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By Arnold O. Tanner

The recession that took hold of the domes-tic mining industry in 1981-82 finally abated somewhat in 1987, resulting from increases in many commodity prices, especially in the metals sector, and from continuing success in lowering operating costs. By no means was the work finished; the mining industry was in a sense entering a new era. The struggle for survival was still very evident for many companies and various commodities, but increasing productivity and profits were accompanied by indications that these trends were more long term than short term. Raw nonfuel minerals produced in the United States during 1987 had an estimated value of $26.3 billion, an increase of $2.9 billion over the 1986 value. This is the fifth consecutive year that the value has increased. Except for a decrease in 1982, the value each year has increased since 1971, or 15 of 16 years. The value of raw metals production increased by an estimated 28%, an impressive improvement since the drastic fall in 1982. Industrial minerals growth was comparatively flat, with an estimated in-crease in value of 0.1 %, continuing a trend of the previous 2 years. Metal mine production dropped considerably in 1982 and maintained its resultant lower level until 1987, when production significantly recovered.

Jan 1, 1989

By Alphonce Wikedzi, Mussa D. Budeba, Samwel V. Manyele, Sospeter P. Maganga

The present study provides an overview of the challenges and opportunities in processing complex gold-copper ores. The systematic literature review was conducted using Scopus database and seven-step methodological approach. The study indicates that the major challenges in processing complex gold-copper ores through the conventional cyanidation method include (1) increase in cyanide consumption; (2) increase in cyanide destruction cost; (3) low gold recovery; (4) decrease in adsorption efficiency; (5) decrease in electrowinning efficiency, and (6) difficulties in the measurement of free cyanide concentration in the leaching system. Moreover, the study indicates that several methods have been developed and some have been implemented in the mining industry for processing complex gold-copper ores. This includes ore segregation, pre-aeration, pre-treatment methods (e.g., ammonia), alternative lixiviants (e.g., thiosulfate, thiocyanate, glycine), cyanide destruction methods, and cyanide and copper recovery technologies. The study concluded that using lixiviant mixtures (e.g., cyanide-glycine), pre-treatment with environmentally friendly reagents (e.g., glycine) and the integrated membrane-based process (SuCy process) are new directions in processing complex gold-copper ores. However, more investigations are required to advance these processes to a commercial scale.

Sep 30, 2023

By Osamu Inoue, Takashi Yamashita, Takashi Ikemoto

The expansion project in Naoshima smelter and refinery to meet enhancing recycling business of E-scrap was successfully completed in 2016 to have a capacity of 110,000 tpa of E-scrap treatment. Increasing treatment of E-scrap has raised the Ni content of copper anode to 4000 ppm on average, which is double the level of 10 years ago, and to 6000 ppm or more occasionally. The tank house has refined such copper anode to copper cathode with starter sheets. Since most Ni in Copper anode dissolves in copper electrolyte, the Ni content of the electrolyte has increased to 27 g/L and more. Ni accumulated in the electrolyte has increased power consumption during the electrolytic refining of copper, although cathode quality has been controlled satisfactory so far. In order to ensure sustainable operation while growing E- scrap business, the NiSO4 process has been expanded recently so as to recover Ni in the electrolyte more and the pressurized-leaching technology will be introduced to the slime leaching process so as to enhance the capacity of slime treatment and to improve Ni recovery in the near future. INTRODUCTION In recent years, the treatment amount of E-scrap at Naoshima smelter and refinery has increased according to the growth of its recycling business as shown in Figure 1, while impurities from E-scrap have concentrated in copper anode as well. Especially, Ni content in anode has been increasing remarkably since 2012, causing to raise Ni content in the electrolyte as shown in Figure 2. The increment of Ni content in copper anode and electrolyte has adversely affected the electrorefining process, slime leaching process, and NiSO4 crystallization process at the tank house. Such severe conditions provided opportunities to redesign the tank house to establish a robust process to which more Ni is acceptable.

Jan 1, 2019

By J. W. Rutter, K. T. Aust

THE object of the experiments to be described in this report was to determine, first, which grains, out of a large number introduced into a sample in which their growth could proceed, were able to grow most successfully; and, second, the factors which control their growth selection. In an earlier study of grain boundary migration in high-purity lead,' it was found that, under some conditions, the most successful grain in an experiment of this type bears a special orientation relationship to the grain into which it is growing. The present work represents an extension of the previous study, directed at the determination of the orientation relationships which appear under a wider variety of conditions. Experiments of this general type have been done using commercial aluminum2 with somewhat conflicting results. In the present experiments, in contrast to the above,' the sample composition was a principal controlled variable, resulting in a considerable clarification of the phenomena observed. EXPERIMENTAL TECHNIQUE The experimental technique used in this investigation was essentially that employed previously in studies of grain boundary migration kinetics.1'3 The material used was zone-refined lead with various small amounts of tin or silver added to study the effect of varying the sample composition. The specimens were in the form of single crystals, about 1/4 in. 1/4 in cross section by 3 to 4 in. in length, grown from the melt in a horizontal graphite boat. A crystal grown in this way generally contained a lineage or "striation" substructure of the type shown in Fig. 1 of Ref. 1. This substructure consists of an array of low-angle boundaries which partition the crystal into regions misoriented from each other by a few degrees. The substructure constitutes a source of driving energy, estimated to be about 4000 ergs per cc, for the migration of a large-angle grain boundary into the striated crystal. New grains were introduced by plastic deformation in compression of a localized reglon at one end of the sample. Re-crystallization occurs at room temperature in the deformed region, introducing a large number of new, striation-free grains into the specimen. These grains are able to grow into the melt-grown crystal on annealing at a suitable temperature. The stria-tions are removed by passage of the grain boundary, as the substructure energy is utilized to produce the boundary migration. Usually, only one or two of the recrystallized grains persist after growth has occurred for about 1 cm out of the deformed region. Laue back-reflection X-ray photographs were obtained to determine the orientation relationship between the melt-grown crystal and the recrystallized grain or grains which grew most successfully in each specimen. EXPERIMENTAL OBSERVATIONS Fig. 1 shows the results obtained for a series of specimens to which had been added tin in the range from 0 to 5 ppm by weight. In this figure is plotted, in the standard stereographic triangle, the single axis about which the most successful recrystallized grain or grains are related to the starting, melt-grown crystal by the smallest rotation. The range of angular rotations observed about such axes is indicated beside each stereographic triangle. The results shown in the stereographic triangle on the left, Fig. l(a), were obtained by localized deformation at one end of each specimen at room temperature, followed by annealing in a furnace which had been preheated to 300°C. The furnace atmosphere was argon. It will be seen that the orientation relationships observed between the melt-grown and recrystallized grains are quite random. On the right, Fig. l(b), are shown results for samples in which the de-

Jan 1, 1961

By Lowell Stroud

Ten natural gases containing from 0.023 to 8.4 percent helium were investigated. In seven high-helium samples, the isotopic abundance of Ne21 was greater than in the atmosphere, being supplemented by 33 to 85 percent of "excess" or "radiogenic" Ne21. The ratio of He4/Ne21(rad) in these gases was evaluated and found to vary between 2.9 x 107 and 5.9 x 107 , a factor of approximately 2. Argon concentrations were determined by the isotope dilution method. The isotopic ratios of Ar40/Ar36 in the high-helium gases were from 5 to 75 times the atmospheric value, with the Ar40 being about 80 to 99 percent radiogenic in nature. The ratios of He4/Ar40(rad) in all 10 gases were evaluated and found to range from 4 to 18. The isotopic ratio of N14/N15 in four of the high-helium gases was essentially the same as in the atmosphere; in three cases it was approximately 5 percent higher than the atmospheric value of 272.0. The genesis of nitrogen and the relationship of nitrogen to helium in natural gases were reviewed and are discussed in terms of a theory for the concurrent generation of nitrogen, helium, radiogenic neon 21, and petroleum (hydrocarbon gases and liquids).

Jan 1, 1967

By Henry S. Rawdon

The structure of wrought iron as usually described by metallographists and workers in metal in general is that of a fairly pure iron. Impurities, if present, are usually considered as being in solid solution in the crystals of the ferrite matrix or as forming part of the ever present "slag streaks." Attention is herein directed to one type of these dissolved impurities; to the detection of such impurities, particularly in low-grade irons, and to their possible influence on the physical properties of the metal. The attention of the Bureau of Standards was first directed to wrought iron of the peculiar and unusual characteristics to be described later, in material which had failed in service and was submitted for test. The examination was extended to other grades of wrought iron, to see whether such features are of common occurrence in this class of material. MICROSTRUCTURE OF WROUGHT IRON Usual Structure The general microstructure of wrought iron is so well known that a detailed description of it here is needless. There is shown in Fig. 2 the structure of a sample of Swedish iron which illustrates well the matrix of ferrite crystals in which are embedded the slag threads so characteristic of the puddling process and the subsequent working of the material. The usual commercial product contains varying amounts of the impurities commonly associated with iron and steel, i,e,, manganese, phosphorus, silicon, and sulphur together with small amounts of carbon. Of these, the larger part of the phosphorus and some of the silicon present are held in solid solution in the ferrite while most of the remaining impurities, other than carbon, exist in the in closures of slag. Aside from the discontinuities introduced by the slag streaks the ferrite matrix has the microstructure and appearance of a pure metal. No definite orientation of the various crystals or grains is apparent; deep etching of the specimens reveals no intracrystalline features (i.e., within the grains) other than those noted in " pure " metals in general (etching pits).

Jan 1, 1918

By D. A. Stevenson, T. Alden, J. Wulff

A portion of the liquidus curve has been determined for the binary alloy systems Ni-Pb and Cr-Pb. The solubility of nickel is 0.53 atomic pet at 372° and 18.63 atomic pet at 1200°C. Chromium shows low solubility, 0.634 atomic pet at 1210°C. Molybdenum and tungsten were also studied and found insoluble in lead, less than 0.005 atomic pet at 1200°C. INCREASED use of liquid metals of low melting X point for heat transfer, coating, joining, and other purposes has renewed interest in the solubility of structural metals in these liquids. A study of Hansen1 and current literature indicates that few liquidus curves at the low melting end of the binary diagrams have been accurately delineated. This statement applies particularly to the binaries of lead. The present paper is limited to nickel, chromium, tungsten, and molybdenum in lead. In early studies2, 3 of the lead end of the Pb-Ni system, a monotectic at 1340°C was established. Tammann and Oelsen' determined the solid solubility of nickel in lead at 20°C to be 0.023 wt pet. Recently Pelzel5 determined the liquidus curve from the eutectic temperature of 327° up to 727°C using a segregation method. In the present paper this part of the curve has been checked and extended to 1244°C. The Pb-Cr system was first studied by Hindrichs.6 He pointed out the existence of a monotectic at 1470°C and indicated a tentative liquidus. Recent corrosion studies of Fe-Cr alloys in lead suggest that chromium is more soluble than iron in lead.7-8 The solubility of tungsten in lead according to Inouye8 is about 30 wt pet at 1200°C. Appreciable solubility of molybdenum in lead might therefore be expected. Experimental Various experimental techniques have been employed in the determination of solubility in liquid metals. For low solubility, thermal analysis is unsatisfactory. A segregation method was used by Pelzel3 in his study of the Pb-Ni system. In this procedure separation of liquid and solid is possible due to difference in density. In the technique of Kleppa10 a single piece of material is maintained in contact with the liquid metal in evacuated Vycor vials. After equilibration, solid and liquid are separated by tilting. Keck and Broder" measured the weight of a piece of the solid solute before and after immersion in a pure solvent bath; the weight loss was a measure of the solubility. All of the above procedures are time-consuming since they permit only one determination per run. Numerous samples for analysis may be taken from the melt in the method described by Gurinsky and CO-workers.10 The rate of extraction of samples is limited only by the time required for equilibration. In the present work, a modification of this method was employed. A 150-g charge of analytical reagent grade lead and the added metal* were contained in an Alun- dum crucible. It rested on firiely divided silica at the closed end of a 45 mm Vycor tube, 500 mm long. The top of the tube was provided with an inlet and

Jan 1, 1959

By Frank H. Macpherson

Few people realize the tremendously important part that Saline and Pulaski Counties in central Arkansas have played in the winning of the war The present favorable war situation might have been very different if we had not had the bauxite produced during the past two years from these two small areas, a total Of about 15 square miles. As a general statement, it can be said that the Arkansas bauxite deposits are, individually, relatively small, irregular in thickness, somewhat scattered and, therefore, compared with coal or iron-ore or open-pit copper deposits, relatively ill adapted to a rapid and drastic expansion in output. A few years ago it would have seemed an impossibility for these two counties to produce over six million long dry tons of bauxite in one year. However, with the cooperation of the operators, that is what happened in 1943, when the state of Arkansas achieved the seemingly impossible with a production of 6,020,684 1 long tons (dried equivalent) of bauxite ore during the calendar year, compared with an average annual production of 323,7252 tons in the period 1931 to 1941. It became apparent early in the year '94' that the united States soon might be drawn into the war, and, therefore, that an immediate study of the domestic metal situation was necessary. Aluminum is by far the most important metal used in the manufacture of aircraft and many other implements of war and it was evident that there would have to be a tremendous increase in the domestic production of bauxite, which is practically the only present source of this metal. AS more than 95 per cent of the known bauxite reserves of the United states was in Arkansas, careful preliminary studies were made in that state by representatives of the united States Bureau of Mines, the United States Geological survey and the War Production Board in the summer of 1941 Reserves in other states also were studied. The result of these studies was a recommendation by the War Production Board that mining in the bauxite.producing areas of Arkansas be geared for maximum production, in order to supply sufficient ore for this country's war requirements and, if necessary, to supply the war needs of Canada as well. The annual goal of eight million long tons (dry weight) set for Arkansas by the war Production Board was exceeded in 1943, when in August the output reached a rate equivalent to more than 8,300,000 long tons, dry basis. Because of the comparatively small tonnage of bauxite reserves, Congress appropriated funds for an extensive drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. Drilling began in May 1942 but owing to delay in delivery of drills, and trucks upon which the drills were mounted the program did not get into peak operation until early in 1943. By the end of July 1944, the Bureau of Mines records indicated an addition to the Arkansas reserves of 10,000,000 long tons (wet basis) in place,

Jan 1, 1946

By Joseph C. Kieffer

THE Duquesne property of the Callahan Zinc-Lead Co. is about 20 miles east of Nogales, in southern Arizona. One mine is near the mill, but most of the mill feed is hauled in by truck from a number of small mines. The same sulphides are found in all the ores, in general, but the amounts vary considerably. All ores contain silver, copper, lead and zinc minerals but one mine ships ore high in silver and lead and low in copper and zinc; while another mine ships ore high in copper and zinc, and low in silver and lead. The common sulphides are galena, carrying most of the silver; chalcopyrite; sphalerite, carrying iron in solid solution; and pyrite, in a gangue consisting of limestone, quartz and garnet. Mineralization is fairly coarse. At the present grind of about 66 per cent minus 200 mesh most of the sulphides are liberated. A small amount of chalcopyrite is locked up with the sphalerite and cannot be liberated at an economic grind, and the copper carried into the zinc concentrate with the sphalerite accounts for the comparatively poor recovery of copper in the copper-lead concentrate. PRODUCTION OF TWO CONCENTRATES The milling problem, which was complicated by the extreme variation in the grade of the feed, was first attacked with the idea of producing a silver-copper-lead concentrate and a zinc concentrate, both with satisfactory grades and recoveries. By February I94I, it was felt that these objectives had been attained, when the grades of the various products and the recoveries were as shown in Table I. [ ] A rough outline of the flowsheet and reagents used is as follows: Minus ¾ -in. feed to a 7-ft. by 36-in. Hardinge ball mill working in closed circuit with a 36-in. Wemco classifier. The classifier overflow passes to the second cell of an 8-cell bank of No. 18 Special Denver Sub-A flotation machines (volume, 22.5 cu. ft. per cell). A rougher concentrate is removed from the second to the fifth cells inclusive, and returned to the first cell, which is the cleaner. A scavenger concentrate is removed from the sixth, seventh, and eighth cells, and returned to the third cell. Consump

Jan 1, 1942

By R. Cooper, K. De Wet, A. Janwong

"Horsehead Metal Products is a zinc refinery in Mooresboro NC treating crude Waelz Oxide (WOX) to produce Special High Grade Zinc by a hydrometallurgical process, comprising leaching, zinc solvent extraction/electrowinning (SX/EW), melting and casting and bleed treatment. Cadmium removal by zinc dust cementation plays an essential role in the bleed treatment circuit to prevent a build-up of cadmium in the circuit. Silica, although not present at significant levels in the WOX feed material (approximately 0.3%), had a significant impact on the efficiency of cadmium cementation with zinc dust, most likely due to the passivation of zinc dust particles with silica gel. Solid/liquid separation efficiency by filter press was also impacted. The silica levels were mapped throughout the circuit in an attempt to identify the source of the silica issues. Adjustments including using PLS as feed to cementation, pH control in WOX leaching and neutralization have been introduced to mitigate the issues created by silica gel in the circuit. INTRODUCTION Located in North Carolina, Horsehead Metal Products Inc. is a hydrometallurgical zinc refinery processing Waelz Oxide (WOX) to produce Special High Grade (SHG) zinc. The flowsheet, known as the Modified Zincex® process, consists of leaching, solvent extraction, electrowinning, melting and casting and bleed treatment as illustrated in Figure 1. Cadmium cementation, part of the bleed treatment process, provides an essential bleed of cadmium from the circuit, as metallic cement. The Cadmium cementation circuit consists of agitated cementation reactors, a zinc dust addition system, filter presses, agitated purification (releach) reactors and a cadmium concentrate filter press Silica can be found in several forms in acid leaching. The first form is fine silicate particles. The size of the particles can vary from one to twenty microns (1). Fine silicate particles can lead to the formation of crud in solvent extraction circuits (2, 3). At Mooresboro, crud has been observed in Depletion, which is part of the solvent extraction circuit. Silica content in the solution in this section is high. The second form of silica is monosilicic acid Si(OH)4, which begins to polymerize almost immediately upon being leached into solution. Monosilicic acid polymerizes to silica gel or a silica precipitate dependent primarily on supersaturation (5). Factors that influence the rate of polymerization include temperature, sulfuric acid concentration / pH, hydrofluoric acid concentration, seeding, and dissolved salts concentration such as zinc and aluminum in the solution (4, 5, 6). In sulfate systems, silica solubility is reported in the range of 150 to 450 ppm of SiO2 (3, 5, 7)."

Jan 1, 2016

By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and ' steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation' concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.' Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

By R. D. Vaughn

The analysis of laminar flow of power-law non-Newtonian fluids in narrow, eccentric annuli is employed in this paper to discuss the problems of lubricant flow in journa! bearings and of errors introduced by eccentricity in experimental studies with concentric annuli on extruders and wellbore annuli. The velocity profile and pressure loss-flow rate equations are developed for the laminar flow region. In addition, the expected error in flow rate and pressure-loss measurements for concentric annuli as a result of eccentricity is determined. For example, a 10 per cent displacement of the core of an almost concentric annul us would cause a 1.8 per cent decrease in the observed pressure loss for a fluid with a power-law exponent n of 0.25. The corresponding increase in the observed volumetric flow rate would be 7. 5 per cent. INTRODUCTION Non-Newtonianism and eccentricity occur simultaneously in two engineering problems: (1) flow of lubricants in journal-bearings and pressure-reducing bushings, and (2) flow of non-Newtonian fluids in plastic extruders and wellbore annuli. The lubricants used for moving parts are often non-Newtonian in character — often they are plastic in behavior. A solution to the problem of flow of non-Newtonian fluids in narrow eccentric annuli is particularly pertinent to this problem. In all experimental studies of laminar flow of fluids in concentric annuli, such as in extruders and well casings, the error due to eccentricity must be estimated or studied. A number of publicationsl-4,6,7 have dealt with this problem for Newtonian fluids; however, I am not aware of work for non-Newtonian fluids. This work is directed to the non-Newtonian problem. Before the solution to the problem is given, the pertinent conclusions from the work on Newtonian fluids will be reviewed. Heyda 1 and Redberger and Charles 2 have published general solutions to the problem of the laminar flow of Newtonian fluids in eccentric annuli, apparently without knowing of the earlier work of Ca ld well 3 and Bairstow and Berry,4 which is reported by Dryden, et al. 5 Although several mathematical routes are encompassed by the work of these authors, the results appear to be equivalent. Redberger and Charles2 show that the error caused by eccentricity in concentric annuli is negligible for small diameter ratios (k < 0.5); however, for large diameter ratios (k + l), the error in the predicted flow rate can be as great as 100 per cent or more. Partial solutions to the problem are available from the work of Dryden,5 Tao and Donovan6 and Piercy, et a1.7 Tao and Donovan examined the case of flow in narrow, eccentric annuli (k + 1) with and without rotation of the annular core. These authors also reviewed previous work on this subject and verified their approach with experimental data. Dryden gives the solution for the limiting case of complete eccentricity or tangency. Piercy, et a l. published an early solution to the problem of narrow eccentric annular flow. The conclusions of Redberger and Charles2 and the experimental proof of Tao and Donovan6 both suggest that the region of large diameter ratios (k + 1) is of main interest and that the parallel planes approximation to the solution in this region is satisfactory. This method will now be extended to the laminar flow of non-Newtonian fluids in narrow eccentric annuli. THEORETICAL SOLUTION The geometrical aspects of the problem are illustrated in Fig. 1. To represent the non-Newtonian fluid the power-law model was selected. This model has many disadvantages which have been pointed out; nevertheless, its simplicity, its frequent and wide applicability justify its use in this work. Fredrickson and Bird8 and Savins9 have used it as a basis for a theoretical study of laminar flow of non-Newtonian fluids in concentric annuli.

Jan 1, 1966

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.&apos;&apos;&apos; At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-&apos;&apos; of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun&apos;s&apos;&apos; most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster&apos; proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By Yoichi Takeda

Copper solubility in SiO2-CaO-FeOx slag equilibrated with copper matte in 10% SO2 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag, A classical thcrmodynamic model postulating CuO0.5 and CuS0.5 moleculcs assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated SiO2-FeO. binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeO.-SiO2-CaO ternary slag saturated with 2CaOSiO2 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By A. S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric pressure and by heat transferred to it from rock at high temperature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. METHODS Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1941

By B. H. Sage, R. T. Carter, W. N. Lacey

The phase behavior of a number of binary systems consisting of parafin hydro-carbons has been determined in recent years. In addition, the composition of the coexisting phases of mixtures of crude oil and natural gas has been investigated.~ However, the latter study did not include information concerning the influence of the concentration of a component upon its distribution between two coexisting phases. Owing to the paucity of such information it was considered desirable to investigate in some detail the composition of the coexisting phases in the methane-propane-n-pentane system throughout the greater part of the two-phase region at a tempera-ture of 100°F. Information of this nature also permits the establishment of the critical behavior of this ternary system. Method The compositions of the coexisting phases in this ternary system at 100°F. were deter-mined by withdrawing samples from a pres-sure vessel containing a heterogeneous mixture of the three components that had been brought 10 equilibrium by mechanical agitation at the desired pressure and tem-perature. The samples were withdrawn under such conditions that the equilibrium was not disturbed and the composition of each of the phases was ascertained by means of the conventional low-temperature fractionation procedure. The apparatus employed in this investi-gation was nearly the same as that utilized in an earlier study of the methane-pentane system.~ Several minor modifica-tions in the arrangement of the apparatus were made in the interest of simplifying the procedure and avoiding the possibility of condensation in the tubing connecting the equilibrium apparatus with the analyti-cal equipment. The pressures were meas-ured by means of a pressure balance with a precision of 0.5 lb. per sq. in. It is believed that the equilibrium pressure was ascer-tained with an uncertainty of not more than 2 lb. per sq. in., even though small varia-tions in pressure obtained during the withdrawal of the samples. The tempera-ture of the equilibrium equipment was maintained by use of an automatically controlled oil bath. The bath temperature was determined by means of a copper-constantan thermocouple, the electromo-tive force being determined by means of a potentiometric circuit of such a nature as to reduce the uncertainty of the tempera ture to less than O.I f. The fractionating column employed in the determination of the composition of the gas phase had a diameter of 0.12 in. and was approximately 4 ft. long, while the column employed in the analysis of the liquid phase was 0.18 in. in diameter and about 5 ft. long. Each column was equipped with the conventional constant-volume receivers, which were maintained at a constant temperature by means of an automatically controlled oil bath. In nearly every case the distillation in thr neighborhood of the transition between

Jan 1, 1941

By W. N. Lacey, R. T. Carter, B. H. Sage

The phase behavior of a number of binary systems consisting of parafin hydro-carbons has been determined in recent years. In addition, the composition of the coexisting phases of mixtures of crude oil and natural gas has been investigated.~ However, the latter study did not include information concerning the influence of the concentration of a component upon its distribution between two coexisting phases. Owing to the paucity of such information it was considered desirable to investigate in some detail the composition of the coexisting phases in the methane-propane-n-pentane system throughout the greater part of the two-phase region at a tempera-ture of 100°F. Information of this nature also permits the establishment of the critical behavior of this ternary system. Method The compositions of the coexisting phases in this ternary system at 100°F. were deter-mined by withdrawing samples from a pres-sure vessel containing a heterogeneous mixture of the three components that had been brought 10 equilibrium by mechanical agitation at the desired pressure and tem-perature. The samples were withdrawn under such conditions that the equilibrium was not disturbed and the composition of each of the phases was ascertained by means of the conventional low-temperature fractionation procedure. The apparatus employed in this investi-gation was nearly the same as that utilized in an earlier study of the methane-pentane system.~ Several minor modifica-tions in the arrangement of the apparatus were made in the interest of simplifying the procedure and avoiding the possibility of condensation in the tubing connecting the equilibrium apparatus with the analyti-cal equipment. The pressures were meas-ured by means of a pressure balance with a precision of 0.5 lb. per sq. in. It is believed that the equilibrium pressure was ascer-tained with an uncertainty of not more than 2 lb. per sq. in., even though small varia-tions in pressure obtained during the withdrawal of the samples. The tempera-ture of the equilibrium equipment was maintained by use of an automatically controlled oil bath. The bath temperature was determined by means of a copper-constantan thermocouple, the electromo-tive force being determined by means of a potentiometric circuit of such a nature as to reduce the uncertainty of the tempera ture to less than O.I f. The fractionating column employed in the determination of the composition of the gas phase had a diameter of 0.12 in. and was approximately 4 ft. long, while the column employed in the analysis of the liquid phase was 0.18 in. in diameter and about 5 ft. long. Each column was equipped with the conventional constant-volume receivers, which were maintained at a constant temperature by means of an automatically controlled oil bath. In nearly every case the distillation in thr neighborhood of the transition between

Jan 1, 1941

By Peter Greenfield, Paul A. Beck

Thirty binary systems of vanadium and chromium group transition elements with second and third long period transition elements were explored in regard to the intermediate phases formed. It was found that the phases predominating in these systems are s, AB type with ordered a-tungsten or C8 structure, close-packed-hexagonal with small unit cell dimensions and, finally, phases isomorphous with 1-manganese. IN recent years, considerable information has become available concerning the intermediate phases in binary systems of the transition elements. Thus, the s phase has been found to occur in most of the binary systems of vanadium, chromium, and molybdenum with the group of elements manganese, iron, cobalt, and nickel.&apos; It was observed that, while the rr phases formed by chromium with manganese, iron, or cobalt possess a considerable temperature range of stability, particularly in the Cr-Co system, the corresponding s phases with molybdenum are limited to a temperature range of less than 400" above about 1200°C. Goldschmidt&apos; reported v phases of tungsten with iron and cobalt, and these are apparently stable only at (and above?) 1400°C." Exploratory work in this laboratory with Fe-W and Co-W alloys of approximately 60 atomic pct W annealed at 1300°C did not produce X-ray patterns suggesting the presence of a phase. It appears then that the phases of iron and cobalt with the chromium group elements decrease in stability as the two components are chosen from long periods further removed from each other. From the available information, it might be concluded that the controlling factor is the increasing difference in atomic radii between the components. In contrast to the a phase, the phases formed by iron and cobalt with chromium group elements&apos; are stable only when the latter have large atomic radii (molybdenum and tungsten); the corresponding phases with chromium do not occur. When the difference in atomic size becomes still larger (r,/r,, approaching the ideal value of 1.225), the u and p phases are replaced by Laves phases (AB,), as in the alloys of iron and cobalt with columbium," tantalum." and titanium."-" However, atomic size certainly cannot be the sole determining factor, since, for instance, in contrast to the very stable (Mo, Co)p phase, no such phase occurs in the Mo-Ni system even though the atomic diameters of cobalt and nickel are nearly the same. Similarly, chromium and cobalt form a a phase in a wide temperature range," but the corresponding s phase in the Cr-Ni system is missing. It has been shown that the composition of the u phase in various binary and ternary systems of transition elements in the first long period may be correlated in a fairly quantitative manner with the number of electron vacancies. The influence of electronic structure is probably present also in binary and ternary phases&apos; and to some extent, apparently, even in Laves phases." " Although the absence of phases in the Cr-Ni and Mo-Ni systems has not as yet been explained on the basis of electronic structure, it appears reasonable to suspect a connection. One of the great difficulties in arriving at well founded rules in regard to the alloying behavior of transition elements lies in the lack of reliable information concerning the details of their electronic structure in the metallic and alloy form. The theoretical penetration of this field appears to be beset by very considerable difficulties, even when the complications due to alloy formation are disregarded. Another great source of uncertainty is the scarcity of phase diagram information even for binary systems of the transition elements so that only a very limited basis is provided for generalizations as to the occurrence of intermediate phases. For instance, very few binary phase diagrams of second and third long period transition element systems have so far been published. The present work was undertaken in order to survey the various types of intermediate phases occurring in 30 binary systems of elements of the group vanadium, columbium, tantalum, chromium, molybdenum, and tungsten with the elements rhenium, ruthenium, rhodium, palladium, and platinum. For most of these binary systems phase diagrams are very incompletely or not at all known, as will be further reviewed.*

Jan 1, 1957

By Y. Baskin

Solid-solubility relationships in the Pseudobinary systems UAS-UP, UAs-US. UAS-UC, aid UAs-UN were investigated. The first two systems exhibit complete mutual solubility, whereas the component compounds in the other two systenzs are immiscible. The above information, together with solid-solubility data joy six additional pseudobinary systems , were analyzed for compliance wilh the Hurrze-Rothery rules for rnetallic systems. The relative size difference of the component nonmetal atoms was found to be the dopainant jactor determining the extent of solid solubility between the NaC1-type uranium compounds. The anionic and covalent radii of the nonmetal atoms appear to be inadequate for these systems, but compuled radii based on rare earth compounds yield consistent results for the uranium compounds. THE actinide elements, like metallic elements of the transition and rare earth series, readily form binary compounds with nonmetallic elements of groups IV, V, and VI of the periodic table. Of particular importance are the NaC1-type equiatomic compounds with carbon, nitrogen, sulfur, phosphorus, and arsenic. The uranium members of this family of compounds have high melting points, are essentially stoichiometric, and exhibit various amounts of mutual solubility. Thus, they are of interest for investigating the factors governing the extent of solid solubility. Previous investigators have determined the solid-solubility limits in the pseudobinary systems between the compounds UC, UN, US, and UP. Anselin et a1 .&apos; reported complete miscibility in the system UC-UN. Baskin and shalek 2 and Allbutt et a1.3 reported that UP and US exhibit complete mutual solubility. Shalek and white4 reported partial miscibility in the system US-UC. At 1800°C the maximum solubility of UC in US is 40 mol pct, but that of US in UC is 4 rnol pct. shalek5 found limited solubility in the system US-UN; the maximum solubility of UN in US is 11 rnol pct at 1800°C, while that of US in UN is only 0.3 mol pct. White and askin 6 found very limited miscibility in the system UP-UC at 1800°C. Approximately 7 mol pct UC is soluble in UP, but there is no solubility of UP in the monocarbide. Phase relations in the pseudo-binary system UN-UP were investigated by askin.&apos; Approximately 0.7 mol pct UN is soluble in UP at 1800°C, while UP is immiscible in UN. The present study was carried out to explore the extent of terminal solubility in the systems UAs-UC, UAs-UN, UAs-US, and UAs-UP. This information, combined with existing data, provided a sufficient basis on which to determine the factors governing solid solubility in pseudobinary systems containing NaC1-type uranium conpounds. I) EXPERIMENTAL 1) Materials. The compounds UC and UN were obtained from the Kerr-McGee Corp. and United Nuclear Co., respectively. The US, UP, and UAs were synthesized by reacting finely divided uranium with H2 S, pH3, or AsH3 gas at low temperature (300° to 500°C), followed by homogenization in a vacuum at moderately high temperatures (1400° to 1700°c).8-10 The materials were essentially stoichiometric, with the exception of UC, which exhibited a C/U ratio of 1.05. Oxygen was the major contaminant in these compounds, ranging from 0.05 wt pct in US to 0.30 wt pct in UC, and it was generally combined with uranium to form UO2. The UO2 content in these materials was usually of the order of 1 wt pct, and did not exceed 2 wt pct. Furthermore, no evidence was found for a high-temperature reaction between uranium dioxide and any of the compounds. Chemical analyses of equilibrated compositions in the systems UAs-UP and UAs-US showed that the non-metal atom to uranium ratios averaged about 1.01, and that the oxygen contents ranged from 0.06 to 0.22 pct. However, the small deviations from stoichiome-try or the presence of minor oxygen impurities do not invalidate the conclusions to be drawn from this study. 2) Experimental Procedures. The component compounds in powdered from were blended in the desired proportions for 5 hr in the ball mill that consisted of stainless-steel balls in a plastic container. Chemical analyses indicated very little metallic pickup from the blending operation and virtually no increase in oxygen content. The pellets were pressed in a 0.270-in.-diam steel die under 40,000 psi pressure. One wt pct of stearic acid dissolved in CCl 4 served both as a binder and as a die lubricant. Chemical analyses revealed that the stearic acid left no carbon residue in the sintered samples. The pellets were sintered in vacuum in an unsealed tantalum crucible. The temperature, measured with a calibrated optical pyrometer, was maintained at 1800" + 30°C for 3 hr. This was sufficient time for attaining equilibrium as no change occurred in either the lattice parameters or the sharpness of the X-ray patterns when samples were annealed for longer periods of time. The pellets were cooled with the furnace. Debye-Scherrer powder patterns were taken at room temperature with a 114.59-mm-diam Norelco powder camera and CuKor radiation (CuGI = 1.5405A). Unit cell dimensions were determined from a Nelson-Riley extrapolation to the high-angle reflections. The values for were precise to k 0.001A. 11) RESULTS X-ray and met allographic investigation revealed that complete mutual solid solubility exists in the pseudobinary systems UAs-UP and UAs-US. The lattice parameter vs composition plots, Fig. 1, show a

Jan 1, 1968

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer&apos;s knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen&apos;s bridge&apos;) was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946