75 Advances in Polymer Science

Transcription

1 75 Advances in Polymer Science

2 Epoxy Resins and Composites II Editor: K. DuSek With Contributions by J. I? Bell, L. T Drzal, J. L. Koenig, E. Mertzel, B.A. Rozenberg, R G. Schmidt With 78 Figures and 22 Tables Springer-Verlag Berlin Heidelberg New York Tokyo

3 ISBN Springer-Veriag Berlin Heidelberg New Y ork Tokyo ISBN Springer-Verlag NewYork Heidelberg Berlin Tokyo Library of Congress Catalog Card Number This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically those of translation, reprinting, re-use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under 9: 54 of the German Copyright Law copies are made for other than private use, a fee is payable to Verwertungsgesellschaft Wart, Munich. 0 by Springer-Verlag Berlin Heidelberg 1986 Printed in GDR The use of registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting and Offsetprinting: Th. Miintzer, GDR; Bookbinding: Liideritz & Bauer, Berlin 2154/

4 Editors Prof. Henri Benoit, CNRS, Centre de Recherches sur les Macromolecules, 6, rue Boussingault, Strasbourg Cedex, France Prof. Hans-Joachim Cantow, Institut fur Makromolekulare Chemie der Universitlt, Stefan-Meier-Str. 31, 7800 Freiburg i. Br., FRG Prof. Gino Dall Asta, Via Pusiano 30, Milano, Italy Prof. Karel DuSek, Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, Prague 616, CSSR Prof. John D. Ferry, Department of Chemistry, The University of Wisconsin, Madison, Wisconsin 53706, U.S.A. Prof. Hiroshi Fujita, Department of Macromolecular Science, Osaka University, Toyonaka, Osaka, Japan Prof. Manfred Gordon, Department of Pure Mathematics and Mathematical Statistics, University of Cambridge CB2 lsb, England Prof. Gisela Henrici-Olive, Chemical Department, University of California, San Diego, La Jolla, CA 92037, U.S.A. Prof. Dr. habil. Giinter Heublein, Sektion Chemie, Friedrich-Schiller-Universitat, HumboldtstraDe 10, 69 Jena, DDR Prof. Dr. Hartwig Hhcker, Universitiit Bayreuth, Makromolekulare Chemie I, Universitatsstr. 30, 8580 Bayreuth, FRG Prof. Hans-Henning Kausch, Laboratoire de Polymeres, Ecole Polytechnique Fed&ale de Lausanne, 32, ch. de Bellerive, 1007 Lausanne, Switzerland Prof. Joseph P. Kennedy, Institute of Polymer Science, The University of Akron, Akron, Ohio 44325, U.S.A. Prof. Anthony Ledwith, Department of Inorganic, Physical and Industrial Chemistry, University of Liverpool, Liverpool L69 3BX, England Prof. Seizo Okamura. No. 24, Minamigoshi-Machi Okazaki, Sakyo-Ku. Kyoto 606, Japan Professor Salvador Olive, Chemical Department, University of California, San Diego, La Jolla, CA 92037, U.S.A. Prof. Charles G. Overberger, Department of Chemistry. The University of Michigan, Ann Arbor, Michigan , U.S.A. Prof. Helmut Ringsdorf, Institut fur Organische Chemie, Johannes-Gutenberg- Universitlt, J.-J.-Becher Weg 18-20, 6500 Mainz, FRG Prof. Takeo Saegusa, Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Kyoto, Japan Prof. Gilnter Victor Schulz, Institut fur Physikalische Chemie der Universitat, 6500 Maim, FRG Prof. William P. Slichter, Chemical Physics Research Department, Bell Telephone Laboratories, Murray Hill, New Jersey 07971, U.S.A. Prof. John K. Stille, Department of Chemistry. Colorado State University, Fort Collins, Colorado 80523, U.S.A.

5 Editorial With the publication of Vol. 51 the editors and the publisher would like to take this opportunity to thank authors and readers for their collaboration and their efforts to meet the scientific requirements of this series. We appreciate the concern of our authors for the progress of "Advances in Polymer Science" and we also welcome the advice and critical comments of our readers. With the publication of Vol. 51 we would also like to refer to a editorial policy: this series publishes invited, critical review articles of new developments in all areas of polymer science in English (authors may naturally also include workes of their own). The responsible editor, that means the editor who has invited the author, discusses the scope of the review with the author on the basis of a tentative outline which the author is asked to provide. The author and editor are responsible for the scientific quality of the contribution. Manuscripts must be submitted in content, language, and form satisfactory to Springer-Verlag. Figures and formulas should be reproducible. To meet the convenience of our readers, the publisher will include "volume index" which characterizes the content of the volume. The editors and the publisher will make all efforts to publish the manuscripts as rapidly as possible, i.e., at the maximum six months after the submission of an accepted paper. Contributions from diverse areas of polymer science must occasionally be united in one volume. In such cases a "volume index" cannot meet all expectations, but will nevertheless provide more information than a mere volume number. Starting with Vol. 51, each volume will contain a subject index. Editors Publisher

6 Preface This volume of ADVANCES IN POLYMER SCIENCE contains the first part of a series of critical reviews on selected topics concerning epoxy resins and composites. The last decade has been marked by an intense development of applications of epoxy resins in traditional and newly developing areas such as coatings, adhesives, civil engineering or electronics and high-performance composites. The growing interest in applications and requirements of high quality and performance has provoked a new wave in fundamental research in the area of resin synthesis, curing systems, properties of cured products and methods of their characterization. The collection of reviews to be published in ADVANCES IN POLYMER SCIENCE is devoted just to these fundamental problems. The epoxy resin-curing agent formulations are typical thermosetting systems of a rather high degree of complexity. Therefore, some of the formation-structure-properties relationships are still of empirical or semiempirical nature. The main objective of this series of articles is to demonstrate the progress in research towards the understanding of these relationships in terms of current theories of macromolecular systems. Because of the complexity of the problems discussed, the theoretical approaches and interpretation of results presented by various authors and schools may be somewhat different. It may be hoped, however, that a confrontation of ideas may positively contribute to the knowledge about this important class of polymeric materials. In view of the wide range of this area, it was impossible to publish all contributions in successive volumes of ADVANCES IN POLYMER SCIENCE. Part I was published in Vol. 72; Part II in this Vol. 75. Part III and Part IV will follow in the beginning of The reader may appreciate receiving a list of all contributions to the series EPOXY RESINS AND COMPOSITES to appear in ADVANCES IN POLYMER SCIENCE: M. T. Aronhime and J. K. Gillham (Princeton University, Princeton, N.J., USA)

7 X Preface The Time-Temperature-Transformation (TTT) Cure Diagram of Thermosetting Polymeric Systems A. Apicella and L. Nicolais (University of Naples, Naples, Italy) Effect of Water on the Properties of Epoxy Matrix and Composites (Part I, Vol. 72) J. M. Barton (Royal Aircraft Establishment, Farnborough, UK): The Application of Differential Scanning Calorimetry (DSC) to the Study of Epoxy Resins Curing Reactions (Part I, Vol. 72) W. Burchard (University of Freiburg, Freiburg i. Br., FRG) Branching in Epoxy Resins Based on Diglycidyl Ethers of Bisphenol A L. T. Drzal (Michigan State University, East Lansing, MI, USA) The Interphase in Epoxy Composites (Part II, Vol. 75) K. Dugek (Institute of Macromolecular Chemistry, Czechoslovak Academy of Sciences, Prague, Czechoslovakia) Network Formation in Curing of Epoxy" Resins M. Fedtke (Technical University, Merseburg, GDR) Elucidation of the Mechanism of Epoxy Curing by Model Reactions A. Gupta (Jet Propulsion Laboratory, Caltech, Pasadena, CA, USA) Mechanism and Kinetics of the Cure Process in Tetraglycidylmethane Dianiline-Diaminodiphenyl Sulphone Thermoset System T. Kamon and H. Furukawa (The Kyoto Municipal Research Institute of Industry, Kyoto, Japan) Curing Mechanism and Mechanical Properties of Cured Epoxy Resins J. L. Kardos and M. P. Dudukovi~ (Washington University, St. Louis. MO, USA) Void Growth and Transport During Processing of Thermosetting Matrix Composites A. J. Kinloch (Imperial College, London, UK) Mechanics and Mechanism of Fracture of Thermosetting Epoxy Polymers E. S. W. Kong (Hewlett-Packard Laboratories, Palo Alto, CA, USA) Physical Aging in Epoxy Matrices and Composites J. D. LeMay and F. N. Kelley (University of Akron, Akron, OH, USA) Structure and Untimate Properties of Epoxy Resisns F. Lohse, and H. Zweifel (Ciba-Geigy, Basle, Switzerland) Photocrosslinking of Epoxy Resins

8 Preface XI J. A. Manson, R. W. Hertzberg, G. Attalla, D. Shah, J. Hwang and J. Turkanis (Lehigh University, Bethlehem, PA, USA) Fatigue in Neat and Rubber-Modified Epoxies E. Mertzel and J. L. Koenig (Case Western Reserve University, Cleveland, OH, USA) Application of FT-IR and NMR to Epoxy Resins (Part 1I, Vol. 75) R. J. Morgan (Lawrence Livermore National Laboratory, Livermore, CA, USA) Structure-Properties Relations of Epoxies Used as Composite Matrices (Part I, Vol. 72) E. F. Oleinik (Institute of Chemical Physics, Academy of Sciences of USSR, Moscow, USSR) Structure and Properties of Epoxy-Aromatic Amine Networks in the Glassy State B. A. Rozenberg (Institute of Chemical Physics, Academy of Sciences of USSR, Moscow, USSR) Kinetics, Thermodynamics and Mechanism of Reactions of Epoxy Oligomers with Amines (Part II, Vol. 75) S. D. Senturia and N. F. Sheppard (Massachusetts Institute of Technology, Cambridge, MA, USA) Dielectric Analysis of Epoxy Cure R. G. Schmidt and J. P. Bell (University of Connecticut, Storrs, CT, USA) Epoxy Adhesion to Metals (Part II, Vol. 75) E. M. Yorkgitis, N. S. Eiss, Jr., C. Tran, G. L. Wilkes and J. E. McGrath (Virginia Polytechnic Institute, Blacksburg, VA, USA) Siloxane Modified Epoxy Resins (Part I, Vol. 72) The editor wishes to express his gratitude to all contributors for their cooperation. Prague, November 1985 Karet Du~ek (Editor)

9 Table of Contents The Interphase in Epoxy Composites L. T. Drzal Epoxy Adhesion to Metals R. G. Schmidt, J. P. Bell Application of Fr-IR and NMR to Epoxy Resins E. Mertzel, J. L. Koenig Kinetics, Thermodynamics and Mechanism of Reactions of Epoxy Oligomers with Amines B. A. Rozenberg Author Index Volumes Subject Index