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By Ling Yang, John Henderson

Self-diffusion coefficients of copper in molten copper have been measured by the capillary reservoir method in the temperature range 1140o to 1260°C. The results can be represented by the equation D = [(1.46 * 0.01) x 10-3) exp [(-9710 * 710)/RT] cm2/sec. The energy of activation agrees within the limit of experimental uncertainty with that for viscous flow. The relationship between the diffusivity and coefficient of viscosity is best described by the equation D = kT/4pnr cm2/sec. MEASUREMENT was made of the self-diffusion coefficient of copper in molten copper in the temperature range 1413º to 1533ºK, using the capillary reservoir technique and CU64 as the radioactive tracer.The procedures for filling the capillaries, making the diffusion run and evaluating Dcu from the counting results were the same as described previously.1,2 All experimental operations involving the melt were carried out in a purified argon atmosphere. A graphite crucible, enclosed in a McDanel tube, was used as a container for the melt because of its satisfactory nature as a refractory material and the low solubility of carbon in copper. Graphite was also used for the capillary material. A McDanel thermocouple sheath, to which graphite radiation shields were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube, the capillaries could be lowered into or raised out of the melt. A Globar furnace with a constant temperature zone (± 2°C) of 2 in. was used to heat the assembly. The temperature of the furnace was the equilibrium value corresponding to a given setting of the transformer. Temperature was measured with a Pt-10 pct Rh/Pt thermocouple and varied during a run

Jan 1, 1962

By A. G. Starliper, H. Kenworthy, A. Ollar

Vapor pressure determinations were made on synthesized germanium sulfides. Germanium and cadmium were removed from sphalerite concentrates by fuming. The fume was retreated to separate some of the cadmium from the germanium and, at the same time, upgrade the germanium to more than 5 pet content. MANY sphalerite concentrates contain certain impurities which have economic value as byproducts. These may include the volatile sulfides of germanium, cadmium, and lead. The objectives of the research reported in this paper were to study the fundamental volatility characteristics of germanium sulfides, to increase the recoveries of ger-

Jan 1, 1957

By G. T. Engel, W. G. Gruzensky

Jan 1, 1960

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By R. Schuhmann, O. W. Moles

at temperatures of 1150°, 1250°, and 1350°C for liquid copper sulphides ranging in composition from saturation with Cu to about 21.5 pct S. From the experimental data, activities of Cu, S, and Cu2S in the melts were calculated. Also, the results furnish a new determination of the location of the curve showing the compositions of Cu-saturoted sulphide melts in the CU-S constitution diagram. THE "white metal" made as an intermediate L product in converting copper matte to blister copper is a matte approximating Cu2S in composition. It has long been known that liquid Cu-S mattes can exist at a given temperature over an appreciable composition range, with S:Cu ratios ranging up from a lower limit corresponding to equilibrium of the matte with a liquid Cu phase. The Cu-saturated matte has somewhat less S than Cu2S, although previous measurements of the compositions of Cu-saturated mattes are not in good agreement.'" As the S:Cu ratio approaches and slightly exceeds that for Cu2S, the partial pressure of sulphur gas over the liquid matte rapidly approaches atmospheric pressure,5 so that Cu-S melts with much more S than Cu2S can be made and handled only in pressure apparatus. Accordingly, the liquid copper sulphides of interest in copper smelting and readily studied experimentally fall in a relatively narrow composi- tion range about Cu2S. The freezing points of Cu-S mattes show a maximum of 1129°C near the composition Cu, dropping to 1105oC for Cu-saturated mattes having less S and dropping under 1100°C for higher S mattes.' Estimates of the sulphur pressure and other thermodynamic properties of liquid Cu,S were made by Kelley; based on extrapolations from equilibrium measurements on solid Cu,S. More recently, Cox and coworkers' studied equilibria in the reaction: Cu,S + H, e 2Cu + H,S over the temperature range 700" to 1250°C. They measured equilibrium H2S:H2 ratios presumably with both the sulphide and the metal phase present, so that their data above the melting point of Cu,S should measure the S pressure of Cu-saturated sulphide melts. The sulphur pressures of liquid copper sulphides of several S:Cu ratios at their freezing points can be estimated from data given by Posnjak, Allen, and Merwin." However, beyond these few data, no systematic study seems to have been made of the relations of sulphur pressure and other chemical properties of liquid copper sulphides to composition and temperature. The measurements of the sulphur pressures of liquid copper sulphides reported in this paper represent a first step in the quantitative study of the chemistry of mattes. Similar work is planned on

Jan 1, 1952

By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By R. E. Boni, G. Derge

SURFACE tensions of molten silicates are of metallurgical importance for many reasons. From a knowledge of their values, an insight into the problem of liquid slag structure can be gained. Also, such problems as separation of slag from metal, slag penetration of refractories, spreading of enamel coats on metals, bonding of cutting wheels, adsorption of gases, frothing of slags, and homogen-ization of slags are related to the surface tensions of the silicates. Because of the absence of a correlated review of the work that has been conducted in this field, the following survey is presented. It is not a complete summary of all the surface tension studies of silicates but only a review of the literature which is pertinent to metallurgical applications and research. Liquid Surface Tension The surface of a liquid differs from the interior in that its particles (ions, atoms, or molecules) are not

Jan 1, 1957

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800' and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,',' in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By Ove Sandberg, Olav Bowitz

The operational characteristics of the Soderberg vertical spike anode are briefly discussed stressing the importance of the flow properties of paste in the fluid zone, the thermal shrinkage in the carbonizing zone, and the surface disintegration in the consumption zone. The requirements for paste recipe and binder quality are combined with design and operation of cell. A low temperature susceptibility of viscosity and low thermal shrinkage of paste together with a low microporosity of the binder coke are important properties. PRACTICAL application of Soderberg's idea of a selfbaking carbon electrode proved successful just before 1920. Shortly after, experimental work was started with the aim of developing a continuous electrode that could be adopted as anode in aluminium reduction cells. The intermittent operation of a large number of small prebaked anodes made the idea of developing a continuous anode for electrolytic production of aluminium especially tempting. Moreover, the electrode consumption in this process, even on a theoretical basis, is very high. Many installations were carried out in the 1930's and during the Second World War. During the tremendous post-war expansion of the aluminium industry, the Soderberg electrode has been steadily more widely adopted. Thus, today more than 60 pct of the Western World's output of aluminium is produced in cells with selfbaking anodes, see Big. 1. The quality of the anode paste of Sfiderberg elec- trodes is considered a major factor influencing the specific carbon consumption. The purpose of this paper is to survey the fundamental requirements which must be met in order to obtain good anode operation. We have limited this paper to a discussion of Elektrokemisk's research on the vertical spike type anode. I) FUNDAMEKI'TALS OF ANODE CARBON PERFORMANCE A) Brief Introduction. The only practical method for producing a conductive carbon anode of the size required is to form and carbonize a mixture of a carbonaceous binder and a precalcined dry aggregate coke. In the Soderberg electrode, the forming and carbonization take place in the electrolytic cell

Jan 1, 1962

By J. L. Wyatt

THE smelting of ilmenite to produce a slag rich in titanium, with pig-iron as a byproduct, introduces new concepts in electric smelting metallurgy. Titanium slags are characterized by low electrical resistance, thereby requiring a different type of electric furnace operation, and power supply sources substantially different from those encountered in normal steel melting and siliceous ore smelting furnaces. This paper describes special apparatus for determining specific electrical resistivity of titanium slags, and reports the values obtained on slags encountered in the process of smelting ilmenite ores. In an induction furnace under conditions approximating normal furnacing operation, 25 general heats and 6 special standardization and comparison heats were run. Results indicate relatively low resistivity. Resistivity depends primarily on slag composition, and, to a lesser degree, on temperature. During the summer of 1947 a cooperative project between the National Lead Co. and the Bureau of Mines was conducted at Boulder City, Nevada, in the Electrometallurgical Laboratories of the Bureau. The project involved smelting of ilmenite ores in electric furnaces, and has been reported in detail.' The author participated as a member of the staff of the National Lead Co. during the entire campaign. One outstanding characteristic of the titaniferous slags, their apparently excellent and variable electrical conductivity, was considered sufficiently important to warrant further study. Although little electric smelting of iron ores has been done in the United States, a certain amount of information is available for comparative purposes. Personal experience in smelting siliceous iron ores in electric furnaces furnished further information for comparison. In general, silicate slags are relatively poor conductors of electricity. Current flow during smelting operations may be maintained through a floating layer of coke on top of the slag bath, or through a bath of molten iron, beneath the slag. Silicate slags are not sufficiently conductive to furnish a path for current passage when normal furnace voltages are used. Experimental smelting of a silicate iron ore was undertaken for comparative purposes. A fluid melt was not obtained until the FeO content was reduced to 15 pct. The resistivity increased as the FeO content decreased, FeO compounds being the most conductive of the various oxides in such a normal slag system. The converse appears to be true in slags containing large percentages of TiO2. It has been found that titanium slags become molten with FeO percentages in excess of 30 pct, and that the conductivity becomes generally better as the FeO con-tent of the slag diminishes. This phenomenon was demonstrated in the furnacing operations at Boulder City. During the initial smelting period furnace electrodes could be held immersed several inches in the slag, with tap selectors set for a no-load voltage of 70 v. As the FeO content decreased, the furnace electrodes would "walk up," until at one point in the process the tips would break the surface and arc on top of the slag. This was undesirable since direct arcing caused losses of important flux additions. The slag compositions under study at that time were such that losses due to surface arcing sometimes caused viscous slags to be formed. Forcing the electrodes into the slag bath by manual control to prevent surface arcing resulted in excessive power input and lack of control. Suitable low voltages were not available. Measurement of the electrical resistivity of titanium slags at various operating temperatures and slag compositions was undertaken. It was believed that this information would be of use in the design of electric furnaces suitable for smelting ilmenite, with voltages, electrode sizes, and electrode spacing adapted specifically to titanium slags.

Jan 1, 1951

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By L. L. McDaniel

Copper smelters of various kinds have operated in the Morenci district since 1872, but all have been abandoned with the exception of the present Morenci Smelter of Phelps Dodge Corporation, which was completed in 1942. During the five-year period starting in 1937, the Morenci ore body was prepared for open pit mining, pilot mill test work was carried out, and a complete reduction works, of which the Smelter is a part, was designed and erected. Actual construction work on the Morenci Smelter was started in the fall of 1940, and warming up of the units began on April 1, 1942. Charging of the reverberatory furnaces commenced on April 18, 1942, and the first anode copper was produced on April 26, 1942. The smelter was originally designed to handle the production of the Morenci Concentrator on a 25,000 ton per day program, but by the time the smelter was in operation, plans were already underway to increase the smelter capacity to handle the production of the concentrator which was being enlarged to 45,000 tons a day capacity as a war-time necessity. This extension to the smelter was completed and the new units were put in operation toward the beginning of 1944. The original smelter consisted of a smelter crushing plant, bedding plant, two direct-smelting reverberatory furnaces with two waste-heat boilers on each furnace, three converters, an anode department, a stack, and all of the usual accessory smelting equipment. The extension consisted of increasing the bedding plant from three to five beds, the reverberatory department from two to four furnaces, and from four to eight waste-heat boilers, and the converter department from three to six converters. A third converter aisle crane was added and additions were made to the flue systems and conveyor systems throughout the smelter; but no change was made in the smelter crushing plant or the anode department, and the same stack was used for all additional Smelter units. A blister casting machine was installed at that time in the south end of the converter aisle to handle excess and emergency production above the capacity of the anode department and in 1947 a converter aisle skull breaker and a lime burning plant were added as the final units for a complete plant. The choice of direct smelting over calcine smelting for the Morenci Smelter was made after careful study by members of the Western organization of Phelps Dodge Corporation and after test runs on direct smelting of Morenci concentrate had been made at the Douglas Smelter of Phelps Dodge Corporation. The Morenci furnace charge is made up of comparatively high grade concentrate with no ores of smelting grade available and with only flux, a small amount of copper precipitate and the usual amount of smelter secondaries to be smelted with the concentrate. The simplicity of direct smelting for this charge and the large amount of waste-heat steam available from direct smelting operations were factors influencing the decision to adopt direct smelting for Morenci. The design of the Morenci Smelter and the type of units selected followed best experience at the Douglas Smelter of Phelps Dodge Corporation. A description of the original smelter before operations started was given in an article in the May 1942 issue of Mining and Metallurgy. The purpose of the present article is to describe the enlarged Morenci Smelter, with a discussion of metallurgy and operating practice and to show tabulations of operating and metallurgical results obtained. Because of beginning operations during the early years of World War 11, many problems caused by labor shortage were encountered, but no major difficulties developed in starting the new plant. However, because of labor shortage, full scale Smelter production was not reached until the fall of 1946. Fig 1 shows a general plan of the Morenci Reduction Works. The arrangement of the smelter equipment is shown in Fig 2, a sectional view of the smelter is shown in Fig 3, and the smelter flow sheet is shown in Fig 4. Metallurgy The metallurgy of direct smelting, being more or less fixed by the character of the charge, is not subject to the control available in calcine smelting. Slags may be modified by the addition of suitable fluxes, but the grade of the matte is determined almost entirely by the iron:copper ratio of the concentrate. The direct smelting operation involves distributing the wet concentrate along the sidewalls and in the bath of a reverberatory furnace by means of some suitable feeding device and raising the temperature of the charge so that first the moisture is driven off, then the first-atom sulphur is eliminated, and finally the sulphide portion of the charge melts and runs into the bath, carrying with it the non-sulphide portion which has been partially fluxed to form a suitable slag. The fusion of the non-sulphide portion is completed by contact with the irony converter slag which is regularly being poured into the reverberatory furnace. The smelting rate of the charge is influenced by the mineralogi-cal composition of the sulphide portion of the concentrate and by the composition and amount of the non-sulphide portion including the fluxes added. The copper in Morenci concentrate is chiefly in the form of chalcocite, intimately associated with pyrite, and non-sulphide content is very low so that

Jan 1, 1950

By R. W. Kewish

The preparation of massive uranium metal containing very low concentrations of a number of light elements by bomb reduction of UF4, with calcium is described. Details of procedures are given for preparing high-purity ingredients for the bomb reduction. The as-reduced uranium metal contained, on the average, less than the following amounts of light element impurities, in ppm: Li, 0.1; Be, 0.1; B, 0.1; C, 25; 0, 70; Na, 1; Mg, 3; Al, 2; and Si, 7. Other impurities for which the metal was examined averaged, in ppm: Ca, < 10; V, < 10; Cr, 2; Mn, 6; Fe, 50; Co, < 5; Ni, 8; and Cu, 1. THE preparation of very high-purity uranium metal in massive form for research purposes is of great importance. Recently the kilogram-scale preparation of uranium metal containing less than 70 ppm of detected impurities was accomplished by Blumen-thal and coworkers by vacuum remelting of high-purity crystals of uranium obtained by fused salt electrolysis.1"3 Albert and coworkers4 have reported successful experiments in lowering the concentrations of certain impurity elements in uranium, notably iron, to a few ppm by the zone-melting method. The present paper describes the preparation of high-purity massive uranium metal by the bomb reduction of UF4, with calcium. Early in 1951 a program was undertaken at the Los Alamos Scientific Laboratory to prepare uranium metal of very high purity with respect to a number of the light elements. The methods considered for this purpose were 1) bomb reduction of a uranium halide with calcium, 2) electrolysis of fused salts, and 3) hot wire decomposition of UI4, The first of these processes had been used extensively at Los Alamos since 1943 (and still is used) for the production of uranium metal.5 In considering the three processes it was evident that either of the last two would require an extensive development program with no certainty of success. On the other hand, a study of available data showed that uranium metal of very high purity with respect to some light elements had occasionally been made in routine processing by the first method. It was therefore decided that an intensive study of the bomb-reduction process would be made to see if it could be improved to yield uranium metal with very low concentrations of light elements. DEVELOPMENT OF PROCEDURES The bomb-reduction process used at Los Alamos consists of reducing UF4 with calcium, using iodine as a booster. The reaction is carried out in a magnesium-oxide crucible enclosed in a steel bomb. Argon is used in the bomb to avoid objectionable side reactions which would occur in the presence of air. All ingredients for this bomb-reduction process were examined as possible sources of light elements. It was known that high-purity UF4 was required. The calcium used in the reductions was a source of carbon and magnesium. The magnesium-oxide crucibles were sources of boron, silicon, and magnesium. The iodine did not appear to be a source of any impurities. Pure UF4- The UF4 for bomb reduction is prepared from U3O3 , by successive reduction to UO2, with hydrogen and hydrofluorination of the UO2, with anhydrous HF. Since it was known that no impurities were normally introduced during the gas-solid reactions, effort was directed toward the preparation of high-purity U3O3. Of the many possible procedures for the purification of uranium solutions the following were investigated: 1) Precipitation of uranium peroxide. (Two procedures were tried. The first consisted of simultaneously adding hydrogen-peroxide and ammonium-hydroxide solutions to a uranyl-nitrate solution, containing citric and malonic acids, at such relative rates that precipitation was carried out at a constant pH of 1.5 The second consisted of simultaneously adding uranyl-nitrate, ammonium-hydroxide, and hydrogen-peroxide solutions to an aqueous solution

Jan 1, 1960

By W. J. Kroll

Jan 1, 1960

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N&apos;,N&apos;-tetraacetic acid and N&apos;-(2-hydroxyethyl)ethylenediarnine-N,N,N &apos;-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1&apos;9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH&apos;s in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH&apos;s. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By Frank E. Woolley, Robert D. Pehlke

Jan 1, 1965

By D. A. Belforti, M. P. Lepie

Spectroscopically pure copper was melted on sapphire plaques in a zydrogen atmosphere. The surface tension of the liquid metal was determined using the sessile drop technique. Measurements were made by direct observation with the aid of a specially const,mcted telescope. The value obtained, 1268 dynes per cm, is compared to that found in the literature. THERE is at this time considerable interest in the use of ceramics for vacuum tubes. The crystalline material is superior to the more conventional glass in mechanical strength, chemical inertness, dielectric properties, ability to withstand high temperatures, and so forth. However, ceramics are much more difficult to seal hermetically with metals than are the glasses. For this reason an investigation was undertaken to determine the wetting and adhesion of metals to ceramics. The sessile drop technique offers a convenient means at elevated temperatures for measuring liquid surface tension, wetting angle, density, spread- ing coefficient, and work of adhesion. Thus, from the contour of a drop of liquid at rest on a solid surface one can obtain a quantitative evaluation of the degree to which the two substances will bond. To this end a special apparatus was constructed so that various molten metals could be observed. Standardization of the apparatus was done initially by measuring the surface tension of copper since this is well documented in the metallurgy literature. Although there are many methods available for the measurement of surface energy,&apos;+ the sessile drop technique has been used most extensively for molten metals and ceramics.5"&apos; Fig. 1 illustrates the dimensions to be measured. From these values, the surface tension of the liquid can be obtained using the Bashforth and bdams&apos; equation and tables.

Jan 1, 1963

By Thomas C. Wilder

Jan 1, 1965