Fluoropolymers 2 Properties TOPICS IN APPLIED CHEMISTRY Series Editor: Alan R. Katritzky, FPS University of Florida Gainesville, Florida Gebran J. Sabongi 3M Company St. Paul, Minnesota Current volumes in the series: ANALYSIS AND DEFORMATION OF POLYMERIC MATERIALS Paints, Plastics, Adhesives, and Inks Jan W. Gooch CHEMISTRY AND APPLICATIONS OF LEUCO DYES Edited by Ramaiah Muthyala FLUOROPOLYMERS 1: Synthesis FLUOROPOLYMERS 2: Properties Edited by Gareth Hougham, Patrick E. Cassidy, Ken Johns, and Theodore Davidson FROM CHEMICAL TOPOLOGY TO THREE-DIMENSIONAL GEOMETRY Edited by Alexandru T. Balaban LEAD-BASED PAINT HANDBOOK Jan W. Gooch ORGANIC PHOTOCHROMIC AND THERMOCHROMIC COMPOUNDS Volume 1: Main Photochromic Families Volume 2: Physicochemical Studies, Biological Applications, and Thermochromism Edited by John C. Crano and Robert J. Guglielmetti ORGANOFLUORINE CHEMISTRY Principles and Commercial Applications Edited by R. E. Banks, B. E. Smart, and J. C. Tatlow PHOSPHATE FIBERS Edward J. Griffith RESORCINOL Its Uses and Derivatives Hans Dressler A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher. Fluoropolymers 2 Properties Edited by Gareth Hougham IBM T. J. Watson Research Center Yorktown Heights, New York Patrick E. Cassidy Southwest Texas State University San Marcos, Texas Ken Johns Chemical and Polymer Windlesham, Surrey, England Theodore Davidson Princeton, New Jersey Kluwer Academic Publishers NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW eBook ISBN 0-306-46919-7 Print ISBN 0-306-46061-0 ©2002 Kluwer Academic Publishers New York, Boston, Dordrecht, London, Moscow Print ©1999 Kluwer Academic / Plenum Publishers, New York 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://www.kluweronline.com and Kluwer's eBookstore at: http://www.ebooks.kluweronline.com Contributors Shinji Ando, Science and Core Technology Group, Nippon Telegraph and Telephone Corp. Musashino-shi, Tokyo 180, Japan. Present address: Department of Polymer Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152, Japan Karol Argasinski, Ausimont USA, Thorofare, New Jersey 08086 S. V. Babu, Department of Chemical Engineering, Clarkson University, Potsdam, New York 13699 Warren H. Buck, Ausimont USA, Thorofare, New Jersey 08086 Jeffrey D. Carbeck, Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139. Present address: Department of Chemical Engineering, Princeton University, Princeton, New Jersey 08544 Stephen Z.D. Cheng, Maurice Morton Institute and Department of Polymer Science, University of Akron, Akron, Ohio 44325-3909 Theodore Davidson, 109 Poe Road, Princeton, New Jersey 08540 C. R. Davis, IBM, Microelectronics Division, Hopewell Junction, New York 12533 Ronald K. Eby, Institute of Polymer Science, University of Akron, Akron, Ohio 44325 v vi Contributors F. D. Egitto, IBM, Microelectronics Division, Endicott, New York 13760 Barry L. Farmer, Department of Materials Science and Engineering, University of Virginia, Charlottesville, Virginia 22903 Vassilios Galiatsatos, Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio 44325-3909. Present address: Huntsman Polymers Corpora- tion, Odessa, Texas 79766 Raj N. Gounder, The Boeing Company, Seattle, Washington 98 124-2499 Mark Grenfell, 3M Company, St. Paul, Minnesota 55144-1000 Frank. W. Harris, Maurice Morton Institute and Department of Polymer Science, University of Akron, Akron, Ohio 44325-3909 David B. Holt, Department of Materials Science and Engineering, University of Virginia, Charlottesville, Virginia 22903 Gareth Hougham, IBM, T. J. Watson Research Center, Yorktown Heights, New York 10598 Ken Johns, Chemical and Polymer (UK), Windlesham, Surrey, GU20 6HR, United Kingdom Fuming Li, Maurice Morton Institute and Department of Polymer Science, University of Akron, Akron, Ohio 44325-3909 Shiow-Ching Lin, Ausimont USA, Thorofare, New Jersey 08086 Roberta Marchetti, Centro Ricerche & Sviluppo, Ausimont S.p.A., 20021 Bollate, Milan, Italy Tohru Matsuura, Science and Core Technology Group, Nippon Telegraph and Telephone Corp., Musashino-shi, Tokyo 180, Japan Re’gis Mercier, UMR 102, IFP/CNRS, 69390 Vernaison, France Stefano Radice, Centro Ricerche & Sviluppo Ausimont S.p.A., 20021 Bollate, Milan, Italy Paul Resnick, DuPont Fluoroproducts, Fayetteville, North Carolina 28306 Contributors vii Gregory C. Rutledge, Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 Aldo Sanguineti, Centro Ricerche & Sviluppo, Ausimont S.p.A., 20021 Bollate Milan, Italy Shigekuni Sasaki, Science and Core Technology Group, Nippon Telegraph and Telephone Corp., Musashino-shi, Tokyo 180, Japan Massimo Scicchitano, Centro Ricerche & Sviluppo, Ausimont S.p.A., 20021 Bollate, Milan, Italy B. Jeffrey Sherman, Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio 44325-3909 Bernard Sillion, UMR 102, IFP/CNRS, 69390 Vernaison, France Carrington D. Smith, UMR 102 IFP/CNS 69390 Vemaison, France. Present address: Air Products and Chemicals Inc., Allentown, Pennsylvania 18195-1501 Gordon Stead, Chemical and Polymer (UK), Windlesham, Surrey, GU20 6HR, United Kingdom William Tuminello, DuPont Company, Experimental Station, Wilmington, Dela- ware 19880-0356 Stefano Turri, Centro Ricerche & Sviluppo, Ausimont S.p.A., 20021 Bollate, Milan, Italy Richard Thomas, DuPont, Jackson Laboratory, Deepwater, New Jersey 08023 Huges Waton, CNRS Service Central d’Analyses, 69390, Vemaison, France David K. Weber, 101 County Shire Drive, Rochester, New York 14626 Sheldon M. Wecker, Abbot Laboratories, Abbott Park, Illinois 60064 Preface The fluorine atom, by virtue of its electronegativity, size, and bond strength with carbon, can be used to create compounds with remarkable properties. Small molecules containing fluorine have many positive impacts on everyday life of which blood substitutes, pharmaceuticals, and surface modifiers are only a few examples. Fluoropolymers, too, while traditionally associated with extreme high- performance applications have found their way into our homes, our clothing, and even our language. A recent American president was often likened to the tribology of PTFE. Since the serendipitous discovery of Teflon at the DuPont Jackson Laboratory in 1938, fluoropolymers have grown steadily in technological and marketplace importance. New synthetic fluorine chemistry, new processes, and new apprecia- tion of the mechanisms by which fluorine imparts exceptional properties all contribute to accelerating growth in fluoropolymers. There are many stories of harrowing close calls in the fluorine chemistry lab, especially from the early years, and synthetic challenges at times remain daunting. But, fortunately, modem techniques and facilities have enabled significant strides toward taming both the hazards and synthetic uncertainties, In contrast to past environmental problems associated with fluorocarbon refrigerants, the exceptional properties of fluorine in polymers have great environmental value. Some fluoropolymers are enabling green technologies such as hydrogen fuel cells for automobiles and oxygen-selective membranes for cleaner diesel combustion. Curiously, fluorine incorporation can result in property shifts to opposite ends of a performance spectrum. Certainly with reactivity, fluorine compounds occupy two extreme positions, and this is true of some physical properties of fluoro- polymers as well. One example depends on the combination of the low electronic polarizability and high dipole moment of the carbon–fluorine bond. At one extreme, some fluoropolymers have the lowest dielectric constants known. At the other, closely related materials are highly capacitive and even piezoelectric. ix x Preface Much progress has been made in understanding the sometimes confounding properties of fluoropolymers. Computer simulation is now contributing to this with new fluorine force fields and other parameters, bringing realistic prediction within reach of the practicing physical chemist. These two volumes attempt to bring together in one place the chemistry, physics, and engineering properties of fluoropolymers. The collection was intended to provide balance between breadth and depth, with contributions ranging from the introduction of fluoropolymer structure-property relationships, to reviews of subfields, to more focused topical reports. GGH Acknowledgments Gareth Hougham thanks G. Teroso, IBM, K. C. Appleby, D. L. Wade, R. H. Henry, and IS. Howell. Patrick Cassidy expresses his appreciation to the Robert A. Welch Foundation, the National Aeronautics and Space Administration, the National Science Foundation, and the Institute for Environmental and Industrial Science at Southwest Texas State University. Ken Johns thanks Diane Kendall and Catherine Haworth, Senior Librarian, of the Paint Research Association. Theodore Davidson wishes to acknowledge his students and collaborators who have shared in the work on polytetrafluoroethylene. Sincere thanks go to Professor Bernhard Wunderlich for providing the stimulus for a career in polymer science.