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By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.' The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By A. W. Schlechten, R. P. Abendroth

Equilibrium H2S/4 ratios were determined as functions of temperatunz and composition in a hydrogen recirculation apparatus. A high-temperature solid solution exists in the range two-phase regionfrom TiS 1.96, to TiS1.30, Various thermodynamic quantities were calculated from the data. COMPOUNDS in the titanium -sulfur system have not receiyed much attention in the past, probably because they do not occur naturally in the earth's crust. However, titanium-sulfur compounds have been used in various metallurgical processes. The U.S. Bureau of klines' studied the formation of ti- tanium-sulfide mattes from charges composed of rutile, pyrite, and carbon, with the resulting sulfide matte being chlorinated to form titanium tetrachlo-ride. Fishel, Roe, and Ellis' investigated the de-sulfurizing action of titanium in steels, and Schwarz and Koster studied the preparation of metallic titanium from the sulfide using aluminum and magnesium reduction. The thermodynamic properties of some of the compounds present in the titanium-sulfur system may prove to be of some use in the consideration of future processes using these sulfides, and would

Jan 1, 1960

By A. W. Schlechten, R. P. Abendroth

Jan 1, 1960

By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By A. L. Labbe

SOON after the Cottrell treater was placed in operation in the Murray plant in 1918 to treat combined lead sinter and Wedge roaster smoke, it was noticed that the power flowing through the treater did not remain constant. This was indicated by the varying milliamperes and also by the total amount of power consumed by the rectifiers. At times, for then unknown reasons, the treater current fluctuated through a wide range of from 40 to 300 milliamperes. Fortunately, these variations in power did not affect the treater's overall recovery, as this installation consisted of three independent units in series, a feature which made the Murray Cottrell an outstanding installation over many years of operation. Water conditioning of the smoke as a means of improving recovery was already known, but was not adaptable to this installation for reasons of excessive corrosion, which had been the case with other treaters using water as a conditioner exclusively. Tests conducted on the smoke had proved conclusively that water vapor played no part in the fluctuation of power, and the same was true of the SO2 contents and dust burden of the smoke. Neither did temperature variations of from 150 to 400°F have any effect on the power. Finally it was noticed that the variation in power taken by the treater, and the efficiency of recovery, had some definite relation to the number of Wedge roasters operating, and particularly to the sulphur contents of the charge. This observation soon led to the discovery that free sulphuric acid was the conditioner for Murray smoke and that variations in acid contents of smoke accounted for fluctuations of treater power. Analysis of recovered dust revealed that only a few hundredths of a per cent free acid was necessary to maintain a very efficient recovery. Once this knowledge was available, the roaster charge was adjusted as to sulphur contents to produce the necessary acid conditioner. For a number of years this practice was followed, but with improvements in the field of flotation, excess pyrites were eliminated from the smelting picture, so with a change in metallurgical practice we were confronted with the problem of providing the deficiency in acid by some other means. The situation was aggravated and our problem of acid conditioning made more difficult by the increase in the lead contents of concentrates roasted resulting from better flotation methods. The first step towards introducing acid vapors into the smoke stream by accessory means was accomplished by boiling sulphuric acid in cast iron pots placed in an open fire box. Acid fumes evaporated from the pots together with the combustion gases from the fire box were discharged into the flue through a cast iron pipe. Capacity of the iron pots was quite limited because of the comparatively slow rate of evaporation and the use of lump coal as a fuel, which did not lend itself to practical temperature control. This method of firing resulted in frequent pot failures due to overheating. In spite of these incidental difficulties, encountered in any new venture, the pot evaporator demonstrated the practicability of fuming sufficient acid to make up the deficiency in that naturally evolved in the Wedge furnace operation. As time progressed, less and less high sulphur material was available for Wedge roasting, and the necessity for accessory acid conditioning reached a climax when the supply of this material was entirely eliminated. Since the cast iron pots could only evaporate a few hundred pounds of acid per day, and were costly to replace, the logical thought presented itself of spraying the acid in a heated chamber. This new type of acid evaporator was simpler and more economical to operate and had sufficient capacity to fume several thousand pounds per day. The attached fig. 1 presents the outstanding features of the new furnace. A is the vaporizing drum, which is heated by the combustion gases of coal stoker fire box, B. Acid is sprayed into the hot gas stream within the drum through a number of air-acid atomizers, C, and the acid vapor, together with combustion gases, is introduced into the smoke stream through two cast iron pipes extending to different points in the flue. The operation of this type of furnace requires control of temperature inside the drum to prevent overheating, which dissociates the acid vapor to SO, and eventually to SO2, with resulting loss of acid. The dissociation to SO, at elevated temperatures is comparatively high, and in some cases accounts for as much as 60 pct of the acid sprayed into the drum. To reduce the loss of acid, through dissociation, some Cottrell plants, where the rate of acid sprayed reaches at times 9 ppm, use two evaporating units. Fuming the acid into the smoke stream is only

Jan 1, 1951

By F. A. Forward, J. Halpern

A new process is described for extracting uranium from ores containing sulphidic minerals, which comprises treating an aqueous pulp of the ore with air or oxygen at elevated temperatures and pressures. The acid required to dissolve the uranium is generated during the leach through oxidation of the sulphides. The chemistry of the process is discussed and laboratory results are presented to illustrate the operation of the method and the variables which control it. With most ores, leaching at a temperature of 130°C and an oxygen partial pressure of 10 psi provides uranium extractions of 90 to 95 pct in 4 to 6 hr. The acidity and level of dissolved impurities in the leach liquor can be kept fairly low. The method is characterized by a number of advantageous features including low reagent cost, short retention times, and high recoveries. RECENTLY there have been developed several processes for extracting metal values from ores by pressure leaching techniques;' -' an example is the carbonate leaching process for uranium ores which has been studied in this laboratory.' Leaching is carried out under oxygen pressure to ensure oxidation of the uranium to hexavalent compounds which are soluble in carbonate solutions. During the course of investigations relating to this process, it was observed that sulphide minerals, such as pyrite, usually were oxidized under the conditions of the leach treatment resulting in the formation of iron hydroxides and sodium sulphate, i.e. 2 FeS= + 7Vz O2 + 8 Na,CO3 + 7 H,,O -* 2 Fe(OH)3 + 4 Na2SO4 + 8 NaHCO.,. [1]

Jan 1, 1956

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By John M. Dealy, Robert D. Pehlke

This note presents a summary of the available literature on activity coefficients at infinite dilution in binary metallic solutions, Table I. These data should prove useful in not only examining the therm-odynamic properties of binary metallic solutions, but also in predicting the activity of a component in a complex alloy. The relationship proposed by wagner1 for expressing the activity coefficient in dilute solution is of the form:

Jan 1, 1963

By Klaus Schwerdtfeger, Hans-Jürgen Engell

Activities of silicon in Ni-Si melts have beelz determined in the temperature range 1480° to 1610°C from electromotive-force measurements involving the cells The data obtained are used to derive the activities of nickel and the integal free energies of mixing. Entropies of mixing are calculated from the free energies of mixing as obtained in the present study and the heats of mixing as available in the literature. ACTIVITIES in Fe-Si and Co-Si melts have been determined recently by the authors&apos; using galvanic cells consisting of alloy, an oxygen electrode, and an oxide melt as electrolyte. The present paper deals with activities in Ni-Si melts as measured with the same technique. A schematic diagram of the cell is shown in Fig. 1. The alloy and the electrolyte consisting of CaO and SiO2 are contained together in a silica-glass crucible. During the experiment the silica glass crystallizes to cristobalite on the surface of the crucible. Nickel contents of the electrolyte are very small (<0.1 pct as checked with chemical analysis), because of the noble character of nickel in comparison with silicon. A tapered silica tube is connected to the crucible through which a platinum or molybdenum wire is inserted, as shown in Fig. 1. A platinum tube reaches the surface of the CaO-SiO2 electrolyte from above. The platinum tube is provided with four holes on its side, through which oxygen of 1 atm pressure is blown over the electrolyte. The cell reaction is given by the equation Si(metal) + O2(gas) = SiO2(electrolyte) [3] and the galvanic electromotive force of the cell is given by the formula

Jan 1, 1965

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company&apos;s technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated&apos; single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-&apos; atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By J. J. Donos

IN the operation of a smelter, continuous and accurate determination of smoke losses is essential for purposes of metals inventories and as a check on the efficiency of smoke recovery apparatus. Previous to the development of a continuous and automatic smoke sampler by R. MacMichael, in 1924, two methods were in vogue, and still are in some smelters, for measuring solids passing out of a flue or stack. These are: (1) the so-called dust concentration method whereby the gas volume passing through the flue is first measured and then the total amount of solids carried in the smoke stream calculated from the weight of suspended matter filtered out of a measured volume of gas; (2) the balanced tube method is independent of gas volume flowing through the flue, and relies for its accuracy on the fact that a true smoke sample may be taken if the velocity of the gas in the sampling tube is constantly maintained at a known ratio of the average flue gas velocity. The total amount of solids passing through the flue is then proportional to the weight of filtered solids and to the ratio of the area of the flue to the area of the sampling tube, corrected for the velocity ratio. The limitations of the first method lie in the uncertainty of the varying volume of gas arising from metallurgical operations and the unreliability of ordinary gas meters to hold their accuracy under

Jan 1, 1951

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By S. J. Noesen, J. R. Hughes

Several four-inch-diameter tungsten ingots were arc melted in vacuum or in hydrogen atmospheres. Melting pressures, melt-off rates, effect of atmospheres, and other pertinent factors were examined. Two of these ingots were extruded at 1650°C. Subsequently, forging and rolling were carried out at lower temperatures. For a 60 per cent area reduction by rolling, a one-hour recrystallization temperature of 1250°C was obtained. This temperature is considerably lower than those reported in previously published work, and can probably be attributed to the extreme purity of the as-cast ingots (N, H, 0 all less than 1 ppm). EVER since W. D. Coolidge, in 1909, described his process for producing tungsten metal of high density and good workability via the powder metallurgy tech-

Jan 1, 1961

By S. F. Radtke, J. A. Snyder, R. M. Scriver

An automatic, continuous casting arc furnace employing a nonconsum-able electrode and a direct current arc has been constructed and operated successfully for titanium. A comparison of the properties of arc and induction-melted titanium indicates that where high ductility, formability, and toughness are required, arc-melted metal is preferable. BECAUSE of the reactivity of titanium metal with all known refractories and the common atmospheric gases, melting of the metal presents numerous problems. It is necessary to provide an inert atmosphere in the furnace as well as a crucible material that will not react with the molten metal, if a ductile ingot is to be produced. Two special furnaces have been developed that meet the requirements and one, the induction heated graphite furnace, has been described in some detail.&apos; Little information is available for sizable units wherein power is applied to the melt through an arc, and the dearth of technical information on such a furnace prompted this report. It has been demonstrated clearly that arc melting produces titanium metal with superior toughness, ductility, and formability. To produce titanium ingots with these properties, an automatic, continuous casting arc furnace has been developed and is described herein. The history of arc melting may be traced to 1800, when Sir Humphrey Davy2 first experimented with Volta&apos;s electric battery and found that light could be produced and an arc formed between two carbon points attached to the cell. The discovery of the arc was followed by the design and construction of an arc furnace by Napier," in 1845, for the reduction of metal oxides. In 1853, Pichou&apos; described a similar furnace, although it was not until the discovery of the dynamo in 1867 that the arc furnace could achieve commercial significance. In 1878, Siemens- esigned the first arc furnace intended for the melting of metals and by 1882 had melted steel and platinum successfully. . This was followed by Moissan&apos;s" classical work with the arc furnace in 1892. W. von Bolton,&apos; in 1905, found that the arc furnace was suited admirably for melting refractory metals. In his work with tantalum, no suitable refractories for retaining the molten metal were found to exist. Together with Otto Simpson, he developed an arc furnace with a water-cooled copper crucible in which tantalum could be melted without contamination. This technique proved eminently successful. In his paper on the preparation of ductile titanium, Krolle first described an application of the von Bolton furnace to the melting of this metal. The

Jan 1, 1952

By S. F. Radtke, J. A. Snyder, R. M. Scriver

DISCUSSION, J. R. Long presiding R. I. Jaffee (Battelle Memorial Institute, Columbus, Ohio)—The authors have written a fine and important paper, and are to be congratulated. I do not entirely follow their discussion of the relationship between the ductility of titanium and its crystal structure. Since high purity titanium is extremely ductile, being capable of cold reductions of ovei- 99 pct, its ductility cannot be unduly restricted by its hexagonal crystal structure. It is true that interstitial solid solutions of nitrogen and oxygen do have a restricting effect on ductility, but this would appear to be an alloying effect rather than a crystal structure effect. The point made by the authors concerning the relative ductility between forged and rolled titanium does not appear to be conclusive, either. It would appear that in the same condition forged material would have equivalent or better ductility than sheet material. The difference between the ductility reported for forged bar and annealed sheet in Table I may be the result of a greater degree of cold work in the as-forged condition. S. F. Radtke, R. M. Scriver, and J. A. Snyder (authors&apos; reply)—We appreciate the discussion by Dr. Jaffee. His point is well taken that the hexagonal structure of titanium does not, in itself, restrict the ductility of iodide material and, therefore, should not be limiting in this case. It is true, however, that the ductility of different grades of titanium is not necessarily related to their hexagonal structure but more likely to their orientation and composition. It is also true that the presence of small amounts of foreign elements in hexagonal metals may have more pronounced influence on ductility than a corresponding quantity in cubic metals. Average values from a large number of tests might show relatively better ductility for forged titanium than is recorded in Table I. The forged bars used in this work were tested in the annealed condition; little is known concerning the effect of forging practice on ductility in titanium metal.

Jan 1, 1952

By H. A. Shaw, H. G. G. Whitton

This paper describes the use of the electric-arc furnace for the production of tough-pitch, horizontal cast copper shapes and the production of copper anodes from tank house anode scrap. This installation is the only one of its kind in the United States. SINCE the initial use of electric-arc furnaces for refined copper melting on a commercial scale at Copper Cliff in 1936, this type of melting has been of extreme interest to everyone in any way connected with copper casting and fabricating. Early in 1948, Kennecott Copper Corp. decided to build an electrolytic copper refinery at Garfield, Utah. One of the major decisions to be made at that time was the type of furnace to be used for melting cathodes for casting into refined copper shapes and for melting anode scrap for the production of anodes. Based on the results obtained from arc furnaces by the Tnternational Nickel Co. of Canada, at Copper Cliff, and by the American Smelting and Refining Co., at Baltimore, coupled with certain important economic factors such as having an adequate amount of relatively cheap power available at the Magna Central Power Plant, high cost of poles and oil in the Salt Lake District, and the lack of natural gas at that time, the final decision was to install electric-arc furnaces rather than the standard type of rever-beratory furnaces. Experience has shown certain parts of the original installation to have been inadequate or in need of modification. Although the present status of arc-furnace melting at the Utah Refinery is far from perfect, nevertheless substantial progress has been made. At the Utah refinery, copper is melted in three 15-ft diam, size "M" Lectromelt furnaces, two of which are used for melting cathodes and one for remelting anode scrap. Each furnace is energized from a 13,800-225 v, 3-phase, 60-cycle, 6000-kva (at 40°C rise) oil-immersed water-cooled transformer. Auxiliary equipment for each refined copper furnace includes a charging machine, launders, ladle, 40 ft diam Walker-type casting wheel, bosh, and inspection conveyor. The anode furnace differs in that it is charged by hand from an elevated platform and the anodes are picked off the 24-ft diam casting wheel by a takeoff hoist and loaded directly into specially designed trailers, Figs. 1 and 2. Electrical Equipment Electric power to operate the arc furnaces is generated at the Kennecott-owned Magna Central Power Station two miles distant and transmitted to the Refinery outdoor substation at 44,000 v. At this point it is stepped down to 13,800 v and carried through concrete-lined underground tunnels to the switchgear and then to the primary side of the furnace transformers. The power is conducted from the Y-connected secondary bus bars of the transformer to the electrode arms by means of 22 flexible copper cable conductors per phase. Each cable has a cross-sectional area of 1,750,000 circular mils, giving a total area of 38,500,000 circular mils per phase. The power is carried from these cables to the three individual electrode holders by means of water-cooled copper bus tubing. The electrode clamps are incorporated in the electrode holders and are released by air pressure working against a spring in the clamp control cylinder. The movement of the electrode arms is either automatic or manual. The automatic control is used during melting and is regulated by three Westing-

Jan 1, 1954

By J. A. B. Forster

The operations of the Electrolytic Zinc Co. of Australasia Ltd. involve the preliminary roasting of zinc concentrate from Broken Hill, New South wales, at a number of acid-making centers on the Australian mainland. The partially roasted material is shipped to the Tasmanian plant where it was formerly re-roasted prior to leaching,&apos; but this practice was gradually abandoned in favor of the flotation of leach residue for the recovery of a concentrate containing about 22 pct sulphide sulphur and known as secontlary or Risdon concentrate.2 This change, together with increased zinc production, called for new furnaces at Risdon for the roasting of 10-50 tonst of secondary concentrcite and 90 tons of new concentrate per day. The war situation made it imperative that construction be commenced without delay and to save time it was decided to base the design on that of Skinner type furnaces which had been built in South Australia twenty years earlier. This involved some sacrifice of desirable features but did not prevent the incorporation of provisions which had enabled small Herreshoff type furnaces to roast secondary concentrate autogenously. The roasting rate in existing furnaces was 10-12 Ib sulphide sulphur per sq ft of hearth area per day, and eleven hearths, 20 ft in diam, were provided in the two new furnaces in anticipation that they would prove capable of the autogenous roasting of 130-140 tons of concentrate per day from 28-29 pct sulphur down to 4.5-5 pct, with an oxidation rate of 11-11.5 lh S/S per sq ft of hearth area per day. It was soon realized, when the first of the furnaces went into operation, that a much better performance than this might be given, and the purpose of this paper is to show how a treatment rate of 100 tons per furnace day, and oxidation rates approaching 15 lb S/S per sq ft per day have been reached. Furnace Design General specifications for the design were based on the results of experience with several other types of furnace and on the special operating conditions

Jan 1, 1950

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By W. R. Opie

The object of this paper is to show the manner in which typical electrodeposits of hexagonal-close-packed metals—zinc, titanium, and zirconium—tend to form. The conditions of electrodeposi-tion markedly affect the nature of the deposits in regard to crystal size, orientation, and appearance. No attempt is made to correlate cell conditions with deposit quality but, rather, characteristic types of deposits were selected and a study made to show the relationship between outward appearance and crystal structure. The zinc deposits were made in aqueous electrolytes and the titanium and zirconium deposited from fused salt baths. ZINC deposits studied were made in the American Smelting and Refining Co.&apos;s Central Research Laboratories. They were representative of bright, shiny, smooth deposits, which can be obtained by using proper current densities and electrolyte addition agents, and of deposits which are dull and tend to be nodular. Four deposits were selected which ranged from smooth and bright to very nodular and dull, and their classifications are shown in Table I. These were examined microscopically and were found to differ quite markedly in outward surface structure and in microstructure. The outward surface variation is illustrated in Figs. 1 to 4. At X50 the texture could be seen to progress from granular to platelike to smooth. The microstructures of the deposits&apos; cross sections from starting sheet to outer surface are shown in Figs. 5 through 8. The dull nodular deposits (sample Nos. 1 and 2) show some tendency for acicular growth. The platelike sample (No. 3) shows tendency for columnar growth development and the smooth deposit (No. 4) has a well developed columnar structure. Back-reflection X-ray patterns of the deposit surfaces revealed some interesting information. The crystal orientation was random in all deposits except the smooth deposit. Fig. 9 is a typical back-reflection pattern of a nodular deposit. All planes are reflecting in the proper relative intensity. The pattern of the smooth deposit is shown in Fig. 10. The only planes which reflect are the (10.4). This series of planes is in the right position, with the FeKa radiation used, to satisfy the Bragg equation if the basal planes {00.1) are at right angles to the X-ray beam. The results were interpreted to mean that in the bright smooth deposit preferred orientation has occurred with the basal hexagonal planes oriented in the plane of the sheet but with all other planes randomly oriented around the c-axis.

Jan 1, 1957