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By J. S. Marsh

AN incomplete statistical analysis performed wearily on the morning after Thursday, Feb. 12, indicates that the unavoidable items of conversation among steelmen were the current shortage of sleeping time and the "Normandie." No analysis is needed, however, to be certain that many thousands of valuable words were uttered, both in and out of technical sessions, concerning matters of deep interest to members of the Iron and Steel Division. The opening session consisted mostly of papers that have appeared, or will appear shortly, in Metals Technology. One, however, that was not finished in time to be printed in any form, but that aroused great interest, was by E. L. Ramsey and L. G. Graper (Wisconsin Steel Works). Its subject was the production of high-sulphur steel by treatment with sulphur dioxide derived from anhydrous sodium sulphite or bisulphite added to the ladle or to the mold. The sulphide distribution in the finished steel is such that increased machinability and longer tool life result. Both items are of obvious importance in these days of mighty production.

Jan 1, 1942

EXECUTIVE COMMITTEE OF THE BOARD OF DIRECTORS W M Peirce, Chairman Philip Kraft, Vice-Chairman Francis B Foley Hjalmar W Johnson Thomas G Moore ENDOWMENT Cleveland E Dodge, Chairman C F Kelley John D Bradley Harvey S Mudd J Coulter W A Sinsheimer N Eavenson Wilfred Sykes C Jackling Clyde E Weed

Jan 1, 1951

THE CHAIRMAN (J. W. RICHARDS, South Bethlehem, Pa.)-The first point on which I wish to speak is that sufficient attention has not been given to the quality of the ores, in estimating the reserves. I made this same criticism of the work on the iron-ore resources of the world issued by

Jan 12, 1918

By K. R. Janowski, H. Conrad

As part of a program to establish the effect of crystal imperfections on laser output, a detailed study was made of the dislocation structure of ruby crystals obtained from varioius sources. Using KHSO4 as an etchant, a detailed mapping of the dislocation structure on the (0001) and the (1150) planes was carried out. A less extensive study was made of the rhombohedral planes. The average dislocation density on the basal plane was 1.5 to 3 x 106 cm&apos;2 and on the (1120) planes -5 x 10&apos; cm-2. Howe7!er, considerable variation existed between areas on a given plane. The subboundaries in the basal plane tended to lie along [1100] type directions while those on the (1120) plane tended to lie: a) parallel to the basal plane, b) along truces of the (1101) plane, and c) along normals to the traces of the (0001) planes. The orientations suggest that mang of the dislocations lie on the (0001), (1701), and (1150) planes A Laue back-rellection nnalysis Of c-axis wander in one crystal revealed a gradual increase in misorientation from me end of the crystal to the other, with a maximum variation of 1°35&apos;. Slight etching of a mechanically polished crystal revealed mumerous polishing scratches, suggesting the existence of a plastic flow layer. It is recognized that chromium concentration, lineage, and other crystalline imperfections play a role in the efficiency of ruby lasers.&apos; Consequently, it is desirable to establish in detail the imperfection structure of ruby crystals to be used as lasers. Some exploratory work along this line had already been done by Barnes&apos; and Dils and Martin.&apos;" How- referred to as the morphological system, as described by Kronberg.4 The Miller indices given in the present paper will be based on this morphological system. In this system, the three common growth planes are the (0001), the {1120}, and the {1101}.5 Since these planes are of high stability, it is expected that they are most suitable for study by the etch-pit technique. In the present investigation, a detailed mapping of the dislocation structure was carried out for the (0001) and the (1130) planes. A less extensive study was made of the etch-pit structure on rhombohedra1 planes. An analysis of dislocations in sapphire (the ruby host) was first made by kronberg,4 who postulated that slip on the (0001) plane occurred by motion of dislocations with Burgers vector 1/3 <1150> and that these dislocations might dissociate into quarter partials. An etch-pit technique using boiling phosphoric acid was developed by Scheuplein and Gibbs6, 7 for identifying dislocations intersecting the (0001) planes and the planes near (2021) in sapphire. Al-ford and Stephens8 were able to reveal dislocations on the (0001) and {1120} planes in sapphire and ruby by etching in fused potassium bisulfate (KHS04) at 675°C. The termini of basal dislocations [(000l), <1120>] were revealed by Palmour and Kriegel9 on {1120} and {1010} by thermally etching sapphire. Bond and Harvey10 were able to decorate dislocations in sapphire by adding 1 pet by weight of ZrO2 to the Al2O3 powder used in the growth of the crystals by the Verneuil technique and then heating the grown crystals for 4 hr at 1500°C. They found, using optical transmission microscopy, that many dislocations had straight segments which were parallel to one of the six [1120] directions in the basal plane. Single dislocation lines curved smoothly from one alignment to the other, turning through angles of 60 to 120 deg. Also observed were isolated hexagonal loops, approximately 10 µ in diameter, the sides of which lay along the same directions as did the longer dislocations. MATERIAL AND ETCHING PROCEDURE The ruby specimens used in this study (all containing approximately 0.04 pet Cr) had been obtained from four different sources: Linde Co., Meller Co., Valpey Crystal Corp., and those grown at Aerospace Corp.* For the initial phase of this study, several specimens were cut from the slab shown schematically in Fig. 1 which had previously been cut from a disk boule obtained from the Linde

Jan 1, 1964

United Engineering Trustees, Inc. W. D. B. MOTTER JR., &apos;44 A. L. QUENEAU, &apos;41 ALBERT ROBERTS, &apos;43 The Engineering Foundation GEORGE D. BARRON, &apos;44 F. F. COLCORD, &apos;42 A. L. QUENRAU, &apos;41 Engineering Societies Library Board A. T. HASTINGS, &apos;41 J. W. LAIST, &apos;44 A. B. PARSONS, EX-Officio T. T. READ, &apos;42

Jan 1, 1941

By Charles Albert Ashburner

THE stratigraphical geology of the vicinity of Buffalo has always been of great interest on account of its bearing on the origin and history of the Niagara-river gorge, between the Falls and Lake Ontario. Recently, however, the character and thickness of the strata which underlie Buffalo have acquired more practical and economic importance on account of their relation to the possible occurrence of natural gas in commercial quantity near the Niagara river. In a paper presented at the Duluth meeting (l887), on " Petroleum and Natural Gas in New york State" (Trans., xvi., 906), I gave a brief description of the four wells which had been drilled by the Buffalo Cement Company between 1883 and that time. One of these wells is 1305 fret deep; and, at the time that my paper was finally revised for the Transactions (June, 1888), it was still an open question whether the drill in this well had reached the Niagara limestone, or had penetrated the Medina sandstones and shales, which latter are boldly exposed in a number of localities in the district, hut more particularly along the Niagara river in the vicinity of Lewiston and Qneenstown. The difficulty in this geological question at Buffalo has lain in the fact that no reliable determination could be made of the thickness of the strata included between the Corniferous limestone, immediately below which the drilling of the Buffalo gas-wells was commenced, and the Niagara limestone. On the other hand, the strata included between the latter limestone and the middle portion of the Medina sandstones and shales, have been minutely measured and studied in the Niagara gorge below the Falls by many American and European geologists. The first reliable section of these strata was constructed by Professor Eaton, and published in 1824 in his report on the Geological and Agricultural Survey of the District adjoining the Erie Canal. This section, extending from Lake Erie to Lewiston, is complete, with the exception that no thickness is given to the Salina or Onoudaga salt group,

Jan 1, 1889

By William H. Case

The Bertha zinc-mines of the Bertha Zinc and Mineral Company are in that part of the State of Virginia popularly known as Southwest Virginia, and are included in that division of the " Great Valley " named in recent years the " New River-Cripple Creek Mineral-Region of Virginia." The mines lie wholly in the southeast part of Wythe county, two miles from Pulaski county on the east, and three miles from Carroll county on the south. The only other zinc-mines that are opened in the region are those of Manning & Squier, which adjoin the Bertha zinc-mines on the northeast, and the mines of the Wythe Lend and Zinc Company, at Austinville, eight miles to the southwest. A little farther southwest of Austinville, near Ivanhoe, a new company is preparing to mine zinc-ores. The mining properties named are included within a distance of ten miles along a direct line, bearing north 55&apos; east, on the south side of New river, which here flows northeastward in a tortuous course. The greatest distance of any of the mine-openings from the river is a little less than two miles. It is not the magnitude of the operations in zinc-mining in this particular region, as compared with that of other well-known districts, that merits especial notice. Aside from the exceptional purity of the spelter made directly from the Bertha ores, some peculiar features of the zinc-ore deposih, as shown at the Bertha mines, and

Jan 1, 1894

Robert T. Hill, Washington, D. C.: Having studied very minutely the geology of the district referred to by Prof. Branner, I beg to state that his quotation of my classification of the Cretaceous deposits of Arkansas is not the one which I originally gave,* nor is it the one which has since been published and is now generally accepted.? I did not assign ally of the Cretaceous formations of Arkansas to the " middle Cretaceous,"

Jan 1, 1898

By N. V. Hansell

l. INTRODUCTION. THE last few years have shown an increasing interest in the subject of beneficiating iron-ores -in all iron-producing countries. In the United States, this movement has been slower than in certain parts of Europe, for the obvious reason that the abundance and relative cheapness of the Lake Superior iron ores has hindered the development of enterprises for the preparation of low-grade ores. Gradually, however, conditions have changed. The world&apos;s consumption of iron is increasing enormously. Being in 1900 about 40,000,000 tons, in 1910 ii was already 60,000000; and there is no reason to doubt that for the near future the increase in iron-consumption will continue at the same rapid rate, especially with, the development of China, certain parts of Africa, and other regions which have hardly been touched as yet by modern industrialism. It is. therefore, not surprising that apprehension is felt that the known available iron-ore resources of the world are gradually being depleted. Signs of this feeling are the recent investigation, under the direction of the U. S. Geological Survey, of the iron-ore resources of the United States, and the estimate presented to the last International Geological Congress, at Stockholm, Sweden, of the iron-ore resources of the world. These investigations have emphasized the fact that the known high-grade ore-deposits are limited in extent, and will, at a not distant future, be exhausted, compelling the iron industry to depend for raw material on the enormous deposits of low-grade ores which are distributed over almost all the world. The discovery of new deposits of high-grade ore, in countries not yet thoroughly explored, will not materially change this prospect. Of course, the part which such new deposits will play in the future cannot be forecast. The difficulty and cost of transportation will probably exclude many of them from use at the present centers of the iron industry.

May 1, 1912

[United Engineering Trustees, Inc. W. D. B. MOTTER, JR., &apos;40 A. L. QUENEAU, &apos;41 ALBERT ROBERTS, &apos;41 The Engineering Foundation GEORGE D. BARRON, &apos;44 F. F. COLCORD, &apos;42 A. L. QUENEAU, &apos;41 Engineering Societies Library Board J. W. LAIST, &apos;40 A. B. PARSONS, Ex-officio T. T. READ, &apos;42 F. F. SHARPLESS, &apos;41]

Jan 1, 1940

By Edgar M. Dunn

Part I. Determination oF Gases in Smelter Flues. General considerations. Regular methods for carbon monoxide, oxygen, nitrogen, moisture. Sulphur oxides-—Methods of Lunge and Hempel tried, and either modified or discarded, with reasons therefor. Gravimetric method developed at Anaconda. Description of apparatus used. Brief notes on Richter and Hawley methods for the direct cietermination of sulphur trioxide. Carbon dioxide, with complete notes on same. Arsenic trioxide. Table of percentages of flue gas constituents found at a Western smelter. Some final notations as to the value of flue gas analysis, in connection with an intelligent log of furnace operations. Part II. Notes on the Determination oF Dust Losses at the Washoe Reduction Works, Anaconda, Mont. Discussion of problem, with description of flue system. Various places and methods for determinations of velocity. Instruments used. Procedure in making determinations for velocity. Soundings of cross-section for depths of dust. Calculation of velocities and areas. Daily volume of gas, and plant operations during tests. Place for dust determinations. Apparatus and methods of &apos;sampling. Results obtained, with table of daily amount of dust losses. Analysis of dusts for values, from various sampling stations. Complete analysis of composite sample of stack emanation. Last analysis totaled to show form in which present. Discussion of recovery as a commercial proposition. References on Pitot tube and calculations.

Jan 1, 1914

NEW MEMBERS The following list comprises the names of those persons who became members during the month of December, 1913: Members ADAMS, CHARLES W., JR., Smelting, American Smelting & Refining Co., Murray, Utah. ARMSTRONG, FRANK H., Mechanical Engineer Vulcan, Mich. ARNOLD, JOHN B., Attorney-at-Law Room 840,200 5th Ave., New York, N. Y. BOYS, HARRY R., Mining Paso Robles, Cal. CAVANAGH, JOHN L., Min. Engr., Nova Scotia Steel & Coal Co.; Wabana, Newfoundland. CHOW, KAI CHI, Student 1120 Amsterdam Ave., New York, N. Y. CLARK, ARTHUR B., Mining Engineer 72 Harbour Bldg., Butte, Mont. CURLEY, JOHN R., State Mine Inspector P. 0. Box 633, Leadville, Colo. DAVIS, ANGUS W., Mining Engineer, Consolidated Mining & Smelting Company of Canada, Trail, B. C., Canada.

Jan 1, 1914

By L. D. Lash, J. R. Ross

Discovery of scandium in the Vitro solvent extraction plant for uranium led to commercial recovery of the byproduct. Micro amounts of scandium were extracted with uranium by dodecyl phosphoric acid, but failed to follow ura-niuminto the hydrochloric acid strip solution and were eventually concentrated in the organic extractant. A fluoride strip system was developed to recover scandium from the solvent in concentrated form. High purity scandium oxide was then prepared in multi-pound lots by chemical separation techniques. The plant recovery operation, final product purification, and analytical procedures are described. Scandium is a pseudo-rare earth which is truly rare and expensive. It has special properties which may make it desirable even at the present price of $2750 per lb. Recently the price was lowered from $5000 per Ib which had prevailed since 1952, and it is anticipated that usage will be stimulated because of the lowered price. This metallic element is distributed widely in trace amounts in the rocks of the earth&apos;s crust. In addition to micro-amounts found in most uranium ores, concentrations of 50 to 100 ppm have been found in Colorado ferberite ore, lateritic nickel ore, heavy sandstone from Utah, Wyoming, and New Mexico, and various zircon sands and monazites from the western part of the U. S. Scandium has been found as an essential constituent of very few minerals, the most important being thortveitite, a scandium silicate. At the present time, this mineral commands a price more than twice that of gold. Chemically, scandium is in group 3A of the periodic table. It is closely associated with yttrium and the rare earths which it strongly resembles in its reactions. It has a valence of three and will form an insoluble hydroxide, fluoride, or oxalate under proper conditions, similar to the rare earths. Eight years before its discovery, scandium was predicted by Mendeleef who ascribed his eka-boron with properties nearly identical to the actual properties of scandium. Its position as the element with Atomic No. 21 and Atomic Weight 44.96 places it between calcium and titanium in Period 4 of the chart. The successful commercial application of scandium must depend on unique properties to justify use of this high cost substance. Greater consumption would allow additional price reductions, but scan- dium will remain a relatively high-priced commodity because of its inherent scarcity. Research reportedly has been oriented toward use of scandium as an agent to achieve high-temperature, low-density alloys with magnesium and tantalum.&apos; Also, the U.S. Air Force sponsored a project for production of research amounts of pure scandium metal.&apos; The oxide has been used experimentally in electronics, ceramics, and metallurgy. The various aspects of scandium are well covered in recent publications.s-5 CONCENTRATE RECOVERY Small amounts of scandium exist in uranium ores and are dissolved during an acid leach yielding up to 0.001 gpl Sc2O9. When Vitro converted their uranium plant from phosphate precipitation to solvent extraction: scandium was found to follow the uranium into the dodecyl phosphoric acid solvent (DDPA). However, scandium did not strip with uranium from the DDPA in hydrochloric acid, but remained in the solvent. Therefore, a concentration of scandium built up in the organic phase. Residues from the solvent were spectrographed by the U.S. Bureau of Mines and found to contain scandium. As a result of this discovery, provisions were made in the plant for recovery of scandium-bearing concentrates. Solvent extraction of uranium was added to a conventional acid leach process in a typical installation? The ore was crushed and ground, and then leached with dilute sulfuric acid. Addition of an oxidant such as sodium chlorate insured conversion of uranium minerals to a soluble form. At this point, the slurry was chemically reduced by a sulfide, such as sodium hydrosulfide, to remove substances such as ferric iron and molybdenum which were partially extracted by the solvent. The solids-liquid separation was accomplished by a four-stage counter cur rent decantation (CCD) thickener circuit. The uranium was extracted from pregnant liquor with 0.1M DDPA in kerosene and stripped with ION

Jan 1, 1961

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO&apos; afe aFeO &apos; aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K&apos;. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO&apos; afe aFeO &apos; aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K&apos;. Making these changes, 7

Jan 1, 1942

By AIME

The following corrections (in italics and bold face) were received too late for the September issue of Transactions: Page 270, Abstract, line 1, spelling should be goethite. Page 270, column 1, authors&apos; box, authors&apos; affiliations should read: L. A. BAKER, formerly Principal Research Scientist, is Pellet Plant Superintendent, Cliffs Western Australian Mining, Cape Lambert, W. A., Australia. C. G. THOMAS is Experimental Officer, Minerals Research Laboratories, C.S.I.R.O., North Ryde, N.S.W., Australia. R. J. CORNELIUS and K. S. LYNCH are General Superintendent, Product and Process Development, and Superintendent, Pellet Plant, respectively, Hamersley Iron Pty. Ltd., Dampier, W. A., Australia. G. J. ARMSTRONG, formerly Chief Metallurgist, Hamersley Iron Pty. Ltd., is Mill Superintendent, Samin Ltd., Burra, S. A., Australia. Page 271, column 2, line 41, should read "highest possible spalling temperature and to adjust the. . :&apos; Page 275, column 1, line 1, should read "(LOI) figures are shown in Table 1 and vary from 2.61..." Page 275, column 1, line 16, spelling should be goethite. Page 276, column 2, line 6, should read "Predicting Grate Speed and Production Rate: The cor-..." Page 276, column 2, line 8, should read "basis of Blends A, B, C, D, and Plant Ore 1, shown in Table..." Page 276, Table 3, heading under "Prediction Method" should read Blend E. Page 277, column 1, line 38, should read "=293 tph of specification pellets (see Table 1 for loss-..." Page 277, column 2, replace caption for Fig. 14 with the following: Fig. 14-Example of calculation of hood temperature profile during downdraft free-water drying, given plant free-water drying time. Page 277, column 2, replace caption for Fig. 15 with the following: Fig. 15-Example of calculation of hood temperature profile during drying, given plant goethite drying time.

Jan 1, 1974

By Clyde E. Williams

THIS review of the progress made in iron and steel metallurgy during the past year is confined to developments in this country. It attempts to give examples to illustrate progress made rather than to appraise results. As a result of the gradually diminishing supply of rich iron ores and of predictions made as to the probable life of the iron-ore reserves of the Lake Superior District, attention of iron and steel executives was directed to the question of beneficiation of iron ores. Laboratory and plant-scale experimental work was conducted on the wash ores .of Minnesota and an investigation, was, begun on the Old Range low-grade ores.

Jan 1, 1931

By A. C. Fieldner

IN the Wall Street journal for March 1, 1941, was a tabulation of the construction under way or under negotiation by thirteen iron and steel companies for a predicted increase in annual coke production of 3,165,600 tons. That even this figure was short of the mark is indicated by other plans, then being considered, for a later expansion of 2,610,000 tons additional. Considerable progress has already been made on thin program, for approximately 500 new ovens were put in operation in 1941. and well over 200 should be completed in 1942. These figures include a number of units that replace older and obsolete equipment.

Jan 1, 1942

By Sheldon Rideout, E. L. Kamen, B. S. Lement, Paul A. Beck, W. D. Manly

The 1200°C isothermal sections of the following ternary phase diagrams were investigated: Cr-Co-Nil Cr-Co-Fe, Cr-Co-Mot and Cr-Ni-Mo. In all these systems the u phase was found to form extended solid solutions. Two new ternary phases of unknown structure were identified. The existence range of intermediate phases of transition elements was correlated with 3d electron vacancy concentrations. THE occurrence of extensive ternary d solid solutions in the Cr-Co-Ni and in the Cr-Co-Fe systems was described in a brief note.&apos; More recently d- solid solutions were also found in the Cr-Fe-Mo system by two independent groups of investigators.2,3 The existence of binary d phases in the V-Co and V-Ni systems, predicted in ref. 1, was experimentally discovered recently by Duwez and Baen and independently by W. B. Pearson, J. W. Christian, and W. Hume-Rothery.5 Duwez and Baen stated two general conditions for the occurrence of the d phase in alloys of the transition elements: "(1) The atomic diameters of the two metals do not differ by more than 8 per cent. (2) One of the two metals has a body-centered cubic structure while the other is face-centered cubic, at least in one of its allotropic forms." In the course of an extensive research program conducted at this Laboratory under the sponsorship of the NACA, several ternary systems, containing d solid solutions and also certain new ternary phases, were investigated. The present report describes the investigated portions of the 1200°C isothermal sections of the following ternary phase diagrams: Cr- Co-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo. It was found that the range of existence of the d phase in these four ternary systems, as well as in one of two ternary systems which were investigated by others, can be fairly consistently described in terms of electron vacancy concentrations. This supports the suggestion of Sully and Heal" that the d phase is an electron compound. Experimental Procedure The ternary alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. Lot analyses of the metals used are given in Table I. Specimens of all alloys were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting mainly of

Jan 1, 1952

By J. M. Blank, V. A. Russell

When the nucleation of silicon on a sapphire substrate is accomplished by gradually decreasing the substrate temperature while subjecting it to a constant impingement rate of hydrogen and silicon tetrachloride, the resulting deposit is characterized by widely separated islands of silicon scattered over an "open sea" of sapphire. Analysis shows that nucleation takes place mainly on sites of large adsorption energy, about 85 kcal per mole, and small surface concentration, about 108 cm-2. Crystal growth proceeds rapidly on these nuclei and results in enough depletion of Sicl4 from the ambient gas to suppress further nucleation. The technological importance of single-crystal films on dielectric substrates has prompted considerable work on the deposition of silicon on sapphire. This paper is concerned with the deposition of silicon, by the reduction of silicon tetrachloride with hydrogen, onto heated sapphire substrates. The apparatus consisted of a temperature-controlled container for the silicon tetrachloride along with gas lines and flow meters necessary to convey a hydrogen-silicon tetrachloride mixture to a reaction chamber constructed of quartz tubing. Heat for the substrate was provided by means of an inductively heated graphite susceptor. The observations pertinent to the present discussion were made with an American Optical Co. high-temperature microscope which allowed us to make motion pictures of the deposition process at a magnification of approximately 50 times. Two main categories of experiments were carried out: one on determination of critical condensation temperatures and the other on the deposition of epitaxial silicon films on the sapphire substrates. Critical condensation temperatures were determined in the traditional way by raising the substrate temperature well above that at which condensation could be expected at the impingement rates being studied and then gradually lowering the temperature until the condensation of the first silicon was observed. This was done initially with ellipsometry-type detection but it was soon discovered that the deposits were occurring as widely separated islands and groups of islands scattered over an "open sea" of sapphire. We have called these archipelago formations. They were most easily detected by optical microscopy. Data gathered from experiments of this type have been collected in Table I. Motion pictures of the formation of archipelago patterns show that the nucleation period lasts about 10 sec if the substrate temperature and impingement rate are kept constant. Essentially all of the nuclei are formed in a few seconds and all subsequent silicon deposition merely adds to the size of the established nuclei. After an archipelago formation has matured at a given substrate temperature and impingement rate, it is very difficult to stimulate any further nucleation in the open space between islands. Lowering the substrate temperature will occasionally stimulate nucleation but increasing the impingement rate hardly ever produces any more new nuclei. It should also be emphasized that the nucleation rates appear to be very small, about 104 cm-2 sec-1. They will receive special attention in the analysis section. Another series of experiments was performed employing a systematic variation of substrate temperatures and impingement rates approximating those expected to produce epitaxy. Sapphire substrates with surfaces normal to the 2233 direction were used. In contrast to the procedure that produces archipelago patterns, these films were deposited by raising the substrate temperature to a desired value at which time the silicon tetrachloride and hydrogen flow was begun. Of course, these depositions produced mainly films that were continuous. After removal from the deposition chamber, the substrate and silicon film were examined microscopically to determine the nature of the deposit and by X-ray diffraction to determine the extent to which a single-crystal film had been achieved. Results of these experiments are summarized in Table 11. Of interest for the present analysis is the fact that epitaxy appears to be confined to a fairly narrow temperature range between about 1050" and 1150°C. This also will be discussed in the analysis section. ANALYSIS In this section we shall apply nucleation theory to the data presented above with the objective of testing

Jan 1, 1967