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By A. A. Smith

THE application of indium to bearings was first advocated by C. F. Smart1 in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. METHOD Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium was deposited and diffusion was carried out at 150°C. for a period of 500 hr. in a thermostatically con- trolled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro- graphically and chemically-the spectro- graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. Also, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at l20°C. for a period of 200 hours.

Jan 1, 1944

The annual meeting of the Mining and Metallurgical Society of America was held on Tuesday, Jan. 8, 1918, at the Engineers' Club, New York, to elect officers and councillors for the ensuing year, to receive the reports of its retiring officers, and for the transaction of any business which might properly be considered. As usual, the meeting was divided into two sessions; the first, more properly the business session, was called to order at 2:30 p.m., with an attendance of 17 members; the second session took place at 8:30 p. m., immediately following an informal dinner, at which 40 guests and members participated. The latter was particularly interesting because it gave the meeting an opportunity to absorb first-hand information regarding the present crisis in Russia. Messrs. F. W. Draper and J. P. Hutchins, the latter a member and long resident in Russia, were the speakers of the evening.

Jan 3, 1918

Discussion of the paper of E. W. Parker, presented at the New York meeting, February, 1913, and printed in Bulletin No. 75, March, 1913, pp. 443 to 451. A MEMBER :-I would like to call attention to the fact that the speaker has failed to indicate where is the center of gravity of the membership of the Institute, while he is dealing with this map. MR. PARKER :-I think you will find that a little further east. CHAIRMAN JAMES F. KEMP :-In connection with Mr. Parker's paper, I would like to inject a little matter of history into our program here, as regards the founding of the Institute. The credit for the founding of the Institute really applies to miners who were engaged in the anthracite coal region. The three men who signed the circular for the call for the meeting which brought the engineers to Wilkes-Barre in May, 1871, were Eckley B. Coxe, Richard P. Rothwell, and Martin Coryell.

Jan 5, 1913

F. McMillan Stanton was born in New York City on May 23, 1865, the son of an English father and of a mother whose family was linked with that of Peter Stuyvesant. Mr. Stanton took his degree from the School of Mines of Columbia University in 1887, worked for two years as an assayer and surveyor and then went into the mining field on his own account. After a few years, he was offered a position with the Atlantic Mining Co., and began the work which was to continue with marked success for twenty-three years. In 1910, Mr. Stanton retired and went to Europe for a rest. Upon his return in 1914, he was elected treasurer and director of the Mohawk Mining Co., the Wolverine Copper Mining Co. and the Michigan Copper Mining Co., to which group was later added the White Pine Extension, Copper Co., and continued to serve these companies until the time of his death, Sept. 12, 1916.

Jan 12, 1916

By W. E. Rice

The ceramic industry has to do with forming or molding articles of clay, and imparting to them their characteristic properties of permanence, strength and color by subjecting them to heat treatment in kilns. This heat treatment is commonly known as "firing" or "burning." The art of firing clay ware antedates the industrial use of coal; hence wood was the fuel first used, and the earliest kilns were built to burn wood. The majority of the clay ware produced today is fired in periodic kilns that are essentially enlarged structures similar to the earliest enclosed kilns; a kiln consists of a large chamber 16 to 32 ft. dia. (or rectangular) in which the ware is charged and fired either in direct contact with flame or hot gases from the fuel, or in saggers which shield the ware from direct contact with the gases. The fuel is burned in a number of small furnaces built in the thick wall that encloses the chamber; these furnaces are from 16 to 36 in. wide and from 3 to 5 ft. long; some of them have horizontal or sloping grates, but many have no grates; the last are called "dead-bottom" furnaces. The temperature necessary to mature the charge in the kiln varies for different clays; for some it is as low as 1800°, and for others as high as 2700" F. Wood was an ideal fuel for the low temperatures that were used in early kilns; it burns freely and produces a long, clean flame, which promotes uniform distribution of the heat in the kiln; it does not coke and so restrict the passage of air through the fuel bed; the ash does not melt in the fuel bed to form clinker; and the ash that is carried into the chamber and deposited on the charge does not contain iron and sulfur to discolor the clay. The extent of the ceramic industry now precludes the general use of wood in kilns, so that today this industry is one of the large users of bituminous coal, burning more than eight million tons annually in kilns. Manufacturing plants usually are at or near the source of clay, with deposits of coal suitable for kilns occurring near the clay. The cost of coal is the largest single item of expense in the manufacture of clay ware, and, because all coals are not equally suitable for the process, the careful selection of coal is important. In this selection the desidera-

Jan 1, 1932

By W. E. Rice

THE ceramic industry has to do with forming or molding articles of clay, and imparting to them their characteristic properties of permanence, strength and color by subjecting them to heat treatment in kilns. This heat treatment is commonly known as "firing" or "burning." The art of firing clay ware antedates the industrial use of coal; hence wood was the fuel first used, and the earliest kilns were built to burn wood. The majority of the clay ware produced today is fired in periodic kilns that are essentially enlarged structures similar to the earliest enclosed kilns; a kiln consists of a large chamber 16 to 32 ft. dia. (or rectangular) in which the ware is charged and fired either in direct contact with flame or hot gases from the fuel, or in saggers which shield the ware from direct contact with the gases. The fuel is burned in a number of small furnaces built in the thick .wall that encloses the chamber; these furnaces are from 16 to 36 in. wide and from 3 to 5 ft. long; some of them have horizontal or sloping grates, but many have no, grates; the last are called "dead-bottom" furnaces. The temperature necessary to mature the charge in the kiln varies for different clays; for some it is as low as 1800°, and for others as high as 2700° F. Wood was an ideal fuel for the low temperatures that were used in early kilns; it burns freely and produces along, clean flame, which promotes uniform distribution of the heat in the kiln; it does not coke and so restrict the passage of air through the fuel bed; the ash does not melt in the fuel bed to form clinker; and the ash that is carried into the chamber and deposited on the charge does not contain iron and sulfur to discolor the clay. The extent of the ceramic industry now precludes the general use of wood in kilns, so that today this industry is one of the large users -of bituminous coal, burning more than eight million tons annually in kilns. Manufacturing plants usually are at or near the source of clay, with deposits of coal suitable for kilns occurring near the clay. The cost of coal is the largest single item of expense in the manufacture of clay ware, and, because all coals are not equally suitable for the process, the careful selection of coal is important. In this selection the desidera-

Jan 1, 1932

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

Jan 1, 1944

By A. A. Smith

The application of indium to bearings was first advocated by C. F. Smsrtl in 1938, for the purpose of inhibiting corrosion of certain bearing alloys. He found that a thin layer of indium plated on the bearing surface and subsequently diffused at elevated temperatures markedly decreased the rate of corrosion in lubricating oils containing organic? acids. Most of his work was done on cadmium-base alloys, although he showed that the treatment was also effective for copper-lead and other; alloys. Since their introduction, indium-treated bearings have found considerable use, particularly in connection with airplane motors.2 Undoubtedly the effectiveness of the indium plate in resisting corrosion depends upon its relative concentration on the bearing surface after the diffusion treatment and after prolonged use at operating temperatures. Some diffusion experiments were made on a number of base metals that had been indium plated, to determine the depth of penetration after heating for reasonably long periods of time. As only the practical aspects were desired, no attempt was made to determine actual diffusion constants. Method Two different series of experiments were carried out to study the diffusion of indium into several base metals. Cast cylinders about one-inch diameter were machined to 0.750-in. diameter, so as to remove all surface imperfections, and final finishing was done with oo sandpaper. The original diameters were very carefully measured with micrometers and then a layer of indium was electrolytically deposited on the cylinders from a sulphate bath.3 In the first series of experiments, about 0.002 in. of indium' was deposited and diffusion, was carried out at 150°C. for a period of 500 hr. in a thermostatically controlled electric oven. After the diffusion period, successive layers were machined from the specimens and analyzed spectro-graphically and chemically—the spectro-graphic examination serving as a guide to determine which layers should be chemically analyzed. Apparently there was some surface oxidation of the indium plate due to the long heat-treatment, which may have had some effect on the diffusion. A1so, the cadmium alloy showed some incipient melting, which probably was caused by the formation of a low-melting eutectic. To eliminate these factors, another series of experiments was carried out by heating in an electrically heated, automatically controlled, oil bath at lower temperature. The preparation of the specimens was the same as before except that a layer of indium 0.0001 in. thick, an amount commonly used commercially on bearings, was deposited on each of the cylinders. Diffusion was carried out at 120°C. for a period of 200

Jan 1, 1944

The Howe Memorial Lecture, in memory of Henry Marion Howe, Past President of the Institute, was authorized in April, 1923, as an annual address to be delivered by invitation under the auspices of the Institute by an individual of recognized and outstanding attainment in the science and practice of iron and steel metallurgy or metallography, chosen by the Board of Directors upon recommendation of the Iron and Steel Division. The following were the Howe lectures and lecturers for the years indicated 1924 What is Steel? By Albert Sauveur. 1925 Austenite and Austenitic Steels. By John A. Mathews. 1926 Twenty-five Years of Metallography. By William Campbell. 1927 Alloy Steels. By Bradley Stoughton. 1928 Significance of the Simple Steel Analysis. By Harry D. Hibbard. 1929 Studies of Hadfield's Manganese Steel with the High-power Microscope. By John Howe Hall. 1930 The Future of the American Iron and Steel Industry. By Zay Jeffries. 1931 On the Art of Metallography. By Francis F. Lucas.

Jan 1, 1923

71 BROADWAY, NEW YORK, Sept. 22, 1913. CHARLES W. GOODALE, Chairman, . DARSIE C. BARD, ESQ., Secretary. Committee on Precious and Base Metals, Butte, Montana. Gentlemen The wonderful success of the meeting of the Institute held in Montana makes it necessary that some public acknowledgment should be made to those to whom this success is due. We are conscious that the securing of the great number of technical papers of lasting value and the carrying to success of most complete detailed arrangements for holding the meeting have called for several months of skilled effort on your part. The benefit of the meeting is very great and extends not only to those who were fortunate enough to be present, but to our four thousand absent members and their friends as well. To you and your associates on the Committee whose efforts have made this never-to-be-forgotten meeting possible we owe far more than can be expressed in votes of thanks. Very respectfully, CHARLES F. RAND, President.

Jan 10, 1913

The Mining Engineering Society of the State College of Washington, Pullman, Wash., has elected the following officers for this semester: F. MASON, President, WILLIAM WHITE, Vice-President,. L. E. TRAEGER, Secretary and Treasurer. The Society holds meetings every two weeks at which papers on mining and metallurgical topics are presented by students and members, of the faculty. At the meeting of Oct. 25, Prof. H. R. Robbins gave an interesting talk upon the Rankin Process for the treatment of base-metal ores. In this process the metals are extracted by the use of nitric acid, the acid -being recovered almost entirely. Prof. Robbins thinks the process has great possibilities, but it has not yet been worked on a commercial scale. The Missouri Mining Association, the student organization at the Missouri School of Mines, Rolla, Mo., has. elected the following officers for the ensuing year: L. W. EHLERS, President, H. A. KLUGE, Treasurer, J. G. REILLY, Vice-President, N. E. RITTER, Secretary.

Jan 12, 1915

(Members are urged 'to, send in for this column any notes of interest concerning themselves or, their fellow-members.) Members and guests who registered at Institute headquarters during the period Sept. 10 to Oct. 10, 1915: George H. Blakemore, Sydney, N. S. W. W. B. A. Dingwall, San Antonio, Tex.. H. Haege, Sydney, N. S. W. R. H. Jeffrey, London, England. C. A. Filteau, New York, N. Y. H. S. Emlaw, Spring Lake, Mich. Myron R. Walker, Cerro de Pasco, Peru. Y. T. Woo,' Tientsin, China. William R. Grunow, Morenci, Ariz. A. L. DeDeken, LouVain, Belgium. E. DeGolyer, Norman, Okla. K. P. Swensen, Tokyo, Japan. William W. Elmer, Tuttletown, Cal. Charles Enzian, Wilkes-Barre, Pa. Huntington Adams, Iquique, Chile. C. F. Schnepp, Cobalt, Ont., Canada. W. Ray Cox, for several years Mineral Inspector of the General Land Office at Portland, Ore., has been appointed Professor of Mining and Metallurgy in the School of Mines, Oregon Agricultural College, Corvallis, Ore.

Jan 11, 1915

The Lead-Line Update held in conjunction with the 1977 SME-AIME Fall Meeting in St. Louis provided sessions on mining, mineral processing, extractive metallurgy, and economies to brief the record on the industry's activities and developments since the 1970 World Symposium on Lead and Line convened, also in St. Louis. Changes in the industry since 1970 have not been profound, notes the program committee, consisting of D. O. Rausch, F. M. Stephens, and B.C. Mariacher, cochairmen; and H. L. Clifford, S. C. Fall), and M. Snedeker. However, various environmental and conservation factors have had a direct impact on process consideration and operating practice; the result has been new mines, improved technology, and changing market opportunities. The general consensus of the participants is that the future for the Lead-zinc industry looks promising as new applications are found and new products resulting from intensive research reach the marketplace. The highlights of the HS technical papers presented at the 1977 session follows.

Jan 11, 1977

B. F. TILLSON,* Franklin Furnace, N. J.-I would like to ask Major Yerkes if he will not give us more examples of the tests than are contained in the printed pamphlet. It would be of great interest to study them more carefully. ROBERT M. YERKES, Washington, D. C.-The reason for not reproducing the methods in any public print is that it lessens their value and necessitates the preparation of new test materials. BRADLEY STOUGHTON, New York, N. Y.-I hope that this matter will be of so much interest to the members of the Institute that the Directors will decide to appoint a committee which can bring further results of this practice before us. I understand that Columbia University, at least in some departments, has already adopted the B and A tests and is using them. I understand that some industries have considered seriously the question of grading their employees in accordance with

Jan 4, 1919

The Students' Organization of the Michigan College of Mines was recognized as an Affiliated Student Society by the Board of Directors of the Institute, at a meeting held on April 28, 1916. At the College of Mines, University of Washington, 30 students and instructors took part in the annual spring excursion early in April. Studies were made of the new reverberatory and casting furnaces at the Tacoma smelter, the Du Pont powder works located on Puget Sound and the Britannia Mining and Smelting Company's mine and mills on Howe Sound, near Vancouver, B.C. The Britannia mills are using Hancock jigs, Burchart tables and Minerals Separation flotation cells to effect a high recovery on low-grade chalcopyrite ore. The Mining Club, University of. Wisconsin, elected the following officers for the second semester of the present school year: J. G. SKIRM, President, H. L. RAU, Vice President, T. C. SHERWOOD, JR., Secretary-Treasurer, H. E. HODGSON, Mucker, , F. M. WOLVERTON, Assistant Mucker. Theo. C. SHERWOOD, Jr., Secretary.

Jan 6, 1916

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By Irving B. Cadoff, Stojan M. Zalar

AgInTe2, CuInTe2, and all Proportions of CuxAg1-xInTe, forMed homogeneous single phase alloys after direct solidification from the nielt. X-ray analysis indicated a zinc-blel~de strzccture typical of the chalcopyrite compounds, and the electrical resistivity and Sccbeck coefficient values were in the semiconducting range. AuInTe, and AuxA4g,-, InTe, formed by what appeared to be a peritectic reaction (the thermal analysis curves showing more than one arrest) and were conseyue~ztly polyphase. Substitution of copper into AgIrzTe, resulted in a continuous transition in the room tenzperature Seebeck coefficient from the negative AgIzTe, to the positive CuInTe,. A zero coefficient was obtained at about Cuo.55 Ago.45 InTe, . The temperatzire variation was similar to that observed for the stoichiometric compounds, that zs, tendency towards "p" concEuction at elevated temperatures. The thernzoelectric figure of merit for the compo~uzds, as determined by the Putley -Harmnn method were in the range 10- to 10-7 "K-l; the thermal conductivities in the order of 0.15 cal per sec-cm-oK. INCREASED interest in semiconducting intermetallic substances is expanding much of recent research from simple binary compounds into polyatomic systems and solid solutions. Ternary compounds A' represent a covalent extension of the binary semiconductors Within the a tin isoelec-tronic series, Ag-Cd-In-Sn-Sb-Te-I, divalent cadmium atoms in CdTe are being substituted for by monovalent silver and trivalent indium atoms to form the compound AgInTe, . By cross-substitution with elements of other isoelectronic series, a great number of ternary compounds A 'B"'c? is possible. In all of them, however, a necessary though not sufficient condition for the covalent, semiconducting bond—that there be four sharing orbital electrons per atom—must be fulfilled. In AgInTe,, each silver or indium atom is tetrahedrally surrounded by four tellurium atoms, while each tellurium atom is co-valently bound to two silver and two indium atoms. Synthetic chalcopyrites A'B"'c~ were first recognized as potential semiconduct&rs by Goodman and Douglas.' Austin, Goodman, and Pengelly discuss preparation difficulties and some electronic measurements on AgInS, , AgInSe, CuInSe, , AgInTe, , and CuInTe,. Chalcopyrites A B c2v are mentioned in papers attempting to classify and predict semiconducting behavior of intermetallic compounds; on the basis of saturated tetrahedral sp3 bonds,3 by specific selection criteria,' and by crystallographic considerations."

Jan 1, 1962

By T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,' sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.' The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By Alfred Fisher

CONSERVATION of mine timber is becoming in-creasingly important, and the consumer is en-couraged to use treated wood to permit longer life of mine timbers, and attempts are also made to substitute other material for wood. The great diffi-culty in substituting metal and concrete props for wood is the inability of these to give yielding resistance to roof pressure as wood supports do. In Europe, where mine timber costs are somewhat more important than in America, many designs of steel props have been tried, but have been unsuccessful, chiefly on account of inability to give yielding resistances. A metal pit prop that gives the desired effect has been extensively used in European mines and has caused a considerable reduction in accidents from falls of roof. Where mining operations have been sus-pended on account of strikes, conditions were found to be much better where such props were used instead of wood props, and machinery, which would have been destroyed by roof falls had wood props been used, was protected by the use of these yielding metal props. As this prop is adjustable, all the work of adjusting and transferring long props through narrow ways is done away with. It can also be drawn with greater ease and safety than wooden props; when properly used it is practically indestructible. European users have reported savings as against wooden props as high as 80 per cent. It gives audible warning of its working because the sliding action takes place in minute jerks. As the prop yields gradually to pressure its force is taken up by friction between the H sections, and this movement progressively increases the resistance of the prop to the increasing roof pressure. In the early development of the prop, it was designed with two steel members a and b of standard H steel sec-tions of equal dimensions provided with guide claws a' and b', held in frictional contact against each other by two differential wedges, f and g, and a floating link, e. In setting up the prop its two members are drawn out to the required length, the loose wedge, g, is then fitted into the space between the left-hand roller of the link d and the lower member of the prop b, and tapped suf-ficiently tight to prevent any relative movement of the two members from taking place prematurely. The prop is then raised to its intended position and secured in the usual way.

Jan 8, 1927