1 Introduction
1.0
HISTORICAL PERSPECTIVE AND PRESENT STATUS OF REFRACTORY CARBIDES AND NITRIDES
Refractory carbides and nitrides are useful materials with numerous industrial applications and a promising future, in addition to being materials of great interest to the scientific community. Although most of their applications are recent, the refractory carbides and nitrides have been known for over one hundred years. Titanium and tungsten carbides were extracted from steel and properly identified around the middle of the nineteenth century. In 1890, E. G. Acheson produced the first silicon carbide, trademarked Carborundum, and by 1900 the French chemist Moissan had synthesized most other refractory carbides in his electric arc-furnace. Titanium carbonitride was first described in 1822 and identified by chemical analysis in 1850. Additional notes of historical interest will be presented in the relevant chapters. The industrial importance of the refractory carbides and nitrides is growing rapidly, not only in the traditional and well-established applications based on the strength and refractory nature of these materials such as cutting tools and abrasives, but also in new and promising fields such as electronics and opto-electronics. Some typical applications are as follows:
I
Handbook of Refractory
Carbides and Nitrides
Silicon-nitride turbines
rotors, blades, rings, and burner tiles for gas cutting tools coatings on high-speed steel drill bits fibers and whiskers abrasive blast nozzles substrates for
Tungsten-carbide Titanium-nitride Silicon-carbide Boron-carbide
Aluminum-nitride high thermal conductivity electronic circuits Silicon carbide burner tubes for gas furnaces
Titanium nitride passivating and electrically coatings for semiconductor devices Silicon carbide high-temperature semiconductor
insulating devices
Silicon carbide blue light-emitting diode (LED) these materilaboratories tools, textile many other part of the
Such a wide range of applications reflects the variety of als and the diversity of the industry, from small research developing new ideas to large plants manufacturing cutting machinery, electronic and semiconductor components, and products. Together, these organizations form an essential ceramic industry throughout the world.
2.0
CARBIDES AND NITRIDES MATERIALS
AS REFRACTORY
The word repuctory defines a material with a high melting point. In the context of this book, this means any carbide and nitride with a melting point arbitrarily selected as greater than 1800C. In addition, to be considered refractory the material must have a high degree of chemical stability. As shown in subsequent chapters, most elements form carbides and nitrides and these can be divided into several types with different physico-chemical structures and characteristics. Of these, however, only the interstitial and covalent materials meet the refractory qualification. This includes the carbides and nitrides of the nine transition elements of Groups IV, V, and VI and the 4th, 5th, and 6th Periods, the carbides and nitrides of boron and silicon, and aluminum nitride.
Introduction
The carbides and nitrides of the lanthanides (the rare-earth elements) and actinides are well-defined and unique families of materials with promising applications, yet they cannot be considered refractory and are not included in this book. Although carbides and nitrides as a group form the most refractory compounds, they are certainly not the only ones. Several borides, oxides, phosphides, silicides, and metals meet the refractory requirements mentioned above. To some degree, these materials complement the refractory carbides and nitrides and may be considered as competitors. Why should the refractory carbides and nitrides be reviewed together in one book?
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They form two families of closely related materials which have similar atomic structures and chemistry Carbon and nitrogen are next to each other the second period of the Table of the Elements and, in many cases, the carbides and nitrides form solid solutions (known as carbonitrides) Many of their properties are similar They have essentially the same processing and basically the same applications In many respects, they complement each other characteristics
3.0
BOOK
OBJECTIVES
A large body of information is available on the subject of refractory carbides and nitrides, including a number of books such as the ones listed in Sec. 6.0. These books provide excellent reviews but the authors have chosen to concentrate on the structural aspects and properties of carbides and nitrides, offering little information concerning processing and even less about applications. Moreover these studies were written several decades ago, and a large amount of research and development has taken place since. The basic understanding of these materials is gradually expanding. Technology is moving rapidly. Improvements in processing techniques appear regularly, and the scope of applications is constantly increasing and reaching into new fields such as aerospace, automotive, semiconductors, optics, and electronics.
Handbook
of Refractory
Carbides and Nitrides
With some of his colleagues, the author has felt the need for an updated and systematic review of refractory carbides and nitrides, which would summarize the scientific aspects of these materials and examine their relationship with the engineering, processing, and applications aspects, coordinate the divergent trends found today in industry and the academic community, and sharpen the focus of research and development by promoting interaction. Industrial secrecy still prevails in many sectors. It is sometimes necessary but also often needlessly hampers progress. Interaction and coordination are limited even though the various technologies and applications share the same scientific basis, the same principles, the same chemistry, and often the same type of equipment. A purpose of this book is to bring these divergent areas together in one unified whole with the hope of providing a useful tool for engineers and scientists. The main objectives of this book can be summarized as follows:
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Provide a complete review of the structures and properties of refractory carbides and nitrides Provide a thorough assessment of the technology, processing, and equipment and systems used in production and R&D, with emphasis on advanced designs Identify and describe the applications, particularly the new and emerging areas of semiconductors and electronics, optics, tool coatings, and wear, oxidation, or corrosion resistant products
4.0
BOOK ORGANIZATION The book is organized in six basic sections: 1. Structure and properties of refractory interstitial carbides (Chs. 2-6) 2. Structure and properties of refractory (Chs. 7 and 8) covalent carbides
3. Structure and properties of refractory interstitial nitrides (Chs. 9-l 1) 4. Structure and properties of refractory (Chs. 12 and 13) covalent nitrides
Introduction 5. Technology and processing (Chs. 14 and 15) 6. Applications (Ch. 16)
In the first eight chapters devoted to carbides, several basic principles are reviewed such as atomic and molecular structure, crystalline arrangement, type of bond, etc. These principles also apply to nitrides but are not repeated and only cross-referenced. Whenever possible, the relationship between structure, properties, and applications is stressed throughout the book.
5.0
GLOSSARY
AND METRIC
CONVERSION
GUIDE
A glossary at the end of the book defines terms which may not be familiar to some readers. These terms are printed in italics in the text. All units in this book are metric, specifically the international system of units (SI) and a metric conversion guide is included at the end of the book.
6.0
BACKGROUND
READING
The following is a representative list of the most important references, periodicals, and conferences dealing with carbides and nitrides. 6.1 General References
Metal Carbides,
Storms, E. K., The Refractory (1967)
Academic Press, New York
Materials and
Campbell, I. E., and Sherwood, E. M., High-Temperature Technology, John Wiley & Sons, New York (1967)
Toth, L. E., Transition Metal Carbides and Nitrides, Academic Press, New York (1971) Kosolapova, T. Ya., Carbides, Plenum Press, New York (1971) Samsonov, G., Refractory
Carbides, Consultant Bureau, New York (1974)
Wehr, M. R., Richards, J. A., Jr. and Adair, T. W., III, Physics of the A tom, Addison-Wesley Publishing Co., Reading, MA (1978) Evans, R. C., An Introduction to Crystal Chemistry, Cambridge Univ. Press, Cambridge (1979)
Handbook
of Refractory
Carbides and Nitrides Chemistry, Interscience
Cotton, F. A. and Wilkinson, G., Advanced lmrgmic Publishers, New York (1980)
Adams, D. M., Inorganic Solids, John Wiley & Sons, New York (1981) Huheey, J. E., Inorganic Chemistry, Third Edition, Harper & Row, New York (1983) March, J., Advancedlnorgunic Chemistry, John Wiley & Sons, New York (1985) Pierson, H. O., Handbook of Chemical Vapor Deposition, Noyes Publications, Park Ridge, NJ (1992) Bunshah, R. F., Handbook of Deposition Technologies for Films and Coatings, 2nd ed., Noyes Publications, Park Ridge, NJ (1994) 6.2 Periodicals Acta Crystallographica Applied Physics Letters Carbon Ceramic Bulletin Ceramic Engineering and Science Proceedings Japanese Journal of Applied Physics Journal of the American Ceramic Society Journal of the American Chemical Society Journal of Applied Physics Journal of the Ceramic Society of Japan Journal of Crystal Growth Journal of the Electra-Chemical Society Journal of the Less-Common Metals Journal of Materials Research Journal of Vacuum Science and Technology Materials and Manufacturing Processes Materials Engineering Materials Research Society Bulletin Nature SPE Journal SAiMPE Quarterly SPIE Publications Science
Introduction 6.3 Conferences
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International Conferences on chemical vapor (CVD) of the Electrochemical Society (biennial) Composites and Advanced Ceramics American Ceramic Society (annual)
deposition of the
Conferences
Materials Research Society Conferences (annual) International Technologies Conference (annual) on Surface Modification
