Search Documents

By C. B. Alcock, R. A. Oriani

Some simple models of solutions are described; these include the regular solution, the subregular solution, and the quasichemical model. The assunzption underlying these models, the physical signzficance thereof, and the experimental manifestations are discussed. Examples are presented from the fields of liquid and solid metallic solutions, liquid slags, mattes, liquid and solid ionic solutions, and mixed carbides to show under what conditions and for which systems these solution models are fair descriptions. The deviations of real solutions from the models are of theoretical interest. Some such deviations, both for dilute and for concentrated solutions, arc pointed out and their Physical sigtzzficance discussed. DURING the past half century there has been a gradual accumulation of thermodynamic data for systems of interest to the metallurgist. There remain many gaps in the data, however, and the metallurgist must often face the problem of estimation of thermodynamic quantities where measured values do not exist. One might hope that the experimental progress would be matched by theoretical advances which would make such estimations possible with a high degree of confidence. However, theoretical progress has been disappointingly slow even for the simplest kinds of solutions, and since the multicomponent systems in which the metallurgist is interested are very complex, one cannot expect theory to be of much help to the metallurgist. In this situation, therefore, it seems worthwhile to examine some simple models of solutions from two points of view: firstly, to see if such crude models represent the thermodynamic facts in as many types of solutions as possible sufficiently well for the needs of the metallurgist, and secondly to see what the deviations from such models show to be important for consideration by theorists. BOND ENERGY MODELS OF SOLUTIONS The simple models that we will examine from these points of view may be termed statistical models, in that they are concerned with the thermodynamic consequences of some simple assumptions about the energy of an assembly of atoms, molecules, or ions, and do not inquire into the physical basis of the interaction. The underlying assumption of these models is that the energy of an assembly of molecules (by which we include also atoms or ions) is given by the sum over all interaction energies of molecules taken two at a time; we will discuss only those models in which the pairwise interactions are restricted to those between nearest neighbors. Thus, in a pure substance of bond energy EAA, the internal energy (with respect to some specific reference state) will be expressed as NAA EAA where NAA is the number of nearest-neighbor pairs. A solution of molecules A and B will be characterized by NAA EAA + NBB EBB + NAB EAB where the Eij represent the bond energies of the nearest-neighbor i-j pairs. If one assumes that the EAA and EBB are the same in the pure components as in the solution, and that the coordination numbers in the two pure substances and in the solution are the same, then the energy of the solution with respect to the pure components (i.e., the energy of solution) is a function of the following linear combination of the bond energies: EAB - 1/2(EAA +EBB) = w. The thermodynamically ideal solution is defined as one in which the activity of each component is equal to the mole fraction of that component at all concentrations and all temperatures. It follows that

Jan 1, 1962

By L. A. White

IN this paper it is proposed to follow the developments in the design of the lead blast furnace at Port Pirie from the time The Broken Hill Associated Smelters Pty. assumed control in 1915 to the present time, with special reference to the development of the system using two superimposed rows of tuyeres as is now in operation. Lead smelting operations first commenced in 1889, when the British Broken Hill Pty. Ltd. started its first furnace. This was followed by installing two more furnaces during the same year and another the following year. In 1892, Broken Hill Proprietary Co. Ltd. acquired the smelting works and combined operations with those at Broken Hill, New South Wales; by 1897, the whole of the smelting operations had been transferred to Port Pirie and thirteen blast furnaces were built to treat the Broken Hill ore production. In 1915, The Broken Hill Associated Smelters Pty. Ltd. took over from the Broken Hill Proprietary and have carried out operations since that time. From its inception, the present company started on a long range program of reconstruction, in which the development of the lead blast furnace has played a prominent part. A definite trend in plant development has been towards the simplification of plant control by a reduction in the number of operating units. The great advantages of technical control which resulted from the very simplified flowsheet established in the continuous refining process stimulated the desire to extend the principle to the smelting operation. Thus in the sequence of furnaces described here, it will be noted that the trend has been towards larger and, of course, fewer units. With each such development it is significant that the operating conditions and metallurgical results have shown steady improvement. Standard Furnace In 1920 there were seven furnaces operating, five of a type subsequently called the standard furnace and two of the original thirteen smaller furnaces, the latter type being used for the treatment of drosses, etc. produced from the refinery section, while the standard type carried out the main, lead-smelting operations. The standard furnace (figs. 1 and 2) had the dimensions given in table I.

Jan 1, 1951

By A. A. Collins

H. R. BIANCO*—I should like to ask Mr. Collins if that statement he made about the addition of drosses to the blast furnace slowing down the blast furnace is a result of his own experience or a result of the experience of some older metallurgists; and perhaps I should ask him to define the type of drosses that he means. A. A. COLLINS (author's reply)— That has been my own personal experience with dross. On various occasions at Chihuahua we attempted to incorporate the dross in our regular blast furnace charge and to shut down the dross re-verberatory to try to save some money. As expected, we had very poor results. I think that Ed Fleming will well remember on one occasion, that was back about 1933, when we attempted the first experiment along this line, and as a result of the sulphur addition to the blast furnace to matte out the copper we ended up with hanging furnaces and mushy slags and abandoned the dross experiment, once again turning to the use of the reverbera-tory for handling dross. H. R. BIANCO—Is that dross you refer to from the drossing kettle ? A. A. COLLINS—Yes, the dross that I am referring to came from drossing kettles. Furthermore, to back up my previous assertion, I had occasion in 1943, while up at Leadville, to once again experience the routing of dross through the blast furnace with its sulphur addition, since they had no dross re-verberatory, and to observe that once thf dross was removed, the furnace was speeded up almost 100 tons a day. All of these are personal experiences and I think that Mr. Feddersen also has had a little experience along this line —in fact, I believe all of us have had some experience. H. R. BIANCO—I know at Trail they recirculate considerable dross through the blast furnaces and we also recirculate dross at Herculaneuin and I am not aware that it has done much towards slowing down the blast furnace. A. A. COLLINS—We have always had very poor results. In the first place you have got to add a sulphur addition to pick up that copper and once you do that, that sulphur is apt to combine with some of the zinc and you are going to form a little mush; before you know it you have furnace hangs and a poor working furnace. Now of course that depends on the amount of zinc you have on charge. But in 1943, Leadville had roughly about 7 pet zinc in their slag and it worked very poorly. Previously when they had 4 or 5 pet zinc in their slag it did not matter. B. L. SACKETT* At Tooele we had a great deal of experience with copper. We have always been able to keep a lead well, however, in spite of the fact we have run as much as 5 pet copper and only 15 pet lead on the charge. But regarding the handling of dross, our dross reverberatory furnace is only 7 or 8 years old. Before that we recirculated the dross through the furnace and thought we were doing a pretty nice job. Of course these things are all more or less relative—in other words you establish a certain condition much better than one of a few years ago and possibly as good as any other of which you know and you think you have pretty good results. When we first took the dross off of the blast furnace and put it through the dross reverberatory furnace we immediately found out that we had gained something very real in furnace speed. Since that time there have been occasions when, because of the dross reverberatory being down, we have had to use dross again through the blast furnace and that has checked our original experience in slowing down the furnace very definitely. So we feel that a dross reverberatory is a very valuable asset at the Tooele Plant. A. A. CENTER*—Mr. Sackett's being here reminds me of trying to run with a minimum of lead concentrates the maximum of dross producing electrolytic zinc plant residue. He came up from International Smelting Co. to help us get started on that. We took an old copper blast furnace at Great Falls, Montana, and made a lead furnace out of it by putting a lead well on the other long side which of course is a very unorthodox lead blast furnace. Our aim was to treat the residue from the electrolytic zinc plant, as I said, with a minimum of lead concentrates. That meant a maximum amount of dross. At that time selective flotation was not general practice, so our zinc concentrates ran relatively high in copper and other dross-producing elements; and of course these were largely in the zinc plant residue. I think we might call it muscle metallurgy, but we had an interesting, successful experience there and we ran for over a year thanks to Mr. Sackett's helping us get started. I have the details, but time does not permit. We did well enough so that the A. S. and R. Co. at East Helena kept boosting up the offer to us for the electrolytic zinc plant residue and there was not enough lead concentrate to supply two lead smelters there in Montana, so the matter finally finished up by the A. S. and R. Co. taking all of the residue under long term contracts.

Jan 1, 1950

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 H. V. Welch

In this paper, as prepared for delivery at the Southern California regional meeting on Oct. 14, 1948, it was thought best to interpret the term "economics" in a rather broad manner and to include, in addition to the material losses and recoveries and associated monetary values (Part I), a limited discussion of the increased difficulties or the particular problem and the special requirements, as the particle sizes of the suspended particles range down from the relatively coarse to 100, to 10, to 1 micron or even to a fraction of one micron (Part II). Further, it is not quite in order to overlook entirely the community and individual health problems, although space requires the economics of this to be considered only very incompletely. Therefore, Part III, covering this phase of the subject, is very limited. This paper, then, is divided into 5 parts or headings as follows: I Losses and/or values in suspended solids. II Particle size. III Dust and fumes in community and individual living. IV Means and Procedures for dust and fume collection. V Description or examples of specific equipment in service and of the several types used for dust and fume collection. Because of the wide extent and wealth of subject material available and the space and time limitation imposed, presentation and discussion are less than originally planned. I—Losses and/or Values in Suspended Solids The weight involved in moving streams of industrial plant gases is commonly not appreciated, neither is their carrying power in the weight of solids maintained in suspension and moved with the gas stream from a point of origin or pick-up to a point of dissipation or settlement. These, however, are major weight figures; for example, in a modern iron blast furnace there may be five tons of gas for every ton of iron produced and by the time this blast furnace gas has been burned in stoves or under boilers the weight of gas discharged to atmosphere is on the order of eight times the weight of iron produced. Similarly for nonferrous metallurgy there may readily be from 10 to 20 times the weight of gases discharged to atmosphere as there is metal produced. A cement kiln in operation or a kiln in service to produce metallurgical lime may have on the order of 5 to 6 times the weight of stack gases as of clinker or lime produced, and at least the cement kiln, because of the very fine nature of its feed, is a very heavy dust producer. It may be noted that there have been two developments in progress for nearly three decades. Both are extraordinary in the industrial economics effected and in their ready availability to ever larger units of operation and their ever widening importance in industry, and both are productive of great quantities of finely divided material in furnacing. The first of these is the flotation process for ores, especially the metallics such as copper, lead, and zinc; and the second, powdered fuel combustion for power plant, industrial plants and metallurgical operations. Today, new developments, for example, flotation for the nonmetallics such as higher grade limestone for cement manufacture which requires still finer grinding and the powdered-coal-fired boilers with production ratings of over 1,000,000 lb of steam per hr, bring still more concentrated and hugely increased quantities of stack emission. Perhaps the honors for the greatest interest in the quantities and values escaping in waste furnace and equipment gases belong to the nonferrous metallurgical operations. Their record of achievement in the installation of dust and fume collection equipment, largely baghouses or Cottrell electrical precipitators, is exceeded by no other industry. Something of the magnitude and variety of equipment utilized in such recovery systems was covered by the writer in two papers presented to the Institute some 10 years ago.1,2 It is not intended to repeat the material of those articles, but it is thought that they complement this offering and should be noted. COPPER ROASTERS As the copper roasters are the first of the series of furnaces handling the copper-bearing concentrates in the usual copper smelter of today, it is in order to make them the first consideration. Multiple hearth sulphide roasters, not hard driven, often maintain their dust loss through exit gases at 3 pet or below of feed to furnace; in hard-driven or maximum-driven furnaces, exit gas losses often approximate 7 pet of charge with a ±2 pet variation for special conditions prevailing at some plants. A 5 pet loss of feed in a roaster gas exit, unless reclaimed, often makes the difference between a profit and loss operation, and in many cases substantial recovery is the very basis of dividend payments. As there is available very practical and successful equipment for the collection of the

Jan 1, 1950

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 C. Pin, J. Bruce Wagner

In order to demonstrate the role of defect chemistry in the solid state to a process-metallurgy reaction, laboratory experiments were carried aut to remove copper from liquid lead using lead sulfide which had been doped to provide definite concentrations of cation vacancies. The removal of copper decreases in the order: bismuth- or antimony-doped PbS, undoped PbS or tin-doped PbS, and silver-doped PbS. The data are explained using the simple mass -action law and in terms of the exceedingly rapid interstitial diffusion of coppw in PbS to vacant cation sites. Results are in agree-ment with thermodynamic predictions and certain industrial practices that copper may be removed from lead below the limit of its coexistence with pure Cu,S and pure PbS. The role of defects in solids has been exploited in semiconductors and many device applications, in explaining tarnish formation, dissolution rates, and mechanical properties. The application of these principles to many process-metallurgical problems has not received as much attention. It was the purpose of this study to illustrate the role of defect structures of solids in a process-metallurgical application. When lead is refined, the ore, galena (PbS), is reduced by a series of operations to liquid lead (lead bullion) containing impurities such as copper, bismuth, antimony, arsenic, and silver depending on the original composition, the fluxes added, and the particular type of operation, see Fig. 1. In order to produce a pure lead, a series of refining operations are carried out. A typical lead-bullion analysis before drossing is shown in Table I. Copper is removed first as its presence increases the zinc consumption during the desilverizing process. For preliminary copper removal the lead bullion is brought to a temperature of 440°C in a kettle of 60 metric tons capacity. Some tar (or sawdust or resins) is usually added and the kettle is cooled slowly to 400°C while the liquid is stirred. A solid phase, called a dross, floats on top of the liquid and the particles of the solid phase adhere to the tar. This "hot dross" is collected. It contains mostly lead and copper which are partly oxidized and/or sulfurized if the lead bullion contains some sulfur.*

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 J. W. Matousek, C. S. Samis

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

Jan 1, 1963

By Thomas C. Wilder

Jan 1, 1965

By T. H. Weldon, L. V. Whiton, R. R. McNaughton, J. H. Hargrave

Oxygen enriched air is being used quite extensively in the metallurgical plants of The Consolidated Mining and Smelting Co. of Canada, Limited, at Trail, B.C. The oxygen used for this purpose is a by-product from the Company&apos;s chemical plants located in the area. Most of the ore treated in the Trail metallurgical plants comes from Com-inco&apos;s Sullivan Mine at Kimberley, B.C. At Kimberley the ore is milled to produce lead and zinc concentrates which are shipped to Trail for further treatment to metal. One section of this paper deals with the use of oxygen enriched air in the suspension roasting of the zinc concentrates. In this process the concentrate is calcined for leaching preparatory to electrolytic recovery of the zinc. A second section of the paper describes the use of oxygen enriched air in operations at the lead smelter. There oxygen enriched air is used in the blast to the lead blast furnaces and in the slag fuming furnace which recovers the lead and zinc contained in lead blast furnace slag. The final section of the paper outlines the precautions necessary for the safe use of oxygen enriched air in any plant operation. The Use of Oxygen Enriched Air in the Suspension Zinc Roasters The suspension roasting of zinc concentrate developed at Trail, B.C., has been described in AIME Vol. 121, "The Electrolytic Zinc Plant of The Consolidated Mining and Smelting Company of Canada, Limited" by B. A. Stimmel, W. 11. Hannay and K. D. McBean. Since the publication of that paper, the use of oxygen enriched air in suspension roasting has been introduced as regular practice with marked advantage. The relative importance of a specific advantage may vary with changing conditions, but, in general, it may be stated that improved operation has been achieved at increased capacities. Suspension roasting is carried out at Trail in converted standard 25 ft diam Wedge roasters. The 2nd, 3rd, 4th and 5th roasting hearths have been removed and the drying hearth covered over. Drying of the concentrate is done on the drying hearth and the 1st roasting hearth. The dried concentrate, after any lump&apos;s have been broken up in a ball mill, is fed to a single burner located in the upper part of the combustion chamber. Oxygen is introduced at the burner fan along with the gases from drying, returned combustion gases from the waste heat boiler outlet and the required amount of new air. Up to 60 pct of the concentrate settles out on the 6th roasting hearth, the rest passilig out of the roaster. The product collected in the waste heat boiler is finished calcine, but the dust collected in the cyclones after the boilers is returned to the base of the combustion chamber where the sulphate is decomposed. Gases from the c&apos;yclones go to a Cottrell precipitator. The discharges from the 7th roasting hearth and the waste heat boiler are combined with the Cottrell dust to give the finished calcine. Following small scale tests started in 1933, oxygen enriched air has been used continuously in the suspension roasting of zinc concentrate in Trail, beginning in 1937. A significant factor in promoting its use in this operation was the availability of by-product oxygen from the Company&apos;s near-by Chemical and Fertilizer Division. To-day it is standard practice at Trail to use oxygen enriched air for zinc concentrate roasting. The most important requirement in roasting a zinc concentrate for an electrolytic plant is that the zinc in the calcine should have maximum solubility. It is also desirable at Trail that the gas produced for the manufacture of suhhuric acid should have a ~naximum concentration of SO2 and that a substantial recovery of waste heat from the gas be achieved. High solubility of zinc requires that the sulphide sulphur and zinc ferrite in the calcine be kept low. These are both functions of temperature and time, with formation of zinc ferrite also dependent on contact between the iron and zinc particles. One of the inherent advantages of suspension roasting is that minimum time and contact are achieved. The limit on temperature is imposed by the fusion point of the concentrate and not by the need to control zinc ferrite formation. Operating temperatures are normally maintained within the limits of 1725" and 1850°F. A relatively low zinc sulphate in the calcine is required at Trail, and this results from discharging the calcine from the high sulphur dioxide atmosphere at a temperature above 1600°F.

Jan 1, 1950

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe&apos;s formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade&apos;s exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.&apos; The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

By H. H. Kellogg

0. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron&apos;s papers today is a matter of some disappointment. Adaptations, modifications and improvements have been made by several organizations or individuals and to complete the record I want to document a number of them. The Nicaro Nickel Co. operated a Government owned plant at Nicaro, Oriente, Cuba, during the past war. A report on the project was written for Reconstruction Finance Corp. and is in the document file collected by the Office of Technical Services, Commerce Department and filed with the Library of Congress, where it can be consulted or bibliofilm or photostat copies obtained by asking for copies of PB 97271. Nicaro Nickel Co. has obtained a series of U.S. Patents, my list (probably incomplete) of which bears the following numbers: 2,400,098; 2,400,114; 2,400,115; 2,400,461; 2,400,612; 2,458,902 and 2,473,795. International Nickel Co. has also studied the problem and U.S. Patent 2,478,942 shows that some of the complications involving occasional low extractions have been unraveled. Forward, Samis, and Kudryk, of the University of British Columbia, have also published a study of copper-nickel sulphide concentrate.&apos; Others are interested and it is evident that this type of hydrometallurgy is likely to find a happy application in the not-too-far distant future. Caron&apos;s two papers practically amount to a summation of his life&apos;s work on the important subject of nickeliferous iron ores and the American Institute of Mining and Metallurgical Engineers is fortunate to have been chosen the medium of publication. M. Rey—The ammonia leaching process has been the subject of certain studies in New Caledonia, but at the present time, the conditions are not very favorable to its adoption. The process is a combination of a thermal and a hydrometallurgical process. As a result, the first costs and the operative costs are rather high. To counteract this unfavorable situation, it would be necessary to make a very high extraction. But unfortunately, the process is delicate and in spite of all of Caron&apos;s valuable work, there are still many unknown factors. It is difficult to obtain regularly a high extraction, exceeding 75 to 80 pct. It would be interesting to have the opinion of Inter-national Nickel on the process and to know what the Dutch are doing in Celebes. M. H. Caron (author&apos;s reply)—I am quite familiar with the different types of nickel and cobalt ores as found on New Caledonia, and it may be pointed out that the Celebes ores are quite the same in their properties. Their behavior when treating the ores by the ammonia-leaching process is also alike and in my opinion, there is no reason why a high extraction of the New Caledonian ores could not be obtained if the process is properly applied. For the sake of completeness I may add that one of my patents has not been discussed in the papers. This patent deals particularly with the treatment of serpentine nickel ores. (Netherlands No. 62693 40a, French No. 965.786 April 21. 1948. and Cuban No. 13.625 Jan. 1950.)

Jan 1, 1951

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy&apos;s law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,&apos; Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962