Some have predicted that the coming several decades will be the decades of "biotechnology," wherein cancer, birth defects, life span increases, cosmetics, biodegradation, oil spills and exploration, solid waste disposal, and almost every aspect of our material life will be affected by this new area of science. There will also be an extension of emphasis on giant molecules: DNA, enzymes, polysaccharides, lignins, proteins, hemoglobin, and many others. Biotechnology has been defined in various ways. In one sense, this field is older than human history and references to the human use of biotechnology-derived materials can be found in the oldest human writings, such as the Bible. In this book, biotechnology refers to the direct usage of naturally occurring materials or their uses as a feedstock, including the associated biological activities and applications of these materials. Bioactive polymers, on the other hand, are polymers which exert some type of activity on living organisms. These polymers are used in agriculture, controlled release systems, medicine and many other areas. The papers in this book describe polymers which essentially combine features of biotechnology and bioactivity.

During recent years a high level of interest has been maintained in the kinetics and mechanisms of inorganic compounds in solution, and there has also been a notable upsurge of literature concerned with reaction mechanisms of organo transition metal compounds. The reviews of the primary literature previously provided by "Inorganic Reaction Mechanisms" (Royal Society of Chemistry) and "Reaction Mechanisms in Inorganic Chemistry" in "MTP International Re views of Science" (Butterworths) continue to be of considerable value to those concerned with mechanistic studies, and it is unfortunate they are no longer published. The objective of the present series is to provide a continuing critical review of literature dealing with mechanisms of inorganic and organometallic reactions in solution. The scope of potentially relevant work is very large, particularly in the field of organotransition metal chemistry, and papers for inclusion have been chosen that specifically probe mechanistic aspects, rather than those of a prep arative nature. This volume covers the literature published during the period July 1979 to December 1980 inclusive. Material is arranged basically by type of reaction and type of compound along generally accepted lines. Numerical data are usually reported in the units used by the original authors, though the units of some results have been converted in order to make comparisons.

Molten salts have been used for many years in a large number of industrial applications, and interest in them has increased mark edly in the present century. There is a vast amount of experi mental data published on molten salt systems, and much of this is due to Russian workers. In 1961 the Russian Academy of Sciences published a manual dealing with work in the period 1886-1955. These were updated in 1979 with the publication of a 3-volume collection of binary phase diagrams. The present volume is a translation of the Russian books but is restricted to the systems involving halides. In order to keep the length of the book within bounds the data have been recast. The Russian work treats each system in detail, giving data, methods of study, references, and figures, where available, all together. In this translation all the information is given, but to keep the length down the methods have been classified, the references collected at the end of the volume, and the data given in tabular form. All the figures for halide systems in the Russian volume are included. In the tables, concentrations are given in mole percent; in some cases these have been converted from weight per cent in the original Russian. Where the Russian work was. in tabular form, these have been translated as given. Where the figures exist, these are referred to in the text."

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.

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 . . . . . . . . . . ."

In the field of plant analysis there is a confusing variety of methods and procedures, both for digestions and determinations. In many cases the digestion and the subsequent determination are interrelated. For example, a separate digestion is needed for trace elements in order to obtain determinable concentrations. The authors have chosen a design in which the digestion/extraction procedure is described in one chapter together with all determination procedures that may be carried out on that particular digest/extract. All the necessary information (such as standardizations) appears in appendices. As a consequence, several determination procedures are described two or three times, however, each based on a particular digestion or extraction method. Two types of determination procedure are described: manual and automated. Manual procedures are mainly used in research laboratories, whereas automated procedures are more frequently applied in routine laboratories. Both types of determinations can be used freely, provided that appropriate equipment is available. The determination procedures are only for inorganic components, usually elements. Besides, most procedures are designed to give a total content value of the element under consideration, regardless of the chemical structure in which it occurs in the plant. The Plant Analysis Manual is intended for the practicing (agricultural) chemist.

"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.

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."

This book is devoted to nonmetal-to-metal transitions. The original ideas of Mott for such a transition in solids have been adapted to describe a broad variety of phenomena in condensed matter physics (solids, liquids, and fluids), in plasma and cluster physics, as well as in nuclear physics (nuclear matter and quark-gluon systems). The book gives a comprehensive overview of theoretical methods and experimental results of the current research on the Mott effect for this wide spectrum of topics. The fundamental problem is the transition from localized to delocalized states which describes the nonmetal-to-metal transition in these diverse systems. Based on the ideas of Mott, Hubbard, Anderson as well as Landau and Zeldovich, internationally respected scientists present the scientific challenges and highlight the enormous progress which has been achieved over the last years. The level of description is aimed to specialists in these fields as well as to young scientists who will get an overview for their own work. A common feature of all contribution is the extensive discussion of bound states," i.e. their formation and dissolution due to medium effects. This applies to atoms and molecules in plasmas, fluids, and small clusters, excitons in semiconductors, or nucleons, deuterons, and alpha-particles in nuclear matter. In this way, the transition from delocalized to localized states and vice versa can be described on a common level."

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.

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."

In recent years many research workers have turned their attention to the quantitative characterization of complex compounds and reactions of complex-formation in solution. Instability constants characterize quantitatively the equili bria in solutions of complex compounds and are extensively used by chemists of widely-varying specialities, in analytical chemistry, electrochemistry, the technology of non-ferrous and rare metals, etc., for calculations of various kinds. Despite the wealth of numerical data, no reasonably full coliection of instability constants of complex compounds has been made until now. The various individual collections of data are far from complete and in most cases omit references to the source materials. Moreover, the present state of the chemistry of complex compounds most urgently demands the complete systematization of data on instability constants and an extension of work in this field which would take advantage of the latest physico-chemical methods. The present work contains instability constants for 1,381 complex compounds. We have considered it convenient to preface the summary of the instability constants with an introductory section of a general theoretical character. This section deals with methods for the calculation of instability constants from experimental data, the influence of external conditions, such as temperature and ionic strength, on the stability of com plexes, and the principal factors determining the stability of complex compounds in aqueous solution. (vii) PREFACE In compiling the summary we have used the original litera ture and abstracts for the most part up to 1954, and some work published in 1955-1956."

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.

For almost a quarter of a century the words "nuclear magnetic reso nance" were synonymous with proton I, leasurements. During this period the literature abounded with a seemingly infinite variety of 1H NHR studies concerned primarily with carbon chemistry. Occasionally a "novel" nucleus was studied and, even in those early days, the poten- 13 14 31 19 tial offered by C, N, P and F was clearly recognized. Despite the allure, the technical difficulties involved in measuring some of these nuclei were far from trivial. Small magnetic moments and low natural abundance in combination with spin-spin coupling from other nuclei, mostly protons, resulted in a signal-to-noise problem whose severity effectively excluded the study of metal complexes with unfa vorable solubility characteristics. The first important breakthrough came with the advent of broad band 1H-decoupling. For example, the featureless broad 31p resonance associated with the commonly used ligand triphenyl phosphine is converted to a sharp, more readily ob served singlet when wide-band decoupling is employed (see Fig. 1). Despite this improvement investigation of more interesting molecules, such as catalytically active complexes was forced to await the devel opment of Fourier Transform methods since only with relatively rapid signal averaging methods could sufficient signal-to-noise ratios be achieved."

In recent years several improvements have been made in the manufacturing of resistive, superconducting and hybrid mag nets. Condensed matter physicists are nowadays doing ex periments in steady magnetic fields of up to 30 Tesla. But the field homogenity {/B}, required in a volume of the order of a 3 few cm is usually several orders of magnitude less severe than the one which is needed for high resolution NMR. Over the last 30 years, with each generation of new high resolution NMR spectrometers, from 100 MHz up to 600 MHz, taking advan tage of the increase in sensitivity and resolution, new areas of research have been opened in chemistry, physical chemistry and biochemistry. The generation of the 20 Tesla supercon ducting magnets is coming. Thus one may seriously start to consider high resolution NMR at 1 GHz. The purpose of this volume is to examine some of the advantages which can be obtained at such high frequencies and some of the problems we shall be facing. An important aspect of NMR at high field which is not presented in this volume concerns the design of the magnet. The building of a superconducting magnet, producing a field 10 3 higher than 20 T, with a field homogeneity IlB/B 10-, in a cm volume still remains today in 1990 a major challenge. Grenoble, France J. B. Robert Guest-Editor Professor J. B. Robert Service National des Champs Intenses B. P."

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 . . . . . . . . . .

Modern Synthetic and Application Aspects of Polysilanes: An Underestimated Class of Materials?, by A. Feigl, A. Bockholt, J. Weis, and B. Rieger;
*
Conjugated Organosilicon Materials for Organic Electronics and Photonics, by Sergei A. Ponomarenko and Stephan Kirchmeyer;
*
Polycarbosilanes Based on Silicon-Carbon Cyclic Monomers, by E.Sh. Finkelshtein, N.V. Ushakov, and M.L. Gringolts;
*
New Synthetic Strategies for Structured Silicones Using B(C6F5)3, by Michael A. Brook, John B. Grande, and Francois Ganachaud;
*
Polyhedral Oligomeric Silsesquioxanes with Controlled Structure: Formation and Application in New Si-Based Polymer Systems, by Yusuke Kawakami, Yuriko Kakihana, Akio Miyazato, Seiji Tateyama, and Md. Asadul Hoque;"

There are both a remote and a proximate history in the development of this book. We would like to acknowledge first the perceptiveness of the technical administrators at RCA Laboratories, Inc. during the 1970s, and in particular Dr. P. N. Yocom. Buoyed up by the financial importance of yttrium oxysulfide: europium as the red phosphor of color television tubes, they allowed us almost a decade of close cooperation aimed at understanding the performance of this phosphor. It is significant that we shared an approach to research in an industrial laboratory which allowed us to avoid the lure of "first-principles" approaches (which would have been severely premature) and freed us to formulate and to study the important issues directly. We searched for a semiquantitative understanding of the properties observed in luminescence, i. e., where energy absorption occurs, where emission occurs, and with what efficiency this conversion process takes place. We were aware that the nonradi ative transition rates found in practice vary enormously with temperature and, for a given activator, with small changes in its environment. We traced the source of this enormous variation to the magnitude of the vibrational overlap integrals, which have strong dependences on the rearrangements occurring during optical transitions and on the vibrational number of the initial electronic state. We were willing to excise from the problem the electronic aspects - the electronic wavefunctions' and their transition integrals -by treating them as parameters to be obtained from the experimental data."

Although the chemistry of boron is still relatively young, it is developing at a pace where even specific areas of research are difficult to compile into a monograph. Besides the boron hydrides, boron-nitrogen compounds are among the most fascinating derivatives of boron. Nitrogen compounds exist in a wide variety of molecular structures and display many interesting properties. The combination of nitrogen and boron, however, has some unusual features that are hard to match in any other combination of elements. This situation was first recognized by ALFRED STOCK and it seems proper to pay tribute to his outstanding work in the area of boron chemistry. One should realize that about forty years ago, STOCK and his coworkers had to develop completely new experimental techniq'\les and that no guidance for the interpreta tion of their rather unusual data had been advanced by theoretical chemists. In this monograph an attempt has been made to explore the general characteristics of structure and the principles involved in the preparation and reactions of boron-nitroge compounds. It was a somewhat difficult task to select that information which appears to be of the most interest to "inorganic and general chemistry" since the electronic relationship between a boron-nitrogen and a carbon-carbon grouping is reflected in the "organic" character of many of the reactions and compounds."