An Introduction to the CHEMISTRY of the SILICONES By EUGENE G. ROCHOW. PREFACE: The organic compounds of silicon, which have been the subject of many scholarly researches during the past 80 years, at last show promise of emerging from the laboratory and finding a place in industry. An understanding of the behavior of organosilicon materials is necessary to their intelligent use and, inasmuch as the chemistry of these substances ordinarily is not treated in our textbooks, it is possible that a compact yet comprehensive survey of our present knowledge in this field would be of service to chemists, engineers, and industrial designers. This volume has just such a purpose. The first few chapters review the silanes and their derivatives in some detail, in order to provide an understanding of the fundamental chemistry of the nonsilicate com pounds of silicon. The later chapters emphasize the silicone polymers which have achieved commercial importance and deal with the methods for their preparation, their chemical and physical properties, and their possible usas. The processes available for large-scale production are treated separately, and a review of methods of analysis is included. In order not to burden the text with definitions and explanations of nomenclature which might already be familiar to some readers, an extensive glossary of terms is appended. An exhaustive review of the literature on organic compounds of sili con cannot very well be included in a volume intended for the non specialist. However, many references are provided, and tables of most of the known compounds and their properties are included in the appropriate chapters. The reader will find comprehensive reviews ofpublications in Friends Textbook of Inorganic Chemistry, Volume 11, Part 2 Krause and von Grossed Chemie der Metallorgamschen Ver bindungen, Dolgows Chemistry of the Silica-Organic Compounds, and Bygdens Silizium als Vertreter des Kohlenstoffs organischen Verbindun gen. A more recent and more complete compilation of the literature on organic compounds of silicon would be welcomed by every investigator in the field. Since this work presents a point of view rather than an uncritical compilation of published fact, the author must assume entire responsi bility for the opinions expressed. However, he is greatly indebted to his coworkers iu the research laboratory of the General Electriq Company for helpful advice and criticisms. In a larger sense this work is the result of many years of common endeavor in a most interesting field of research. Contents include: 1. THE SIMPLE COVALENT COMPOUNDS OF SILICON 1 Introduction 1 Chemical Behavior of the Element 3 The Hydrides 4 The Halides 9 The Esters or Ethers 12 Index of Representative Compounds 16 2. THE ORGANOSILICON MONOMERS 18 Methods for Carbon-Silicon Bonds 19 The Alkyls 30 The Alkylsilanes 32 The Alkylhalosilanes 33 The Alkylalkoxysilanes 37 Index of Representative Compounds 39 3. TYPES OF ORGANOSI LICON POLYMERS 45 Silicon Chains 45 Silicon-Carbon Chains 46 Siloxane Chains 49 Siloxane Networks 53 Index of Representative Compounds 58 4. PROPERTIES OF THE SPECIFIC SILICONS POLYMERS 60 Alkyl Silicones 62 Methyl Silicone Oil 64 Methyl Silicone Resins 70 Silicone Rubber 72 Ethyl Silicone Resins 73 Other Alkyl Silicone Resins 74 Aryl Silicones 77 Alkyl-Aryl Silicones 80 5. WATER-REPELLENT FILMS FROM ORGANOSILICON MATERIALS 83 Reaction ofMethylchlorosilanes 83 Uses 85 6. TECHNICAL ASPECTS OF SILICONES 89 The Intermediates 90 The Grignard Method 91 The Direct Method 96 Processing 101 Toxicity 103 Future Expansion 104 ix

Following three printings of the First Edition (1978), the publisher has asked for a Second Edition to bring the contents up to date. In doing so the authors aim to show how the newer microscopies are related to the older types with respect to theoretical resolving power (what you pay for) and resolution (what you get). The book is an introduction to students, technicians, technologists, and scientists in biology, medicine, science, and engineering. It should be useful in academic and industrial research, consulting, and forensics; how ever, the book is not intended to be encyclopedic. The authors are greatly indebted to the College of Textiles of North Carolina State University at Raleigh for support from the administration there for typing, word processing, stationery, mailing, drafting diagrams, and general assistance. We personally thank Joann Fish for word process ing, Teresa M. Langley and Grace Parnell for typing services, Mark Bowen for drawing graphs and diagrams, Chuck Gardner for photographic ser vices, Deepak Bhattavahalli for his work with the proofs, and all the other people who have given us their assistance. The authors wish to acknowledge the many valuable suggestions given by Eugene G. Rochow and the significant editorial contributions made by Elizabeth Cook Rochow."

Using the metaphor of 'constitutional space', this thought-provoking book describes the confluence and convergence of powers in a constitutional system, comprised of the principled exercise of the legislative, executive and judicial powers of constitutional government. The book asserts that when governance is guided by principle, convergence creates greater space for all human rights and fundamental freedoms; both community and individuals thrive. Conversely when any right or freedom is given precedence over any other for reasons of political expediency, this results in the loss or diminution of human rights and fundamental freedoms. Addressing the issues surrounding the freedom of religion or belief, this timely book explores the dimensions of constitutional space and the content of this freedom, as well as comparative approaches to defining and protecting this freedom. Freedom of Religion or Belief will be a key resource for academics working in the fields of law and religion, law and society and human rights law. It will also appeal to practitioners and policy-makers working on the issue of religious freedom. Contributors include: P.T. Babie, R. Barker, A.P. Bhanu, A. Deagon, C. Evans, J. Forrester, N. Foster, M. Fowler, J. Harrison, M. Hill, J. Neoh, E.U. Ochab, J. Patrick, C. Read, N.G. Rochow, V.-I. Savic, B.G. Scharffs, P. Taylor, P. Xiong

It is said that behind every successful man there stands a devoted and capable woman. The three famous chemists Perkin, Kipping and their collaborator Lapworth married three sisters: Mina, Lily, and Kathleen Holland. The three Holland sisters kept their husbands in close and very productive collaboration throughout their lives, thereby greatly increasing their scientific output. They functioned as a productive scientific family. However, the life and work of the men is thoroughly documented, but little is known about their wives. Professor Eugene G. Rochow, a world-renowned scientist, wrote this biographical historical novel with the help of a grandson, Dr. Brian Kipping. Professor Rochow did not intend to write a bare-bones biography. He took care to make the book factually accurate. Wherever there are no facts, he has not hesitated to flesh out the account with imagination and actual experience of others in order to make the text more readable.

It is said that behind every successful man there stands a devoted and capable woman. The three famous chemists Perkin, Kipping and their collaborator Lapworth married three sisters: Mina, Lily, and Kathleen Holland. The three Holland sisters kept their husbands in close and very productive collaboration throughout their lives, thereby greatly increasing their scientific output. They functioned as a productive scientific family. However, the life and work of the men is thoroughly documented, but little is known about their wives. Professor Eugene G. Rochow, a world-renowned scientist, wrote this biographical historical novel with the help of a grandson, Dr. Brian Kipping. Professor Rochow did not intend to write a bare-bones biography. He took care to make the book factually accurate. Wherever there are no facts, he has not hesitated to flesh out the account with imagination and actual experience of others in order to make the text more readable.

Following three printings of the First Edition (1978), the publisher has asked for a Second Edition to bring the contents up to date. In doing so the authors aim to show how the newer microscopies are related to the older types with respect to theoretical resolving power (what you pay for) and resolution (what you get). The book is an introduction to students, technicians, technologists, and scientists in biology, medicine, science, and engineering. It should be useful in academic and industrial research, consulting, and forensics; how ever, the book is not intended to be encyclopedic. The authors are greatly indebted to the College of Textiles of North Carolina State University at Raleigh for support from the administration there for typing, word processing, stationery, mailing, drafting diagrams, and general assistance. We personally thank Joann Fish for word process ing, Teresa M. Langley and Grace Parnell for typing services, Mark Bowen for drawing graphs and diagrams, Chuck Gardner for photographic ser vices, Deepak Bhattavahalli for his work with the proofs, and all the other people who have given us their assistance. The authors wish to acknowledge the many valuable suggestions given by Eugene G. Rochow and the significant editorial contributions made by Elizabeth Cook Rochow.

Many people look upon a microscope as a mere instrument(l); to them microscopy is instrumentation. Other people consider a microscope to be simply an aid to the eye; to them microscopy is primarily an expan sion of macroscopy. In actuality, microscopy is both objective and sub jective; it is seeing through an instrument by means of the eye, and more importantly, the brain. The function of the brain is to interpret the eye's image in terms of the object's structure. Thought and experience are required to distinguish structure from artifact. It is said that Galileo (1564-1642) had his associates first look through his telescope microscope at very familiar objects to convince them that the image was a true representation of the object. Then he would have them proceed to hitherto unknown worlds too far or too small to be seen with the un aided eye. Since Galileo's time, light microscopes have been improved so much that performance is now very close to theoretical limits. Electron microscopes have been developed in the last four decades to exhibit thousands of times the resolving power of the light microscope. Through the news media everyone is made aware of the marvelous microscopical accomplishments in imagery. However, little or no hint is given as to what parts of the image are derived from the specimen itself and what parts are from the instrumentation, to say nothing of the changes made during preparation of the specimen.

Resinography is a strange new word to many people. Like all scientific terms, it is a word coined for a specific purpose: to indicate (in this case) that resins, polymers, and plastics write their own history on the molecular and other structural levels. The word indicates further that anyone trained and equipped to ask the right questions (by means of instruments and techniques) will be able to read that history. That person must have sufficient training and experience to interpret the answers, of course, and he or she needs to have the temperament of a detective. But in the end, as readers of this book will discover, one is able to identify the material, to determine its history of treatment, and to learn much about its possible field of usefulness. Obviously, the resinographer seeks to do the same thing with res ins, polymers, and plastics that the metallographer does with metals and their alloys. Often the investigative techniques and the instru ments, too, are similar, but sometimes they are decidedly different. Perhaps it would be best to say that resinography and metallographyl (and petrography as well) share a common origin, and that origin is deeply rooted in microscopy. The "grandfather" of all three "ographies" was Henry Clifton Sorby (1826-1908),2 who initiated 3 metallography and petrography, and was the first to report on the microstructure of a resin (amber, a natural fossil resin)."

An Overview for the General Reader The fact that silicone rubber boots made those footprints on the moon, and that other silicone polymers made possible the construc tion and functioning of space suits and space vehicles, has led to the general belief that silicones are very modem materials conjured up to meet the needs of space travel. Actually, though, silicone chemis try has deep roots in human history, dating from the dawn of the race and extending through all of geology, mineralogy, and the ancient ceramic arts. This little book seeks to put the development of silicone materials in perspective as part of the fascinating involvement of the element silicon in our daily lives, from the stuff the earth and the moon are made of to the modem use of ultra pure silicon in transistors and computers, and the use of ordi nary elementary silicon to make silicone rubber, silicone oil, sili cone resins, and silicon or silicone-containing polishes, drugs, and fragrances. Of course these are not our only connections with silicon. The natural compounds of silicon and oxygen (the silicates) are the starting materials for making bricks, tile, cement, glass, and a host of modem ceramic products. The widespread usefulness of silicon and its compounds comes about for two reasons: first, there is so much of it, and second, it is so versatile.

Eugene G. Rochow, Prof. emerit. der Harvard UniversitAt, fA1/4hrte am 10. Mai 1940 ein Laborexperiment durch, das fA1/4r die industrielle Produktion von Siliconen von grundlegender Bedeutung war: die Rochow-Synthese. Durch diese Synthese wurden die "Wundermaterialien" zugAnglich fA1/4r viele Anwendungen zur Verbesserung von GebrauchsgegenstAnden, zur Miniaturisierung von elektronischen Bauelementen und zur Herstellung von RaumanzA1/4gen fA1/4r Astronauten, die die extreme Hitze und KAlte auf dem Mond aushielten.