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The ability of activated charcoal or carbon to adsorb complex metal ions has been recognized for many years, but it wasn't until the late 1940s and early 1950s that attempts were made to employ carbon-In-Pulp or C. I. P. processing to the recovery of gold. Early plants using the process were those at the Golden Cycle in Cripple Creek, Colorado, the Getchell Mine near Golconda, Nevada, and at the Idria Mine in Honduras. Recovery of the carbon from the pulp was done by screening or flotation, and recovery of gold from the carbon was done by burning the carbon (a very difficult task) or by sending it to a smelter. Unfortunately at the time, the price of gold was still fixed at $3-5 per ounce and labor costs were rising to the point where these mines were no longer able to operate. Consequently, C. I. P. treatment was temporarily forgotten. In the early 1970s, however, Homestake Mining Company at Lead, South Dakota, were being forced by environmental regulations to discontinue the use of mercury for amalgamation in their 7,500 ton per day plant, and at the same time were encountering high labor costs in the slime circuit of the plant, where over 2,000 tons of slimes were filtered each day in Merrill plate and frame filter presses. Shortly before that, researchers of the United States Bureau of Mines had developed the caustic -cyanide method of stripping gold from activated carbon and an electrolytic cell (now known as the Zadra cell) to recover gold from the carbon strip liquor. Homestake and the United States Bureau of Mines then jointly operated a C. I. P. pilot plant at Lead. Results were immediately favorable and a 2,400 ton per day C. I. P. plant was then built to treat the slime fraction of the Homestake ore. (See Au and Ag Cyanidation Plant Practice, Volume I, SME of AIME, 1975. Later, Homestake built a second plant at Creede, Colorado, to treat the slime fraction of the tailings from a silver-lead flotation plant. Next was Duval Corporation's 3,000 ton per day C. I. P. plant at Battle Mountain, Nevada. Both of these latter plants are described in this volume. C. I. P. operations under construction at the time of this writing are as follows: Pinson Mining Co. , Nevada Gold Freeport Gold Company, Nevada Gold Compania Minera El Indio, Chile. Silver and Gold

Jan 1, 1981

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By A. M. Gaudin

CHANGES in industrial practice, in plant design, and in research methods which are so clearly to be seen on every hand, have affected the mineral industry as well as others. In particular, ore dressing has passed through a revolution in practice brought about by the introduction of flotation and other quasi-chemical methods, until it has ceased to be solely the mechanical preparation of ores. In fact, the term "ore dressing" itself is obsolescent, and "mineral dressing" has been growing in popularity. This assures adequate recognition of the fact that mineral substances other than ores, e.g. coals, clays, and cement rock, are treated by the same general methods. As a result of these industrial changes it was felt that a complete rearrangement of the curriculum and laboratories at the Massachusetts Institute of Technology would be ad-vantageous. Such a rearrangement would allow instruction and research to proceed in wider accord with industrial evolution and the needs of our times.

Jan 1, 1942

By Oscar Weiss

An aerial magnetometer survey was carried out by the author's geophysical organization over the Vredefort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well- known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales -cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies.

Jan 1, 1949

By A. W. Griffith, R. G. Beverly, W. A. Millsap

THE Grand Junction Pilot Plant, operated by National Lead Co. Inc., for the U. S. Atomic Energy Commission, is engaged in the amenability testing of orebodies to establish design and cost data for commercial mills and to test new processes for recovery of uranium from ores. Test work was performed to study the effects of several variables on leaching of uranium ores in carbonate solutions. Many of these variables had been investigated in the laboratory, but pilot plant tests were desirable to evaluate their importance in semi-works equipment and to predict optimum operating conditions for future commercial mills. The results of these tests should serve as a guide in selecting the most efficient and economical method of leaching uranium ores amenable to a carbonate process. This article is concerned with a process in which uranium is extracted from the ore by a hot Na2CO3- NaHCO3 solution; the uranium-bearing solution is separated from the solid residue by filtration, and uranium is then precipitated by chemical means.

Jan 9, 1957

By Scott Tzcrner

WITHIN recent years people have begun to realize the importance and significance of the mining and allied industries. The leading part the engineer plays in civilization is becoming recognized. However accurate quantitative knowledge of the industrial importance of mining is still seldom possessed except by those close to this business. It is true that there are a few who go to the extreme and represent the whole progress of civilization as a reflection of man's gradual mastery of mineral utilization, but on the whole, the magnitude of the-industry is underestimated. In this paper I shall call attention briefly to the importance of mining in the United States, in Canada, and in the world. Ordinarily, the annual primary mineral production of the United States is about $5,500,000,000. The average for the last 5 years has been a little over that, but last year, sadly enough, it was less than 31/4 billion. Just now, we are on the decline, and have been for the last two years. In Canada, the 5-year average was about $268,000,000, and last year it was 227 million. Due in part to gold mines (in 1930, for the first time, Canada's gold production exceeded that of the United States), the Canadian average is holding up better than ours. Average world mineral production over the last -5 years has been estimated at about $12,000,000;000 whereas in 1931 it was less than than 8 billion.

Jan 1, 1932

?AARONSON, ALFRED E , Vice-Pres , Mid-Co Petroleum Co, Mid-Co Bldg, Tulsa, Okla '18 ABADIE, EMILE R, Min Engr Address wanted '76 || ABADILLA, QUIRICO A, Geol Dept, Cia Mexicana de Petroleo "El Aguila," S A, Edifico "El Aguila," Esq, Calles Aurora y Comercio, Tampico, Tamaulipas, Mexico '20 ABBOTT, CLARENCE E, Gen'l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co, 1405 Minnesota Ave, Bessemer, Ala '04 ABBOTT, LOUIS BENJAMIN, Chief Engr, Consolidation Coal Co, Elkhorn Div, Jenkins, Ky '15 ABBOTT, ROBERT R Met Engr, Peerless Motor Car Co, Cleveland, Ohio '12 ABE, ASAKA Fujita Min Co, Dojima, Osaka, Japan '14 ABEEL, GEORGE H, JR, Cons Min Engr, 635 St Paul Ave, Los Angeles, Cal '18 ABEL, ALBERT E, Asst to Pres, Valley Mould & Iron Corpn, Sharpsville, Pea '19 ABEL, W D, Min Engr Forum Bldg, Sacramento, Cal '19 ABELL, O J, Pres & Treas, Abell-Howe Co, 332 South Michigan Ave, Chicago, Ill '19 ABERNATHY G E Willow Springs, Mo '20

Jan 1, 1923

By J. H. Swisher

ALUMINUM deoxidation equilibrium in liquid iron has been the subject of many investigations. Sawamura and Sano1 have written a critical survey of the literature on this subject and consider the data of Gokcen and chipman2 and of d'Entremont, Guernsey, and Chip-man3 to be most reliable. The present study was undertaken to check these data and extend the range of the experiments to lower temperature. The experiments consisted of equilibrating 5-lb Fe-Al melts with recrystallized alumina crucibles at 1580o + 10oC, and analyzing the solidified ingots for aluminum and oxygen. The electrolytic iron stock contained 100 ppm C, 20 ppm 0, and trace amounts of other elements.* The stock was induction-melted in an atmosphere of 5 pet H2 in argon to attain equilibrium between the melt and the crucible. The temperature was measured with a W, 3 pet Re/W, 26 pet Re thermocouple, and the equilibration time was about 4 hr. The results are plotted in Fig. 1 along with curves obtained from the data of d'Entremont et al.,3 for temperatures of 1740o and 1910°C. The present results can be seen to be consistent with the previously reported high-temperature data. The reaction under study is AI2O3 (s) = 2 Al (l) +3O [1] for which the deoxidation product is Kl =[% Al]2 [%O]3 [2] (Under the experimental conditions, Fe A12O4 is not expected to form.4) In Fig. 2, values of log Ki evaluated at 0.01 pet A1 are plotted against 1/T, using data obtained from all the investigations under consideration. The deoxidation product is plotted in Fig. 2 in lieu of the equilibrium constant (normally obtained by evaluating Ki as pet A1 — 0) because of the uncertainty involved in extrapolating to zero concentration. The difficulty in extrapolating the present data for 1580°C is apparent curvature in the log Ki vs pet Al plot. This curvature is perhaps due to the uncertainty in oxygen analysis for concentrations of 5 ppm and below. For the data of Gokeen and chipman,' the extrapolation is also difficult because of experimental scatter. The line drawn through the points plotted in Fig. 2 may be represented by the equation:

Jan 1, 1968

The Institute has prepared a list of Societies' publications, magazines, . etc., which were duplicates and were discarded at the time of the consolidation of the libraries of the three Founder Societies. These books will be disposed of about March 1, 1916 by the Board of Directors of the Institute through the Library Committee. If, meanwhile, members who have incomplete sets of these books, or for any other reason desire to secure some of them, they are asked to communicate immediately with the Secretary, as this is in unusual opportunity to secure books at a very low price. American Gas Light Journal, viols. 31 to 39. American Institute of Electrical Engineers, Transactions, vols. 5 to 26. American Machinist, vols. 3 to 20, 22 to 29. American Society of Civil Engineers, Transactions, vols. 2 to 10, 21 to 24, 26 to 33, 39 to 49, 52, 55, 58, 74. Index, viols. 1 to 21. American Society of Mechanical Engineers, Transactions, vols. 1 to 28. Index, vols. 1 to 20, vols. 1 to 25.

Jan 1, 1916

By Charles E. Heinrichs

IN the last decade one of our oldest and largest non-metallic metallic mineral industries has been the subject of persistent technical research, the results of which are another example of the benefits following the systematic application of scientific principles. The consequent improvement in the technique of phosphate recovery represents the greatest material advance in the industry since the discovery of phosphate in Florida in 1881. Moreover, these successes have stimulated interest and development in numerous other nonmetallic industries. Strange as it may seem, and despite the fact that the phosphate deposits of Giles County, Tennessee, together with those of Polk and Hillsborough Counties, Florida, have yielded more than 50,000,000 long tons in the last twenty years, the mineralogy of phosphates has been given scarcely any space in our technical literature. For many years it was the general consensus that these so-called phosphate rocks represented a physical mixture composed principally of tri-calcium phosphate, together with smaller quantities of calcium carbonate, calcium fluoride, iron phosphate, aluminum phosphate and other less important constituents. More recent investigations, however, led to the conclusion that these phosphates really represent a complex mineral in which calcium, iron, aluminum, phosphorus pentoxide, carbon dioxide, and fluorine all form a definite part of the molecule. Colony, after a careful study, utilizing chemical, microscopic, and X-ray diffraction methods, reported that American phosphates consist principally of calcium-carbono-phosphate of the staffalite type.

Jan 1, 1933

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members) Member, Graduate Colorado School of Mines. Four years' experience in West and Northwest. Two years with American Smelting and Refining Co. Wishes to join field party on geological work, mining or areal, where opportunity will be given to be of direct assistance to chief of party in solution of field problems. Age, 26. Unmarried. At liberty June 1. No. 342. Member, technical graduate, aged 30, with' 7 years' experience in concentrating and mining, desires a position of authority with reliable company. At present employed. No. 343. Member. Ambitious, energetic, tactful engineer, college graduate, married, aged 30, desires location with a large coal mining organization. Seven years with present employers -n middle west; has had broad experience in the past eight years on examination, development and construction; successful record in handling men. Position must carry responsible work and a future. Will go anywhere for proper opportunity. Exceptional references as to reliability, character and capacity for work. No. 344.

Jan 3, 1917

By John Stewart

The market at present supplied by shipments from the phosphate districts of Quebec, Ontario, and New York State requires high-grade ore, carrying from 75 per cent. to 90 per cent. of phosphate of lime. In sorting out such material by hand, much valuable phosphate is necessarily left in the "culls" or refuse, besides which, much phosphate-rock of low-grade is not now mined at all, because it cannot be made available by the crude method of cobbing and hand-sorting. The utilization of such material, which would, of course, greatly benefit this industry, requires either a mechanical separation or a chemical process which would concentrate the phosphate in a form suitable for agriculture. Considering the rich phosphate now shipped as the first class, we may arrange the lower grades in three classes, as follows: Second Class.—Cull-ore from the first class, and the mass of deposits having, as gangue, pyroxene or hornblende. The following table gives the hardness and specific gravity of the minerals concerned: Hardness Spec. gravity. Apatite,....... . 5 3.1 to 3.25 Crystalline limestone (pink calcite),. 3 to 4 2.5 to 2.9 Pyroxene,..5 to 6 3.23 to 3.5 Hornblende,.5 to 6 2.9 to 3.4 Feldspar (orthoclase),. .. . 6 to 6.5 2.5 to 2.6 It is evident that when pyroxene and hornblende are present in large proportions, this ore cannot be successfully concentrated by crushing and jigging. It may be reduced to fine powder by successive treatment in a rock-breaker and a Sturtevant or Frisbee-Lucop mill, or other suitable apparatus, and in this condition it could be largely used by applying it freely upon exhausted clay soils, such as occur in Quebec and Ontario. The occupants of these once fertile river-lands are, however, hard to move in the direction of such improvements. When water-power is at hand, the cost of crushing

Jan 1, 1893

THE shipments of high-grade manganese ore, con-taining 35 per cent or more of manganese, from the mines in the United States in 1926 were slightly less than half as large as similar shipments in 1925, accord-ing to the United States Bureau of Mines, Department of Commerce. The shipments in 1926 by 45 producers amounted to 46,258 long tons as compared with 98,324 long tons by 42 producers in 1925. This decrease was due to the falling off of the shipments from Montana. The domestic production of metallurgical ore in 1926 was 26,530 tons; that of chemical ore, 19,728 tons. Montana was the largest shipper with 5713 tons of metallurgical ore and 17,904 tons of chemical ore. The largest individual shipper of metallurgical ore was the Crescent Mine in the Olympic Mountain Region, Clallam Co., Washington, from which the shipments for the year were 3162 tons. The mine was operated by lessees and reverted to the owners in July, and thereafter to the close of the year no .ore was shipped.

Jan 6, 1927

By Marcus A. Grossman

THE institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it," All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we should review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks.

Jan 1, 1946

By Bieniawski, Z. T.

The importance of understanding the phenomena associated with rock fracture has long been fully appreciated in rock mechanics. This is clearly apparent from the special attention paid to rock fracture in the comprehensive papers published within the past four years. These papers present a picture of how the knowledge of brittle fracture of rock was gradually enriched and also show that what was often taken for granted three or four years ago is no longer considered as valid today.

Jan 1, 1972

By M. E. Bell

The term "operational research" was probably first used to describe work started under E. C. Williams, now Director, SHAPE Air Defense Technical Center, late in 1937 or 1938, at the Bawdsey Research Station of the British Air Ministry, a laboratory center concerned with the development of radar equipment. After the practicability of the early techniques had been demonstrated, a large (for those days) program of development and installation was authorized. It was very soon realized, both by the Royal Air Force and by the scientists that almost as important as the gear itself was the way in which it should be used. Accordingly, it was decided that some scientists should cooperate to study the way in which the equipment should be deployed and operated in conjunction with the Royal Air Force. To distinguish this work from the normal work of a research and development establishment, the term "operational research" was coined. It merely meant at this time that this particular section of scientists was to be concerned with the use of the gear rather than with its technical development and it seemed natural to those concerned to adopt the word "operations" which has a specific connotation in the armed forces.' This method was later extended to peacetime business enterprise, government operations and other human activities. Operations research appears to have penetrated the extractive industries more slowly and less completely than other industries, the military, or the government. This may be due (1) to a difference in the attitude of management towards operations research, or towards research of any kind, for that matter; (2) to unsuitability of the extractive industries for application of the operations research method; (3) to inaccessibility of the data; (4) or to a lack of trained personnel who are interested in applying operations research to the mineral industries.

Jan 8, 1963

By David T. Day

IN 1897 I published a proposed explanation t for the variation in color and specific gravity of Pennsylvania oils. A resume of this subject was also presented at the First International Petroleum Congress, in Paris, in 1900. Since that time much experimental work bearing upon this explanation has been carried on by myself, in the United States Geological Survey, and under my direction, by Dr. J. Elliott Gilpin, Marshall P. Cram, and 0. E. Bransky, at the Johns Hopkins University. The experimental results thus accumulated seem to throw considerable additional light upon the variations in color and specific gravity of petroleum, as found in different parts of the world, and also upon the variations in chemical composition. Therefore, it seems as if a, summary of the evidence thus obtained might be of value to those members of the Institute who are interested in the examination of oil-fields. The summary is here presented for that purpose. The phenomenon has often been observed in many oil-fields that oils of different color, specific gravity, and chemical composition may be found within short distances of each other. A conspicuous example of this is the occurrence at Jennings, Welsh, and Anse la Butte, La., of petroleum chemically somewhat similar to Russian petroleum; that is, characterized by the presence of naphthenes. Another characteristic is the presence of considerable percentages of asphaltic compounds, sufficient in quantity to disguise the presence of solid paraffin wax, and perhaps also to render that paraffin wax more soluble * Published by permission of the Director of the United States Geological Survey. 1 Proceedings of the American Philosophical Society of Philadelphia, vol. xxxvi., No. 154, pp. 112 to 115 (January, 1897).

Jun 1, 1910

By AIME AIME

ON THE occasion of the eightieth birthday of Captain Robert W. Hunt, the Iron and Steel Committee of the Institute, desiring to commemorate the great contributions made to the steel industry by Captain Hunt during his long career, conceived the idea of a Hunt Medal to be awarded annually by the Institute for meritorious contributions to the art of making steel. The project was received enthusiastically by all to whom it was proposed, especially by Captain Hunt's partners and employees who considered it their right, and asked for the privilege of -. - raising the necessary funds within their own circle. This was agreed to, and the Institute has received from them $7500 as an endowment fund to provide an annual award, and $1000 for the expenses of providing of medal.

Jan 1, 1920

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965