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Executive SIDNEY .J. JENNINGS, Chairman GEORGE D. BAR HON .I. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, chairman LEWIS W. FRANCIS .1. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR. L. WALKER Finance GEORGE D. BARRON. Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY1 Chairman ALEX C. HUMIPHREYS3 GEORGE C. STONE .J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 10, 1918

By John F. Elliott

STAFF: Editor, Gerhard Derge Acting Editor, Poul G. Shewmon Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, PO. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Rich-ard C. Cole, President; Karl L. Fetters, Past-President; J. H. Scoff, Vice President; R. L. Henneboch, Treasurer, R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairmon; T. E. Dancy, P. R. Gouwens, W. A. Krivsky, F. C. Longenberg, E. R. Morgan, R.R. Nosh, Poul Queneou, W.O. Philbrook, J. H. Scoff, L. L. Seigle, and M. E. Wadsworth. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: M. E. Wadsworth, Chairmon; R. E. Grace, Vice Chairman; D. H. Baker, Jr., G. M. Bell, D. H. Bridges, J. M. Cigon, G. W. Healy, R. A. Lewis, C. E. O'Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. E. Dancy, Chairman; A. Muan, D.W. Murphy, R. D. Pehlke, J. M. Uys, J. 5. Wagstoff, and R. G. Word. lnstitute of Metals Division: R. R. Nash, Chairman, H. H. Johnson, Jr., Vice Chairman; M. R. Achter, P. A. Beck, J. J. Becker, G. F. Bolling, J. 0. Brittain, J. 8. Clark, R. 5. Davis, A. E. Dwight, R. W. Fountain, L. A. Girifalco, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, R. H. Richmao, H.C.Rogers, W. Rostoker, 0. D. Sherby. E. A. Steigawald, R. Steinitz, H. C. Stumpf, R. A. Swalin, W. A. Tiller, W. R. Upthegrove, D. Walton, H.W. Weart, and D. Wilsdorf. Published bimonthly by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc 345 East 47th Street, New York 17. N. Y. Telephone PLaza 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign;$30per $7 50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1963 by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc....Registered cable address, AlME New York . .. Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . Second class postage paid ot New York, N. Y., and Ann Arbor, Mich. Volume 227, Number 4.

Jan 1, 1963

By H. K. Najarian

AT Josephtown, Pa., on the south hank of the Ohio River about thirty miles northwest of Pittsburgh, is the Josephtown electrothermic zinc smelter, which operates as a custom smelter receiving both domestic and foreign concentrates. Constructed in 1930, the plant was designed to produce zinc oxide and to process 124 tons per day of zinc concentrate obtained mainly from the Company's New York State mines. Zinc condensing equipment was developed in conjunction with the St. Joe electrothermic. furnace and commercial production of zinc metal started in 1936. Expansion of the plant and equipment during 1939 and 1940 brought the processing. capacity to upwards of 300 tons of concentrate per day; and the plant operated at peak capacity during the war years, earning the Army-Navy "E" award and three subsequent stars. A postwar plant expansion is now under way, designed to increase the capacity to 500 tons per day of concentrate, with an estimated daily production of 160 tons of zinc metal of various grades, about 100 tons of zinc oxide, and 425 tons of sulphuric acid as major products.

Jan 1, 1947

By P. Barnes

The sums given in the accompanying table are those actually paid for material and labor up to about August, 1875; but, as some parts of the machinery were not wholly completed at the starting of the works in September, 1875, the statement cannot be taken as an absolutely correct note of the total cost. A complete description, with engravings of the building and machinery, was given in Engineering, April 26th, 1878, in a paper by Messrs. A. L. Holley and Lenox Smith, to which convenient reference may be made. A detailed list of the construction accounts has been given in a paper, by the present writer, in vol. vi, Transactions of the Institute. A summary is given in the table of the items in each class which enter into the total cost, and also a note of the proportion which each of these items forms of the whole. A concise view may thus he obtained of the facts embodied in the statement as a whole, even though it cannot lay claim to completeness in showing the entire or final cost. An urgent suggestion has reached the writer from a distant country that such statements of cost to be really most serviceable should give the details in days of labor, in weight of iron, and in number of brick, and to this an assent is most cordially yielded. It is true, however, that the mere labor of copying arid compiling these details to such a degree of minuteness, would be very great, and, in any event, the probable difference between the plans of an existing establishment and one projected, would be so wide as to render even so complete a statement of cost of little more real service than the approximate notes given herewith.

Jan 1, 1879

By P. Barnes

THE sums given in the accompanying table are those actually paid for material and labor up to about August, 1875; but, as some parts of the machinery were not wholly completed at the starting of the works in September, 1875, the statement cannot be taken as an absolutely correct note of the total cost. A complete description, with engravings of the building and machinery, was given in Engineering, April 26th, 1878, in a paper by Messrs. A. L. Holley and Lenox Smith, to which convenient reference may be made. A detailed list of the construction accounts has been given in a paper, by the present writer, in vol. vi, Transactions of the Institute. A summary is given in the table of the items in each class which enter into the total cost, and also a note of the proportion which each of these items forms of the whole. A concise view may thus be obtained of the facts embodied in the statement, as a whole, even though it cannot lay claim to completeness in showing the entire or final cost. An urgent suggestion has reached the writer from a distant country that such statements of cost to be really most serviceable should give the details in days of labor, in weight of iron, and in number of brick, and to this an assent is most cordially yielded. It is true, however, that the mere labor of copying and compiling these details to such a degree of minuteness, would be very great, and, in any event, the probable difference between the plans of an existing establishment and one projected, would be so wide as to render even so complete a statement of cost of little more real service than the approximate notes given herewith.

Jan 1, 1879

EUROPE continued to be unsettled, financially, commercially and socially. October opened with Germany in a state of turmoil following the Government's cessation of passive resistance to the French and Belgians. In many places there were riots with much bloodshed. In Bavaria a military dictator-ship was set up in order to keep peace. In the meanwhile France continued in an uncom-promising position.. Great Britain, having been diplo-matically discredited, disappeared from any prominence in the international picture. Under the constraint of circumstances the policy of deflation in Great. Britain was temporarily abandoned. Perhaps no other course was open, for with declining trade and heavily reduced revenue, and no chance for cutting expenses propor-tionately, a check to deflation comes of its own accord. The effects of this should become manifest in the course of a few months and should appear in the form of an improved margin between the prices for commodities and the wage costs in producing them. About Oct. 20 an effort was made to set up the Rheinland as a separate republic. On Oct. 26 were published communications from Lord Curzon to Secre-tary Hughes and the latter's reply. In these Lord Curzon drew attention to the gravity of the situation in Europe and expressed the hope that France might listen to renewed suggestions for a general inquiry. Secretary Hughes promised American cooperation, in this, with the reservation that the question of inter-national debts should not enter into the situation. In the latter part of October there were military mutinies and disorders in Greece, which resulted in the reestablishment of martial law by order of Col. Plas-tiras, who is virtually the dictator of Greece. The incipient revolt was promptly crushed.

Jan 10, 1923

Prof. Henry S. Jacoby, Cornell University,Ithaca, N.Y. (communication to the Secretary): When a simple beam supports any given load, the lower fibers me in tension while the upper fibers are in compression, and if its cross-section is rectangular the neutral surface, where the stresses pass through zero from tension to compression, is at mid-depth, provided the elastic limit is not exceeded. In addition to the longitudinal stresses, there are horizontal shearing-stresses between the fibers which have their maximum value in the neutral surface, and which equal zero at the upper and lower surfaces, while there are also vertical shearing-stresses. Let another beam of the same dimensions be placed on top of this one, and the load be doubled, it then produces stresses in each beam of the same character, magnitude and distribution as in the preceding case, provided there be no friction between the adjacent surfaces of the beams. Next let these two beams be so firmly united that there will be no motion between them when the same load is again applied. All the fibers in the upper beam are now in compression, and those in the lower beam in tension, while the maximum stresses in the outer fibers are only one-half as large as before. The strength of the combined beams is therefore doubled. If, however, some motion occurs between the beams, then the stresses in some of the lower fibers of the upper beam pass from compression to tension, and those in some of the upper fibers of the lower beam from tension to compression, while the stresses in the outer fibers have a magnitude between the two values previously stated. These fundamental facts relating to the flexure of beams indicate the necessity of carefully designing the keys or brace-

Jan 1, 1898

By Chas. B. Dudley

A Discussion of the papers of Mr. James Gayley, on "The Application of the Dry-Air Blast to the Manufacture of Iron," and of Mr. J. E. Johnson, Jr., on "The Physical Action of the Blast-Furnace," by Messrs. Charles B. Dudley, R. W. Raymond, J. E. Johnson, Jr., William F. Mattes, James Gayley, David Baker, John Birkinbine and F. E. Bachman. (Washington Meeting, May, 1905.) CHAS. B. DUDLEY, Altoona, Pa.:-Pam not a blast-furnace man, and this always puts me it a disadvantage because I cannot go into the details of the making of iron and steel. I have not the experience, and have to take the statements of other people, so what I say regarding the subject of this paper is not in the sense of an expert. When I first heard of Mr. Gayley's experiments, I said to myself, " I fear they will result in failure, since, apparently, Mr. Gayley has forgotten one chemical fact, namely, that carbon does not combine with oxygen in the absence of water-vapor." This fact which was so astonishing when it was first brought out some years ago, and which those who are interested may find in the Journal of the Chemical Society of London, for 18S5, page 349, and 1894, page 611, led me to think that the drying of the air would be a mistake. The general subject of the influence of water-vapor on chemical action is a large one; but the special point in which we are for the moment interested, namely, the influence of water-vapor on the combustion of carbon, was especially treated by Mr. H. B. Baker, in the papers referred to. Apparently, however, as the result of Mr. Gayley's experiments, we are to learn that the amount of moisture still left in the desiccated air is sufficient to secure perfectly satis¬factory combustion. In thinking over Mr. Gayley's paper, it occurred to me that there were two alternatives, either of which might be chosen, namely, we might dry the air as Mr. Gayley does, or possibly we might, in a very much simpler way, simply saturate the air at a constant temperature, and thus get uniform working and

Sep 1, 1905

By John V. Beall

During the last quarter of 1948, two new machines, which may revolutionize the coal mining industry, made their first public appearance within two months of each other. Both are designed to mine and load coal continuously. On Oct. 27, the "Colmol," invented by C. H. Snyder and A. E. Lamm, president and executive vice-president, respectively, of the Sunnyhill Coal Co., was demonstrated at the No. 8 mine of that Company at New Lexington, Ohio. The "Joy Continuous Miner," invented by H. F. Silver, president of the Silver Engineering Works, Denver, and developed and manufactured by the Joy Manufacturing Co., was demonstrated at the Mathies mine, near Finleyville, Pa., in the Pittsburgh coal seam.

Jan 1, 1949

By Warren B. Davis

Introduction If a subject this broad were to be covered in even moderate detail, it would require a set of books about the size of an encyclopedia. Since an acceptable length for this paper is a small fraction of one book, it will have to consist of a few samples of the subjects that I think are the most pertinent to World Fossil Fuel Economics. I plan to discuss the trends in world energy demand, particularly in the U. S. and Europe; the consumption patterns and cost patterns of oil, gas and coal; the prospects of synthetics; and some of the effects of government regulation of fuel economics. World Energy Demands Fig. 1 shows Free World energy consumption by principal areas for the period from 1950 to 1970 and a forecast for the period from 1970 to 1985. These figures include only the measurable forms of energy. An example of energy consumption that is not measured is the wood a peasant might cut in the forest and bum in a fireplace to heat his home. This omission probably is a very small part of the total. This forecast is not identical with that of Wayne E. Glenn (see Page 22), but the differences in total energy consumption are not significant. The U. S. consumption, which was 55 percent of the world total in 1950, had declined to 45 percent by 1970, and is expected to decline further to 38 percent by 1985. Western Europe has consumed 28 percent of the total from 1950 to 1970 and is expected to lose share slightly between 1970 and 1985. The most spectacular gainer is Japan, which increased consumption from 2.5 percent in 1950 to 7.5 percent in 1970, and is expected to reach nearly 17 percent by 1985. The over-all Free World total has grown from 62 quadrillion Btu (equivalent to 29 million B/D of crude oil) in 1950 to 151 quadrillion by 1970, an average growth rate of 4.5 percent/year. This total is expected to grow at a rate of 5 percent/year between now and 1985, reaching 315 quadrillion Btu (equivalent to nearly 150 million B/D). Fig. 2 shows which fuels supplied this energy between 1950 and 1970, and gives an estimate of how it will be supplied between 1970 and 1985.

Jan 1, 1971

By T. E. Evans, C. T. Baroch

ZrB2 was produced in batches of 4 to 6 Ib by interaction of ZrO2, B4C, B203, and carbon at around 2000°C in a simple graphite resistance furnace. Techniques of production are discussed and the final design of a suitable furnace is described in detail. Several other borides were made by the same technique and the process appears to have possibilities for commercial production. N seeking out new hard and refractory com- pounds, many researchers have turned to the investigation of the borides and excellent papers have been published on the properties of these compounds. Few papers, however, have appeared on the techniques and problems concerned with the production of these high temperature substances. This report describes progress made in developing a method for preparing zirconium diboride, ZrB2, on a pilot plant scale. The literature of the borides and other refractory hard metals recently has been reviewed, annotated, and classified so completely' that it is needless to attempt such an outline here. It is enough to say that three borides of zirconium have been reported: ZrB, ZrB2, and ZrB12.2 ZrB2 is the most stable of these and is especially stable in the presence of carbon up to and including its melting point of around 3000°C. Like most borides, it can be prepared in several ways. It can be prepared by synthesis of the elements, but these are expensive and difficult to produce in a high state of purity. Obviously, production directly from the oxides would have decided economic advantages. In electrolytic production such as that of calcium boride,:' the product is recovered as a sludge mixed with electrolyte; and separation of product from adhering electrolyte and regeneration of the electrolyte is an involved and difficult process. The work on borides was started on a small scale in 1948. Late in 1949, Naval Ordnance expressed a specific interest in ZrB2 and the project then centered on this compound. After the usual experimental work necessary in a new field, ZrB2 of good quality was produced by heating mixtures of B4C, ZrO2, B2O3, and carbon to a temperature of about 2000 °C in a resistance-type electric furnace. Over 100 lb was made for experimental use tests, and the method of production probably could be expanded into a commercial operation. A similar process has been described by Kieffer and coworkers.' The main chemical problems were the development of proper charges to insure complete reduction of the elements, determination of the proper temperature range at which these reductions took place, and adoption of techniques necessary to pre- vent inclusion of such impurities as carbon and nitrides. The mechanical problems consisted of developing a simple practical furnace that would attain the high temperatures required and permit use of a controlled atmosphere when necessary and determining of suitable refractories. Both problems were solved by designing a crucible resistance furnace. Crucible Resistance Electric Furnace Attempts were first made to produce ZrB2 in an electric arc furnace, but such a furnace would not provide the degree of carbon control required for producing clean graphite-free borides, so it was decided to try working in a crucible. Obviously, the furnace would have to be constructed of graphite, as the temperatures required are too high for other refractories or heating elements. Crucibles were made by hollowing out segments of graphite electrodes, which were fitted with a cover and clamped between two electrodes so that the current passing through the thin wall of the crucible would generate heat, using the principle of the Helberger crucible furnace."? Preliminary tests with this type of furnace were encouraging and led to the furnace design shown in Fig. 1. The essential components were a thin-walled graphite crucible resting on a graphite block, which formed the lower electrode assembly, and a top electrode assembly swung from a pipe column making contact with the top of the crucible. The space around the crucible was filled with graphite prepared from waste electrodes crushed to about ¼ in. This packing had excellent insulating properties, both electrically and thermally, and could be removed easily and quickly from around the crucible by means of an industrial vacuum cleaner. The largest resistor crucibles were machined from 8 in. electrode stock and were 26 in. long, with a side wall Yi in. thick and a 1 in. bottom. Temperatures were determined optically by sighting down a 1 in. hole drilled longitudinally through the top electrode and the crucible cover. Sealing this hole at the top was a water-cooled brass sight-glass assembly, shown in Fig. 2. An opening was provided for a light flow of helium to keep the sight opening clear of smoke, and a glass prism above the sight glass changed the line of sight to the horizontal for easier reading. More recently, the prism and optical pyrometer were replaced by a photoelectric recording pyrometer. At first the charges were placed directly in the resistor crucible but this meant that everything had to be withdrawn from the furnace every time the charge was emptied. Later, smaller crucibles were made up that could be placed inside the resistor

Jan 1, 1956

Jan 1, 1880

By Thomas T., Read

THE decades immediately before and after the end of the nineteenth century (1890-1910) were a period of increased activity in mineral industry education. One reason for ,this, undoubtedly, was the rapid increase in mineral production in the decade 1880-1890; pig iron and copper production tripled; coal, lead, and zinc output more than doubled. Most of the other mineral substances followed the same general trend. Aluminum production began in 1886; petroleum output, which in 1888 was less than it was in 1882, almost doubled in the next three years. Gold alone showed no appreciable change until its discovery at Cripple Creek in 1891, followed by the Klondike in 1896, brought to boiling a public interest in minerals that had been simmering for some years previously. The first cyanide plant in the United States was erected at Bodie in 1893, and the first chlorination plant at Cripple Creek* the next year. Silver- lead smelting had already greatly developed, and the metallurgy of copper was almost transformed. The hearth area and smelting capacity of copper reverberatory furnaces more than quadrupled between 1878 and 1894; matte converters were first erected at Butte in 1884. Copper production of the United States in 1899 was 30 times that of 1872. While it was the increased technology used in mineral production that really made the field attractive for educated young men, undoubtedly they did not realize that, and were impressed mainly by the quantitative increase in output. Another factor was the increased general interest in engineering education; three times as many men took engineering degrees in the United States in 1890 as in 1880; 1893 showed almost a 56 per cent increase over 1890. Industry had come to recognize that technical training was worth while. The mineral industry lagged somewhat at first; the total number of mining degrees

Jan 1, 1941

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By M. D. Curran

AS applied to coal, the term processing is subject to many interpretations. To some it means preparation of coal for the market by mechanical means such as crushing, sizing, washing, or treating with oil or chemicals to eliminate dust or improve combustion quality. To others it means conversion of the coal to other commodities as in carbonization to produce coke and by- products, or to liquids by application of the hydrogenation process. I prefer to classify the various forms of mechanical treatment under the heading of beneficiation and apply the term processing to those methods of treatment that destroy the coal sub- stance through distillation or hydrogenation.

Jan 1, 1939

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

September 1 to 6, 1918 COMMITTEE IN CHARGE Spencer Penrose, Chairman. George M. Taylor, Vice-Chairman. A. E. Carlton, Chairman. Finance Committee J. Dawson Hawkins, Secretary DENVER COLORADO SPRINGS CRIPPLE CREEK Finance Finance Thomas B. Crowe T. B. Stearns A. E. Canton , E. P. Arthur, Jr. Richard A. Parker Spencer Penrose N. S. Greensfelder T. B. Burbridge George M. Taylor A. E. Carlton. A. L. Blomfield, Treasurer B. F. Hill Arrangement I F. G. Willis Dave G. Miller Registration Norris E. Eads Frank Bulkley Loren C. Lennox 1V. E. Ryan Geo. E. Collins Horace F. Lunt Fred Jones .1. M. Tippett F. D. Smale Entertainment J. H. Haynes F. H. Bostwick Arrangement and Entertainment L. W. Lennox F. E. Shepard George M. Taylor A. L. Blomfield M. R.. Valentine Howland Bancroft J. D. Hawkins Thomas B. Crowe B. P. Morse A. E. Carlton E. P. Arthur J. G. Perry G. H. Clevenger Etienne A. Ritter Ladies Ladies , PUEBLO Mrs. T. B. Stearns, Mrs. C. M. Taylor, Mrs. C. H. Clevenger J. F. Welborn Chairman. Chairman H. B. Carpenter Mrs. C. Loughridge Mrs. S.-Penrose Mrs. A. E. Carlton L. B. Eames Mrs. H. Bancroft Mrs. J. D. Hawkins Mrs. A. L. Blomfield F. Robinson Mrs. G. Bancroft Mrs. L. C. Lennox Mrs. J. M. Tippett . Mrs. W. D. Leonard Mrs. H. F. Lunt -Mrs. E. C. van Diest Mrs. C. Chase Mrs. E. A. Ritter Mrs. AV. Strieby Mrs. F. H. Bostwick Mrs. L. S. Harner Mrs. C. L. Bailey Mrs. F. Bulkley Miss F. Dickerman Mrs. E. P. Shove Mrs. C. L. Tutt Mrs. F. C. Peck Mrs. F. D. Pastorius

Jan 10, 1918

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Bever M. B., Floe Carl F., Hung Liang

Data on the solubility of hydrogen in iron-silicon alloys are of practical interest, as hydrogen causes gas unsoundness and embrittlement in iron and steel and is also a factor in the metallurgy of cast iron. Zapffe and Simsl have recently demonstrated that in deoxidized iron and steel castings gassiness and bleeding are primarily functions of the hydrogen content of the liquid metal. These authors also suggested convincingly that ordinary melting and casting practice provides several sources of hydrogen for absorption by the metal. Norbury and Morgan2 and Boyles3 have shown that dissolved hydrogen affects the graphitization of cast iron. Schneble and Chipman4 included in a study of the effects of superheating on the properties of cast iron an investigation of the part played by hydrogen. Schwartz, Guiler and Barnett5 investigated the significance of hydrogen in the metallurgy of malleable cast iron. A complete interpretation of investigations of this kind calls for equilibrium values of the solubility of hydrogen in the liquid and solid phases. From the theoretical standpoint, the solubility of gases, especially hydrogen, may reveal some aspects of the nature of liquid metallic solutions. This was implied in the early work of Sieverts6 on the effect of alloying additions on the solubility of hydrogen in copper. Recent work by Bever and Floe7 has shown that in liquid copper-tin alloys the solubility of hydrogen changes abruptly at the composition of the intermetallic compound Cu3Sn. It is of considerable interest to determine whether liquid alloys of iron also have compositions at which the solubility of hydrogen exhibits a discontinuous or otherwise unique behavior. Among the various alloys of iron the iron-silicon system is important because of the presence of silicon in various structural alloy steels, transformer sheets, cast irons and special acid-resisting castings. The various grades of ferrosilicon, finally, cover almost the entire remainder of the composition range. Published information on the solubility of hydrogen in iron-silicon alloys is meager. The first values for pure liquid iron were reported in 1910-191 1 sieverts and Krumbhaar8 and by sieverts.9 They found that 100 grams of iron absorbs 28 c.c. of hydrogen at 1550°C and One atmosphere pressure, and 31 C.C. at 1650°C. In 1938 Sieverts, Zapf and Moritz10 published a value of 26.3 C.C. at 1550°C. Data on the solubility of hydrogen in liquid iron-silicon alloys and in liquid silicon are not available. Martin1' investigated

Jan 1, 1947

By Edward Judd

CANADA'S mining industry is rapidly recovering from the depression through which it passed in 1921. Its total output of $183,029,600 in 1922 was 6.4 per cent. greater than that of 1921, and was exceeded by only three previous years, 1917, 1918, and 1920. Table 1 compares the output of a few of 'the more important items selected from preliminary data published' by the Dominion Bureau of Statistics. TABLE 1.-OUTPUT OF CERTAIN MINERAL PRODUCTS IN CANADA PER CENT. 1921 1922 CHANGE Cobalt, metal and in compounds, lb 252,000 443,800 +76.1; Copper contents of blister, matte, and exported ores, lb 47,620,820 43,321,400 - 9.0 Refined copper, lb 4,286,000 730,000 -83.0 Gold, fine oz 926,329 1,230,985 +32.8 Pig iron, sh. tons 665,676 429,024 -35.5 Lead, sh. tons 33,340 47,085 +41.2 Nickel contents of matte, etc., lb. 19,293,060 17,496,490 - 9.3 Silver, including that in base bullion, gold bullion, etc., fine, oz. 13,543,198 17,611,646 +30.0 Zinc (nearly all refined), sh. tons. 26,545 28,199 + 6.2 Asbestos shipments, sh. tons 92,761 136,657 +47.3 Coal, all grades, sh. tons 15,057,500 15,045,300 Gypsum shipments, sh. tons 386,550 441,160 +14.1 Natural gas, M. cu. ft 14,077,600 14,954,100 + 6.2 Petroleum, bbl : 187,540 178,570 - 4.8 Cement, bbl 5,752,885 6,943,968 +21.0 Brick, structural, all kinds, M. , , 109,009 127,137 +17.0 On the basis of estimated market values, the whole output of 1922 was contributed as follows: Metals, 33.4 per cent.; non-metallic minerals, 45.1 per cent.; structural materials and clay products, 21.5 percent.; this distribution indicates a return of the metal mining. industry nearly to the position of relative importance that it occupied. before 1921, in which year metals contributed only 28.7 per cent. to the total value. of output while non-metallics gave 51.1 per cent. Canadian cobalt originates entirely in the ores of the Cobalt district, which are mainly treated at smelters in southern Ontario, although some quantities of residues have been exported to England and Europe. Exports during 1922 increased even more than production, consisting of about four-fifths . cobalt oxides and salts, and one-fifth of cobalt alloys and other metal combinations.

Jan 8, 1923