today, therefore, characterisation is a very important part of polymer science. The polymer chemist must know the chain length, chain microstructure and chain conformation of the polymers he or she has prepared, i.e. the determination of molecular properties. The scientist involved in exploiting polymers in such applications as plastics, elastomers, fibres, surface coatings and adhesives must be informed on the morphology and physical and mechanical behaviour of his or her products, i.e. the determination of bulk and surface properties and their dependence on molecular properties. The techniques required for these determinations now cover an extremely wide field. Our aim has been to review a number of techniques critically and in sufficient depth so that the present state and future potential of each technique may be judged by the reader. Three criteria were used in the selection of techniques. First, we wished to present new methods which have been developed actively in the polymer field during the past five years. Both 13C nuclear magnetic resonance spectroscopy and small angle neutron scattering, applied to both bulk polymers and polymers in solution, are in this category, and both techniques have provided new and important v Vi PREFACE characterisation data which could not be obtained by other methods. Second, we wished to include the significant developments which have occurred recently in using established techniques for polymer character isation. These are (a) gel permeation chromatography-fast and efficient determinations of molecular weight distribution and average molecular weights; (b) light scattering-Brillouin scattering for transition tempera tures of polymeric solids, Rayleigh line broadening for diffusion coefficients of polymers in solution, and scattering measurements in the region between the binodal and spinodal in polymer solutions; (c) small angle X-ray scattering--characterisation of two-phase polymeric systems; (d) differen tial scanning calorimetry-quantitative thermodynamic interpretation of the glass transition, heat of fusion and crystallinity; (e) microscopy-range of methods for the surface topography of polymers. Third, we wished to include any technique which although well established has not been widely employed in polymer characterisation. In Chapter 2, the potential of mass spectrometry for studies of the structural characterisation and degradation behaviour of oligomers and polymers is described. It is hoped that the topics presented will appeal not only to specialists but also to those polymer scientists having a general interest in characterisation methods. CONTENTS Preface v List of Contributors IX 1. 13C NMR Spectroscopy of Polymers A. V. CUNLIFFE 2. Mass Spectrometry 41 R. D. SEDGWICK 3. High Performance Gel Permeation Chromatography 71 1. V. DAWKINS and G. YEADON 4. Light Scattering in Synthetic Polymer Systems 99 A. 1. HYDE 5. Molecular Dimensions of Amorphous Polymers by Neutron Scattering 117 R. W. RICHARDS 6. Recent Advances in the Study of Polymers by Small Angle X-ray Scattering 157 D. S. BROWN and R. E. WETTON 7. Quantitative Differential Scanning Calorimetry 205 M. 1. RICHARDSON VII viii CONTENTS 8. Microscopy of Polymer Surfaces 245 D. HEMSLEY Index 277 LIST OF CONTRIBUTORS D. S. BROWN Department of Chemistry, Loughborough University of Technology, Loughborough, Leicestershire LEI I 3TU, UK. A. V. CUNLIFFE Propellants, Explosives & Rocket Motor Establishment, Powdermill Lane, Waltham Abbey, Essex EN9 IBP, UK. 1. V. DAWKINS Department of Chemistry, Loughborough University of Technology, Loughborough, Leicestershire LEll 3TU, UK. D. HEMSLEY Institute of Polymer Technology, Loughborough University of Technology, Loughborough, Leicestershire LEll 3TU, UK. A. 1. HYDE Department ofP ure and Applied Chemistry, University ofStrathclyde, Thomas Graham Building, 295 Cathedral Street, Glasgow GI I XL, UK. R. W. RICHARDS Department of Pure and Applied Chemistry, University ofStrathclyde, Thomas Graham Building, Cathedral Street, Glasgow GI I XL, UK. ix x LIST OF CONTRIBUTORS M. 1. RICHARDSON Department of Industry, National Physical Laboratory, Teddington, Middlesex, UK. R. D. SEDGWICK Department of Chemistry, The Unirersity of Manchester Institute of Science and Technology, PO Box 88, Manchester M60 IQD, UK. R. E. WETTON Department of Chemistry, Loughborough Unirersity of Technology, Loughborough, Leicestershire LEI I 3TU, UK. G. YEADON Department of Chemistry, Loughborough Unirersity of Technology, Loughborough, Leicestershire LEI I 3TU, UK. Chapter 1 NMR SPECTROSCOPY OF POLYMERS 13C A. V. CUNLIFFE Propellants, Explosives & Rocket Motor Establishment, Waltham Abbey, UK SUMMARY An account is given of the application of13C N M R to polymer systems. The introduction emphasises the advantages and differences between carbon N M R and proton N M R. A brief description is given of the new techniques and instrumentation involved, including a discussion of the d(fficulties invoh'ed in accurate quantitative measurements. Applications of the technique are divided into three main areas. These are, high resolution structural studies, the study of polymer mobility from relaxation phenomena both in solution andfor solid elastomers, and the high resolution spectra ofs olids. Examples ofs tructural studies are chosen where 13C N M R has been successful in providing new information, and include studies of chain branching in polyethylene, tacticity measurements of vinyl polymers-particularly polypropylene, sequence distribution of copolymers and studies ofdiene polymers. An account is given of the various relaxation experiments which can be made on solutions and solid elastomers using conventional high resolution equipment, and of the way in which these can be interpreted to give information about polymer dynamics. Finally, 13C NMR experiments on the solid state are described which promise to greatly extend the usefulness of the NMR technique. 1
The list of books you might like
