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By H. M. Faust

THERE are a number of different types of power plants. Some use coal to generate steam, others use oil or gas either in the form of steam or internal combustion equipment, while still others avail themselves of water power as a source of energy. A general comparison of the relative power production with different sources of energy in the United States, for several different years is set up in Table 1. This table shows that coal was used to generate 85.6 per cent of the total heat power requirements of 1909, and only 59.2 per cent of the 1930 requirements. The increasing proportion of modern heat energy generated by the use of fuel other than coal is apparent. If coal is to maintain its importance as a source of heat energy, the necessity for its improved perform-ance, in which preparation plays an -important part, cannot be stressed too strongly.

Jan 1, 1933

By H. G. Moulton

The increasing scale of mining operations over the past decade, particularly in connection with the exploitation of large bodies of comparatively low-grade copper ores, has made necessary the study of the behavior of rock under failure. When extractions of as high as 40,000 tons a day are reached in steam-shovel operations and as high as 20,000 tons per day in underground mining operations, it is evident that excavations soon become of such size that the behavior of the rock will often be dependent on fundamental principles applicable to more or less homogeneous materials under stress, rather than on weathering or local planes of weakness. In the ordinary rock excavations encountered in civil-engineering practice, such as excavations for subways, highways, railroads, etc., rock faces are not carried to depths sufficient to develop any pressures, or consequently any failures, except those due to loose masses resulting from local planes of weakness. When, however, orebodies whose tonnage is measured by hundreds of thousands are to be extracted by steam-shovel operations in open pits, it is necessary to determine if possible in advance the slopes that the sides of the pits will assume, for these slopes influence the shape of the excavations and thereby the amount of ore that may be extracted by the open-pit method. When large orebodies are mined underground at depths of 300 to 500 ft. (91 to 152 m.) by caving methods, the surface subsiding as the ore is withdrawn, it is necessary to determine in advance the outermost limits of fracture in the subsiding surface, for on the delineation of these limits depends the location of surface improvements, mills, smelters, etc. and also the location of development work, such as hoisting shafts, main haulage levels, and all other underground openings that must remain undisturbed during the period of ore extraction. Heretofore, in civil-engineering practice, it has been assumed that earth and rock behave differently in failure. For the calculation of earth pressures, formulas are used in which the assumption is made that earth banks fail by sliding along the slope determined by the frictional resistance of the material. The line of failure and the resulting pressure is held to be dependent on the angle of repose, which is different for varying

Jan 1, 1920

By Stephen Taber

Introduction.............................. 62 Asbestiform Minerals.......................... 63 Chemical and Mineralogical Relations............... 63 Physical Properties........................ 64 Types of Asbestos............................ 65 Origin of the Fibrous Structure...................... 66 Views of Previous Investigators.................... 66 Discussion of the Evidence.................... 67 Conclusions........................... 69 Origin of Cross-fiber Veins....................... 71 Chrysotile Veins......................... 72 Structural Features of Cross-fiber Veins............... 78 Veins of Crocidolite and Other Fibrous Amphiboles........... 83 Origin of Slip-fiber........................... 84 Origin of Mass-fiber........................... 86 Discussion............................... 87 IntRoduCtion The term asbestos, as commonly used, includes half a dozen minerals all having a well-developed fibrous structure, but differing in chemical composition and in some of their physical properties. In its strict application the name is limited to the fibrous varieties of the monoclinic amphiboles. Commercially, however, the most important of the asbestiform minerals is chrysotile, a fibrous variety of serpentine. About 95 per cent. of the asbestos used in manufacturing is chrysotile, and it commands a much higher price than any of the other fibrous minerals now on the market. Although the production of asbestos has increased rapidly in recent years, comparatively little has been published concerning its origin. The present paper is preliminary in its nature, and therefore does not pretend to exhaust the subject. The ideas herein developed are the result of field investigation, laboratory experiments in the growth of fibrous

Jan 1, 1918

By W. L. Fink, R. S. Archer

This paper describes results obtained on aluminum-beryllium alloys and aluminum-beryllium-copper alloys in the preparation of which aluminum of 99.95 per cent. purity was used. The constitution and structure of the high purity binary alloys are given. The aluminum-beryllium eutectic occurs at 0.87 per cent. beryllium and 645° C. The solid solubility of beryllium in aluminum at 631° C. is 0.05 per cent, beryllium, and at room temperature is less than 0.013 per cent. beryllium. The densities of the alloys are substantially the same as the values calculated on the assumption that the densities of the elements are not changed by alloying. All of the alloys age-harden at room temperature after a solution heat treatment, and the chill cast aluminum-beryllium-copper alloys age-harden at room temperature without a prior solution heat treatment. Hardness and tensile properties are given. Salt spray corrosion tests on sheet specimens are described. It is shown that beryllium docs not lower the corrosion resistance of aluminum to salt spray provided the alloy has received a solution heat treatment. Commercial Possibilities of Beryllium Alloys Beryllium has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to thc strength and corrosion resistance of thc aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a

By Ingvar Janelid

13.7-1. General. Iron ore mining in western Europe is mostly carried out underground and only a minor part is mined by open pit methods. Actual open pits of importance in this connection are, among others, Svappavaara in Sweden, Mo i Rana and Sydvaranger in Norway, Corby Mines, Colsterworth, and Scunthorpe in Great Britain, and in western Africa, Nimba and Bong Range in Liberia, and Kedia d’Idjil in Mauritania. The open pit mines of western Africa are of great interest in this connection as they are designed according to European practice and have accepted the same techniques, methods, equipment, etc. as the European mines. In the surface mining of limestone, granite, shale, etc., the technical conditions generally are similar with those in the iron ore mines. Some information will therefore be submitted from typical quarries. The geological conditions at the various iron ore mines and limestone and other quarries vary extensively. In Scandinavia the iron ores occur exclusively in Precambrian rocks. The ore is hard, mostly magnetite or hematite, folded and steep dipping, and hence accessible to surface mining only in the shallow sections. In the mines referred to, open pit mining will last for another 10 to 30 years, whereupon mining has to be continued by underground methods. In France the Minette iron ore has previously been mined in open pits but, because of increased overburden, mining underground with room and pillar methods now dominates. The iron ores are Jurassic, flatlying strata of oolitic type, containing chamosite, siderite, and brown hematite. The British iron ores are mostly of the same origin and appearance as the French deposits, but despite heavy overburden they are preferably mined from the surface. In western Africa, the iron ores are of the same type as in Brazil, i.e., itabirites with high-grade portions resulting from silica-leaching and weathering. The ore contains mostly brown and blue hematite and magnetite. Nimba and Kedia d’Idjil are very similar regarding ore quality and geology. Bong Range is a deposit of low-grade ore which has to be concentrated.

Jan 1, 1968

By A. E. J. Gallagher, W. D. Charles

The chapter is a review of published and unpublished data concerning energy usage and material wear in commercial crushing and grinding operations. Examples are given from practice and factors influencing power and wear are discussed.

Jan 1, 1982

J. R. Lane (Metals Research Laboratory, Washington)—A new type of deformation called "kinking" has recently been described. Is there any relation between the "rumpling" described in this paper and "kinking?" D. C. Jillson (author's reply)—Both are manifestations of bending about [210] axis. The difference is one of degree. W. C. Ellis (Bell Telephone Laboratories, New York) —Some observations of deformation in zinc recorded in this paper may be applicable generally to flow in metals. One of these, deformation in torsion without evidence of slip or twinning in the early stages and with startling ease, when the twist is about the hexagonal axis, adds another method of flow to the presently increasing list of mechanisms. This illustrates again that a crystal will utilize any realizable process to flow and relieve stress. The process is not necessarily classical directional slip—& this case, it is rotational slip. The question naturally occurs: Will face-centered cubic metas stressed by twisting about an octahedral axis flow in a similar manner by rotation on an octahedral plane? I would like to ask Dr. Jillson if he has made any experiments or knows of any experiments of this type on face-centered cubic metals? Face-centered cubic metals possibly would behave differently from zinc, since, for one thing, the stacking sequence is different for the two structures. The results of such experiments, however, would be instructive in providing more information about deformation processes. D. C. Jillson—Dr. Roy E. Swift, working in the Hammond Laboratory at Yale, performed a twist test on a single crystal of brass. The work has not been published, and I do not know the crystallographic direction of the axis of the specimen used. Lo-ching Chang (Columbia University, New York)— Observations similar to Figs. 1 and 2 of the paper were obtained by us during the bending and unbending of an orthorhombic Au-Cd alloy.'l This orthorhombic alloy is the product of diffusionless transformation from a single crystal of p Au-Cd alloy (CsC1 structure) containing 47.5 atomic pct Cd on cooling to about 60 "C.62 Referring to the effects of annealing, has the author tried any loilg time high temperature anneal, such as 150 to 200 hr at 40O°C? D. C. Jillson—No. C. Crussard (Ecole des Mines, Paris: France)—I

Jan 1, 1952

By R. K. Ham, M. L. Wayman

TD-Nickel has been broken in tension and in fatigue at voom temperature. Rod specimens failed in tension by necking, with axial cracks attributed to voids elongated in the extrusion direction. Fatigue specimens failed in shear. Thin-film electron microscopy showed that the subgrain structure of TD-Nickel was very stable, and that particle-matrix detachment was very difficult, in tension and fatigue. TD-Nickel softened slightly during fatigue but had a high fatigue ratio (0.5at 10' cycles). Fractography suggested that Stage I fatigue crack propagation is greatly extended in TD-Nickel. Td-NICKEL* is a dispersion of 2 pct by volume of thoria (ThO2) in nickel, produced by powder-metallurgical methods including compaction, sintering, and extrusion. The spherical thoria particles, which may have a mean diameter of a few hundred angstroms, are dispersed with a mean planar spacing of a few thousand angstroms. By a combination of cold working and annealing, a subgrain or cell structure of dislocations intimately associated with the dispersion can be produced.' This gives the material useful tensile properties which are extremely resistant to exposure to high temperatures.'-= At the same time, the material shows considerable ductility.3'4 At the beginning of the present work, it was considered of great interest to investigate the mechanical stability of TD-Nickel under conditions of fatigue. On the one hand, materials which derive strength from a cold-worked structure are unstable in that they are susceptible to fatigue softening: in addition, the presence of discontinuities such as the particle-matrix interfaces might be expected to assist in the initiation and propagation of fatigue cracks, in that they may provide local concentrations of internal stress and sites for the initiation of voids." On the other hand, the substantial ductility of TD-Nickel suggests that if it obeys Coffin's relation8 (or the more refined form proposed by Manson9) it should have good fatigue resistance. The initial purpose of this investigation was to assess the importance of these factors. Also, relatively little fundamental work has been done on the mechanism of fatigue in dispersion-strengthened materials. Work on overaged A1-4 pct CU10-12 revealed a very large Bauschinger effect indicative of internal stresses at the particles, and very great fatigue hardening1' presumably due to the multiple slip stimulated by these internal stresses, followed by softening which was initially due to softening in the matrix, but later might have arisen from cracking at the particle-matrix interfaces. The study of overaged Al-4 pct Cu could not settle this latter point by the electron microscopy of thin films, since the dispersion is too coarse. A previous study of the fatigue of internally oxidized copper13 was complicated by inter granular failure, attributed to oxide particles at grain bouhdaries; internal oxidation of single crystals, however, improved their fatigue properties.'3 Investigations of SAP (sintered aluminum powder) are complicated by the complex particle shapes, and the possibility of continuous internal oxide films.14 It was hoped to avoid these difficulties with TD-Nickel, which had the further advantages that it was commercially available and suitable for study by the thin-film technique. 1) MATERIALS AND EXPERIMENTAL PROCEDURE TD-Nickel was purchased from the Driver-Harris Co. as 3/9-in.-diam rod which had been extruded, swaged, and "stress-relieved" (normally at 1010°C for 1 hr). Continuous-radius fatigue specimens with a minimum diameter of -0.1 in. were ground to shape and electropolished in 40 pct phosphoric, 35 pct sul-furic, 25 pct water at 25oC, with a stainless-steel cathode, at -6 v. Fatigue tests were carried out at room temperature with a Sonntag SF-1-U machine operating in push-pull at 1800 cycles per min, and in an Instron TT-C-L modified for reversed stressing at 26 cycles per min as described elsewhere.10 Round tensile specimens were ground with 0.85-in. gage lengths of 0.135 in, diam, electropolished, and tested in a Tinius Olsen hydraulic machine. The surfaces of fatigue specimens were examined with a Reichert metallograph. Discs for electron microscopy with a Siemens Elmiskop I were spark-cut 0.01 in. thick with a modified Servomet 11 employing a tool of moving molybdenum wire, cleaned in 50 pct acetic, 30 pct nitric, 10 pct phosphoric, and 10pctsul-furic at 85oC, and thinned by the window method in the electropolishing solution at -20°C and -6 v. Two-stage replicas (parlodion, then Pt-50 pct C self-shadowed at 40 deg) were taken from fatigue fracture surfaces for electron microscopy. Plane sections parallel to the specimen axis and containing the direction of fatigue crack propagation were polished, etched with Carapella's reagent, and examined optically. Transmission Laue X-ray photographs of as-received material electropolished to a point were used to determine preferred orientation. 2) RESULTS 2.1) The Structure of As-Received Material. Grains -1 µ diam and elongated 20 to 30 u in the direction of the rod axis were observed, With' elongated "intergran-ular" voids (-4 p diam and -90 µ long and identified as such using longitudinal and transverse sections and

Jan 1, 1968

By H. S. Munroe

THE native copper of Lake Superior occurs in the form of fine grains and scales, disseminated in small percentage through the copper-bearing rock ; and in large and small masses, from a few pounds to several hundred tons in weight. Formerly the bulk of the copper came from the mines of Ontonagon and Keweenaw counties, producing mass copper. At present these mines furnish less than one-tenth of the total product, and fully one-half of this is from a single mine. The masses are usually found irregularly distributed in nearly vertical fissure veins, and require much dead work in sinking, drifting, and stoping for their development. The risk and expense attending the working of these mines have made them, with few exceptions, anything but profitable. * Read at the Montreal meeting, September, 1880.

Jan 1, 1880

University of Alabama University, Alabama Mining and Metallurgical Society JOSEPH CHARLES MEAD, President WAYNE G. BRIGGS, Secretary J. R. CUDWORTH, Faculty Sponsor RICHARD L. BOWRON, Counselor University of Arizona Tucson, Arizona Miners' Society W. JAMES THOMAS, President LAMONT WEST, Secretary J. B. CUNNINGHAM, Faculty Sponsor B. R. HATCHER, Counselor

Jan 1, 1938

By Sherwin Kelly

IN presenting this brief historical perspective, it is not my purpose to address myself to the geophysicists, to most of whom the story is already well known. My objective is to draw the attention of those who hold the belief that geophysics is something new, typically twentieth century, to the fact that fundamentally, whether it was known by the name of geo-physics or not, the science is an ancient and an honorable one. It began many centuries ago, and our modern civilization and its commerce owe a great debt to its founders, who today are likely to he overlooked and their names forgotten. The word "geophysics" means the physics of the earth, and is descriptive of a science that in many ways bears the same relationship to geology that astrophysics does to astronomy. When dealing with dis-tant stars or deeply buried rocks, the experimenter cannot reach them to obtain samples, which can be taken to his laboratory for study. He therefore exhibits the resourcefulness of Mahomet in the mountain episode, and makes the terrestrial globe or the cosmic universe his labora-tory, studying the effects of distant bodies on certain "fields of force"" which come to him across interstellar space, or through the rocks that make our earth. The application of these techniques of the physics laboratory to the study of the stars is the science of astrophysics, and to the investigation of the earth is geophysics. Yet the origin of the most valuable contribution to the world's trade and commerce ever made by geophysics remains lost in deep obscurity. Unknown even is the country wherein lived the unsung genius who invented the first geophysical instrument, the mariner's compass! Worse yet, it is not certain whether this invaluable guide of man had its begin-nings in Europe or in Asia. A Chinese legend tells of the Emperor Hwang-ti, who attacked his enemy Tchi-yeou on the plains of Tchou-lou in the year 2634 B.C., whereupon the latter magically raised such a fog that the Emperor could not pursue the retreating troops. Not to be outdone, the mighty ruler constructed a chariot that indicated the cardi-

Jan 1, 1938

By Calvin Pierson, R. S. Dean, E. P. Barrett

MANY studies have been made of the properties of steel produced by adding varying amounts of sponge iron to the charges used in steelmaking furnaces.1-3 The results of these previous studies, however, have failed to disclose a reason for the belief of steelmakers that steel made in this way is definitely different from steel made entirely from scrap or iron melting stock. This paper deals chiefly with the structure of the sponge iron, of the wrought iron made by welding the sponge iron into blooms, and of the steel made by melting the forged and rolled blooms. It is believed that the structure of the final steel is inherited from the ore and that this inherited structure produces marked differences in the properties of the steel and explains the feeling of steelmakers which is based on their experience. Three kinds of sponge iron were used in this investigation: One made from a limonite ore reduced with natural gas, one made from a hematite ore reduced with natural gas, and one made from a magnetite ore reduced with charcoal. The sponge iron made by reduction with natural gas

Jan 1, 1935

By Thomas Kesler

THE Cartersville mining district, 35 miles northwest of Atlanta, Ga., has been of varying but continuous importance in the southern mineral industry during the past century. Noted chiefly for its production of brown iron ore, manganese oxide ores, barite, sienna, and magnesian limestone, the district and its environs have produced brick and tile clays, slate, gold, bauxite, and graphitic schist. Minor deposits of serpentine, sericite schist, copper ore, and red iron oxide have been prospected. The obvious deposits of brown iron ore, together with some associated specular hematite, were mined out years ago, although a little ore was left in the workings. Moderately steady production of sienna reached a peak about 1930, then declined rapidly. Manganese mining passed through a relatively active period from the World War to 1931, but has subsided to a small but rather constant output for the Birmingham market. How-ever, the White Manganese Corporation has prepared for possible increased production by constructing a new washer capable of handling about 300 tons of ore per day. Principal activity in the district proper has centered for some years in the production of barite and magne-sian limestone.

Jan 1, 1940

By Andrew Hyslop

In our never ending search for new and better ways of underground mining, we find that transportation has had its share of new ideas in the past few years. The old and still effective method of track haulage has had some competition from rubber-tired cars and belt conveyors, each of which has its own safety hazards which demand close scrutiny in any safety study. The use of shuttle cars, in particular, has introduced clearance hazards caused by the absence of the more or less positive guides formed by the rails of a track sys- tem; likewise the requirement of greater clearance tends to increase roof hazards which we all know to be great enough with the best of methods. However, the subject of transportation hazards is too broad to be covered entirely in one paper, so I will confine myself to track methods which carry the preponderance of underground tonnage. I am quite sure that to this group it is an evident fact that haulage accidents are of major importance. However, to stress the point, it may be well to look at a few figures. Safety statistics can be quite boring and often are subject to question as to mathematical accuracy because of different

Jan 1, 1949

Jan 1, 1969

By F. F. Aplan

For the past year, MBD has been engaged in a lively discussion on a name change for the Division. To complicate things, more than one name change has been proposed! There has been much discussion on the subject, as anyone who has attended the Annual MBD Business Meeting or read [jE] knows. The position of many of our members is well known. There is, however, one group that has not been heard from. These are the future members-the present students and those even younger who are yet to elect our profession. As one who has traversed the academic-industrial interface several times, I think I am qualified to speak for this group. Before going further I think it wise to state unequivocally that our Division should adequately represent our profession. The whole profession is just too small to chop into a plethora of pieces: "I'm not a mineral processing engineer, I'm an ore dresser-well, actually, I specialize in comminution, specifically in grinding, mostly in autogeneous grinding-primary autogeneous grinding that is-and my 'thing' is really iron ores, taconites, mind you!" Enough to confuse even those that keep the faith, and certainly we can't build a profession on such narrow pieces. Either an employer can hire a professional who knows the entire profession or he can't. As more and more companies search out opportunities in the mining and metallurgical fields and as environmental considerations bring into question even our technically well proven processes and procedures, there is a greater need than ever be- fore for a well-rounded mineral processing engineer well versed in all of the process possibilities. What is needed is one who can take an ore-or municipal trash for that matter-and produce there from a valuable product by the most appropriate means. It doesn't really matter if this is done physically, chemically or thermally.

Jan 1, 1971

By C. E. Brown, D. C. Helms, O. W. Shimer

The early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. . The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 3½ million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20" to 90 and some are on the invert in many sharp folds and faults. Planning The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been . maintained. Locations of stripping areas are determined as follows: I. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness

Jan 1, 1944

By John Chipman, Carl F. Floe

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968