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By C. H. Gorski

A method for preparing titanium tetrachloride is described which consists of reducing rutile with coke and chlorinating the reduced product at 200° to 500°C. The crude distillate is purified by treatment with copper powder and distillation. Recoveries, exceeding 90 pct of the titanium in the rutile, were obtained. IN recent years considerable interest in metallic titanium has been aroused because of its outstanding physical and chemical properties. The present commercial processes for preparing titanium are modifications of the Kroll1 process and consist essentially of the reduction of titanium tetrachloride with magnesium in an inert atmosphere to produce metallic titanium with magnesium chloride as a byproduct. At present,' commercial titanium tetrachloride costs $0.32 a pound, which makes the price of the included titanium $1.28 a pound. As the titanium tetrachloride must be purified further before processing into metal, its ultimate cost obviously will be higher. Consequently, one of the prime requisites for the production of lower cost titanium metal is a source of low-cost titanium tetrachloride. Recently, Knickerbocker, Gorski, Kenworthy, and Starliper3 escribed a method for preparing titanium tetrachloride from low-grade Arkansas rutile by smelting the rutile with pyrite and coke to form a titanium matte and then chlorinating the titanium matte to prepare a crude titanium tetrachloride. This process had several inherent advantages. Low-grade rutile concentrates were utilized, the chlorination temperature was relatively low (approximately 200°C), and the reaction was strongly exothermic. However, this process had several disadvantages, chief of them being the rather low recoveries of titanium tetrachloride (65 to 81 pct) and the difficulty in purifying the crude titanium tetrachloride obtained. Because of the high-titanium and low-iron con- tents of rutile as compared to ilmenite, rutile should be of greater potential value as a source of titanium tetrachloride than ilmenite. Rutile, however, is not chlorinated directly in commercial practice, because reaction temperatures above 700 °C are required, at which point chlorine attacks most of the common materials of construction. The process now in use consists of converting the titanium in rutile to the cyanonitride by high-temperature reduction in an electric furnace, and then chlorinating this compound. The disadvantages of this process are the difficulty of producing the cyanonitride, the use of high-grade rutile concentrates in the charge, and the presence of several percent of silicon tetrachloride in the finished product. It would be of considerable interest to develop a new process for the preparation of titanium tetrachloride from rutile by chlorination at 200" to 500°C. Process Development Several investigators'-' have studied the reduction of titanium dioxide with carbon in an effort to prepare titanium monoxide. Invariably, the titanium monoxide formed in this manner was not pure, as it contained titanium carbide and one or more of the lower oxides of titanium. As these lower oxides of titanium are more reactive chemically than rutile, and as it is known that titanium carbide may be chlorinated readily, a study was made of the chlorination of carbon-reduced rutile. A sample of rutile concentrates from Hot Spring County, Ark., containing 76.19 pct TiO,, 5.65 pct Fe2O3, 4.18 pct SiO2, and 2.88 pct Al2O3, was used for this investigation. The experimental procedure consisted of making an intimate mixture of —100-mesh rutile and petroleum coke, adding water and molasses as a binder to foi-m a paste, charging into a graphite crucible that was covered, except for a vent to allow the

Jan 1, 1952

By J. W. Matousek, C. S. Samis

me thermodynamic properties of the components in the Cu-Ni-S ternary system have been studied by measuring the H2S/H2 ratios in a gas phase equilibrated with the molten matte at 1200°C. The measured sulficr potentials have been extended by extrapolation and combtned with previously published data to permit the thermodynamic analysis of the ternary system by integration techniques. A simplifying assumption of ideality in the Ni3Sz-CuS pseudobinary has been made. SINCE copper and nickel metals were first extracted from their sulfide ores the interaction between the two metals and sulfur has been of industrial and theoretical interest. The processes developed to extract copper and nickel have been reported periodically in the literature. The theoretical studies on the Cu-Ni-S ternary have been restricted to problems directly associated with production. It is only within recent years that the binary systems related to this ternary have been analyzed thermodynamically and mathematical devices developed to permit a corresponding treatment of the ternary system. In 1910 an investigation of the role of nickel in Cu-Ni-Fe-S mattes was reported,' It was concluded from this work that nickel is not an element replacing iron in mattes, but rather that Cu-Ni alloys behave as a single metal during the matte converting operation. The laws which govern the converting of Cu-Ni alloys were found to be the same laws as those that govern the conventional converting of copper alone. Although considerable information has been reported on the theoretical aspects of copper smelting, little data is available on the smelting of Cu-Ni ores except for phase diagrams and process descriptions. The available information on the Cu-Fe-S ternary and related systems prior to 1953 has been summarized by Ruddle.2 Since Ruddle's publication, Rosenqvist and coworkers have completed phase equilibria investigations of the Fe-S, Co-S, and Ni-S binaries,3 the Fe-S-O ternary,4 and the Cu-Fe-S-O quaternary.4 An extensive investigation of the Cu-Fe-S ternary system at smelting temperatures has been made by Krivsky and Schuhmann.5 At these temperatures, the Cu-Fe-S system is very similar to the Cu-Ni-S ternary with respect to the location of the single-phase and two-phase liquid matte regions. In the former, however, the area of immiscibility is more extensive and the region of liquid matte-liquid metal-solid metal equilibria is much more extensive. Krivsky and Schumann observed that the Cu2S-FeS pseudobinary system is, for practical purposes, an ideal mixture. This investigation has served as a valuable guide in analyzing the Cu-Ni-S ternary. EXPERIMENTAL The experimental procedure employed in this investigation was the conventional technique of equilibration of the sulfide matte with gaseous mixtures of hydrogen and hydrogen sulfide at 1200°C. The thermodynamic properties of sulfur (S2) in the gas phase are determined by means of Eq. [I] and the activity of sulfur in the matte by Eq. [2].

Jan 1, 1963

By F. R. Morral

HOT-DIPPED heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature of the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped FIG. I.-SYSTEM IRON-ZINC ACCORDING TO J. SCHRAMM.11 heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schueler1 by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva-nized wire, which was assumed to be the FeZn10 phase.

Jan 1, 1940

By J. D. Shaw, E. B. Gebert, D. O. Noel

It is, of course, expected that manufacture of the various metal powders should involve numerous methods adapted to the specific characteristics of the metals themselves. Several methods for powdering a particular metal may be available, but the physical characteristics of the powder as produced by the several methods may be quite different. In the final analysis, the application of the metal powder dictates the physical properties that the metal powder must possess, and this, to a very large extent, will determine which of several possible methods of manufacture is adopted. Sometimes powder of the same metal is produced by more than one method, each powder having specific characteristics that make it particularly suitable for its application. For purposes of classification, the various methods of powdering metals can be grouped as follows: 1. Machining. 2. Milling (by ball mills, stamps, attrition mills, etc.). 3. Shotting (pouring molten metal into water, air, etc.). 4. Granulation (by stirring molten metal while solidifying). 5. Atomizing (disintegrating by steam, compressed air, etc.). 6. Condensation of metal vapor. 7. Reduction of oxide powders. 8. Chemical precipitation. 9. Electrolytic deposition. 10. Sintering (for producing alloy powders). 11. Formation of an alloy followed by dissolving or otherwise removing one of the alloying constituents. Machining Turnings, cuttings, filings, etc., are, of course, produced as by-products in machine work of various kinds, and find certain applications as metal powders. For example, iron powder so produced is used extensively as a reducing or precipitating agent and as a constituent in certain hard-finish cements.

Jan 1, 1938

By D. O. Noel, E. B. Gebert, J. D. Shaw

It is, of course, expected that manufacture of the various metal powders should involve numerous methods adapted to the specific characteristics of the metals themselves. Several methods for powdering a particular metal may be available, but the physical characteristics of the powder as produced by the several methods may be quite different. In the final analysis, the application of the metal powder dictates the physical properties that the metal powder must possess, and this, to a very large extent, will determine which of several possible methods of manufacture is adopted. Sometimes powder of the same metal is produced by more than one method, each powder having specific characteristics that make it particularly suitable for its application. For purposes of classification, the various methods of powdering metals can be grouped as follows: 1. Machining. 2. Milling (by ball mills, stamps, attrition mills, etc.). 3. Shotting (pouring molten metal into water, air, etc.). 4. Granulation (by stirring molten metal while solidifying). 5. Atomizing (disintegrating by steam, compressed air, etc.). 6. Condensation of metal vapor. 7. Reduction of oxide powders. 8. Chemical precipitation. 9. Electrolytic deposition. 10. Sintering (for producing alloy powders). 11. Formation of an alloy followed by dissolving or otherwise removing one of the alloying constituents. Machining Turnings, cuttings, filings, etc., are, of course, produced as by-products in machine work of various kinds, and find certain applications as metal powders. For example, iron powder so produced is used extensively as a reducing or precipitating agent and as a constituent in certain hard-finish cements.

Jan 1, 1938

By K. B. Nowels

DATA pertaining to pipe line flow for both oil and gas in horizontal or nearly horizontal pipe lines are both extensive and accurate. However, the pipe formulas used to determine pressure drop for flowing fluids (liquids and gases) under conditions of horizontal flow are not generally applicable to flowing oil and/or gas wells. Except for some data developed in small laboratory set-ups, little or no information was available concerning flow of oil and gas mixtures in vertical pipes, when, in 1928, the writer began the development of a method for computing pressure drops in the pipes of flowing oil wells, as outlined in this paper. In 1929, Uren1 presented some findings based on laboratory experi-ments in which vertical flow of an extremely heavy crude oil was induced, by means of air through a 2-in. pipe, 41 ft. long. The friction factors derived from the experiment, as well as values for pressure drop per 100 ft., are not believed satisfactory in their application to flow problems in the field. Versluys,2 also in 1929, presented a mathematical development of the theory of flowing oil wells, and in 1930, gave a companion paper3 setting forth some principles governing the choice of length and diameter of tubing in oil wells. Since the termination of the study presented in this paper, another. valuable contribution pertaining to the problem, of vertical flow was made by Moore and Wilde.4 Although there were writings dealing with the principles of the gas-lift, a search of the available literature indicated that specific information on vertical flow was lacking with the exception of the writings of Uren, Versluys, and Moore and Wilde, to which reference .has been made.

Jan 1, 1932

By L. W. Kesler

Kansas produced 41,966,773 bbl. of oil in the year 1927, thereby taking fourth place among the oil-producing states of the Union. The daily average production decreased from 121,609 bbl. in January to 110,244 bbl. in December. Due to excessive flush production and the resulting decline in the price of crude during the year, operations, both in proved and outlying districts, were reduced materially from those of 1926. There were 2338 completions in 1926, but only a total of 1333 in 1927. Regardless of this decrease in the total number of completions, Kansas made a slight gain in total production for the year, producing 620,262 bbl. more than in 1926. This is accounted for, in part, by the comparative long life of the settled production from the Bartlesville sand areas to the east of the Nemaha granite ridge, and by prolific production in eastern Summer County from horizons new in their importance in the state, productive here at two localities along the axis of the granite ridge (Table 1 and Figs. 1, 2 and 3.) For convenience in further consideration, the state is divided into Eastern and "Western" Kansas. Special emphasis will be placed on those areas in the state of which but little is generally known, and which have not been given detailed consideration in previous publications.

Jan 1, 1928

By Henry A. Stiff, J. P. Hammond, A. B. Westerman, H. C. 195-000-000-014 Cross, and Lawrence E. Davis

The phases in Cr-Fe-Mo alloys have been investigated with homo-genization, aging temperature, composition range, and alloy addition as variables. Metallography, three X-ray methods, and hardness were used as methods of study. The behavior of s, M23,C8, and Z phase are reported for cornpasition range 60 pct Cr-15 to 25 pct Fe-15 to 25 pct Mo-<0.005 to 0.36 pct C with aging at 1400º to 2000°F. With 2 pct Ti, Tic and TiC-TiC are formed; with nitrogen Cr2N. THE recently developed class of chromium-base heat-resistant alloys shows appreciably higher strength than commercially used high temperature alloys. However, further developmental work is required to impart needed shock resistance and some degree of room-temperature ductility to these alloys. Extensive exploratory work on chromium-base alloys was begun in a program initiated by the War Metallurgy Committee of the National Defense Research Council at the Climax Molybdenum Co. in the early part of 1942.&apos; Alloys were sought for gas-turbine blades for use at 1600°F. A minimum of 5 pct elongation in the stress-rupture test was a requirement. From the Climax work, ternary alloys of chromium, iron, and molybdenum appeared to show the greatest promise as materials for gas-turbine blades. The composition line in the ternary diagram joining the 60 pct Cr-15 pct Fe-25 pct Mo and 60 pct Cr-25 pct Fe-15 pct Mo alloys was indicated as representing the most useful combination of strength and ductility.&apos; Strength increased while ductility decreased as molybdenum was raised in this composition range.&apos; The 60 pct Cr-15 pct Fe-25 pct Mo type alloy was thought to have the most suitable properties for gas-turbine blades.&apos; Concurrent with the study reported here, other investigations were being made on Cr-Fe-Mo alloys. The liquidus temperatures on a series of low carbon, ternary alloys were being determined, and isothermal sections drawn at 2370°, 2010°, and 1650°F (1300°, 1100°, and 900°C).2 Also, various methods of preparation and some mechanical and physical properties of chromium-base alloys, particularly the 60 pct Cr-15 pct Fe-25 pct Mo type, were being investigated., At the inception of the present program, only a limited study had been made of etchants for developing the microstructures of chromium-base alloys; X-ray analysis of the microconstituents had not been made. A review of the literature revealed that no phase-diagram work had been reported on the Cr-Fe-Mo system. Scope of Work The work on chromium-base alloys includes the following: 1—The development of etching methods for differentiating between the microconstituents; 2—The identification of microconstituents by X-ray diffraction methods; and 3—A comprehensive metallographic and hardness study after various heat treatments. The phases were studied by three standard X-ray techniques: 1—The block-sample focusing-camera method; 2—The powder-diffraction method on elec-trolytically separated residues; and 3—The powder-diffraction method on cold-worked aggregate samples. The results by the first two methods were correlated with the metallographic data. The third method was used largely to study conditions approaching equilibrium, since cold working prior to heat treating accelerated precipitation. Seven types of alloys were investigated: 50 pct Cr-50 pct Fe, 40 pct Cr-40 pct Fe-20 pct Mo, 55 pct

Jan 1, 1953

By W. H. McFarland

The mechanical properties have been determined for a large number of alloy-free martensitic steels with carbon contents ranging from 0.08 to 0.20 pct and with manganese contents of about 0.4 to 0.5 pet. These steels were tested 1) as water-quenched, 2) after quenching, temper rolling, and tinning, and 3) after tempering treatments which involved temperatures from 400o to 1300oF and times from 1 min to 8 hr. The majority of these tests represent steel from commercial-size coils, i.e., strip 32 in. wide, coil weights up to 20,000 16, and steel thicknesses from 0.0055 to 0.024 in. As a result of these treatments, it has been shown that as-quenched low-carbon alloy-free steels can be produced with tensile strengths ranging from 140,000 to 220,000 psi and tensile elongations from 3.0 to 4.0 pet in 2 in. The tensile strength of the as-quenched martensites can be represented by the equation, tensile strength (ksi) = 119 + 560 (wt pet C). The response to tempering of these steels is related to previous work by Muir, Averbach, and Cohen and by Grange and Baughman. Strain aging of low-carbon martensite has also been investigated. If low-carbon steels are defined as those steels with a maximum carbon content of 0.2 pet, it is found that the literature on low-carbon, alloy-free martensites contains little data on the mechanical properties of these steels. However, the following facts concerning low-carbon alloy-free martensites seem firmly established:&apos;-&apos; 1) The major factors in controlling the strength of the martensite appear to be a) fine structure, b) the internal strain resulting from the transformation, and, particularly, c) the amount of carbon in solid solution. 2) In low-carbon steels, the martensite is auto-tempered and is in the form of needles with only minor amounts of internal twinning, whereas the martensite in high-carbon steels forms as plates which are internally twinned on a fine scale. 3) Care must be taken in comparing the results of work that has been done on low-carbon steels with varying amounts of alloying elements to data on plain carbon steels. As has been noted by Irvine, Pickering, and Garstone,6 alloying elements generally lower the martensite start temperature and, thereby, decrease the amount of auto tempering obtained during the quench. This makes it difficult to

Jan 1, 1965

By Kenneth K. Humphreys, Joseph W. Leonard, Robert L. Llewellyn, William F. Lawrence

INTRODUCTION Cleaning fine coal sizes utilizing air currents in machines as the primary separating medium is called dry concentration or pneumatic cleaning. In 1947 approximately 18 million tons (16.38 million mt) of bituminous coal were cleaned by air machines; in 1965, 25.4 million tons (23.1 14 million mt); but in 1975, only 7 million tons (6.37 million mt). Table 11-1 shows the tonnages cleaned of bituminous coal and lignite in the United States by various types of equipment from 1938-1963. Table 11-2 shows only tonnages cleaned by pneumatic methods from 1964-1975. The decrease in tonnage to approximately 7 million tons (6.3 million mt) is due to a higher moisture content in the mined coal and the greater difficulty in cleaning the coal by air. There also was a definite trend to load raw coal at the mines, especially the slack which is the most expensive to clean due to the dewatering and drying requirements. While there have not been any applications of pneumatic cleaning in the anthracite field, its use has not been fully explored. The same is true for lignite and subbituminous coals.

Jan 1, 1979

By William Ian Wark, Alwyn Birchmore Cox

DIFFERENT parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. EXPERIMENTAL METHOD The methods used have been described previously.1-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution &apos; composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1938

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.&apos;-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,&apos; and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By C. W. Lawr

THE ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, are mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 lb.) KCN per ton of solution. As the daily discharge to. the dam was 1600 tons1 of slime of a 2: 1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and its recovery held alluring possibilities.

Jan 1, 1929

By R. G. Knickerbocker, W. H. Yarroll, P. E. Churchward, J. W. Hunter, J. H. Jacobs

THE present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.1 A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. DEVELOPMENT OF THE PROCESS The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton.2 Until the method of continuous production of manganese by electrolysis was perfected by Shelton2-4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solution containing 25 grams manganese per liter as manganese sulphate and 200 grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.05 gram iron per liter as ferrous sulphate followed by oxidation

Jan 1, 1944

By J. L. Lamont, W. Crafts

Studies of the effect of composition of steel on hardenability by Grossmann,&apos; and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0&apos;65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc&apos; The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By W. Crafts, J. L. Lamont

Studies of the effect of composition of steel on hardenability by Grossmann,&apos; and as-quenched hardness by Field2 and by the authors, have made it possible to predict the results of quenching when the composition and cooling rate are known In order to extend the application of the hardenability calculation to the quenched and tempered condition in which steel is finally used, a survey has been made of the hardness changes caused by tempering. From this study a method has been developed for the prediction of hardness and tensile strength of steel in the tempered condition. The method of calculation was developed from Rockwell C hardness tests on quenched and tempered Jominy specimens and is expressed in Rockwell C hardness units. It is of an additive type in which the degree of softening from as-quenched hardness is estimated. Tem-pred properties may be calculated within about plus or minus 5 Rockwell C hardness or plus or minus 15,000 lb. per sq, in. tensile strength. This degree of accuracy is less than that necessary for the control of heat-treatment, but is adequate for the comparative evaluation and selection of alloy steels. The formula indicates that tempered hardness is primarily dependent on as-quenched hardness and, as in the hardening reaction, the progress of tempering is controlled mainly by the carbon content. Alloys tend to retard softening by a secondary hardening mechanism in which the alloy appears to migrate from ferrite to the carbide phase. The factors for the effects of alloys in tempering vary so much from the effects of alloys in hardening that different steels of equivalent hardenability may, after like heat-treatment, differ considerably in tensile strength. Procedure In developing the method for calculating tempered Rockwell C hardness, simple and complex steels were tested over a range from 0.08 to 0&apos;65 per cent carbon and up to 2.68 per cent manganese, 2.18 silicon, 3.50 chromium, 4.94 nickel, and 1.06 molybdenum. The steels were made as small induction-furnace heats at the Union Carbide and Carbon Research Laboratories, Inc&apos; The accuracy of the method was finally checked on a variety of carbon, low-alloy and high-alloy types of heat-treating steels produced under commercial conditions. The method was based on a study of tempered Jominy bars, and its validity was tested by correlation with the center hardness and tensile strength of oil-quenched and tempered bars from 1/2 to 4 in. in diameter. The method of calculation was derived from the differences in Rockwell C hardness between as-quenched and quenched and tempered Jominy specimens. Prenormalized Jominy hardenability speci-menS quenched from a normal temperature for austenitizatios were used to obtain a range of as-quenched Rockwell C

Jan 1, 1948

By C. E. Sims, C. A. Zapffe

AN investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. APPARATUS The apparatus is shown in Fig. I and the system is shown by diagram in Fig. 2. Furnace Atmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermo-couple and potentiometer (9) and is controlled by a slidewire resistance (10). In [ ] this furnace free oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1942

By C. S. Smith

The solubility of tantalum at 1100°C is 0.025 pct in pure copper, 1.2 pct with 20 pct Ni, and 2.7 pct with -30 pct Ni. The solubility decreases with temperature, and the alloys are precipitation hardenable. A 79/20/1 Cu-Ni-Ta alloy reaches maximum hardness after aging at about 750°C and, if cold worked, does not recrystal-lize below that temperature. The alloys have good tensile properties at moderately elevated temperatures and, since they can be hot and cold worked nearly as easily as cupronickel, they are suggested for service at temperatures above the usual limits for copper alloys. MASSIVE tantalum dissolves extremely slowly in copper-rich alloys, and tantalum powder forms refractory surface layers which prevent its solution unless special precautions are taken. After many trials, an 80 pit recovery was consistently obtained by using a mixture of a finely divided tantalum powder with two or three times its volume of potassium tantalum fluoride (K2TaF1,-melting point about 750°C) poured in a slow stream directly on to the surface of the molten copper alloy, so that each particle would remain coated with flux and be immediately and individually wetted by the molten metal. A 50-50 nickel-tantalum alloy has a melting point of about 1400°C and small lumps of it slowly but satisfactorily dissolve in molten copper-nickel alloys as does commerical "ferro-tantalum." The high affinity of tantalum for carbon makes it necessary to avoid carbonaceous crucibles. COPPER-TANTALUM ALLOYS Castings with good shrinkage resulted when 0.1 pct Ta or more was added to copper melted under charcoal and cast in air. Copper in two-pound melts to which 0.1, 0.15, and 0.2 pct Ta had been added retained residual amounts, by analysis, of 0.025, 0.023 and 0.026 pct, respectively. The solubility of tantalum in molten copper at about 1200 °C is therefore about 0.025 pct. The electrical conductivity of these three samples was 100.48, 100.00 and 100.20 pct IACS in the annealed condition, and 98.24, 97.98 and 98.08 in the cold-drawn condition. Wires 0.080 in. in diam withstood from thirteen to nineteen reversed bends after annealing for 30 min in hydrogen at 850°C and the metal was therefore completely deoxidized. The annealing temperature corresponding to 50 pct loss of work hardness in 1 hr in a strip cold rolled 77 pct reduction was 175C, compared to 230°C for equivalent undeoxidized material. It is unusual for a decrease of recrystallization temperature to result from an alloying addition, and the tantalum probably combines with and removes some minor impurity in the original copper that restrained its recrystalliza- tion. No difficulty whatever was encountered in hot or cold rolling or drawing these ingots, and were tantalum not so expensive it would make an excellent deoxidizer for copper. COPPER-NIcKEL-TANTALUM ALLOYS Studies were made of the solubility of tantalum in a large number of copper-rich alloys, but of these significant solubilities were found only in the case of an iron alloy (which, however, separated into two immiscible liquid layers) and alloys of copper and nickel, in which tantalum is freely soluble and which were found to have interesting properties. The latter alloys are the subject of U. S. Patent No. 2,430,306 (1947). They are not at present available commercially. The Ternary Constitution Diagram—The copper-rich corner of the constitution diagram was constructed on the basis of microscopic examination of samples of various composition and treatments. The alloys were hot rolled to 0.25 in. from castings 0.625 in. thick, then annealed for 1 hr at 1000°C, quenched, cold rolled to 0.10 in. and finally annealed for various periods of time at temperatures between 800" and 1100°C in a nonoxidizing atmosphere and quenched. When the solid-solubility limit had been transgressed, particles of a compound believed to be Ni2Ta*were

Jan 1, 1960

By Hiroshi Oikawa, R. G. Blake, A. G. Guy

An equatzon has been derivedfor conveniently calculatzng the couvse of homogenzzation in a three-corviDonent solid solutiorz. The necessary assumptions are that the initial distributions of concentration are sinusoidal and that the four interdiffusion coefficients are constant. Employed in the deriuation were the Laplace transform and the fouter Fourier sine transfovwz. The final equation is shown to be in good agveetnent with the experimental results of Kirkaldyet al. on Cu-Sn-Zn alloys. COMMON boundary conditions for representing physical problems are those of the finite solid and of the infinite solid. Many metallurgical phenomena, however, have the geometrical form of a finite pattern reproduced throughout an infinite solid. Precipitation within a uniform matrix and segregation during solidification are examples. The purpose of this treatment is to show that a convenient and useful mathematical analysis is possible in those cases in which the finite pattern can be approximated by a sine function. The particular topic to be considered here is the elimination of segregation by diffusion, but the mathematical model has applicability in many other areas. It should be recalled that the mathematical solution of a typical problem involving a finite solid, such as diffusion into a thin layer, is quite involved.&apos; Various types of solutions are used depending on the degree of advancement of the diffusion process and on the initial conditions. A step function is the simplest initial condition, but even in this case the general solution has the form of an infinite series. Kirkaldy et a1.2 have

Jan 1, 1968

By H. F. Silliman, Daniel R. Hull, John R. Freeman

In the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of cold-work and a considerable number of anneals. This condition has been disturbed by the preponderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2:r brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. Hot-rolled 2:1 Brass For illustration, therefore, a typical cake of hot-rolled 2:I brass has been chosen. This was rolled to a slab 36 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. I. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it would be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945