ADVANCING MATERIALS RESEARCH

National Academy of Engineering

National Academy of Sciences

with the participation of the National Materials Advisory Board and the Solid State Sciences Committee of the National Research Council

Peter A.Psaras and H.Dale Langford, editors

Foreword by Frederick Seitz

NATIONAL ACADEMY PRESS
Washington, D.C.
1987



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Advancing Materials Research ADVANCING MATERIALS RESEARCH National Academy of Engineering National Academy of Sciences with the participation of the National Materials Advisory Board and the Solid State Sciences Committee of the National Research Council Peter A.Psaras and H.Dale Langford, editors Foreword by Frederick Seitz NATIONAL ACADEMY PRESS Washington, D.C. 1987

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Advancing Materials Research National Academy Press 2101 Constitution Ave., NW Washington, DC 20418 The National Academy of Sciences is a private organization chartered by the United States Congress in 1863 to advise the federal government on questions of science and technology. The National Academy of Engineering is a private organization established in 1964 to share in the chartered responsibilities of the National Academy of Sciences. The National Research Council was established in 1916 and is the operating division of the two Academies. Funds for the program on Advancing Materials Research were provided by the National Science Foundation (Grant No. DMR-8511336), the Defense Advanced Research Projects Agency of the Department of Defense, the Department of Energy, the Andrew W.Mellon Foundation, Carnegie Corporation of New York, and the Technological Leadership Program of the National Academy of Engineering. A program initiative designed to lead to a funded project on this topic also led to the development of this report. The initiative was approved by the National Research Council Fund’s Committee, whose members are the Presidents of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine. The views expressed in this volume are those of the authors and are not presented as those of the sponsors. Library of Congress Cataloging-in-Publication Data Advancing materials research. Based on presentations and discussions from a symposium held in Washington, D.C., 28–29 Oct. 1985. Bibliography: p. Includes index. 1. Materials—Research—Congresses. I. Psaras, Peter A. II. Langford, H.Dale. III. National Academy of Engineering. IV. National Academy of Sciences (U.S.) TA404.2.A39 1986 620.1′1 86–23656 ISBN 0-309-03697-6 Copyright © 1987 by the National Academy of Sciences No part of this book may be reproduced by any mechanical, photographic, electronic or phonographic recording system, nor may it be stored in a retrieval system, transmitted or otherwise copied for public or private use without written permission from the publisher, except for the purposes of official use by the United States government. Printed in the United States of America ON THE COVER (left to right): Top row: Potter in his workshop, from The Progress of Man and Society, John Trusler, 1791; Computed diffraction pattern for an ideal icosahedral quasicrystal; Bakelite billiard and cue balls, 1910, courtesy of Union Carbide Corporation. Middle row: Water wheel, from The Iconographic Encyclopedia of Science, Literature, and Art, 1851; Silicon wafer, courtesy of IBM Corporation; Corinthian capital, from The Iconographic Encyclopedia. Bottom row: Glass blower, from The Progress of Man and Society; Schematic of cross-linking in a polymer negative resist used in fabricating integrated circuits; Machine part, Jeff Zaraba/FOLIO. First Printing, November 1986 Second Printing, July 1987 Third Printing, September 1988

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Advancing Materials Research ADVISORY COMMITTEE MEMBERS THEODORE H.GEBALLE,* Director, Center for Materials Research, Stanford University DAVID WHITE,* Director, Laboratory for Research on the Structure of Matter, University of Pennsylvania WILLIAM O.BAKER, Former Chairman, Board of Directors, AT&T Bell Laboratories JOHN BARDEEN, Professor of Electrical Engineering and Physics Emeritus, University of Illinois at Urbana-Champaign ARDEN L.BEMENT, JR., Vice President, Technical Resources, TRW Inc. WILLIAM F.BRINKMAN, Vice President, Research, Sandia National Laboratories PRAVEEN CHAUDHARI, Vice President, Science, International Business Machines Corporation MORREL H.COHEN, Senior Scientific Advisor, Exxon Research and Engineering Company HENRY EHRENREICH, Clowes Professor of Science, Division of Applied Science, Harvard University MORRIS E.FINE, Walter P.Murphy Professor of Materials Science and Engineering and Associate Dean for Graduate Studies and Research, Northwestern University ROBERT GOMER, Carl W.Eisendrath Distinguished Service Professor of Chemistry, University of Chicago STIG B.HAGSTROM, Manager, General Sciences Laboratory, Xerox Corporation N.BRUCE HANNAY, Former Vice President, Research and Patents, AT&T Bell Laboratories ARTHUR H.HEUER, Professor of Ceramics, Department of Metallurgy and Materials Science, Case Western Reserve University JOHN P.HIRTH, Professor, Department of Metallurgical Engineering, Ohio State University JURGEN M.HONIG, Professor of Chemistry, Purdue University JOHN K.HULM, Director, Corporate Research and Research & Development Planning, Westinghouse Electric Corporation HERBERT H.JOHNSON, Professor, Department of Materials Science and Engineering, Cornell University J.DAVID LITSTER, Director, Center for Materials Science and Engineering, Massachusetts Institute of Technology *   Cochairman, Advancing Materials Research Program

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Advancing Materials Research WILLIAM W. MULLINS, University Professor, Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University ALBERT NARATH, Vice President, Government Systems, AT&T Bell Laboratories ROGER S. PORTER, Professor, Department of Polymer Science and Engineering, University of Massachusetts FREDERICK SEITZ, President Emeritus, The Rockefeller University ROBERT L. SPROULL, President Emeritus and Professor of Physics, University of Rochester ROBERT J. STOKES, Principal Staff Scientist, Computer Sciences Center, Honeywell Incorporated JAN TAUC, L. Herbert Ballou Professor of Engineering and Physics, Materials Research Laboratory, Brown University GARETH THOMAS, Professor, Department of Materials Science and Mineral Engineering, Scientific Director, National Center for Electron Microscopy, University of California, Berkeley Program Staff Members JESSE H. AUSUBEL, Director, Program Office, National Academy of Engineering PENELOPE J. GIBBS, Administrative Assistant, National Academy of Engineering H.DALE LANGFORD, Editor, National Academy of Engineering PETER A. PSARAS,* Fellow, National Academy of Engineering *   Permanent affiliation: International Business Machines Corporation, Corporate Technical Institute, Thornwood, N.Y.

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Advancing Materials Research Contents FOREWORD Frederick Seitz   ix PREFACE AND ACKNOWLEDGMENTS Theodore H.Geballe and David White   xiii Part 1 HISTORICAL PERSPECTIVES         ADVANCES IN MATERIALS RESEARCH AND DEVELOPMENT William O.Baker   3     MATERIALS RESEARCH LABORATORIES: THE EARLY YEARS Robert L.Sproull   25     MATERIALS RESEARCH LABORATORIES: REVIEWING THE FIRST TWENTY-FIVE YEARS Lyle H.Schwartz   35

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Advancing Materials Research Part 2 THE STATUS OF SELECTED SCIENTIFIC AND TECHNICAL AREAS         PROGRESS AND PROSPECTS IN METALLURGICAL RESEARCH Morris Cohen   51     MICROSTRUCTURE AND MECHANICAL PROPERTIES OF METALS John P.Hirth   111     CONDENSED-MATTER PHYSICS AND MATERIALS RESEARCH Bertrand I.Halperin   131     QUASI-PERIODIC CRYSTALS: A REVOLUTION IN CRYSTALLOGRAPHY John W.Cahn and Denis Gratias   151     NEW AND ARTIFICIALLY STRUCTURED ELECTRONIC AND MAGNETIC MATERIALS Francis J.Di Salvo   161     MATERIALS RESEARCH IN CATALYSIS John H.Sinfelt   177     THE ROLE OF CHEMISTRY IN MATERIALS SCIENCE George M.Whitesides, Mark S.Wrighton, and George Parshall   203     ADVANCED CERAMICS Albert R.C.Westwood and Stephen R.Winzer   225     ORGANIC POLYMERS John D.Hoffman and Robert L.Miller   245     NEW WAYS OF LOOKING AT SURFACES E.Ward Plummer, Torgny Gustafsson, Donald R.Hamann, Ingolf Lindau, Douglas L.Mills, Calvin F.Quate, and Y.Ronald Shen   283

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Advancing Materials Research     MATERIALS SYNTHESIS AND PROCESSING William F.Brinkman   307 Part 3 CURRENT TOPICS IN MATERIALS RESEARCH         ENSURING CONTRIBUTIONS TO MATERIALS SCIENCE FROM SMALL-, INTERMEDIATE-, AND LARGE-SCALE SCIENCE Herbert H.Johnson, William D.Nix, Mildred S.Dresselhaus, Albert M.Clogston, and Praveen Chaudhari   321     PERSPECTIVES ON FACILITIES AND INSTRUMENTATION FOR MATERIALS RESEARCH Dean E.Eastman, Martin Blume, C.Peter Flynn, and J.David Litster   335     MATERIALS RESEARCH AND THE CORPORATE SECTOR Arden L.Bement, Jr., Julius J.Harwood, John K. Hulm, Harold W.Paxton, and Alan G.Chynoweth   347 CONTRIBUTORS   369 INDEX   377

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Advancing Materials Research This page in the original is blank.

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Advancing Materials Research Foreword The field of materials research has an extended past as well as a long and promising future. As an area of human technical endeavor it is as old as Homo faber—the first member of our species to seek a stone or piece of wood to help accomplish a difficult task. The field came a long way as an empirical art in the hands of successive generations of individuals who sought to reach out ever further in helping their local societies develop a better physical relationship with the surrounding world. The edge of a stone sharpened by flaking was better for cutting or scraping than a typical natural stone. Flint and obsidian had great advantages over the more common fieldstone. A hafted stone hammer could be more effective in certain situations than a stone merely held in the hand. Copper, and particularly bronze, was less brittle and more malleable than stone. Moreover, it was learned that the metals could be melted and cast into form. Iron eventually proved better than bronze, and was much more available than copper and tin once one learned to reduce its ores with carbon, although it was probably first used in the relatively rare meteoric form—“skystone” to the ancients. Perhaps what is most significant about materials research throughout its history is that, in parallel with the development of social organization and advances in the art of language, it tended to be a major limiting factor in determining the rate at which civilization could advance. The effectiveness of equipment of all kinds is conditioned in substantial part by the materials of which it is made. The nature and quality of materials in a device are as important as the ingenuity with which it is designed. Moreover, improvements in equipment have increased working efficiency and permitted greater freedom in society to promote both the expansion of population and the degree of specialization of those engaged in arts, crafts, and the management

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Advancing Materials Research of social organization. In the past as at present, materials research became a major factor in setting the pace of civilization. In the days before the formalization of modern science, the art of materials research was guided as much by mysticism or ritual magic as by logical reason. The metallurgist and the ceramicist were looked upon as practitioners of the black arts, as well as creators of indispensable products. Although they were neither of the nobility nor of the warrior or priestly classes, they gained a special position of veneration in society. The god of technology in Roman mythology—Vulcan—is a lame, swarthy genius who is among the least-favored of the gods. Yet, in recognition of his ingenuity and service, he is given as his wife Venus, the goddess of love and beauty. In medieval literature the processor of materials was looked upon as a close cousin of the alchemist. Basic science in the modern sense first worked its way into materials research almost through the back door with the rise of the science of chemistry. This started some 200 years ago at the time of the first clear understanding of the nature of elements of which matter is composed. Actually, the process of wedding fields such as metallurgy and ceramics to science was slow, even though inevitable, because the development of useful materials depended fully as much on the art of fabrication as on the raw chemical composition of the product. This bifurcation in the technological base is reflected in more modern times by the emergence of the concept of “structure sensitivity” of materials—a concept that retained an aura of mysticism until the past few decades. Nevertheless the die was cast. Materials research could not escape becoming a field of modern science even though nearly two centuries were required for the transition to become complete. It was helped along by applications of the optical microscope, x-ray and neutron diffraction, and the electron microscope—devices and techniques that became increasingly indispensable as new demands and new standards arose. Interestingly enough, the purely scientific study of materials emerged in the last century as a result of the curiosity of chemists, physicists, and mineralogists and generated basic questions that have had a major impact on the evolution of the mainstream of modern science, particularly what is now called quantum physics. One thinks of the first observation of photoelectric emission from metal surfaces and of the deviations of specific heats of condensed matter at low temperatures from the values predicted by Dulong and Petit’s law, or of the fundamental concern raised by such phenomena as the anomalous Hall effect and superconductivity regarding quantitative aspects of electron conduction in metals, insulators, and semiconductors. Alongside of this were, of course, scientific observations on material systems that were intriguing in their own right as part of the lore surrounding subsystems. Notable examples are the studies of slip bands and associated phe-

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Advancing Materials Research nomena in single crystals of metals and salts, the observations of internal photoconductivity and photoluminescence in condensed systems, the discovery of the rectification of electric currents at interfaces between solids, and the study of the special elastic and plastic properties of what we now term polymeric materials. The transition of materials research from a primarily empirical, technological endeavor to a truly scientific endeavor achieved its climax in the period following World War II. A large contingent of imaginative and talented young scientists from several disciplines joined in a concerted study of materials with the intention of leaving no area of investigation unexplored. They brought to bear high standards of precision and analysis in both experiment and theory. This movement has continued almost unabated. Whatever the initial impetus for the movement may have been, there is little doubt that it has been sustained at a substantial level in academic, industrial, and governmental laboratories on an international scale in significant part because of its influence on many areas of technology, including electronics, optics, ceramics, metallurgy, and plastics. In fact, much of the advanced exploratory research is now carried on as a normal part of the engineering disciplines. This includes fields such as chemical engineering, in which there is much interest in catalysts as well as the behavior of materials in severe environments. It is interesting to note that some of the techniques that were exploited along the way to gain a deeper understanding of organic and inorganic materials systems are now finding extensive use in biochemistry and medicine. Not least among these techniques are x-ray diffraction, nuclear resonance, and laser technology. The conference upon which this volume is based had a twofold goal: first, to commemorate the twenty-fifth anniversary of the Materials Research Laboratories in our country and, second, to demonstrate not only that the field is far from being exhausted but even more that the continued advance of the technological aspects of our complex civilization will inevitably be limited by advances in materials research. The field is and will remain one of the pacemakers that determine the nature and effectiveness of the devices we construct for the continued uplift of mankind. The present volume, while reviewing history and accomplishments and describing developments at today’s frontiers, also emphasizes the promises for the future. Some of these will emerge naturally as extensions of present work. Others will require new forms of instrumentation and the development of new techniques to optimize the use of such facilities. Here lies a challenge for our society. As is clearly described in the introductory chapters by William O.Baker, Robert L.Sproull, and Lyle H.Schwartz, the Department of Defense deserves much credit for initiating the first series of Materials Research Laboratories

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Advancing Materials Research in 1960. The department was influenced by a convincing and inspired report by Sproull and his colleagues and guided by the President’s Scientific Advisory Committee on which Baker played a key role. Moreover, we must not fail to recognize the important part played by the National Science Foundation a decade later when changing circumstances required that another agency assume the responsibility not only of accepting the sponsoring role, but of maintaining the standards and expanding the program as circumstances made possible. It was my privilege to witness the germination and growth of the concept of the Materials Research Laboratories throughout the 1950s. It is a pleasure to emphasize here again the role played by John von Neumann, one of the most prescient scientists of our time. Had he not died prematurely (in 1957 at the age of 53), he would undoubtedly have initiated the laboratory system through his role as a commissioner in the Atomic Energy Commission and as an individual intensely interested in the application of research. His prescience was illustrated in many instances, not least in his early appreciation of the potentialities of the digital electronic computer and the transistor. FREDERICK SEITZ President Emeritus The Rockefeller University

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Advancing Materials Research Preface and Acknowledgments Twenty-five years ago the Advanced Research Projects Agency of the Department of Defense established at several universities the first in a network of Materials Research Laboratories. A symposium entitled Advancing Materials Research was held in Washington, D.C., on 28–29 October 1985 in part to celebrate that anniversary. For planners of the event, however, the opportunity proved irresistible to undertake a project to explore broadly the status and prospects in materials research. The timing was especially significant. The twenty-fifth anniversary of the Materials Research Laboratories marks on the one hand the end of the first generation of a major national effort in materials research. On the other hand, it marks the entry into an era when materials research is advancing at an ever-increasing pace, generating both scientific and technological opportunities. This volume is based on the discussions and formal presentations at the symposium. Anyone who scans these pages will be aware of the kinds of materials research carried out at university, industry, and government laboratories and leading to major advances in fields ranging from physics and chemistry to ceramics and metallurgy. Often the greatest excitement lies at the interfaces between fields or between basic science and engineering, and in fact we are now seeing a rapid diffusion of scientific advances in materials into new technology crucial to our well-being and security. Authors stress repeatedly that this flow of new technology requires a flow of talent nurtured through fundamental materials research. Evidence of the importance that members of the participating and sponsoring organizations attach to sustaining and extending materials research and training in the United States can be found in the chapters that follow. The project was designed to achieve several goals. One was to look to

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Advancing Materials Research the past for guidance to the future, and on that score we benefit from the perspective provided by those farsighted pioneers of 25 years ago, Frederick Seitz, William O.Baker, and Robert L.Sproull. Their combined contributions, and that of Lyle H.Schwartz, describe the birth of materials research in the United States and the status of the resulting educational experiment represented by the network of Materials Research Laboratories and other materials-oriented centers at universities throughout the country. Universities are naturally conservative institutions, slow to respond to new fields of study that affect time-honored disciplines. Thus, this experiment is still far from complete. Its success depends, as ever, on the development of academic programs that retain the strengths of individual disciplines yet afford the broad multidisciplinary perspective required in materials research and on the institutional infrastructure and external support mechanisms that underlie the effort. A second goal of the project was for a representative group of practitioners to provide snapshots of some of the frontiers of materials research and to help map these areas by showing as many of their features as possible. Obviously a single symposium could not survey this diverse field in its entirety. The chapters in Part 2 of this volume survey recent developments and future directions in selected areas of materials science and engineering— polymers, ceramics, metals, catalysis, crystallography, mechanical and microstructural properties of materials, artificially structured materials, electronic and magnetic materials, materials chemistry and surface science, solid-state physics, and materials processing. The authors have projected the excitement, vigor, and open-endedness of research at the Materials Research Laboratories and other interdisciplinary laboratories in universities, industry, and government. Although any selection of authors and subjects in so diverse an enterprise must be somewhat arbitrary, these timely surveys reaffirm one’s belief in the immense progress that multidisciplinary research is leading to, and they portray the breadth and depth of this flourishing field. All authors were encouraged to seek guidance from their peers; as a consequence, a rich, up-to-date selection of topics in materials research is presented. A third goal was to explore present-day issues in the objectives, organization, administration, methods, and progress of materials research. Thus, Part 3 of this volume presents the views of members of panels drawn from the academic, governmental, and industrial communities. In a rapidly developing field such as materials, established methods for allocation of resources must be adapted to the needs of an emerging science and technology, and there is ample room for different points of view. The discussions in Part 3 reveal organizational challenges to the institutions involved in materials research. Yet, a common theme of these discussions is that collaboration among individual scientists and researchers from different disciplines holds the key to continued success in materials science and engineering.

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Advancing Materials Research In this context, the report of the Committee on the Survey of Materials Science and Engineering (COSMAT) in 1974 provided a frame of reference for the symposium. That landmark survey, carried out under the direction of Morris Cohen and William O.Baker, covered new ground in linking the scientific and technical branches of materials research with each other and with other fields of science and technology. We have tried to continue in that tradition, and note with satisfaction that the symposium served as a focal point for the current National Research Council survey of materials science and engineering. It is our hope and expectation that this book will be helpful during the next few years while a successor to the COSMAT report is being prepared under the leadership of Merton C.Flemings and Praveen Chaudhari. The fourth and perhaps most important goal of the project, crystallized in the symposium itself, was to bring together the materials research community in the hope of developing greater consensus about its mission and needs. The community is diverse in its institutional and disciplinary bases. This diversity is the source of its richness and great scientific impact but also the cause for fragmentation that has made difficult the coherent articulation of its strengths and weaknesses. It was our hope that the symposium would enhance the cooperative spirit so much a part of the actual conduct of materials research and encourage dialogue between materials researchers and those in government and industry for whom materials are a key consideration. We are indebted to the speakers and the other participants for using the opportunity afforded by this symposium in this way. We also acknowledge the contributions that many others have made to the success of the symposium and the completion of this book. Much of the early impetus for the effort came from Lyle H.Schwartz. We are grateful to Morris E.Fine for providing the right links with the National Academy of Sciences and the National Academy of Engineering and to Robert M. White and Frank Press for their enthusiastic and timely backing. Among the many members of the Advisory Committee who took key roles, we would like to single out William O.Baker, Herbert H.Johnson, John K.Hulm, J.David Litster, and Albert Narath. Strong support came from the National Science Foundation (NSF), the Advanced Research Projects Agency of the Department of Defense (DOD), and the Department of Energy (DOE). We particularly note the constructive roles of Erich Bloch, Lewis Nosanow, and Adriaan de Graaf for NSF; Leo Young, Benjamin Wilcox, and Richard Reynolds for DOD; and Donald Stevens and Louis Ianniello for DOE. Numerous hands are required to go from an idea to a conference to a book, and in this regard we would like to thank Jesse H.Ausubel, Peter A.Psaras, Penelope J.Gibbs, and Loretta A.Sprissler of the National Academy of Engineering Program Office and H.Dale Langford, editor for the National Academy of Engineering. The offices of the Academy complex most concerned with materials, the National Materials Advisory Board (directed by

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Advancing Materials Research Klaus Zwilsky) and the Solid State Sciences Committee (tended by Donald C.Shapero), were most generous at several key points. Robert N.Smith and David Patterson ensured a remarkably smooth meeting program; Walter Boyne and Darlene Rose of the National Air and Space Museum proved gracious hosts for the MRLs’ twenty-fifth birthday celebration at the museum. Pamela Steele designed the memorable artwork for the meeting and the book’s cover, and James M.Gormley and Dorothy M.Sawicki provided experienced guidance in the publication process. Finally, we would like to recognize Roman J.Wasilewski, who very much would have liked to be a part of this activity. Roman died on 3 February 1985. Those of us who knew him remember his fierce dedication to the cause of materials research. We take this opportunity to recall the great efforts he exerted on our behalf and to dedicate these proceedings to his memory. THEODORE H.GEBALLE Director, Center for Materials Research Stanford University DAVID WHITE Director, Laboratory for Research on the Structure of Matter, and Professor of Chemistry, University of Pennsylvania