Order in the Amorphous “State” of Polymers PDF
Preview Order in the Amorphous “State” of Polymers
ORDER IN THE AMORPHOUS "STATE" OF POLYMERS ORDER IN THE AMORPHOUS "ST ATE" OF POLYMERS Edited by Steven E. Keinath and Robert L. Miller Michigan Molecular Institute Midland, Michigan and James K. Rieke Dow Chemical Company Midland, Michigan PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging in Publication Data International Symposium on Order in the Amorphous "State" of Polymers (17th: 1985: Midland, Mich.) Order in the amorphous "state" of polymers. "Proceedings of the 17th International Symposium on Order in the Amorphous "State" of Polymers, held August 18-21,1985, in Midland, Michigan"-T.p. verso. Dedicated to Raymond F. Boyer in honor of his 75th birthday. Includes bibliographical references and indexes. 1. Polymers and polymerization-Congresses. 2. Phase rule and equilibriufn- Congresses. 3. Boyer, Raymond F. I. Keinath, Steven E., 1954- . II. Miller, Robert L., date. III. Rieke, James K. IV. Boyer, Raymond F. V. Title. QD380.I585 1985 530.4'1 87-7811 ISBN-13: 978-1-4612-9041-4 e-ISBN-13: 978-1-4613-1867-5 DOl: 10.1007/978-1-4613-1867-5 Proceedings of the 17th International Symposium on Order in the Amorphous "State" of Polymers, held August 18-21, 1985, in Midland, Michigan © 1987 Plenum Press, New York Softcover reprint ofthe hardcover lst edition 1987 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE In 1975, a symposium was held in Midland, Michigan, co-sponsored by the Dow Chemical Company and the then Midland Macromolecular Institute in honor of Raymond F. Boyer on the occasion of his 65th birthday and retirement from Dow. The topic of that first Boyer symposium dealt with an area of interest to Boyer, namely, polymer transitions and relaxations. One decade later, after ten years of additional fruitful scientific endeavor at MMI, Ray Boyer was again honored with a symposium, this time celebrating his 75th birthday and 10th anniversary at the Michigan Molecular Institute. The topic of the second Boyer symposium in 1985 was somewhat more focused, this time concentrating on the subject of order (or structure) in the amorphous state of polymers and the attendant polymer transitions that are observed. This volume contains the full manuscripts of the contributors to the 17th MMI International Symposium, held in Midland, Michigan on August 18-21, 1985. Eleven one-hour plenary lectures and ten 20-minute contributed papers were presented during the Symposium. An open forum panel discussion was also scheduled; the edited transcript of that session is included at the end of this volume. One of our tasks in organizing this Symposium was to attempt to gather together a number of speakers who would be able to define what, if any, physical structure might be present in anwrplwus polymers and what the nature of this order might be. The first section of this book begins with three reports by G.R. Mitchell, R.L. Miller, and 1.H. Wendorff on x-ray scattering studies of polymers and the implications of the experimental results toward identifying amorplwus structure. The paper by A. Yelon compares x-ray and neutron scattering results in polystyrene. P.H. Geil discusses the phenomenon of double glass transitions in ultraquenched, amorphous semicrystalline polymers. The final paper in this section by A. Hiltner discusses the nature of and transitions in polymer gels. Based upon this foundation of structural studies, we next include a great many discussants in the area of polymer transition studies. These contributions clearly indicate that a plethora of techniques are available to detect and observe transitions in temperature regions where polymers are traditionally considered to be amorphous. The reports on polymer transition studies take up the balance of this volume with the papers being grouped into two main subdivisions: (1) contributions by Boyer and colleagues and (2) contributions by others. Transitions both above and below the glass transition temperature in amorphous polymers and above the melting point transition in semicrystalline polymers are discussed. A paper by R.F. Boyer leads off the second section with an exhaustive analysis of the inferences that may be made in postulating the existence of structure in anwrphous polymers. This paper is a significant companion paper to that published in late 1985 as a part of the first edition of v the Polymer Yearbook. The next paper by S.E. Keinath presents a capsule summary of about ten techniques developed at MMI over the past decade to study the Til transition above Tg. The four manuscripts that follow, by J.B. Enns, L.R Denny, K. Varadarajan, and D.R Smith, go into more detail on several of the techniques introduced in that paper. The third section of the book starts off with a paper by lK. Kruger who introduces several experimental techniques applied to the study of the Tu transition above T m in semicrystalline polymers. The next paper by C. Lacabanne illustrates the utility of the TSC technique in studying the Til transition in a wide range of polymers. lM.G. Cowie's paper discusses multiple transition behavior in a series of polymers based on itaconic acid derivatives; here, one frequently finds significantly strong polymer transitions arising from side chain motions. R.A. Bubeck and A. Letton next discuss the implications of sub-T relaxations in polycarbonate and polysulfone, g respectively, in regard to the physical aging phenomenon and long-term physical and mechanical properties of these materials. The paper by J.P. Ibar questions the fundamental thermodynamic nature of multiple transition phenomena and suggests that the T p, Tg, and Til transitions may all be derived from a single primary relaxation process. A clear case of polymer physical integrity in the melt above Tg is presented in the next two papers by B. Maxwell and C.P. Bosnyak, both of which indicate that at least one and maybe two rheologically detected transitions are present in polystyrene above Tg. The final paper in this section by R.D. Sanderson presents some recent work in measuring the amount of energy released from stressed polymer samples upon heating them above the Til transition temperature range. One of the delights we experienced during the Symposium was the enthusiastic discussion engendered by each of the speaker's presentations. An edited transcript of the discussion period following each of the talks is appended to each of the respective papers in this volume; some of these question/answer sessions were quite lively. In addition, an edited transcript of a round-table panel discussion held at the end of the Symposium appears as the fourth section of this volume. Finally, an all-inclusive name index and an extensive cross-referenced subject index appear at the end of the volume for the convenience of the reader. No organized symposium or published proceedings volume ever comes to fruition without the assistance of many willing helpers. First, we'd like to acknowledge those individuals that helped make the Symposium itself run smoothly. These include S.l Butler (Symposium Secretary) for her role in coordinating all physical arrangements for meals, lodging, and transportation for the speakers and attendees; K.P. Battjes and RA. Long for their assistance in doing almost anything and everything that needed to be done at a moment's notice to serve the needs of the symposium participants; and K.P. Battjes for preparing the first typed draft transcript of the question/answer sessions and the panel discussion. Three organizations are acknowledged for providing additional support in the form of external funding: Dow Chemical Company, Midland, Michigan; Dow Coming Corporation, Midland, Michigan; and the Army Research Office, Research Triangle Park, North Carolina. Without their financial support we would not have been able to run the style of meeting that we did. All manuscript submissions were retyped using either an Exxon word processor or an.Apple Macintosh computer. Three typists had a hand in the preparation of the word-processed manuscripts: K.J. Costley, S.A. Matzek, and K.A. Thomas, the last of which keyboarded nearly half of the final pages before leaving the Midland area. We are indeed indebted to D.R. Smith for providing many, many hours of computer expertise and counseling in getting us up and running and working out all the vagaries of merging Exxon and Macintosh files, figuring out ways for doing the special typing requirements we needed, and suggesting word processing formats that appeared just vi right when printed with a laser printer. Finally, we acknowledge with appreciation all of the individual contributors to this volume who responded in a timely manner working with the Editors to bring this proceedings volume to final publication as quickly as possible. Steven E. Keinath Michigan Molecular Institute Robert L. Miller Michigan Molecular Institute James K. Rieke Dow Chemical Company vii RAYMOND F. BOYER DEDICATION This volume is dedicated to Dr. Raymond F. Boyer, Research Professor of Polymer Physics and Affiliate Scientist at the Michigan Molecular Institute, in honor of his 75th birthday and 10th anniversary at MMI. Boyer is one of the world's leading scientists in macromolecular physics. His fields of specialization include: the glass transition temperature, multiple transitions in polymers, molecular weight and molecular weight distributions, and physical property -chemical structure correlations. His experimental and theoretical studies on multiple transitions and relaxations in amorphous and semicrystalline polymers, and more recently with special emphasis on the liquid state, are widely recognized by the international scientific community. When Ray Boyer joined MMI in 1975 upon his retirement from a very successful40-year career at the Dow Chemical Company, he had some 90 publications to his credit. By 1985, after one short decade at MMI, he had nearly doubled this figure, primarily \yriting and publishing in the area of polymer transitions and relaxations, in particular, transitions in the liquid state. Boyer was named as Honorary Chairman of the Symposium from which this proceedings volume is derived in recognition of his pioneering research effort in this area. It is both fitting and proper for this volume to be dedicated to Dr. Raymond F. Boyer. ix BIOGRAPIllCAL SKETCH OF RAYMOND F. BOYER Birthdate and Place February 6, 1910, Denver, Colorado. Education B.S., Physics (1933) Case Institute of Technology M.S., Physics (1935) Case Institute of Technology D.Sc. (Honorary) (1955) Case Institute of Technology Professional Experience 1935-75 Dow Chemical Company Various research and research administration posts in the field of polymers, Assistant Director of Corporate Research at retirement, named as Dow's first Research Fellow in 1972. 1975 to date Michigan Molecular Institute Currently Research Professor of Polymer Physics and Affiliate Scientist. Adjunct Professorships 1979 Case Western Reserve University 1980 Central Michigan University 1986 Michigan Technological University Inyited Visitin~ Professorships 1972 Guest, Soviet Academy of Sciences 1973 Guest, Polish Academy of Sciences 1974 Case Western Reserve University 1975 Senior Visiting Fellow, University of Manchester 1978 Guest, Soviet Academy of Sciences 1980 Guest, Soviet Academy of Sciences x Honors and A wards 1968 International Award in Polymer Science and Engineering, Society of Plastics Engineers 1970 Borden Award in Organic Coatings and Plastics Chemistry, American Chemical Society 1972 Biennial Swinburne Award, Plastics Institute of Great Britain 1978 Elected to the National Academy of Engineering 1983 Best Papers A ward, Midland Section of Sigma Xi 1985 Midland Section Award, Midland Section of the American Chemical Society Professional Associations American Association for the Advancement of Science American Chemical Society American Physical Society (Fellow) National Academy of Engineering New York Academy of Sciences Sigma Xi Society of Plastics Engineers Professional Listinis Who's Who in the World Who's Who in America American Men and Women of Science Publications Author of over 180 publications on molecular weight distributions, plasticizer behavior, and polymer transitions and relaxations, 21 patents in the field of light and heat stabilizers for plastics, and 344 internal scientific publications of the Dow Chemical Company, and editor of four books. Editorships Journal ofA pplied Polymer Science (advisory board until mid-1983) Journal of Macromolecular Science, Physics (advisory board) Macromolecules (member, original editorial advisory board) Polymer News (editorial board) xi
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