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By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .' The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By C. W. Price, G. A. Wheeler

BERYLLIUM has always been a difficult material to prepare for metallographic examination. Severe surface deformation occurs during mechanical grinding and polishing, and a suitable bright-field etchant has not been developed. Certain electrolytic techniques produce satisfactory polishes, but these techniques have not yielded entirely consistent results. Furthermore, they have not provided satisfactory bright-field etches. The purpose of this paper is to describe an electrolytic polishing technique that can also provide an excellent bright-field etch. In addition to the bright-field etch, other advantages of this technique are excellent reproducibility, rapidity, and ease of polishing and etching. Experimental Technique. Specimen Preparation. Beryllium specimens may be either mounted or unmounted for the use of this technique, and the size of the specimens is not important. Specimens with surface areas up to 4 sq cm have been electrolytically polished and etched successfully with this technique. The most important requirement is to provide a good electrical contact to the specimens, preferably on the back of the specimens. When specimens are mounted, a hole is drilled through the back of the mount so that the specimen can be contacted with a probe. Conventional metallographic grinding techniques are used to prepare the specimens for electrolytic polishing. The specimens are ground on silicon carbide papers. Grinding through the usual series of papers down to the 600-grit paper is recommended to minimize the electropolishing time, although successful electrolytic polishes and etches have been obtained by grinding only through the coarser papers. A continuous flow of water is used during grinding to provide lubrication and to minimize contamination. Mechanical polishing is not required because high rates of material removal are achieved with the electrolytic polishing. Polishing. Most of the results reported in this paper were obtained with a "Disa-Electropol", manufactured by Struers Scientific Instruments of Copenhagen, Denmark. Satisfactory results have also been obtained with the conventional beaker technique of electrolytic polishing, however, the conditions applicable to both the Disa unit and the beaker technique will be described. Stainless-steel cathodes are used in both techniques. In the beaker technique, a flat cathode, with an area at least twice that of the specimen, is used, and the specimen is held parallel to the cathode. The distance between the specimen and the cathode affects the quality of the electropolish. This distance is set at about 7 mm in the Disa unit; the same distance produces the best results in the beaker technique. Specimen-cathode distances greater than about 20 mm produce considerable relief, while distances less than 7 mm cause high current densities that are difficult to control. An electrolyte of 2 pct HC1, 2 pct HNO3, and 2 pct HCIOl in ethylene glycol gives the most satisfactory results for both electrolytic polishing and etching. This electrolyte was developed by altering the composition of a similar electrolyte used for electrolytic lapping1 and adding HClOl to improve the etching characteristics of the electrolyte. Variations of from 0.25 pct to as much as 5 pct of each of the acids do not significantly affect the results, but the greatest amount of control and reproducibility can be obtained with the composition of 2 pct of each acid. Generally, lesser amounts of the acids produce lower polishing and etching rates, while greater amounts of acids cause high current densities that are difficult to control.

Jan 1, 1968

By Mark J. Klein, Robert A. Haggins

The pesence of a small amount of oxygen was found to cause significant grain growth restraint in 99.99 pct Ag. This behavior does not seem to be due to the presence of an oxide dispersion, but instead, to be related to the existence of minute amounts of oxygen m solid solution. In the amounts necessary to cause the observed effects it was found that oxygen migrates with extreme rapidity, probably along extended structural imperfections, such as dislocations and grain boundaries. A number of years ago, hastton' observed that the presence of small amounts of oxygen caused a retardation of grain growth in silver. He attributed this behavior to the formation of a fine dispersion of oxide particles by the internal oxidation of trace impurities. More recently, wood2 also found that oxygen caused grain growth restraint in copper. Experiments using both copper and a dilute solution of aluminum in copper led to the conclusion that the effects observed in copper were due to oxygen in solid solution, rather than an oxide dispersion. During the course of a study of the influence of several solutes on the recrystallization of Silver, the presence of minute amounts of oxygen was found to exert a very significant influence on grain growth. The experiments reported here were undertaken to determine whether the grain growth restraint observed in silver due to the presence of oxygen is related to oxygen in solution or to an oxide dispersion. Because of the difficulty in measurement and control of the very small oxygen concentrations causing the observed effects no attempt was made to treat the data in a quantitative manner. EXPERIMENTAL PROCEDURE AND RESULTS Silver of 99.99 pct purity was melted and cast into slabs in a vacuum of better than 0.1 p. These slabs were reduced 50 pct by cold rolling to a thickness of approximately 2.5 mm. Samples cut from this material were annealed in vacuum for a series of different times at 803°C. Another group of samples was similarly annealed in air. This temperature is well above the recrystallization range for silver of this purity (150" to 200°C). The mean grain diameter of these samples was measured, both in the center and near the edge, using the line-intel-cept method, and is shown as a function of annealing time in Fig. 1. The grain size in the centers of the samples annealed in air was found to be larger than that of the surface regions, while the grain growth behavior of the edge and center regions annealed in a vacuum was approximately the same. he edge measurements were taken at a distance of 0.2 mm from the surface.) A few samples were annealed in nitrogen. Their behavior was identical to that of the vacuum-annealed samples. Samples annealed in oxygen had approximately the same grain growth behavior as those annealed in air, leading to the conclusion that this behaviouer is due to oxygen. The microstructure of a sample annealed in air at 803" for. 30 minutes is shown in Fig. 2. The smaller grain size near the surface is characteristic of the iir-annealed specimens. Possible causes of this grain growth restraint in the air-annealed specimen are the formation of an im-

Jan 1, 1962

By John E. Conley, John A. Ruppert

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By John A. Ruppert, John E. Conley

W. B. Mather—A minor recommendation that may be offered to improve the paper is the inclusion of a map of Oregon showing the general location of the various deposits. This is of especial importance to persons like myself who are not familiar with the various areas and counties mentioned. N. S. Wagner and R. S. Mason (authors' reply)—We agree that an index map of Oregon showing the location of the various nonmetallic deposits would add to the paper (fig. 1).

Jan 1, 1951

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By Volker Weiss, George Sachs, AE. P. Klier

PHYSICAL chemistry contributes to the understanding and efficient operation of hydrometal-lurgical processes in many ways, among them by providing quantitative answers to the following questions. 1) Can a given chemical reaction or process be made to operate and. if so, under what conditions? 2) what are the' factors which determine the rate of the reaction and how can this rate be regulated in practice? Thermodynamics attempts to answer the first of these questions and kinetics the second. The answer

Jan 1, 1958

By Fred D. DeVaney

DURING the past few years a radically new process for the magnetic roasting of iron ores has been investigated and developed by Pickands Mather & Co. and the Erie Mining Co. in the Erie laboratory at Hibbing, Minn. This process, originally devised by Dr. P. H. Royster of Washington, D. C., involves the use of a roasting technique quite different from older methods. It has now been demonstrated that iron-bearing materials can be roasted as effectively as by any previously known method, and at a much lower cost. The increasing shortage of highgrade iron ores in this country has accelerated the search for new methods that would permit low grade materials to be utilized. The concept of magnetically roasting low grade nonmagnetic ores such as the oxidized taconites and then separating such material magnetically has always had considerable appeal. The magnetic concentration idea is attractive because of the sharpness of the separations and cheapness of the method. Heretofore, however, the equipment and the processes available for the magnetizing-roasting -step have left much to be desired. The customary equipment available for reduction roasting has been: 1-multiple hearth furnaces, 2-rotary kilns, and 3-shaft type kilns. In addition, it is understood that some work has been done in magnetically roasting fine ores by a process using the FluoSolids principle, but little information on this process is available. The multiple hearth kiln has been used the most but first costs and operating costs have been high because of low capacity, high maintenance, and poor gas utilization. Magnetic roasting can be done in a rotary kiln, but the radiation losses are high and the conversion to magnetite is usually unsatisfactory because of poor contact between the gases and the solids. Of the shaft-type furnaces, probably the most efficient yet developed is that designed by E. W. Davis of the Minnesota Mines Experiment Station. This furnace was operated at Cooley, Minn., during 1934-1937 but was abandoned in 1937 because the operation was uneconomic. Heretofore the basic concept behind most magnetic roasting processes has been the idea of heating iron ore to a temperature of 800° to 1100 °F in a strong reducing atmosphere, preferably either carbon monoxide or hydrogen. Temperatures under 800°F were undesirable since excessive roasting time was required. Temperatures over 1100°F were avoided because of the danger of converting part of the iron to ferrous oxide which is nonmagnetic. In the new roasting process, the operation is carried on in a shaft furnace using a controlled atmosphere containing a low percentage of reducing gas. The temperature in the roasting zone is considerably higher than with the usual reducing gas and this speeds up the reduction time. Portions of the spent furnace gases are cooled and recirculated and this together with the good contact between ore and gas makes for high reducing gas utilization. High heat economy is secured by recuperating heat from the roasted ore by passing the cold reducing gases countercurrent to flow of ore. The heat transfer principle is similar to that employed in a pebble stove and to that used in the Erie Mining Co. furnace at Aurora, Minn., for pelletizing fine magnetite concentrates derived from taconite. The theory of controlled atmosphere during the roasting operation can best be appreciated by inspecting the equilibrium diagram of the Fe-C-O system shown in Fig. 1. An inspection of this diagram shows that in certain areas magnetite, Fe3O4, is the only stable form of iron. A further inspection of this table shows that if the proper ratio is maintained between carbon dioxide to carbon monoxide, such a gas will be reducing with respect to hematite, Fe2O3, and will be oxidizing with respect to both ferrous oxide, FeO, and iron, Fe. It should be kept in mind that the formation of ferrous oxide in a roasting operation is harmful, since this oxide is nonmagnetic; if it forms in any quantity, it will cause substantial loss of iron in the ensuing magnetic separation step. If a ratio of approximately three parts carbon dioxide to one of carbon monoxide is maintained, the resulting operation can be carried on at a relatively high temperature without fear of over-reduction. Specifically, most of the tests in the Erie furnace have been made at a temperature of 1500° to 1600°F, with an entrant gas containing approximately 5 pct carbon monoxide and 15 pct carbon dioxide, with the remainder largely nitrogen. It should be remembered that the ratios of carbon monoxide to carbon dioxide shown in Fig. 1 hold even though the bulk of the gas is an inert gas such as nitrogen. It may surprise many to learn that a gas containing as low as 3 pct carbon monoxide, and 12 pct carbon dioxide with the remainder nitrogen is an extremely effective reducing gas in the 1000° to 1600°F temperature range. The reducing gas is not limited to carbon monoxide, and mixtures of hydrogen and carbon monoxide may be used effectively, provided that a similar ratio is maintained between the reducing gases and carbon dioxide and water vapor. For a more detailed explanation of the theory involved, the reader is referred to U. S. patents 2,528,552 and 2,528,553. From a safety standpoint, the weak reducing gas used in the furnace offers an advantage. Its composition is such that it is well below the limits of explosion should air enter a hot furnace. This condition is not true with the usual reducing furnace, in which a gas rich in carbon monoxide or hydrogen is used. The general furnace design and method of operation may best be understood by an inspection of

Jan 1, 1952

By I. C. White

ONLY two factors appear to be directly responsible for the geographic distribution of sulfur in the coal fields of West Virginia, these, are the FIG. 1. stratigraphic position of the coals in question., and the eastward or westward location of the deposits. There appears to be a progressive increase in the sulfur content of West Virginia coals from the oldest Pennsylvanian deposits in the Pocahontas, New River, and Kanawha Groups of the Pottsville Series up through the Allegheny, Conemaugh, and

Jan 9, 1919

EXECUTIVE COMMITTEES OF LOCAL SECTIONS Arizona E. P. MATHEWSON, Chairman W. V. DECAMP, First Vice-chairman F. W. MACLENNAN, Second Vice-chairman E. D. GARDNER, Secretary-Treasurer, U. S. Bureau Of Mines, Tucson, Ariz. MICHAEL CURLEY J. P. HODGSON HENRY F.1 ASTER CLYDE E. WEED Boston Meets first Monday each winter month GEORGE A. PACKARD, Chairman FRANKLIN B. RICHARDS, Vice-chairman F. LEROY FOSTER, Secretary-Treasurer Rooms 8-219 Mass. Inst. of Tech., Cambridge, Mass. G. W. METCALFE D. H. MCLAUGHLIN

Jan 1, 1932

By C. A. Shook, W. H. W. Husband, D. B. Haas

Introduction Although previous studies1,2,3 have been made, no correlations for pressure drop have been proposed. This is probably because severe particle breakage occurred and pressure drops changed substantially with time. A quantitative statement of the relationship of pressure drop to the parameters of the system is desirable for lignite since, unlike higher rank coals, lignite slurries are thixotropic. The present investigation was undertaken to quantify the pipeline behavior and required continuous monitoring of pressure drop and size distribution.

Jan 1, 1980

By F. W. Bloecher

D ETERMINATION of the surface area of finely divided minerals is of interest to mineral engineers engaged in flotation, comminution, and dewatering studies. In the industrial minerals field, many materials are classified as to fineness according to their specific surface (surface area per unit weight). A method of surface area determination has been tested and used in the Richards Mineral Engineering Laboratories at M.I.T. It involves low temperature krypton adsorption measurements using the technique described by Beebe.1

Jan 3, 1951

By Mark J. Klein

The behavior of nitrogen in Cr-0.12 at. pct Y was studied in specimens of varying interstitial concentration and thermal history. It was found that soluble nitrogen can be introduced into this alloy by increasing the concentrations of either oxygen or nitrogen. For low nitrogen concentrations the nitrogen in solution is low relative to that in unalloyed chromium. However, the nitrogen in solution increases with increasing nitrogen concentration, approaching that in unalloyed chromium. When the alloy is supersaturated with nitrogen, the nitrogen precipitates readily from solution as a chromium nitride. The stress -induced relaxation of nitrogen is influenced by internal oxidation or internal nitrification of this alloy. THE addition of small concentrations of reactive elements such as yttrium have been found to enhance the low-temperature ductility of chromium.&apos; However, the mechanism by which the ductility is increased is not known. It has been suggested that this effect is caused by a drastic reduction in the concentration of nitrogen retained in solution and therefore a decrease in the number of dislocations locked by nitrogen, a factor that has been associated with an increase in ductility.1,2 However, a change in the type of interstitial precipitate induced by yttrium could also contribute to enhanced ductility of the alloy, since chromium nitride precipitates appear to be embrittling.&apos; In this regard, it has been shown that yttrium scavenges nitrogen in chromium to form YN,4 thus reducing the embrittling chromium nitride phase. However, the change in nitrogen solubility induced by yttrium and the partition of nitrogen between chromium and yttrium nitrides are not known. The object of this investigation is to study the effect of yttrium on the behavior of nitrogen in chromium to obtain information relevant to the mechanism by which scavengers enhance the ductility of chromium. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation have been described in detail elsewhere.5,6 Wires of Cr-0.12 at. pct Y, 15 cm in length and 1 mm in diam, were drawn from rods 0.6 cm in diam supplied by the General Electric Co. The grain size of the wires after recrystallization at 1150°C was somewhat nonuniform, varying from 0.006 to 0.06 mm in diam. The interstitial analysis for the wires in ppm by weight was about 160 0, 80 N, 12 C, and <2 H. Heat treatments were carried out after encapsulation of the specimens in quartz tubes containing argon. Changes in interstitial concentrations, or interstitial "loading" as it is termed in this study, were generally accomplished by annealing in oxygen, ammonia or methane at 1150°C. The internal friction was measured using a conventional torsional pendulum enclosed in an evacuated chamber. Electrical-resistivity measurements were made at liquid-nitrogen temperature.

Jan 1, 1967

By R. I. Jaffee, J. G. Dunleavy, H. R. Ogden, Webster Hodge

INTRODUCTION EARLY in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fick1 and Ruer and Goerens2 definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line off immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 1570°C in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Ford5 have shown that, when hot-rolled copper iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have 150,000 psi tensile strength, and about 41 pct IACS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult, In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation 0f this type of alloy. As a result 0f this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1948

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart&apos;s chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By E. P. Abrahamson II

The effect of transitiorz element bitzary solid solution additions upon the recrystallization temperature of columbium has been investigated. The elements Mn, Fe, Co, Ni, W, Re, and 0s OWY the yecystallization tempel-aturye, while Ti, V, CY, zr, Mo, Ru, Rh, Pd, Hf, Ta, W, Ir, and Pt mise it. A correlation is kloted between the rate of chatzge of recyystallization tewaperature with atomic hercent solute and the free atom electron configuration of the solute element. The work of Abrahamson and Grant1 has indicated a correlation between the free atom ground-state electron configuration and the change in brittle-ductile transition temperature per atomic percent solute in chromium base alloys. A similar correlation was observed for the change in the recrystallization temperature of iron base alloys by Abrahamson and Blakeney and Abrahamson. It was also observed that the limit of rapid change in recrystallization temperature also Correlated with the electronic configuration of the free solute atom. A further study by Abrahamson4 established the generality of the phenomenon by yielding similar results for vanadium base dilute alloys. It has been inferred that a peri- odicity might be expected with changes in the free atom electron configuration of the solvent element. This study is the third set of transition base metal systems to be studied. It is the object of this and further studies on transitional metal systems to detect any systematic variations in the observed correlation which might contribute to the understanding of the electron interactions which are evidently exhibiting themselves. PROCEDURE All alloys were made using 99.9 pct Cb with 0.030 Ta, 0.016 0, 0.0025 H, 0.003 Mo, 0.021 Fe, 0.005 C, and 0.002 N. The solute elements were 99.9 pct pure. According to the published binary phase diagrams5 and metallographic examinations at X750, all additions were in solid solution. The alloys were arc melted and remelted 6 times in the form of cubic 400-g buttons under an argon atmosphere. They were then hot forged at 1200oC to 0.6-in. diameter, annealed for 3 hr at 1200o under argon, and furnace cooled. The specimens were then machined to 0.400 -in. diameter. Grain size was checked and found to remain essentially constant at 150 i 30 grains per sq mm. The specimens were then cold swaged to 0.187-in. diameter, yielding 46 i 1 pct cold work. All alloys were chemically analyzed for the major solute. Analyses of random samples indicated that the impurity content remained at the values of the starting material. Tungsten contamination was held to 0.007 pet.

Jan 1, 1962

By B. W. Levinger

THE lattice parameter of the ß form of pure titanium has been measured at elevated temperature.&apos;, &apos; No attempt was made, however, to correct the parameter obtained to room temperature. In the course of phase diagram studies at Armour Research Foundation and elsewhere, the variation of ß-phase lattice parameter with composition has been established in a number of binary and ternary systems involving titanium. It was possible to extrapolate in these instances to 100 pct Ti to find the apparent lattice parameter of ß titanium at room temperature. Table I lists the results thus obtained. The suggested value for the lattice parameter of ß titanium is the average of the extrapolated values 3.276 ±0.003 kX. This suggested value gives an interatomic distance in ± titanium of 2.837 kX and hence a Goldschmidt atomic diameter (coordination number 12) of 2.925 kX. The latter agrees closely with the value of 2.93 given by Hume-Rothery." From the data of Adenstedt and coworkers&apos; it was possible to determine by extrapolation the mean coefficient of linear expansion for /3 titanium in the range from room temperature to 1000°C. This value, 10.1x10-8 per degree C, compares with about 11x10-8 for a titanium in a similar range." It was thus possible to calculate the parameter at 900 °C. The value of 3.305 kX agrees well with 3.3065 given by Eppel-sheimer.&apos; The majority of values reported in the literature7-&apos;, &apos; were given as Angstroms. In at least one case, ref. 8, it was shown that they actually represented kX units. The source of this confusion appears to be that a large number of tables of X-ray emission spectra list wavelengths as Angstroms and give values in kX units. The accepted conversion factor for kX units to Angstroms (10.&apos; cm) is 1.00202. Thus the parameter of ß titanium suggested corresponds to 3.282A. References J. H. de Boer, W. G. Burgers, and J. D. Fast: Proc. Acad. Amsterdam (1936) 39, p. 515. 2D. S. Eppelsheimer and R. R. Penman: Nature (Dec. 2, 1950) 166, p. 960. 3 W. Hume-Rothery: The Structure of Metals and Alloys (1945) London. Inst. Metals. 4 H. K. Adenstedt, J. R. Pequignot, and J. M. Raymer: Trans. ASM (1952) 44, p. 990. 5 Gmelins Handbuch der Anorganischen Chemie. Titan, Verlag Chemie, Weinhein (1951). 8 P. Pietrokowsky and P. Duwez: Trans. AIME (1952) 194, p. 627; Journal of Metals (June 1952). 7 P. Duwez and J. L. Taylor: Trans. ASM (1952) 44. D. 495. 8 M. Hansen, E. L. Kamen, H. D. Kessler, and D. J. McPherson: Trans. AIME (1951) 191, p, 881; Journal of Metals (October 1951). 8 Unpublished Research, Armour Research Foundation.

Jan 1, 1954

By W. D. Robertson, E. G. Grenier, V. F. Nole

The electrical, mechanical, and corrosion cracking properties of an age-hardenable Cu-Ni-Si alloy have been studied over a range of time, temperature, and deformation states for the purpose of determining the relationship between the properties and the structural state. The precifitate has been identi3ed as and the sites of preferred precipitation have been located by electron microscope studies of the structures developed by various combinations of heat treatment and plastic deformation. An extreme form of deformation banding has been observed in the aged alloy that results in high strain concentration in bands lying parallel to {111} planes. These bands are the structural paths along which transcrys-talline cracks propagate in the deformed alloy. The observations provide a basis for a general mechanism of transgranu-lar corrosion cracking of face-centered cubic alloys in terms of stacking fault probability. AMONG the age-hardening copper alloys the copper-nickel-silicon (Silnic Bronze) type is outstanding in exhibiting a high strength combined with a considerable capacity for cold working, a relatively high conductivity, and a low to negligible susceptibility to stress corrosion cracking. It is not a new alloy and it has been the subject of a number of investigations,1-5 which were made primarily to establish practical composition and heat treatment limits. The structural characteristics of the aging processes in this alloy have not previously been studied in detail. This particular investigation was undertaken to explore, in detail, and over a wide range of conditions, the properties obtainable by various combinations of working and heat treatment and to correlate structural changes with the observed mechanical, electrical and corrosion properties. MATERIAL AND PROCESSING Eight different commercial heats of the alloy were made and used in the investigation. The range of composition among the eight heats is shown in Table I. Billets, 8 by 24 in., were cast into water-cooled molds, extruded to 1.687-in. rod, and quenched in water after extrusion. Extruded material was rod rolled to 0.750 in., annealed at 1450° F for 2.5 hr, and quenched in water. Subsequent working operations were performed by tandem rolling to various sizes depending on the degree of reduction required. Final cold-working operations were performed by drawing to a uniform size of 0.187 in. diam and straightening by a roller straightening machine (Lewis). The combinations of heat treatment, working and aging that were investigated are summarized in Table 11; the various treatments were performed in the order given in each row of the table, and they will be subsequently identified by the symbols shown in the first column. SOLUTION TREATMENT All material investigated in the cold-worked condition, or cold worked prior to aging, was solution

Jan 1, 1962

By J. R. Long, C. E. Armantrout, A. H. Roberson, T. R. Graham

The preparation and fabrication of copper-manganese-zinc alloys and the evaluation of their engineering properties have for some time been an integral part of a research program of the Federal Bureau of Mines. In this project, the use of electrolytic manganese, along with high purity copper and zinc, has permitted the preparation of alloys which contain a minimum of impurities which are capable of producing detectable effects in the properties studied. The initial work on the physical properties of wrought alpha solid solution alloys and a general outline of the alpha solid solution area for alloys containing up to 40 pct manganese have been presented in previous reports. 1,2,3,4,5 The evidence accumulated in these investigations clearly showed that additions of manganese to the copper-zinc alloys improve the strength properties of the brasses without seriously reducing their characteristic ductility and that considerable quantities of manganese could be added to the copper-zinc alloys without exceeding the mutual solubilities of manganese and zinc in copper. In continuation of these studies, additional data have been obtained in a more extensive investigation of the phase relationships of the copper-manganese-zinc ternary system. The present report delineates the solid phase boundaries of the ternary system from the copper-zinc binary to the manganese-zinc binary for alloys containing up to 50 pct zinc. Summary The alloys used in this investigation were conditioned by working schedules designed to homogenize the structures prior to heat treatments required for the equilibrium phase sludy. The treated alloys were examined by metallographic methods including hardness and X ray data for confirmation. The composite data of the investigation are summarily presented in a series of isothermal sections of the ternary system at 1100, 1200, 1300, 1200, and 1500°F. The salient features of the system as outlined by these data are: (1) the continuous alpha solid solution which extends across the diagram to the gamma-manganese phase of the manganese-zinc system at temperatures of 1200°F and higher, (2) the beta phase of the copper-zinc system similarly forms a continuous solid solution with its counterpart the beta field of the manganese-zinc binary, (3) at 1100°F (593°C) these alpha and beta fields are greatly restricted by complications arising from the allotropic transitions of manganese and the decreasing solubility of manganese in the alpha solid solution. The alpha + beta fields intersect the alpha + alpha manganese field to produce the beta + alpha manganese field and two adjacent three phase fields consisting of alpha + beta + alpha manganese and gamma + beta + alpha manganese. Typical microstructures representative of the various phase areas at each temperature are also presented. Review of Previous Work The copper-manganese-zinc alloys have periodically been the subject of numerous investigatioris of both prac-

Jan 1, 1950

By George A. Roberts, Arthur H. Grobe

Tensile, hardness and density properties are presented for a new 18-8 stainless steel powder for the —50, —100, and —140 mesh cuts and also for a prepared blend containing 62 pct —325 mesh powder. The data were obtained for sintering temperatures of 2100° to 2350°F and for compacting pressures of 30 to 50 tons per sq in. A NEED has existed for a stainless steel powder of uniform composition from particle to particle, which could be readily molded and sintered, and which would yield moderate to high strength and ductility when processed into parts by standard powder metallurgy techniques. The literature reveals that previously available powders have been lacking in one or several of these desirable characteristics. Originally attempts to produce stainless steel powder by blending and diffusing elemental metal powders were unsuccessfu1.l A truly alloyed stainless steel powder reported by Dale in 1947 yielded reasonable mechanical properties but required an exceptionally high sintering temperature of 2400°F in pure dry hydrogen.&apos; A later development reported in 1950 by Stern provided a stainless type powder of excellent molding properties&apos; but this powder likewise required sintering at temperatures over 2350 °F and did not yield properties as high as those previously reported. The powder was not truly alloyed prior to sintering. A prealloyed stainless steel powder has been developed that is readily moldable at 30 to 50 tons per sq in., can be sintered at low temperatures (2100" to 2300°F), and which yields compacts with both high strength and ductility. The powder is prepared by the liquid disintegration method," direct from molten metal. Early attempts to make 18 pct Cr, 8 pct Ni stainless steel powder by this method did not produce a usable powder for pressing and sintering because of a preponderance of spherical particles with relatively high, surface oxide content. It was learned that silicon additions to iron alloys, powdered by this process, gave bright powder of low-oxide content and such additions were made to 18-8 stainless with similar results. An attendant change in particle shape occurred reducing the number of spheroids materially. The optimum composition which has been studied and is reported here contains approximately 2.5 pct Si. Silicon additions to stainless steel of the 18-8 type improve the resistance to high-temperature oxidation and promote the formation of ferrite. Corrosion resistance is, however, controlled by chromium content and even though ferrite may exist the corrosion resistance is not generally impaired.4 Experimental Procedure A detailed study of the 18-8, 2.5 pct Si powder has been made in accordance with the following outline: 1. Four blends a. — 50 mesh b. —100 mesh

Jan 1, 1952