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By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By Luther Wagoner

Having given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and believing it might be interesting to extend the work to include some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S. steamer Albatross, and marked as follows: Depth in No. station. Locality. Latitude. Longitude. Fathoms. 1. 2103. Off Delaware bay. 38' 47' 20" N., 72o 37' W., 1,091. 2. 2265 to Between Chesapeake 35° 37' N., 74O to 75O W., 49 to 70. 2297. bay and Hatteras. 3. 2420. Off Chesapeake bay. 37' 03' 20" N., 74O 31' 40" W., 104. 4. 2528. East of Georges 41° 47' N., 65o 37' 30" W., 677. bank. 5. 2572. SE. of Georges bank. 40° 29' N., 66O 041 W., 1,769. 6. 2681 South of Nantucket. 39' 43' N., 70' 29' W., 990. The above samples were assayed by the cyanide-method, described in my former paper (p. 807), about 30 g. of sample being used, and the following results were obtained: Value in Milligrams Per Metric Ton. No. Station. Gold. Silver. 1. 2103. 145 1,014 2. 2265 to 2297. 44 304 3. 2420. 15 353 4. 2628. 267 1,963 5. 2572. 125 377 6. 2681. 66 414 No. 4, Station 2528, consisting of red clay and volcanic ash, mas re-assayed ; 35 g. was roasted at a low heat for one hour and weighed 34.05 g. after roasting; the color was changed to a deep brick-red; and when assayed by the cyanide-method

Jan 1, 1908

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers'-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,' reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By D. G. Westlake

Alloys of poly crystalline Nb-H have been tensile tested at 77" and 120°K after slow-cooling and after quenching from room temperature. A rationale has been developed to explain the effect of cooling rate on ductility in terms of microstructure. The inferior ductility of the slow-cooled alloys in this temperature range can be attributed to the precipitation of coarse hydride particles that fracture in the early stages of plastic deformation. Quenching Produced much smaller hydride particles and a decreased tendency for initia-tion and popagation of cracks. Prismatic dislocation loops, punched into the matrix of quenched alloys, eliminate the yield point and may Play some role in the low temperature ductility of the quenched alloys. The difference in ductility between quenched and slow-cooled V-H alloys was even greater than that observed in the N b-H alloys. It is well known that the ductility of Nb-H and V-H alloys decreases with increasing hydrogen concentra-tion and with decreasing temperature.1-l1 The follow-ing are some of the numerous mechanisms that have been adopted in attempts to explain these observations: 1) hydrogen-dislocation interarction,4'6 2) lowering of the crack surface energy by adsorbed hydrogen,9'10 3) localized lowering of the niobium bond strength,9 and 4) exertion of pressure inside voids by molecular hydrogen.6 A recent study1' indicates that, in some way, the embrittlement is related to the precipitation of a hydrogen-rich phase, because embrittlement and hydrogen solubility have the same temperature dependence. Most of the investigators observed that at very low temperatures there was a return of the ductility. Thus, hydrogenated niobium and vanadium may be said to exhibit a low temperature ductility minimum."1'8'9 It has been reasoned by most observers that diffusion is required for the embrittlement mechanism to be operative, and that as hydrogen becomes immobile at very low temperatures, the ductility increases. This investigation of the mechanical behavior of Nb-H al-loys under various conditions is an attempt to gain a better understanding of the low temperature ductility minimum. EXPERIMENTAL Tensile specimens, with gage length dimensions 20 by 3 mm, were machined from sheet stock" and both faces were ground on wet 600 grit Sic paper to obtain a final thickness of 0.5 mm. Annealing as described earlier12 resulted in average grain diameters of 0.3 mm. The recrystallized niobium tensile specimens were electropolished in 90 parts H2S04, 10 parts HF (48.9 pct) by volume, at 287°K and 30 v. Hydrogen, which may have been present in the starting material and/or added during specimen preparation, was removed by annealing at 1073°K in a dynamic vacuum of 2 X 10-6 torr. Hydrogenated specimens (1.15 at. pct H) were prepared by reaction with a known quantity of pure hydrogen (obtained by thermal decomposition of UH3) at 1073oK, followed by cooling at the rate of 100" per hr. These were vacuum encapsulated, homogenized at 573°K for 3 to 5 hr, and furnace-cooled. Tensile tests were conducted on an Instron machine at a strain rate of 4 x l0-5 per sec. The gripping device was such that the specimen was positioned below the crosshead. Thus, subambient test temperatures could be obtained by immersion of the device in a cooling bath of either liquid nitrogen or Freon-12. The temperature of the Freon-12 was controlled within ± 0.1°K of the desired temperature by automatically monitoring the flow of liquid nitrogen through a copper coil in the bath. Slow-cooling to 77°K was accomplished as follows. The testing device was surrounded by a rubber jacket, open at the top and with small holes in the bottom. Liquid nitrogen, brought up to the bottom of the jacket, entered the holes and vaporized quickly. The temperature was monitored at the specimen with a copper-constantan thermocouple, and a constant cooling rate of 2 deg per min was easily achieved by controlling the level of the liquid nitrogen outside the jacket. RESULTS AND DISCUSSION Low Temperature Ductility Minimum. Resistometric studies of both Nb-H12 and V-H13 indicated that at tem-peratures less than 150°K, virtually all of the hydrogen

Jan 1, 1970

By L. G. E. Bignell, E. A. Hanson, J. O. Lewis

There was a general upward trend of all petroleum activities in Oklahoma during 1933, especially in the last quarter, though the average price for crude oil for the year was below 1932 and overproduction in East Texas demoralized conditions for several months. As the Federal Agencies established under the National Industry Recovery Act began to function conditions in Oklahoma were visibly affected and production of "hot oil" from Oklahoma City field practically ceased. More oil wells were completed, six new fields discovered, extensive geophysical prospecting carried on in many parts of the state, and an increased amount of clean-out and reconditioning work done in older pools during the past year. To increase quantity and rate of recovery of oil many wells producing from limestone formations were treated with hydrochloric acid. The Oklahoma City field had a reported production of 66,984,570 bbl. of oil during 1933, or almost exactly twice the amount reported for 1932. Potential tests and other indicators show that the wells are rapidly approaching the stage where mechanical lift must be applied to all of them, including the wells in the Wilcox sand zone. The major pipe-line companies serving the oil fields of Oklahoma have been anxious to make connections to all wells during 1933 and have indicated a willingness to accept all oil available. The amount offered has been restricted by proration orders, but the state did produce 178,356,-449 bbl. during the year, an increase of about 18.6 per cent over 1932. This increase was practically all due to the greater demand for Oklahoma City oil, as all other pools of any importance showed loss in production or very small gains last year. The U. S. Bureau of Mines' laboratory reports the lubricating distillate content of Oklahoma City crude from Arbuckle and Lower Simpson formations about 17 per cent by volume. East Texas oil is reported to contain about 5.6 per cent lubricating distillates. The desire of the transportation companies to keep their equipment operating at maximum capacity and the need of some refineries for more

Jan 1, 1934

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By R. J. Mellen

IN a chloridizing roasting and cyanidation plant treating a manganese-silver ore, certain experiments pointed out the way to an improvement in roasting conditions by a change in the degree of crushing. The following short article is simply a description of the various changes that were necessary throughout the plant and of the results obtained. There is nothing unusual in these changes but they are of some interest in that they constitute a good many of the alterations usually resorted to in increasing production. In the beginning, the changes were brought about by an experiment that was not successful, but which clearly pointed to means of improving the operation, and is an example of the fact that often experimental work may result in failure and still be of value in arriving at correct fundamentals. This experiment also shows how far a metallurgist can get out of line in his deductions, particularly in a field with which he is not thoroughly familiar. The ore at the plant of Compania Minera Kildun y Anexas is crushed through a 13-in. gyratory, a 3-ft. standard Symons cone crusher and a set of 16 by 42in. rolls, the latter in closed circuit with two Tyler 400-mesh screens. The crushed ore is then conveyed to two fine-ore bins. These provide storage and feed for two 6 by 90-ft. kiln roasters, which discharge directly to coolers. The coolers in turn discharge to a 6 by 12-ft. ball mill, where the ore is ground for cyanidation. Laboratory and pilot-plant tests previous to the mill construction had indicated that minus ¼ -in. crushing was satisfactory for roasting, although results did not vary greatly with some coarser or considerably finer crushing. The plant was designed for a capacity of 300 tons per day on this basis. After a few months operation, the initial operating problems were overcome and the anticipated milling rate was reached but the results being obtained were not really good. The plant seemingly did not have much excess capacity in any department but the roasting operation was the most critically limiting factor both as to tonnage and the results obtained. If this could be improved there seemed some possibility of improving the total tonnage rate to some extent. Segregation of the calcine into various screen sizes showed that the coarser sizes ,were not giving the expected recoveries. In all of the laboratory and pilot-plant testing, any limiting conditions as to the percentage of salt used, temperatures, feed rates, etc., had affected the fine material more than it had the coarse, and even in making laboratory tests at this time the mill conditions could not be exactly duplicated. Further laboratory testing indicated that a segregation of the crushed ore into a coarse and fine product for roasting might result in some improvement in roast-

Jan 1, 1945

By John A. Oberteuffer, James E. Lawver, Ionel Wechsler, Bo Arvidson

INTRODUCTION The demand for aluminum metal and thus for alumina and bauxite (the primary sources), is expected to increase at an annual rate of about 6% through the year 1980. It appears that about 90% of the future aluminum metal requirements could be produced at domestic plants but the production would remain dependent on the use of imported bauxite and alumina. The U.S. dependence on foreign bauxite and alumina is of considerable economic and strategic concern because availability and prices are very sensitive to changes in the political climate in the exporting countries. Dependence of the United States on foreign sources of bauxite closely parallels its dependence on foreign sources of oil, particularly since ten countries, including most of the world's major bauxite exporting countries, recently have formed the Inter- national Bauxite Association (IBA) for the specific purpose of increasing revenue for the participating countries. Although it is clear that long-term aluminum requirements cannot be fulfilled by domestic resources of bauxite,; the U.S. has an almost unlimited supply of aluminous resources such as Kaolinite (38% Al203), Alunite (37% Al203), Dawsonite (35% A1203), and Anorthosite (29% A1203)

Jan 1, 1976

By J. Stringer, I. W. Edington, C. R. Rarey

THE geometrical interpretation of transmission electron micrographs of hcp metals is more complicated than the equivalent interpretation of cubic metal for two reasons: firstly, prominent zone axes are not in general normal to prominent planes, so that a simple diffraction pattern often corresponds to a nonra-tional foil plane; and secondly, the Miller-Bravais sys-tem of indexing directions is not easy to visualize. In this, the indexing is referred to the Bravais four-axis system, and the direction is labeled [hkil], chosen so that and I are shown in Fig. 1. Some geometrical relationships useful for the interpretation of transmission micrographs have been calculated and are tabulated below: 6) Direction of the intersection of two planes; this is easily calculated by applying Condition 4 to both planes: a direction that lies in both planes is clearly their direction of intersection. Some of the above expressions have also recently been given by Otte and Crocker;' Expression 5 is of course in most standard crystallographic texts. It is generally considered easier and quicker to use graphical methods for the interpretation of electron micrographs than analytical methods. For this purpose, it is most convenient to use a "double stereo-gram" in which both the poles alzd the rational directions are plotted. It is, of course, necessary to orient

Jan 1, 1967

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By Strathmore R. B. Cooke, Iwao Iwasaki, Hyung Sup Choi

The effect of temperature as a parameter in ore flotation has not been systematically studied, although for some ores it has been known for many years that selectivity and grade of concentrates can be improved by conditioning or flotation at moderately or substantially elevated temperatures. In 1934 Coghill and Clemmer' stated that "elevated temperature seems to make hard water more tolerable" in soap flotation, and a cursory examination of the literature indicates that some earlier investigators were aware of beneficial results obtained by floating above room or mill-water temperatures. Tartaron,' Mitchell et al.,3 and particularly Hamilton et al." have shown that high pulp temperatures give high recovery and selectivity in soap flotation of fluorite from a variety of gangue minerals. As a result of the work of these and of other investigators, high-temperature flotation has been successfully applied to industrial flotation of fluorite. Falconer" stated: "The use of high temperature conditioning (above 35°C and preferably above 60°C) in connection with the soap flotation of nonsulphide ores, as covered in B. Kalinowski's French Patent No. 847,- 215, Dec. 7, 1938, is claimed to provide more intense activation, better separation of values from gangue, and reduction in quantity of reagents." The various investigations quoted above clearly demonstrate the improvements to be realized by increasing the temperature at which fluorite is floated, and it is surprising that little or no information has been published on systematic investigation of the same method as applied to other ores.

Jan 5, 1960

Through the generosity of Sir Robert Hadfield, Honorary Member, the Directors of the American Institute of Mining Engineers are enabled to announce the Hadfield Research Prize of $1,000 for the best contribution to the publications of the Institute upon the general subject of The Different Forms and Combinations of Carbon with Iron, including those in Iron Alloys. The prize will be awarded at the Annual Meeting of the Institute in February, 1916, to the best paper upon this subject which is presented to the Institute before Nov. 1, 1915, provided such paper is deemed worthy by the Institute's Iron and Steel Committee. The following suggestions are also added for the guidance of those who may take part in this research. While' it is not desired to define closely the exact lines or scope of the proposed research, as it is advisable to make these as broad as possible, the object in mind maybe said to be generally as follows: To elaborate and find out the best methods of determining the forms of carbon in steel or iron, including those in iron alloys. A portion of the work would probably be a continuation of the researches which have in the past been carried out by Jullien, Abel, Muller, Ledebur, T. Sterry Hunt, Akerman, Arnold, Stead, E. D. Campbell, Hogg, Parry, Upton, and others. In a generic way, metallurgists now speak of carbides, sub-carbides, double carbides, special carbides, and other combinations. It is very desirable that these should be accurately defined and understood. It is also desirable to know whether there are other or new forms; if so, can these be separated and their characteristics obtained. It may be interesting to point out that the carbon compounds now definitely known are stated to number over 80,000. It is very probable, therefore, that there is room for much valuable and useful research to be carried out with the object of increasing our knowledge of the various combinations of carbon with iron, as probably some of these are still unknown

Jan 5, 1914

By William H. Emmons

The problem of the metalliferous veins has always been an outstanding one in the science of ore deposits. In recent years interest has been stimulated by Spurr, who maintains that veins have consolidated from magmas that have densities as great as the densities of ordinary rocks. Lindgren published a noteworthy paper1 in 1926, in which he supports the theory that veins are deposited chiefly by hot waters. Lindgren's paper was discussed by Singewald, Spurr, Kemp, Anderson, Colony, Bateman, Porter and others. The discussion, in the main, was centered on the interpretation of fragments that are included in veins. This paper also treats the problems of fragments in veins and includes a reply to a review by Spurr2 of a bulletin by Larsen and myself3 published by the United States Geological Survey on the geology and ore deposits of Creede, Colorado. Mineral veins containing fragments of the wall rock are common. At many places the fragments are completely isolated, one from the other, and are entirely surrounded by vein matter. It has been stated that the vein matter around the fragments was heavier than the fragments and that the latter were floated in a magma. J. E. Spurr, who is the leading advocate of this hypothesis, 4 urges that normal mineral veins were deposited by solutions heavy enough to float fragments of the country rock, and it is mainly on this relation that he bases his theory that veins are deposited by solidification of magmas. If it can be shown that vein-forming solutions have a specific gravity greater than rock (2.77), one is justified in regarding them as true mag-matic solutions. It is shown later in this paper, however, that at Lead, S. D., water not more highly concentrated than ordinary drinking water is depositing vein matter around fragments of schist and of steel in such a manner that the fragments are completely isolated and completely surrounded by the mineral cement.

Jan 1, 1928

By Ralph Nichols

THE mines are near the town of Gilmore, in the Texas mining district. This district was organized in 1880. The present producing mines are near the terminus of the Gilmore & Pittsburg railroad. This railroad connects with the main line of the Oregon Short Line at Armstead, Mont. The distance from Gilmore to Armstead is 70 miles. The town of Gilmore is near the head of the Lemhi river at an elevation of 7,000 ft., while the mines are from 400 to 1,300 ft. higher. The range of mountains upon which the mines are situated forms the water shed for the Little Lost river on the west and the, Lemhi river on the east. The winters are severe and the snow fall is heavy, but the mines ship right through the year. There is an abundance of timber suitable for all mining purposes in the immediate vicinity. Water is piped into the camp from a lake about 2.5 miles distant. This lake is about 1,400 ft. above the town of Gilmore. The water is exceptionally good for boiler and domestic purposes. The mining companies now producing are. the Pittsburg Idaho Co., Ltd. ; the Latest Out Mining & Smelting Co:, Ltd. ; and the Gilmore Mining Co., Ltd. Besides the above properties, there are a number .of prospects in different stages of development. The producing mines of the district are fissures in limestone, with a general northeast-southwest course .and a dip to the west of from 40° to 70°. These fissures are at about right angles to the bedding of the limestones. The veins are regular and the ore shoots strong, both laterally and in depth, so far as developed. The ore shoots have a rake or pitch to the south. The character of the formation is shown in Fig. 1, a section of the Latest Out mine.

Jan 11, 1913

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period May 10,1917, to June 10, 1917. F. J. Anderson, Cali, Colombia. W. F. Jahn, Kirkland Lake, Ont., Canada. George J. Bancroft, Denver, Colo. W. McA. Johnson, Hartford, Conn. W. F. B. Berger, Denver, Colo. J. E. Jopling, Marquette, Mich. F. J. Brulé, Toronto, Ont., Canada. William Kelley, Vulcan, Mich. J. Murray Clark, Toronto, Ont., Canada. H. M. LaFollette, La Follette, Tenn. Will L. Clark, Jerome, Ariz.. Dorsey A. Lyon, Washington, D. C. G. H. Clevenger, Palo Alto, Cal. James F. Magee, Lancaster, Pa. Paul S. Couldrey, Sound Beach, Conn. M. Ortin, Nijni-Novgorod, Russia. C. W. Crispell, Kingston, N. Y. - C. H. Palmer, Jr., Los Angeles, Cal. George A. Easley, La Paz, Bolivia. Edison S. Pettis, ?Mill Valley, Cal. Bancroft Gore, Butte, Mont. Mortimer A. Sears, Paintsville, Ky. John B. Guernsey, Roanoke, Va. W. J. Uren, Houghton, Mich. Rush M. Hess, St. Louis, Mo. C. E. Visel, New Haven, Conn. E. Hibbert, Nickelton, Ont., Canada. Percy E. Barbour, has resigned his position as managing editor of the Engineering & Mining Journal, to accept the appointment of Deputy Superintendent of the New York State Troopers, with headquarters at Albany, N. Y., with the rank of captain.. He has also been commissioned as captain in the 22nd Regiment, N: Y. N. G., having been formerly 1st Lieutenant.

Jan 7, 1917

By Georges Fleming

The new burden preparation plant of ARBED Luxembourg, Belval- Works, which comprises 2 large sinter strands, is equipped with a process computer connected to a comprehensive process control system. The main jobs done by the computer are the control of the raw mix composition, and thus the monitoring of the stacking of the piles at the bed-blending plant, and the optimization of the sintering process. Among the optimization criteria, quality is considered as the most important. The sinter quality, characterized by the mechanical strength and the state of oxidation, is controlled automatically. The control system which we have dev loped is highly reliable; as a result, the standard deviation of Fe++, for the control of bivalent iron, has been narrowed to 0,5 % and the standard deviation of the IS0 + 6, 3 mm index, for the control of the mechanical strength, has been kept within 1 %. Thanks to these results, the combined savings in fuel consumption at the sinter plant and at the blast furnaces have covered the total costs of the optimization project in 2 years. By applying automatic control, the optimum driving range of the sinter plant has been defined and these new guidelines are used for monitoring the sinter production.

Jan 1, 1977

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969

By R. V. Sara

Determination of the Hf-C phase diagram was conducted primarily by metallographic and X-ray diffraction studies on appropriate alloys. The only intermediate phase observed in this binary system was HfC. This phase was found to be homogeneous between 34.0 and 48.0 at. pct C at 2200°c and between 36.0 and 49.3 at. pct C at 3150°C. The lattice-parameter variation was also determined for HfCI-, compositions prepared at 2200° and 3150°C. The most most refractory composition, with a melting point of 3830°c, was established at 47.5 at. pct C from melting-point data. Solidus temperatures of 2240' and 3150°C occur on the high-kafnium and high-carbon sides of the monocarbide, respectively. The invariant point between HfC and carbon is located at 66.0 at. pct C, whereas the 2240°C solidus corresponds to the peritectic temperature at which hafnium is formed from HfC and hafnium-rick liquid. Hafnium has a melting temperature of 2208°C and is capable of taking carbon into solution to the extent of 10.5 at. pct at this temperature. ALTHOUGH the Hf-C phase diagram has not been previously evaluated experimentally in its entirety, the belief has been that the general configuration would resemble the chemically similar Group rV carbide systems, Ti-C and Zr-c.' These binaries are characterized by a single carbide phase with a simple NaC1-type structure which is maintained over wide compositional ranges. This family of carbides has high thermal stability that increases substantially as the atomic number of the metal component increases. This trend characterizes HfC as one of the highest melting materials. According to Agte and Alterthum,2 the melting point for this monocarbide is 3890°C, a value that has been quoted quite extensively for the past several decades. Recently, in repeating the work of Agte and Alter-thum, Adams and Beall3 determined the melting point of HfC to be 3895°C. A significant departure from the commonly accepted version of the Hf-C system was reported by Avarbe and his coworkers,4 who proposed that there is an extreme stabilization of a hafnium in a narrow field to 2820°C, above which it melts peritectically to form HfC and liquid. Their study was also concerned with the melting temperature of various HfCI-, compositions, but the peak melting point was taken from the work of Agte and Alterthum. Avarbe and his associates were not concerned with the high-carbon region of the system. However, three widely varying temperatures have been reported for the HfC-C solidus by other investigators. Cotter and Kohn5 observed approximately 2800°C; Portnoy et al.' reported 3260°C; and, more recently, Krikorian7 indicated 2915°C. Equally as uncertain is the solidus between hafnium and HfC. As noted above, Avarbe et al. report a peritectic temperature of 2820°C, Krikorian7 measured 2150°C, and Benesovsky and Rudy' estimated 2000°C on their diagram. I) EXPERIMENTAL PROCEDURE The starting materials for this study consisted of reactor-grade hafnium hydride obtained from Fair-mount Chemical Co., Newark, N.J., hafnium carbide supplied by Wah Chang Corp., Albany, Ore., and Union Carbide spectroscopic-grade graphite, SP-1. The graphite analysis indicated impurities at levels of only 0.5 ppm or less. According to the suppliers, the hydride and carbide contained the typical impurities listed in Table I. The samples required for these studies were prepared by dry blending either graphite and hafnium hydride or hafnium hydride and hafnium carbide powders for approximately 5 min in a "Spex Mixer Mill". The latter combination was used only for preparing several samples in the HfC1-, melting-point studies. Small pellets, varying between 3/16

Jan 1, 1965

By William Emmons

THE problem of the metalliferous veins has always been an outstanding one in the science of ore deposits. In recent years interest has been stimulated by Spurr, who maintains that veins have consolidated from magmas that have densities as great as the densities of ordinary rocks. Lindgren published a noteworthy paper1 in 1926, in which he supports the theory that veins are deposited chiefly by hot waters. Lindgren's paper was discussed by Singewald, Spurr, Kemp, Anderson, Colony, Bateman, Porter and others. The discussion, in the main, was centered on the interpretation of fragments that are included in veins. This paper also treats the problems of fragments in veins and includes a reply to a review by Spurr2 of a bulletin by Larsen, and myself published by the United States Geological Survey on the geology and ore deposits of Creede, Colorado. Mineral veins containing fragments of the wall rock are common. At many places the fragments are completely, isolated, one from the other, and are entirely surrounded by vein matter. It has been stated that the vein matter around the fragments was heavier than the fragments and that the latter were floated in a magma. J. E. Spurr, who is the leading advocate of this hypothesis,4 urges that normal mineral veins were deposited by solutions heavy enough to float fragments of the country rock, and it is mainly on this relation that he bases his theory that veins are deposited by solidification of magmas. If it can be shown that vein-forming solutions have a specific gravity greater than rock (2.77), one is justified in regarding them as true magmatic solutions. It is shown later in this, paper,. however, that at Lead, S. D., water not more highly concentrated' than ordinary drinking water is depositing vein matter around fragments of schist and of steel in such a manner that the fragments are completely isolated and completely surrounded by the mineral cement.

Jan 1, 1928

By Clarence Wright

THE average lead and zinc content of the ores mined and milled in the Joplin district is low as compared with that of other lead and zinc deposits throughout the United States. Because of this fact and of the high grade of the concentrates, the ratio of concentration is unusually high. Most of the operating companies have aimed to produce as high a grade of concentrate as possible in order to obtain the highest price for their product. They have done this at the sacrifice of the percentage of zinc recovered. The average percentage of zinc recovery is from 60 to 70 per cent. For percentage of recoveries from actual mill tests, see tables. The concentration is commonly effected by crushing the ore to h-in. (12.7 mm.) size and subjecting it to a roughing and cleaning over two or more large Cooley jigs, of the Harz type, the finer sands being treated on the usual types of sand and slime tables. The treatment of slimes by flotation is being tested at several of the larger mills. COARSE CONCENTRATION When the ore. has been hoisted from the mine it is dumped onto a chute leading to a grizzly made of iron bars, usually heavy rails, spaced 4 to -5 in. (101 to 127 mm.) apart. The oversize is caught on the grizzly, the mineralized pieces are broken with sledge hammers so as to pass through, and the boulders that are practically barren are sorted out by hand and trammed to the waste-rock pile. The proportion of waste rock thus sorted out varies from a fraction of 1 per cent to 15 per cent., depending on the nature of the rock.

Jan 10, 1917