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By S. F. Radtke

The properties and characteristics of lead and zinc have made these metals useful to man in many ways since the days of antiquity. Despite their long history of use, however, these metals have proved to be extremely resilient and responsive to modern needs. New alloys and compounds continue to be developed, adding to the growth of these metals. Consumption data is given for 1969 and compared with one and two decades ago. Trends in major markets also are cited and explained. Uses for lead and zinc which have come into prominence within the past few years are described and explained, with emphasis on the role played by the industry's cooperative research program. Current efforts in the research phase are discussed, with details given on major efforts for both metals, including new alloys, process developments, applications research, finishes, coating, paints and pigments, batteries and fundamental research. A forecast is given of promising new areas and a projection made on a longer term of new applications that may emerge from current research.

Jan 1, 1970

By Lawrence S. Darken

STAFF: Editor, Gerhord Derge Cornegie Institute of Technology Schenley Pork Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: J. S. Smart, Jr., President; C. C. Long, Past-President; K. L. Fetters, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: C. L. McCabe, Chairman; H. L. Bishop, K. L. Fetters, J. J. Harwood, W. A. Krivsky, F. C. Longenberg, R. E. Lund, W. 0. Philbrook, L. L. Seigle, R. L. Smith, and F. L. Vogal. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: C. L. McCabe, Chairman; R. E. Lund, Vice-chairman; D. H. Baker, Jr., W. A. Krivsky, R. A. Lewis, Paul Qusneau, A. S. Russell, R, E. Shinkoskey, W. W. Stephens, and M. E. Wadsworth. Institute of Metals Division: L. L.Seigle, Chair-man, P. A. Back, J. J. Backer, l.l. Bessen, J. 0. Betterton, Jr., J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, R. B. Gordon, C. D. Graham, Jr., R. W. Guard, J. C. Gurland, E. L. Harmon, J. J. Hager, A. A. Hendrickson, M. Harmon, J. N. Hobstatter, H. H. Johnson, Jr., H. 5. Kolish, R. R. Nash, T. N. Rhodin, R. H. Richman, W. Rostokar, P. G. Shawmon, C. W. Spencer, L. Slifkin, J. K. Stanley, C. D. Starr, R. Steinitz, and H. C. Stumpf. Iron and Steel Division: H. L. Bishop, Chairman; 2. E. Boni, F. C. Langenberg, J. B. Wagstaff, and T. V. Wainwright. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription PetroleumEngineers,$30 per year for non-AIME members in United States and North, South, and Central America; 332, foreign; $5 for AlME members. Single copies, $4.00, single copies foreign, $5.00. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1%1 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address; AIME New York ..Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts.. .Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 221, Number 4.

Jan 1, 1962

By M. F. Trice

PYROPHYLLITE is a hydrous aluminum silicate (A12Si4010(OH)2)1 that occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mobs' scale.1 The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey,2 contain pyro-phyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, "are noticed in but small quantities to the extent they might occur as accessory constitu-ents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 percent and the alumina from 22 to 33 percent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent.

Jan 1, 1940

By Thomas Donnelly

Introduction THE Province of San Cristobal is situated on the south side of the island of Santo Domingo about 25 miles west of Santo Domingo city, the capital of the republic. The copper mineralization is found about 1.-CAMP BUCARO. THE TOP OF THE RIDGE IN THE BACKGROUND MARKS THE CONTACT OF THE LIMESTONE AND TUFFS. S miles north of the town of San Cristobal, in the section known as Bucaro Hill; in San Francisco Hill; on the Nigua River; and on the Jaina (Liver. The district is reached by automobile from Santo Domingo city over an excellent road for 25 miles to San Cristobal, and then, by horse-back 6 or 8 miles up the Nigua River to what is locally known as "Camp

Jan 8, 1915

By E. B. Johnson

Cleveland-Cliffs lron Co., which operates Marquette lron Mining Co.'s Republic mine, conducted a test whereby 35,000 tons of self-fluxed pellets were produced in the grate-kiln system from specular hematite flotation concentrates. A brief description of the pelletizing plant is presented along with pertinent operating details. Date is included which compare operating conditions and the chemical and physical properties of the green and fired pellets for the self-fluxing pelletizing test with the normal acid pelletizing operation. The success of self-fluxed sinter in enhancing the operation of the blast furnace during the past few years has reasonably led to the assumption that the use of self-fluxed pellets might result in even greater furnace efficiencies. A great share of development work in agglomeration has been directed towards techniques related to the production of self-fluxed pellets, but only a limited tonnage of self-fluxed pellets had been produced on a commercial scale until this past year when The Cleveland-Cliffs Iron Co. produced 35,000 tons of such pellets by the grate kiln system at the Republic mine during the period May 21-June 5, 1962. REPUBLIC'S GRATE-KILN PLANT The grate-kiln pelletizing process consists of four stages, namely: feed or balling circuit, traveling grate, rotary kiln and annular cooler (Fig. 1). The balling section is conventional and utilizes four 9x30-ft balling drums in closed circuit with 5x14-ft vibrating screens having 3/8-in. rod decks. The traveling grate is 12 ft wide by 126 ft long and has 14 windboxes — six in the drying section and eight in the preheat section. The rotary kiln is 15 ft ID shell and 114 ft long. The annular cooler is 40 ft in diameter and has 12 windboxes. The cooler is divided into two zones by a moveable curtain wall. The high temperature air from the first zone is used as secondary combustion air in the kiln. Normally the only heat supplied is through the burning of No. 6 oil in the single kiln burner. Hot gases pass counter to the pellet flow through the system. The exit gases from the kiln pass down draft through the preheat section through cyclones and are drawn through the drying bed prior to exiting via the stack. The temperatures are normally held within the following ranges: Kiln 2400-2445 °F Preheat 1850-1950°F Drying 480-520°F Exit gas 200°F Pellets 120°F The design capacity of the Republic mine grate-kiln system was 2500 Itpd. Sustained production in excess of 35% over design capacity has been achieved. No screening of the cooler product is practiced. PELLETIZING TEST CONDITIONS When a decision was made to proceed with a test at the Republic mine pelletizing plant to produce 35,000 tons of self-fluxed pellets, several potential failure factors had to be carefully considered. Research work on a batch and pilot plant scale indicated that the grate-kiln system at Republic would require some major changes in order to obtain optimum conditions. In many cases compromises were agreed upon as major equipment changes and revisions were not feasible. The pelletizing conditions which laboratory development tests revealed were required in order to insure successful production of self-fluxed pellets were: 1) Good mixing of limestone and concentrate and proper moisture control; 2) Higher gas flow rates in the preheat section than are normally used; 3) Higher preheat temperatures than normal; 4) Maximum kiln temperature 2350°F. There was just cause for concern about balling problems that might occur. Approximately 10% of dry pulverized limestone was to be added to the specular hematite concentrate just ahead of the Pekay mixers on the belt feeding the balling drum. Large scale

Jan 1, 1963

By B. W. Prof. Frazier

I PROPOSE in this paper to treat of the chimney merely as a heat engine, as one of the devices resorted to in practice for the conversion of heat into mechanical work. For the sake of simplicity and clearness in the discussion, let us consider the subject in its simplest form. Conceive a chamber, heated from without, in free communicatioH at one end with the external atmosphere, and at the other end opening into a vertical chimney. Let the. cross-section of the chamber be so great, relatively to that of the chimney, that we can neglect the actual energy of the air passing through the chamber. We will neglect, also, all passive resistances to the passage of the air. We will assume that the cross-section of the chimney is constant, and that the air in passing through it neither gains nor loses heat. The following symbols will be employed in the discussion : Po = the normal pressure of the atmosphere, which, it is assumed, is the pressure existing at the level of the chamber. Po = 10332.96 kilograms per square meter. P2 = the pressure of the external atmosphere at the top of the chimney. To = the, absolute temperature of melting ice by the centigrade scale. This is assumed to be the temperature of the external air at the level of the chamber. To = 273°. T2 =the absolute temperature of the air as it passes from the chamber to the chimney. T3 =the absolute temperature of the air as it issues from the chimney. to, t2, t3 are the temperatures, as recorded on the centigrade ther¬mometer, corresponding to the absolute temperatures To, T2, T3 re-spectively to = 0° C. In general, t = T- 273. Io, I2, I3, represent the intrinsic energy of the air at the temperatures To, T2, T3 respectively.

Jan 1, 1882

By Robert B. Fulton

The use of industrial minerals by the chemical industry as raw materials for manufacturing and in processing spans a wide assortment of minerals. This chapter aims to supplement rather than duplicate the commodity chapters. Its objective, to describe the uses of industrial minerals in the manufacture of chemicals, is attained by considering minerals used by the chemical industry in terms of the chemical element required and by giving particular emphasis to market factors. The mineral aspect, which is covered in the commodity chapters, is subordinated and attention is focused on the chemical and market aspects. Condensing this broad subject into a few pages permits treating only the most important elements derived from industrial minerals. The elements derived from petroleum, hydrogen and carbon, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potash, and nitrogen for fertilizers and titanium dioxide for pigments. After eliminating on this basis, our definition leaves six elements of major importance: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Salt brines have particular importance as raw material sources for the chemical industry as shown in Table 1 "Salt Brine Derivatives" (Anon., 1967), which charts the chemical compounds derived from four types of brines: (1) Owens Lake type brines which are sources of boron and sodium compounds; (2) Midland type brines from which bromine, iodine, and chlorides of calcium, magnesium, potassium, and sodium are derived; (3) Searles Lake type yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak type produced mainly for lithium. Table 2 (Jones, 1973) affords an overview of the chief industrial minerals, the chemical products derived from them, and end uses of the products.

Jan 1, 1975

By N. A. D. Parlee, I. D. Shah, W. C. Phelps

THIS note reports on a continuation of a program on the thermodynamics of Fe-S-X systems in the "steel-burning" temperature range begun by Bock, Barloga, and parlee.' Small coils of 0.039-in.-diameter pure iron (Ferrovac-E) wire were equilibrated with Fe-S-0 melts in ingot iron crucibles under argon at 1324°C in the assembly shown in Fig. 1, the lower part of which was heated in a large Globar furnace. Fig. 1 shows (R) the coiled iron wire sample, (M) the Fe-S-0 melt prepared from desired proportions of ferrous sulfide and ferric oxide, (K) the iron crucible, (I) a mullite guide tube, (J) an alumina crucible, (L) alundum sand, (N) crushed mullite, (Q) hollow cylinders of K30 brick, (C) a steel rod, (B), (El, (F), (G), (P), and (O), details of brass water-cooled head, and (H) a mullite tube 2-3/4 in. ID and 26 in. long. The rod (C) bearing the sample could be removed at will and be replaced by a tube for sampling the melt, or by a thermocouple for comparing the melt temperature with a control thermocouple not far from the 2-3/4-in. mullite tube. After equilibration the iron coils were treated with acid to remove the outer layer of metal and then they were analyzed for sulfur by a standard combustion method. The melt samples were analyzed for oxygen by a variation of Lander's2 hydrogen-reduction method for mattes, and for sulfur by the ASTM combustion-iodometric method NO. E 30-47. When the results of some forty-two runs were examined it was found that the sulfur and oxygen contents of the equilibrated melts showed good consistency, in that the plotted compositions fell along the smooth curve shown in Fig. 2. The points on this curve represent the experimental compositions of melts in equilibrium with ?-iron (Fe-S-0) solid solutions. These solid solutions are saturated with sulfur and oxygen with respect to the melt and therefore have the same sulfur and oxygen activities as the melt. The curve drawn through the points therefore delineates the ? liquidus. It falls in such a position as to roughly confirm the liquidus curves of Hilty and crafts3 at 1200" and 1300°C which are

Jan 1, 1965

By L. A. Updegraff

Before discussing the application of capacitance for the measurement of moisture content in a moving stream of coal it might be well to first give a brief description of the process and then show how it can be applied to the coal industry. A capacitor may be described as a device having two conductors separated by an insulator, the conductors hereafter being designated as a test cell or test plates and the insulator as the dielectric. Capacitance, therefore, is a measure of the ability of a capacitor to store an electrical charge. Two basic factors that affect capacitance are the dimensions of the capacitor and the dielectric constant of the insulator. Capacitor dimensions which affect its capacity are the area A of the conductive surface, and the distance d between plates. Capacitance is inversely proportional to the distance between plates and directly proportional to area A, so if capacitance is indicated as C and the dielectric constant as K the equation for capacitance would be C = AK/d. The dielectric constant can be described as the ratio of the actual capacitance of any given material to that of a vacuum, which is unity. In industrial applications the area of the plates remains constant as also does the distance between them, leaving the dielectric constant as the only variable to affect the capacitance measurement. Figure 1 is a schematic diagram of an r-f excited capacitance bridge in which a test cell is part of the circuit. This bridge consists of four capacitors in two pairs connected across an a-c voltage source. In one side of the circuit the two capacitors are fixed but in the other side they are variable, one being the rebalance capacitor operated by the servo motor and the other the test plates between which the dielectric passes. Capacity of the plates is a function of the dielectric constant of the material between them and is measured at radio frequency. Within the recording instrument is an r-f oscillator and a 60 c ps modulator. The radio frequency signal is generated by the oscillator, modulated by a 60 cps wave, and sent to the bridge. Therefore the signal entering the capacitive bridge is a radio frequency carrier with a 60 cycle envelope, If the bridge is in balance as the signal enters there would be no voltage drop and so no output by the detector. As long as the dielectric constant remains the same the bridge will stay in balance. However, any change in the dielectric constant, which in this case would be a change in moisture content, would affect the bridge. Higher moisture increases the capacity of the test cell which causes less voltage to develop across it causing imbalance of the bridge. This in turn causes a radio frequency signal to appear at the detector. Output from the detector is a 60 cycle ripple which is in proportion to the imbalance of the circuit. A 60 cycle amplifier boosts the detector signal to enough power to drive the servo motor which positions the recording pen and also rotates the variable capacitor, to which it is mechanically connected, to bring the bridge back in balance. An increase in moisture causes the servo motor to rotate in one direction, but a decrease causes imbalance in the opposite direction, and thus rotates the motor in that direction. This brings the bridge back in balance and stops the motor. The bridge shown in Figure 1 has been modified so as to provide a wide range of adjustments. Coarse and fine span adjustments located in the recording instrument are set to govern the amount of pen movement for a given change in capacitance. A measuring head unit contains coarse and fine zero adjustments for

Jan 1, 1961

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By D. J. Coolidge, H. L. Sheakley

THIS paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, produced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is commonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. 1). Above the sand rock an overburden of Joachim limestone appears, which thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. PROPERTIES OF THE ST. PETER SAND From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1942

By H. Kazemi, M. S. Seth

The effects of anisotropy and stratification on flow behavior and production performance of oil and gas wells have been studied by numerous authors.1-3 Lefkovits et al.l studied the performance of totally penetrated, stratified bounded reservoirs with no crossflow. Others have studied a similar problem, but with crossflow; Russell and Prats2 have summarized the findings of these papers. Muskat3 studied the steady-state behavior of liquid flow for a partially penetrating well in an anisotropic system and concluded that the productivity weakly depended on the directional permeability ratios (kz/kr>0.1). Nisle4 used the classical method of point source solution to the diffusivity equation to study the effect of partial penetration on pressure buildup of oil wells in an isotropic system. He found that the theoretical pressure buildup curves consisted of two straight lines, the one at early buildup times having a slope proportional to the flow capacity of the open interval (l-d)k, and the other having a slope proportional to the flow capacity of the entire formation hk,. Later Brons and Marting5 supplemented the findings of Nisle and concluded that partial penetration gave rise to a pseudo damage, which reflected itself as a skin factor in pressure buildup calculations. Using the pseudo skin, they calculated the impairment of productivity of the production wells, which agreed well with the results of Muskat.6 Pizzi et al.,? using an electrical analog of a stratified system, concluded that a high pseudo damage resulted if the reservoir was partially penetrated. Harriss studied the optimum spacing and arrangement of perforations in cased holes. Hantush9 derived an expression for pressure distribution in an unbounded reservoir with restricted flow entry. Seth10 extended Hantush's work to a bounded reservoir. Odehl1 has studied a similar problem for steady-state conditions. The purpose of this work was to investigate: (1) the combined effects of anisotropy, stratification with crossflow, and restricted flow entry on pressure transient analysis of flow and buildup tests, (2) the feasibility of calculating the horizontal permeabilities of intercommunicating stratified systems, and (3) the pressure interference tests in such systems. Theory The partial differential equation governing the isothermal flow of homogeneous fluids of constant compressibility is given by Eq. 1: The initial and the boundary conditions are: 1. The reservoir potential is initially constant, say 4v

Jan 1, 1970

By S. A. Falconer

The benefication of non-sulfide or non-metallic minerals by froth flotation has been practiced commercially for at least 30 years. In the pioneer stages of development of this flotation art, most of the promoters investigated were fatty acids or soaps that had been found to float sulfide minerals. When commercial application of froth flotation started to assume importance in the late 1920' s and 1930's, a great deal of fundamental research work was done in the laboratory (11-14, 19, 22, 23, 26, 29, 32). Among other subjects, this work included studies of the relative effectiveness of the different fatty acids and their salts on the flotability of various non-sulfide and non-metallic minerals. The successful present-day use of fatty acid and petroleum sulfonate type promoters results from better understanding of the principles of non-sulfide flotation plus the developnent of effective selectivity modifying agents. Many investigators have contributed to a greater appreciation of the numerous interrelated factors involved in fatty acid and soap flotation of non-sulfide minerals. Of these, mention should be made of recent fundamental studies by Tagart and Arbiter (31); Wolstenholme and Schulman (35); Schulman and Smith (28); Wark and his co-workers(3,4) Du FIietz(l5); and J. Leja(24). According to J. Rogers, K. L. Sutherland and E. E. and I. W. Wark(27), "the basic requirements for a 'collector' in flotation are that it shall form a film over the surface of the mineral to be floated and that this film should be oriented so that hydrocarbon (non-polar) groups form the effective surface." When modified in that way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince (33)that such a film can be produced only if the collector compound contains an active (polar) group to be attracted to the mineral surface, as well as the non-polar group. The commonly used anionic-type promoters for non-sulfide, non-metallic and metallic oxide ores include: 1. Fatty acids, and their soaps and emulsions. 2. Fatty acids residues — "pitches" and "foots." 3. Sulfonated and sulfated fatty acids and so-called "petroleum sulfonates." 4. Paraffin chain salts — sulfonated and sulfated higher alcohols. 5. Cyclic organic acids or salts, such as naph-thenic acid and naphthenates. Certain fatty acids are more effective than others as promoters for particular minerals under certain specified conditions. Some of the more costly fatty acids or collectors of the paraffin chain salt type may give improved selectivity in some instances and are being used commercially in a limited number of operations. Local availability may dictate the choice of the fatty acid used — for example, the use of palmoil fatty acid for flotation of copper carbonate ores in the Belgian Congo. Coconut oil fatty acids have also found limited use.

Jan 1, 1961

Jan 1, 1969

By C. Crussard, R. Tamhankar

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers accord-ing to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Gerhurd Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Staff Coordinator, James J. Burke THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chiprnan, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman; Dennis Carney, John Chip-man, J. C. Fulton, J. H. Hollomon, H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman, F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham, .Jr., Robert F. Hehemonn, R. I. Jaffee, F. E. Jaumot, Jr., Irving R. Kramer, A. J. Lena, Harold Margolin, C. J. McHorgue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alan U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B. King, F. C. Langenberg, W. 0. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts... Second class postage paid at New Yark, N. Y., and Ann Arbor, Mich. Volume 212, Number 6.

Jan 1, 1959

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

Jan 1, 1964

By E. S. Wheeler

The rapid increase in the use of monel metal and malleable nickel in the form of sheet, rod and tube has resulted in a similar increase in the demand for these metals in the form of castings. These castings range in size from small valves and pipe fittings weighing a few ounces to large centrifugal pumps, gate valves and marine propellers, some of the last weighing as much as 24,000 lb. A group of such castings is shown in Fig. 1. A large nickel agitator is shown in Fig. 2. Monel metal castings are widely used in accessories for steam power plants and in a variety of chemical plant equipment where the corrosion resistance, high strength and toughness characteristic of this metal render it particularly valuable. Nickel castings find extensive use in the construction of corrosion-resistant apparatus, and are often used in conjunction with wrought nickel sheet and tube in the fabrication of equipment for handling a variety of chemical and food products, particularly dairy products. In response to this demand for castings, numerous foundries have undertaken the production of castings of these metals and have met with varying degrees of success. The successful production of castings of monel metal and nickel requires careful attention to molding practice, proper melting equipment

Jan 1, 1930

By Maxwell Gensamer

Jan 1, 1960

By M. E. Wadsworth, T. D. Chatwin

The kinetics of sulfidization of hematite (Fe203) by H2S gas at various partial pressures have been determined over the temperature range of 170° to 500°C. The process was controlled by thin films of pyrite (FeS2) and troilite (FeS) which were protective and formed diffusional layers. At higher temperatures the thermodynamic drive to form FeS2 decreased, and consequently the rate of formation of FeS, decreased. Conditions for the development of thin layers of FeSz consisting of 10 to 100 atomic diameters are presented. Laboratory flotation results on synethetic ores indicate floatability identical to that of pyrite of normal xanthate flotation. The prospect of high-temperature sulfidization of metal oxides using H2S, S, or other sulfur bearing compounds is intriguing as a potential activation process for flotation since the thermodynamics are very favorable for a large number of systems. If the kinetic parameters are sufficiently well understood it may be possible to provide surface sulfide layers a few angstroms thick, thus imparting normal sulfide floatability characteristics to the oxide. For thin layers the total sulfur pick-up would be small except for very high surface area materials but in most cases this sulfur could be readily removed by roasting if necessary. The general reactions for the sul-fidization of metal oxide MxO, to a metal sulfide MpSq using H2S may be written for the three conditions py > xq; py < xq; and py = xq: A large thermodynamic advantage is obtained in many systems because of the relatively large negative free energy of formation of H,O compared to H,S. For the temperature range 2S° to 1500°C &apos; where AFOis the standard free energy and T is absolute temperature. As is evident from Eqs. 4 and 5, the free energy of formation of H ,0 is approximately 35 to 37 kilocalories per mole greater than that for H,S over broad variations of temperature. For oxide-sulfide systems as outlined above, sulfidization may be expected to occur for the conditions: Groups I and 111: that is, if the terms on the right are more negative than those on the left the reaction is expected to occur thermodynamically. The value hFg,(,) is included in Eq. 6 since hFLzs is based upon gaseous S2 rather than the normal reference state, orthorhombic sulfur. The

Jan 1, 1969