Microcharacterization of materials is a rapidly advancing field. Among the many electron and ion probe techniques, the cathodoluminescence mode of an electron probe instrument has reached a certain maturity, which is reflected by an increas ing number of publications in this field. The rapid rate of progress in applications of cathodoluminescence techniques in characterizing inorganic solids has been especially noticeable in recent years. The main purpose of the book is to outline the applications of cath odoluminescence techniques in the assessment of optical and electronic proper ties of inorganic solids, such as semiconductors, phosphors, ceramics, and min erals. The assessment provides, for example, information on impurity levels derived from cathodoluminescence spectroscopy, analysis of dopant concentra tions at a level that, in some cases, is several orders of magnitude lower than that attainable by x-ray microanalysis, the mapping of defects, and the determination of carrier lifetimes and the charge carrier capture cross sections of impurities. In order to make the book self-contained, some basic concepts of solid-state phys ics, as well as various cathodoluminescence techniques and the processes leading to luminescence phenomena in inorganic solids, are also described. We hope that this book will be useful to both scientists and graduate students interested in microcharacterization of inorganic solids. This book, however, was not intended as a definitive account of cathodoluminescence analysis of in organic solids. In considering the results presented here, readers should re member that many materials have properties that vary widely as a function of preparation conditions."

This and its companion Volume 2 chronicle the proceedings of the First Technical Conference on Polyimides: Synthesis, Char acterization and Applications held under the auspices of the Mid Hudson Section of the Society of Plastics Engineers at Ellenville, New York, November 10-12, 1982. In the last decade or so there has been an accelerated interest in the use of polyimides for a variety of applications in a number of widely differing technologies. The applications of polyimides range from aerospace to microelectronics to medical field, and this is attributed to the fact that polyimides offer certain desirable traits, inter alia, high temperature stability. Polyimides are used as organic insulators, as adhesives, as coat ings, in composites, just to name a few of their uses. Even a casual search of the literature will underscore the importance of this class of materials and the high tempo of R&D activity taking place in the area of polyimides. So it was deemed that a conference on polyimides was both timely and needed. This conference was designed to provide a forum for discussion of various ramifications of polyimides, to bring together scientists and technologists interested in all aspects of polyimides and thus to provide an opportunity for cross-pollination of ideas, and to highlight areas which needed further and intensi fied R&D efforts. If the comments from the attendees are a baro meter of the success of a conference, then this event was highly successful and fulfilled amply its stated objectives.

Cryogenics is an emerging technology filled with promises. Many cryogenic systems demand the use of nonmetallics and composites for adequate or increased performance. Thermal and electrical insulations, potting for superconducting magnets' mechanical sta bility, and composite structures appear to be some of the most significant applications. Research on nonmetallics at cryogenic temperatures has not progressed to the degree of research on metals. Nor can room temperature research be extrapolated to low tempera tures; most polymers undergo a phase transformation to the glassy state below room temperature. Research by producers, for the most part, has not been prac tical, because, except for LNG applications, the market for large material sales is not imminent. There are, however, many government stimulated developmental programs. Research on nonmetallics thus is dictated by development project needs, which require studies orien ted toward prototype hardware and specific objectives. As a result, research continuity suffers. Under these conditions, periodic topical conferences on this subject are needed. Industry and uni versity studies must be encouraged. Designers and project research material specialists need to exchange experiences and data. Low temperature-oriented research groups, such as the National Bureau of Standards and the Institute for Technical Physics - Karlsruhe, must contribute by assisting with fundamentals, interpreting proj ect data, and contributing to project programs through their materials research."

Syracuse University and the Army Materials and Mechanics Research Center of Watertown, Massachusetts have conducted the Sagamore Army Materials Research Conference since 1954. In ce1ebration of the 25th Anniversary of this conference, these proceedings are dedicated to the founding members of the Sagamore Conferences. They are Prof. Dr. George Sachs, Dr. James L. Martin, Colonel Benjamin S. Mesik, Dr. Reinier Beeuwkes, Mr. Norman L. Reed and Dr. J. D. Lubahn. This vo1ume, ADVANCES IN METAL PROCESSING, addresses Rapid Solidification Processing, Powder Processing and Conso1idation, We1ding and Joining, Thermal and. Mechanica1 Processing, Meta1 Removal and Process Mode1ing. The dedicated assistance of Mr. Joseph M. Bernier of the Army Materials and Mechanics Research Center and He1en Brown DeMascio of Syracuse University throughout the stages of the conference p1anning and fina11y the pub1ication of this book is deep1y appreciated. Syracuse University Syracuse, New York The Editors vii CONTENTS OVERVIEW Materials Processing - A Perspective of the Field 1 M.C. Flemings and R. Mehrabian SESSION I RAPID SOLIDIFICATION PROCESSING B.B. Rath, Moderator Heat Flow Limitations in Rapid Solidification Processing . . . . . . . . . . . 13 R. Mehrabian, S.C. Hsu, C.G. Levi, and S. Kou Laser Processing of Materials . . . . . 45 B.H. Kear, E.M. Breinan, and E.R. Thompson Electrohydrodynamic Techniques in Metals 79 Processing . . . . . . . . . . ."

"Relativistic Methods for Chemists," written by a highly qualified team of authors, is targeted at both experimentalists and theoreticians interested in the area of relativistic effects in atomic and molecular systems and processes and in their consequences for the interpretation of the heavy element's chemistry.

The theoretical part of the book focuses on the relativistic methods for molecular calculations discussing relativistic two-component theory, density functional theory, pseudopotentials and correlations. The experimentally oriented chapters describe the use of relativistic methods in different applications focusing on the design of new materials based on heavy element compounds, the role of the spin-orbit coupling in photochemistry and photobiology, and chirality and its relations to relativistic description of matter and radiation.

This book is written at an intermediate level in order to appeal to a broader audience than just experts working in the field of relativistic theory.

This book arose from a symposium titled 'Transition Metal Carbides and Nitrides: Preparation, Properties, and Reactivity' organized by Jae Sung Lee, Masatoshi Nagai and myself. The symposium was part of the 1995 Congress of Pacific Rim Chemical Societies, held in Honolulu, Hawaii between December 17-22, 1995. The meeting was the first major conference to exclusively address the theme of metal carbides and nitrides, and brought together many of the major researchers in the field. Over 50 scientists and engineers reported their latest findings in five sessions of presentations and discussions. The book closely follows the topics covered in the conference: Theory of bonding Structure and composition Catalytic properties Physical properties New methods of preparation Spectroscopy and microscopy The book is unique in its coverage. It provides a general introduction to the properties and nature of the materials, but also covers their latest applications in a wide variety of fields. It should thus be of interest to both experts and nonexperts in the fields of material science, solid-state chemistry, physics, ceramics engineering, and catalysis. The first chapter gives an overview, and many of the chapters provide summaries of advanced topics. All contributions were peer-reviewed.

Self-assembly is undoubtedly a topic of special interest in current chemistry and is related to very wide scientific areas. Recent progress in this field seems to be featured by the construction of well-defined discrete systems exploiting complementary hydrogen bonding as well as coordination bonding. Seven leading international experts introduce the current topics in this very interesting field, focusing on two major subjects: organic assemblies and inorganic assemblies. All researchers who are interested in molecular recognition, material science, nanotechnology, and supramolecular chemistry will welcome this book as an inspiring source for creative research ideas.

Some of the more interesting elements in the chemistry of life are less commonly occuring ones such as nickel and molybdenum. This volume elucidates the chemistry of these elements in important enzymes and also explores the chemistry of elements that do not normally occur in biological molecules, but are useful in probing their structure and function. Topics include: Acquisition and transport of Ni. Mechanistic action of Ni in a wide variety of enzymes. Multielectron redox systems involving pterins in proteins. Chemistry of the pterin and flavin complexes of Mo, Fe, Cu and Ru ions. Replacement of iron in transferrin by a number of other metal ions. Use of polypyridyl complexes of ruthenium and other transition metals as probes of nucleic acid structure through photochemical reactions.

General The making and breaking of carbon-metal bonds is fundamental to all the p- cesses of organometallic chemistry and moreover plays a significant role in - mogeneous as well as heterogeneous catalysis. This rather blunt statement - phasises the extent to which a proper understanding of the structure, energetics and reactivity of C-M bonds is at the core of the discipline. In order to accept it, a proper definition of the terms involved is required. Quite simply we define the metal-carbon bond in its broadest sense to embrace carbon linked to transiti- metals, lanthanides and actinides, and main group metals. We do not dist- guish between formally covalent single or multiple bonding on the one hand and q-bonding on the other. In the studies to be described in the following chapters, the emphasis will be on transition metal complexes and insofar as the fun- mentals come under scrutiny, simple metal alkyls or related species (metal al- nyl, alkynyl, aryl, or allyl) will play an emphatic part. The central role of metal alkyls and their congeners and especially the role of their metal carbon linkage in homogeneous catalysis may be appreciated by considering some key reaction steps leading to their formation or breakdown. There follows a few prominent examples of transition metal mediated stoichiometric or catalytic processes: - In homogeneous hydrogenation of double bonds, the stepwise reaction of an q2-coordinated alkene with dihydrogen gives first an alkyl metal hydride, and then the decoordinated alkane by elimination.

After the success of the previous summer schools organized by the Nuclear Physics Division of the Netherlands' Physical Society in 1975 and 1977, we thought it worthwhile to continue this tradition. The immediate very positive reactions received from all invited speakers encouraged us to proceed with the orgaization. Although the number of students had to be restricted to about one hundred, the international character of the School was evident from about thirty nationalities which were represented. The material contained in this book covers the talks given by all speakers invited to lecture on the subject of nuclear structure research. These proceedings should therefore serve as an excellent introduction to many topics of current interest in this exciting field. We hope that the lectures and discussions as well as the many informal contacts made during the various social activities will greatly stimulate interest in nuclear structure investigations among all the participants. The organization of the summer school has been made possible by substantial support given by the Scientific Affairs Division of the North Atlantic Treaty Organization, the Netherlands' Ministry of Education and Science and the Netherlands' Physical Society. The invaluable help of the "Bureau Congressen" of the Ministry of Education and Science and the friendly assistance of the manage ment of the College of Agriculture in Dronten contributed greatly to the pleasant atmosphere during the summer school."

Phthalocyanines exhibit intriguing physic-chemical properties that render them important as a class of molecular functional materials. In addition to their tra- tional industrial applications as dyes and pigments, more recently their use as the organic semiconductors,photodynamictherapy medicines, non-linear optical ma- rials, catalysts for the photo oxidation, optical recording materials, and gas sensors attracts great research interests in these tetrapyrrole species. As manifested by the rapidly increasing number of related scienti?c publications in recent years, great progress has been made in the ?eld of advanced phthalocyaninematerials. Tremendous efforts have been paid toward the development of new phtha- cyanine molecular materials as well as toward their applications. Recent emphasis in both academic researches and technical ?eld has been put on the design and synthesis of novel phthalocyanine species, the structure-propertyrelationship, se- assembly properties, molecular electronics and opto-electronics, and dye-sensitized solarcells.Althoughexcellentreviewsandmonographsaboutphthalocyanineswere publishedseveralyearsago,it is time to providea surveyof a numberof newimp- tant developments in this fascinating area of phthalocyanine chemistry. The aim of this book is to bring both the academic and industrial researchers an easy way to the new progress of phthalocyanines made lately in related ?eld.

The present volume of this series, following the tradition of the previous volumes, covers three major lines of research on crystallization: growth from vapor and epitaxy, growth from solution, and growth from melt. As in the previous volumes, preference is given to papers that provide original results and reviews of results obtained by the authors and those from published sources, although some of the papers are either purely original or purely of review character. The first section deals with crystal growth from vapor and epitaxy and contains three papers. One of them, on artificial epitaxy, discusses and reviews published results from the last three years in this rapidly developing area. The results are used in outlining mechanisms for oriented film growth on amorphous substrates. Another paper in this section deals with classical epitaxy, namely oriented growth on single-crystal substrates, where some important conclusions are drawn from the growth of gallium nitride films on sapphire, which concern the orientation relationships in that pair of substances. The last paper in the section deals with film growth under ion bombardment (the corresponding techniques in film crystallization have already advanced from theory to practical applications).

Primarily, the aim of this book is to provide a reference work for senior students and research workers engaged in the synthetic aspects of chemistry. The various classes of compounds under discussion provide useful interme diates for the synthesis of numerous nitrogen-containing derivatives. Imidoyl halides are also intermediates in several classical name reactions, such as the Gattermann, Houben-Hoesch, and Vilsmeier-Haack syntheses of aldehydes and ketones, the Beckmann rearrangement, and the v. Braun degradation. Some imidoyl halides have shown interesting agricultural activities, and the generation of highly reactive species (ketenimines, nitrile oxides, nitrile imides, carbodiimides, etc.) from imidoyl halides has contributed to the study of polar cycloaddition reactions. To enable researchers to utilize this chemistry without consulting the original references, I have included a number of selected working examples. This procedure will facilitate the transformation of written information into well designed experiments, especially since part of the cited literature is not readily available. The book is organized around classes of imidoyl halides, with synthesis and chemistry discussed in an orderly fashion. The physical properties of the known imidoyl halides are listed in tables, and I have attempted to draw attention to the more recent literature. The one or two references provided for each compound represent those which best describe its physical constants and synthesis.

This book is intended to provide a fundamental basis for the study of the interaction of polymers with living systems, biochemicals, and with aqueous solutions. The surface chemistry and physics of polymeric materials is a subject not normally covered to any significant extent in classical surface chemistry textbooks. Many of the assumptions of classical surface chemistry are invalid when applied to polymer surfaces. Surface properties of polymers are important in the development of medical devices and diagnostic products. Surface properties are also of vital importance in fields such as adhesion, paints and coatings, polymer-filler interactions, heterogeneous catalysis, composites, and polymers for energy generation. The book begins with a chapter considering the current sources of information on polymer surface chemistry and physics. It moves on to consider the question of the dynamics of polymer surfaces and the implica tions of polymer surface dynamics on all subsequent characterization and interfacial studies. Two chapters are directed toward the question of model polymers for preparing model surfaces and interfaces. Complete treatments of X-ray photoelectron spectroscopy and attenuated total reflection infrared spectroscopy are given. There is a detailed treatment of the contact angle with particular emphasis on contact angle hysteresis in aqueous systems, followed by chapters on interfacial electrochemistry and interface acid-base charge-transfer properties. The very difficult problem of block and graft copolymer surfaces is also discussed. The problem of theoretical calculations of surface and interfacial tensions is presented. Raman spectroscopy is considered as an analytical technique for polymer surface characterization."

Since the early 1930's, Soviet chemists have played a lead ing role in the study of unfamiliar oxidation state compounds of the peroxide, superoxide, and ozonide types. Interest in the alkali and alkaline earth metal derivatives is now widespread and diverse, and numerous practical applications of these com pounds have evolved, ranging from their use as air revitaliza tion materials in space cabins to their use in compounding semiconductor materials. Professor Vol'nov is eminently qualified to write this monograph since for many years he has been a leading investi gator and prolific writer in the field of peroxide, superoxide, and ozonide chemistry. He has succeeded in presenting a lucid and detailed discussion of past work, the present state, and the future potential of this area of unfamiliar oxidation state chemistry. Of particular interest is Professor Vol 'nov's extensive compilation of available thermodynamic, kinetic, and structural data for the alkali and alkaline earth peroxides, superoxides, and ozonides. In addition, he has reviewed the known methods of synthesis, as well as the practical applications for which these compounds are suited. This monograph will be of interest and value to chemists, not only for the information it imparts, but equally for the information it does not impart, thereby illuminating the re search paths and investigation which must be undertaken in order to increase our knowledge concerning the chemistry of this important class of chemical compounds."

Phosphorus is essential to all life. A critical component of fertilizers, Phosphorus currently has no known substitute in agriculture. Without it, crops cannot grow. With too much of it, waterways are polluted. Across the globe, social, political, and economic pressures are influencing the biogeochemical cycle of phosphorus. A better understanding of this non-renewable resource and its impacts on the environment is critical to conserving our global supply and increasing agricultural productivity. Most of the phosphorus-focused discussion within the academic community is highly fragmented. Phosphorus, Food, and Our Future will bring together the necessary multi-disciplinary perspectives to build a cohesive knowledge base of phosphorus sustainability. The book is a direct continuation of processes associated with the first international conference on sustainable phosphorus held in the United States, the Frontiers in Life Sciences: Sustainable Phosphorus Summit, though it is not a book of conference proceedings; rather, the book is part of an integrated, coordinated process that builds on the momentum of the Summit. The first chapter will introduce the biological and chemical necessity of phosphorus. The subsequent ten chapters will explore different facets of phosphorus sustainability and the role of policy on future global phosphorus supplies. The final chapter will synthesize all of the emerging views contained in the book, drawing out the leading dilemmas and opportunities for phosphorus sustainability.

As natural minerals, silica and silicates constitute by far the largest part of the earth's crust and mantle. They are equally important as raw materials and as mass produced items. For this reason they have been the subject of scientific research by geoscientists as well as by applied scientists in cement, ceramic, glass, and other industries. Moreover, intensive fun damental research on silicates has been carried out for many years because silicates are, due to their enormous variability, ideally suited for the study of general chemical and crystallographic principles. Several excellent books on mineralogy and cement, ceramics, glass, etc. give brief, usually descriptive synopses of the structure of silicates, but do not contain detailed discussions of their structural chemistry. A number of monographs on special groups of silicates, such as the micas and clay min erals, amphiboles, feldspars, and zeolites have been published which con tain more crystal chemical information. However, no modern text has been published which is devoted to the structural chemistry of silicates as a whole. Within the last 2 decades experimental and theoretical methods have been so much improved to the extent that not only have a large number of silicate structures been accurately determined, but also a better under standing has been obtained of the correlation between the chemical composition of a silicate and its structure. Therefore, the time has been reached when a modern review of the structural chemistry of silicates has become necessary."

The upsurge in development of homogeneous catalysis in both aca- demic and industrial areas has prompted us to organize the Second Interna- tional Workshop at Shiga, Japan, 1977. The objective of this workshop was similar to that of the first: to identify opportunities for the solution of energy problems and industrial production problems by homogeneous catalysis. This workshop on homogeneous catalysis was sponsored by the Toray Science Foundation, the Yoshida Foundation for Science and Technology, the Yamada Science Foundation, and the National Science Foundation. The Robert A. Welch Foundation Grant A-420 partially supported the time spent by M. Tsutsui for the organization of the workshop and the edi- torial work of these proceedings. Organizing Committee, April, 1978 Jack Halpern (U.S.A.) Yoshio Ishii Oapan) Jiro Tsuji Oapan) Minoru Tsutsui (U.S.A.) Akio Yamamoto Oapan) v Contents Metal Clusters in Catalysis XVII: Catalytic Hydrocarbon Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 E.L. Muetterties Cluster Catalysis: Homogeneous Catalytic Oxidation of Carbon Monoxide and of Ketones with Molecular Oxygen Using Complexes of Rhodium(O), Iridium(I), and Platinum(O). . . . . . 11 D.M. Roundhill Metal Carbonyl Catalysis of Carbon Monoxide Reactions. . . . . . . . . . 25 . R.B. King, A.D. King, Jr., M.Z. Iqbal, C.C. Frazer and R.M. Hanes Activation of Saturated Hydrocarbons by Ruthenium(I) Complexes? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35 . . . . . . . . . . Brian R. James and Daniel K.W. Wang Oxidative Addition to Metal Atoms: Mechanism, Use of Resultant Reactive RMX and R2M Species in Homogeneous Catalysis Processes and Metal Atom-Alkane Interactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 . . . . . . . . . .

This was the third meeting in the series of special topical conferences on Non-Metallic materials at low temperatures. The first meeting was in Munich in 1978, the second in Geneva (1980) and so Heidelberg 1984 seemed an obvious time to review some of the hopes and objectives of the earlier meetings. It is also appropriate to consider the changing needs of the cryogenic community and how best the theory and practice of Non-metallic materials can be applied to suit this dynamic young science. The aims and objectives of the International Cryogenic Materials Board in sponsoring this meeting remain the same. Namely, to provide a forum where practicing Engineers can meet with materials suppliers and researchers in an attempt to ensure that a real understanding exists between the two sides of the Cryogenic Materials Community. In this atmosphere, real problems can be addressed together with full discussions of tried and tested practical solutions. It is in this way that knowledge and confidence may grow hand in hand with the logical growth of the industry.

Polymer science is a technology-driven science. More often than not, technological breakthroughs opened the gates to rapid fundamental and theoretical advances, dramatically broadening the understanding of experimental observations, and expanding the science itself. Some of the breakthroughs involved the creation of new materials. Among these one may enumerate the vulcanization of natural rubber, the derivatization of cellulose, the giant advances right before and during World War II in the preparation and characterization of synthetic elastomers and semi crystalline polymers such as polyesters and polyamides, the subsequent creation of aromatic high-temperature resistant amorphous and semi-crystal line polymers, and the more recent development of liquid-crystalline polymers mostly with n~in-chain mesogenicity. other breakthroughs involve the development of powerful characterization techniques. Among the recent ones, the photon correlation spectroscopy owes its success to the advent of laser technology, small angle neutron scattering evolved from n~clear reactors technology, and modern solid-state nuclear magnetic resonance spectroscopy exists because of advances in superconductivity. The growing need for high modulus, high-temperature resistant polymers is opening at present a new technology, that of more or less rigid networks. The use of such networks is rapidly growing in applications where they are used as such or where they serve as matrices for fibers or other load bearing elements. The rigid networks are largely aromatic. Many of them are prepared from multifunctional wholly or almost-wholly aromatic kernels, while others contain large amount of stiff difunctional residus leading to the presence of many main-chain "liquid-crystalline" segments in the "infinite" network.