6 Literature of Refractories
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L . J . T R O S T E L , J R . , J. H A Y , and N . N .
AULT
Research and Development Department, Refractories Division, Norton Co., Worcester, Mass.
About 70%
of the refractories
manufactured
iron and steel industry
and public
users are the nuclear
and aerospace
of refractories zirconia,
magnesite,
and silicon struct
manufactured
carbide.
iron
chrome, From
furnaces
and
nitrides,
steadily
and
diversified
techniques nology.
the
literature
these changes and
industries.
the
other
The
types
fire clay, silica,
zircon,
dolmite,
high alumina,
carbon,
the use of siliceous to
the
refractory
its raw of the
present industry
materials
to meet the ever changing The
are used in the Among
include
in 1645
borides
utilities.
rock to day has
and industry
of
grown
production
needs of modern
refractory
con-
use
techreflects
advancements.
T
he term "refractory" stems from the L a t i n w o r d "refractarius" meaning to oppose or resist. It implies a material that is difficult to fuse or corrode— one which is capable of enduring high temperatures. A current industrial definition of a refractory is a nonmetallic material capable of resisting high temperatures and other destructive forces present i n furnaces such as slag corrosion, abrasion, load, and thermal shock. The refractory industry is composed primarily of materials manufacturers who supply linings to withstand and contain severe conditions. These conditions may be only high temperatures, but they frequently involve abrasion and chemical attack also. The linings are supplied largely as fired bricks, blocks, plates, and as many special shapes. They also may be supplied as a monolith-forming material of w h i c h plastic refractories, gunning mixes, and castables are the principal types. Processes involving high temperature include: iron, steel, and nonferrous metallurgy; glass, ceramic, and cement manufacture; the steam generating plants of the large electric utilities, industrial heating units, and even the home oil burner. M u n i c i p a l incinerators lined with refractories are used to dispose of the mountains of refuse our civilization generates daily. 105 In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
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106
LITERATURE
OF CHEMICAL TECHNOLOGY
Refractories manufacturers also supply linings for vessels used i n the chemical industry. These conditions involve moderate temperatures, but the linings must resist the corrosive action of chemicals. The bulk of the industry is concerned w i t h supplying the needs of the iron and steel industry. Indeed, about 7 0 % of the total refractories' consumption is accounted for by the combination of the iron and steel industry and public utilities. The remaining 3 0 % is divided among other users. Included i n this group are many of the special refractory users, including the more exotic applications i n the nuclear and aerospace industries, where extreme environmental conditions demand the durable refractories. Intensive research and new development effort i n refractories since the m i d 1940's have been directed toward solving the problems of these fields although much effort continues to be directed toward the problems of the conventional refractory user. History There are few records of the early history of refractories i n N o r t h America. Undoubtedly the earliest type of refractory used was quarried mica schist or siliceous rock. It was used to construct the first successful iron furnaces i n 1645. The earliest use of clay refractories was for glass pots i n 1638. These probably were made from imported English or German clays. Domestic clay was first used for furnace firebrick shortly after 1793 i n Boston. In the early 1800's firebrick manufacturing plants were established first at Boston and Baltimore, then i n N e w Jersey, Vermont, and Connecticut. Before the C i v i l W a r refractories manufacture had spread westward through Pennsylvania and Ohio to the Mississippi River and south to Georgia. The first silica bricks were manufactured i n the U n i t e d States about 1860 although they had been manufactured i n E n g l a n d earlier. T h e area around M t . U n i o n , P a . became a center for manufacturing modern limebonded ganister silica brick. Magnesite was first used i n Europe for steel melting about 1880. It was used successfully i n this country about 1888, and domestic manufacture of magnesite refractories began soon after. H i g h alumina refractories from bauxite were introduced i n 1890. M i s souri diaspore was used first about 1920 for super-refractories. Gibbsite and kaolin are also used to manufacture these refractories. The investigation, manufacture, and use of h i g h purity oxide refractories began i n Europe about 1930. This special refractory technology had spread to the U n i t e d States by the advent of W o r l d W a r II. It has expanded since then because the demands have become so exacting that only certain high purity materials possess the extreme high melting points and high temperature strengths demanded by these applications. A l u m i n a , zirconia, and magnesia are a l l consumed i n considerable quantity today. Non-oxidic refractories have greatly increased i n use w i t h the more severe use requirements of modern technology. The most widely used is silicon carbide, first produced i n 1891. Its high thermal conductivity and high hot
In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
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6.
TROSTEL E T A L .
Refractories
107
strength result i n its application i n many furnaces where abrasion resistance or good heat transfer is demanded. Its semiconductor properties result i n its use as electrical heating elements. The refractory industry has grown along w i t h heavy manufacturing, especially iron and steel. T h e changing technologies of the principal consumers of refractories have been reflected i n changes i n types of refractories produced. A s steel plant operating temperatures increased, silica brick replaced fireclay brick i n applications, only to be replaced i n turn b y basic brick of the magnesite-chrome type. Fireclay refractories used i n the hearth of blast furnaces have been replaced b y carbon refractories. T h e recent technological revolution i n steel making has increased the use of tar-bonded or tar-impregnated refractories of magnesite, either alone or i n combination with dolomite. Glass tanks, the large furnaces used to melt the quantities of glass consumed today have gone to denser refractories to minimize the corrosion w h i c h occurs between the glass melt and the furnace wall. This has l e d to the extensive use of fused-cast refractories. The high cost of labor needed to b u i l d refractory structures has l e d recently to the increased use of monolithic walls. These monolithic walls, instead of being laid u p as bricks, are cast, rammed, or gunned, using refractory specialty products. As the demands of the users of refractories have increased, the technical level of the refractories industry has increased. A scientific basis for the industry was laid i n the early 1920's w i t h the beginning of much of the research on refractories. This technical and scientific approach to the problems of the refractories industry, both i n manufacturing a n d applications, has intensified since the 1940's until today the refractories segment of the ceramic field is one of the most technically advanced. T h e field today actively utilizes the latest a d vances i n sintering, hot pressing, and high temperature solid state chemistry. The latest investigative methods and tools are employed i n this technical effort. Automated mass production techniques are used i n manufacturing refractories to an increasing extent. The literature of the refractories industry reflects a l l these changes and the great technological and scientific growth of the industry. Materials
Used as
Refractories
The majority of industrial refractories is composed of aluminum silicates. Silica a n d semi-silica refractories constitute the silica-rich end of this system. Fireclay refractories lie midway between the two end members of the system, alumina and silica. Mullite refractories are about 60 to 7 0 % alumina, the balance being silica. H i g h alumina refractories range u p to the top of the scale on the alumina end of the system. Refractories based on magnesia either alone or i n combination w i t h chrome ore are being used i n increasing quantities, particularly i n open hearth furnaces. F o r the lining of the newer basic oxygen furnaces used for steel pro-
In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
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108
LITERATURE
OF C H E M I C A L TECHNOLOGY
duction, tar-bonded magnesia or magnesia-dolomite compositions have been used. Pure oxides are valuable as refractories because they are stable both i n air and less active atmospheres. H i g h purity alumina refractories have been used widely for 35 years. Other oxide refractories of significant importance are zircon, zirconia, beryllia, and thoria. Carbon and graphite have been used as refractories for centuries. H i g h temperature strength, inertness to many molten metals and slags, electrical conductivity, and low rate of thermal expansion make carbon and graphite unique. Carbides are used as refractories because of their extremely high melting points, some above 3500°C. L a c k of stability i n air limits their applications. Silicon carbide is the exception. The viscous silica film developed on the surfaces of the carbide's grains protect the silicon carbide beneath. Borides of the high melting metals of the fourth, fifth, and sixth periodic groups have properties making them valuable as refractories. Their melting points range from 2000° to 3000 ° C , and they have low volatility. Their oxidation resistance is fair, and they maintain their strength up to extremely high temperatures. Nitrides, having high melting points and thus considered refractories, are formed by transition elements of the third, fourth, and fifth groups of the periodic chart. Stable, high melting nitrides are also formed by beryllium, boron, aluminum, and silicon. Nitride-bonded carbides now are available commercially. Literature Books. Because the term refractories comprises such a broad scope of materials, processes, products, and industries, there is a tremendous volume of literature available. F o r a comprehensive look at refractories, the reader should begin w i t h the standard textbook i n this field for many years. This is F . H . Norton's "Refractories" which covers the range of refractories from the fireclay brick to the thoria crucible, from clay-graphite shapes to yttrium carbide, and from bauxite to fused cast alumina blocks. Besides about 2000 references to these refractory subjects, the author also lists some 54 books on refractories published prior to 1949. This book is an excellent reference source on any phase of refractories up to 1949, including refractories history, raw materials, manufacturing methods, testing, and physical and chemical properties, as well as the uses of refractories i n industry. Another basic text of refractories technology is "Phase Diagrams for Ceramists" w h i c h is a compendium of phase equilibria of primarily the oxide systems. The 2066 phase diagrams are i n themselves a bibliography of references for the refractory oxides. The American Ceramic Society has also published "Refractories B i b l i ography, 1928-1947" and "Refractories Bibliography, 1947-1956," w h i c h are ready reference sources to a large volume of the literature. F o r more recent literature of a general nature on refractories (and ceramics as w e l l ) , the books "Elements of Ceramics" and "Introduction to
In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
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6.
TROSTEL E T A L .
Refractories
109
Ceramics" are recommended. T h e majority of other reference books given in this bibliography were selected as recent additions to the refractories technology w h i c h show current technical trends and involve more specific segments of refractories technology. Periodicals and Journals. T h e majority of the technical literature p u b lished i n the U n i t e d States can be found i n the Journal, Bulletin, and Abstracts of the American Ceramic Society. M a n y other domestic and foreign journals publish articles on refractories, a n d the abstracts of the American and British Ceramic Societies provide excellent coverage of world-wide literature. Chemical Abstracts is also useful for specific materials. A number of other publications included i n the bibliography are likely to be found i n a good technical library. Patents. Patent references can be found i n the bibliographies discussed previously or i n Ceramic Abstracts. U . S . patent literature can be located through the " M a n u a l of Classification" and its accompanying index. Pertinent classes a n d subclasses are listed i n the Bibliography.
BIBLIOGRAPHY Books, Including
Proceedings
" A S T M Standards," Part 13—Refractories, Glass, Ceramic Materials, American Society for Testing and Materials, Philadelphia, Pa., 1968 (annually in April). Budnikov, P. P., ed., "The Technology of Ceramics and Refractories," M I T Press, Cambridge, Mass., 1964. Burke, J . E . , ed., "Progress in Ceramic Science," 3 vols., Pergamon Press, New York, 1961-63. Campbell, I. E . , "High Temperature Technology," John Wiley and Sons, New York, 1956. Carroll-Porczynski, Charles Z., "Advanced Materials: Refractory Fibres, Fibrous Metals, Composites," Chemical Publishing Co., New York, 1962. Chesters, J . H . , "Steelplant Refractories," United Steel Co., L t d . (England) 1963. Coxey, J . R., "Refractories," Pennsylvania State College Press, State College, Pa., 1950. Gerard, G., "Extractive Metallurgy of Aluminum," V o l . 2, Interscience Publishers, Inc., New York, 1963. Green, Arnold T., Stewart, G. H . , eds., "Ceramics—A Symposium," British Ceramic Society, Stoke-on-Trent, England, 1953. Grofcsik, J . , "Mullite, Its Structure, Formation, and Significance," Publishing House of the Hungarian Academy of Science, Budapest, 1961. Harders, F., Kienow, S., "Feurfest-Kunde," Springer-Verlag, Berlin, 1960. "High Temperature Technology," International Union of Pure and Applied Chemistry, Butterworth & Co., London, 1964. Hove, J . E . , Riley, W . C., eds., "Ceramics for Advanced Technologies," John Wiley & Sons, New York, 1965. Hove, J . E., Riley, W . C., eds., "Modern Ceramics—Some Principles and Concepts," John Wiley & Sons, New York, 1965. Huminick, J . , ed., "High Temperature Inorganic Coatings," Reinhold Publishing Corp., New York, 1963. Kingery, W . D., "Introduction to Ceramics," John Wiley & Sons, New York, 1960. Kingery, W . D . , "Kinetics of High Temperature Processes," John Wiley & Sons, New York, 1959. Kingery, W . D., ed., "Ceramic Fabrication Processes," John Wiley & Sons, New York, 1958.
In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
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110
LITERATURE OF CHEMICAL TECHNOLOGY
Kriegel, W. W., Palmour, H., eds., "Mechanical Properties of Engineering Ceramics," Interscience Publishers, New York, 1961. Litbakovskii, A. A., "Fused Cast Refractories," Clearinghouse for Federal Scientific and Technical Information, Springfield, Va., 1961 (TT 60-51137). McNamara, E. P., "Ceramics," 3 vols., Pennsylvania State College Press, State College, Pa., 1939-44. Norton, F. H., "Refractories," 4th ed., McGraw-Hill Book Co., New York, 1968. Norton, F. H., "Elements of Ceramics," Addison-Wesley Publishing Co., Inc., Reading, Mass., 1952. "Phase Diagrams for Ceramists," compiled by Ernest M. Levin, Carl R. Robbins, and Howard F. McMurdie and edited by Margie K. Reser, American Ceramic Society, Columbus, Ohio, 1964. Popper, P., ed., "Special Ceramics," Heywood & Co., London, 1960. Popper, P., ed., "Special Ceramics, 1962," Academic Press, New York, 1963. "Refractory Ceramics for Aerospace," Battelle Memorial Institute and American Ceramic Society, Columbus, Ohio, 1964. Ryschkewitch, Eugene, "Oxide Ceramics," Academic Press, New York, 1960. Salmang, H., "Ceramics—Physical and Chemical Fundamentals," 4th ed., Butterworth & Co., London, 1961. Shaffer, P. T. B., Samsanov, G. V., "High Temperature Materials," Vols. I and II, Plenum Press, New York, 1964. Sosman, R. B., "Phases of Silica," Rutgers University Press, New Brunswick, N. J., 1965. "Symposium on Thermal Insulating Materials," American Society for Testing and Materials, Philadelphia, Pa., 1939. "Thermophysical Properties of Solid Materials," Vol. III—Ceramics, WADC, 1959. Tinklepaugh, J. R., Crandall, W. B., eds., "Cermets," Reinhold Publishing Corp., New York, 1960. Van Vlack, L. H., "Physical Ceramics for Engineers," Addison-Wesley Publishing Co., Reading, Mass., 1964. Wulff, J., "Powder Metallurgy," American Society for Metals, Metals Park, Ohio, 1942. Abstracts,
Indexes, and Information
Services
British Ceramic Abstracts, bound with Transactions of the British Ceramic Society, which see. Ceramic Abstracts, published with the Journal of the American Ceramic Society, which see. Chemical Abstracts, American Chemical Society, 1155 Sixteenth St., N . W., Washington, D. C. 20036, weekly. Year Section 1912 19. Glass & Ceramics 1961 19. Glass, Clay Products, Refractories, & Enameled Metals 1962 17. Ceramics 1963 21. Ceramics 1967 57. Ceramics Chemical Titles, American Chemical Society, semimonthly. Index of Patents Issued from the U. S. Patent Office, Superintendent of Documents, U . S. Government Printing Office, Washington, D. C. 20402, annual. Official Gazette, U . S. Patent Office, Superintendent of Documents, weekly. Review of Recent Developments, Battelle Memorial Institute, weekly. U. S. Government Research Reports, Clearinghouse for Federal Scientific and Technical Information, 5285 Port Royal Rd., Springfield, Va. 22151, monthly. Periodicals American Ceramic Society Bulletin, American Ceramic Society, 4055 North High St., Columbus, Ohio 43214, monthly. Berichte der Deutschen Keramischen Gesellschaft, Verlag Deutschen Keramischen Gesellschaft e.V., 47 Menzenberger Str., Bad Honnef/Rhein, Germany, monthly.
In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
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6.
TROSTEL
ET
AL.
111
Refractories
Ceramic Age, Ceramic Publications, Inc., 2728 Euclid Ave., Cleveland, Ohio 44115, monthly. Ceramic Industry, Industrial Publications, Inc., 5 S. Wabash Ave., Chicago, Ill. 60603, monthly. Industrial Heating, National Industrial Publishing Co., Union Trust Bldg., Pittsburgh, Pa. 15219, monthly. Interceram, Verlag G. Schmid, Kaiser Joseph-Str. 217, P. O. Box 1722, Freiburg/ Breigsgau, Germany, semiannual. Journal of the American Ceramic Society, American Ceramic Society, monthly. Journal of the British Ceramic Society, Shelton House, Stoke Rd., Shelton, Stoke-onTrent, England, semiannual. Ogneupory, SSSR (Refractories), English translation available from Pergamon Press, Inc., 122 East 55th St., New York 10022, bimonthly. Refractories Journal, London and Sheffield Publishing Co., L t d . , 7 Chesterfield Gardens, Curzon St., Mayfair, London W 1 , monthly. Refractories Institute Technical Bulletin, Ohio State University, Columbus, Ohio. Taika Zairyo (Refractory Materials), Kurosaki Yogyo Kabushikigaisha 535, Fujita, Yawatashi, Fukuokaken, Japan, quarterly. Taikabutsu Kogyo (Refractories), Taikarenga Giiitu Kai, 7-2 Ginza-nisi, Tyuo-ku, Tokyo, Japan, bimonthly. Transactions of the British Ceramic Society (incorporating British Ceramic Abstracts), The British Ceramic Society, Federation House, Stoke-on-Trent, England, monthly. Verres et Refractaires, Societe d' Editions Verrieres et Ceramiques, 34 rue MichelAnge, Paris (16 ), bimonthly. e
Bibliographies "Refractories Bibliography, 1928-1947," American Ceramic Society, Columbus, Ohio. "Refractories Bibliography, 1947-1956," American Ceramic Society, Columbus, Ohio. U . S. Department of Commerce, Clearinghouse for Scientific and Technical Information, 2585 Port Royal Rd., Springfield, Va. 22151, Selective Bibliographies: "High Temperature Research," Feb. 1961, 473 refs., SB-453. "Oxygen Steel Making—Foreign Literature," Feb. 1962, 115 refs., SB-489. "Refractories and Ceramics," July 1959, 569 refs., CTR-373. Patents Refractory Material Checker brick furnace structure Compositions Gas generator Kilns, Saggers Fire brick
Class: Subclass 263:51 106:43 through 122 48:74 25:153 75:95
RECEIVED April 12, 1965. Updated 1968.
In Literature of Chemical Technology; Smith, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1968.
