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By R. E. Hudrlik, G. W. Preckshot

The diffusion coefficients of silver from solid silver in molten lead were measured to within ± 0.8 pet in a columnar type diffusion cell ower, the temperature range of 326° to 530°C. Fick's law describes the process up to 530°C where the laminar mechanism appareltly breaks down. These is negligible resistance at the interface as shown by mathematical analyses. The diffusion coefficients are found concentration independent. IT would seem that diffusion in liquid metals would be free of such effects as molecular structure, dissociation. polarization. and compound formation. This view was taken by Gorman and preckshot in their study of diffusion of copper from solid copper into molten lead. They reported diffusion coefficients which were independent of the concentration over the range of 478° to 750°C. They found that the Stokes-Einstein equation with constant radius of the diffusing specie represented the diffusion data better than Eyring's rate theory equation and Sheibel's correlation. The radius of diffusion was found to be that of the doubly charged copper. There appeared to be no resistance across the solid-liquid boundary. In the present work the diffusion coefficients for silver in liquid lead were measured over a range of temperatures of 350° to 505°C. The solubility of silver in lead over the range of 303° to 630°C was also obtained. These results are compared with calculated or correlated values or with data in the literature. EXPERIMENTAL Procedure—The experimental equipment techniques and procedures were those reported in detail by Gorman and preckshot9 and will not be repeated here. Measured values of WT, Co, A. L were obtained for various diffusion times and the diffusion coefficient was computed for the case of no resistance at the interface9, 11 by: WT/CoAL = 1- 8/p2 n=1 1/(2n - 1)2 exp[-(2n - 1)2p2 Dt/4L2] [1] or where there was resistance at the interface by: WT = 1- ?n=1 2h2/ap2L [sxp [-Dan2t]/[(h2 + an2) L + h] The roots an are those of the transcendental equation3 tan (an L) = Iz/cun. The diffusion coefficient is that defined by Hartley and Crank.7 The total silver in the lead cylinder and equilibrium slug was determined by a cupellation technique' with proper correction for losses. Analysis of known samples showed that this method is surprisingly accurate. The amount of silver in the lead adhering to the silver cylinder was obtained in the same fashion as shown by Gorman and preckshot.9 The small errors involved in this determination are not critical since the silver in this adhering lead layer is only 3 to 15 pet of the total diffused. Materials—Electrolytic silver containing 99.9+ pet Ag obtained from General Refineries of Minneapolis, Minn. was used for all but runs 7 and 8. For the balance of the runs this silver was reduced with hydrogen at 1100°C and its oxygen content was found to be about 0.017 pet. For the runs. 7 and 8, phosphorous-reduced silver of the same purity was obtained from Handy and Harman Co. of Chicago, Ill. The densities of the phosphorus-reduced silver and the hydrogen-reduced electrolytic silver were 10.484 and 10.487 g per cm3, respectively. These values agree with those reported for pure silver. Silver which was reduced at 900 C had an average density of 9.998 g per cm3, indicating porosity. This silver was used for a number of runs which were not tabulated in Table I. These are indicated by crosses on Fig. 2. The 99.999 pet Pb was obtained from the National Lead Co. Research Laboratory of Brooklyn, New York. DISCUSSION OF RESULTS The diffusion and solubility results are reported in Table I for eleven runs using either phosphorus-reduced electrolytic silver or hydrogen-reduced silver at 1100° C. The solubility data shown in Fig. 1 show the excellent agreement with that reported by Heycock and Neville.8 The data of Friedrichs5 apparently are in error. The experimental solubility data of this work are reported to 0.3 pet. The experimental diffusion coefficients computed from Eq. [1] are reported within 1.2 pet of the mean and are plotted in Fig. 2. These are expressed within +0.8 pet of the experimental values over the entire temperature range by: D= 8.26 x 10 -5 e-1925/RT . [3] There appears to be little difference due to the

Jan 1, 1961

By F. F. Poland

The purpose of this paper is to describe the recent applications and improvements made in the process and equipment for the recovery of metallic zinc from secondary metals by means of high temperature electric resistor furnace distillation. The process and high temperature furnace, as developed by Revere Copper and Brass Incorporated, Research and Development Department, was described in a previous paper. † Since the publication of that paper the process and equipment have been licensed to others. Consequently its field of application has been expanded, particularly for the treatment of scrap brass, galvanizers dross and scrap zinc. Other applications are being considered, particularly the melting of metallic titanium and special alloys requiring a controlled atmosphere. Consideration is also being given to modification in design that would allow the melting of copper cathodes for the production of oxygen-free and electrolytic tough pitch copper shapes without the necessity of blowing and poling. In the design of a furnace for melting copper cathodes it is intended that the fundamental principle of charging the solid material into a large pool of molten metal through a double door charging vestibule as shown in Fig 3 of the previous paper, † would be adhered to and, in addition, either dehydrated and desulphurized producer gas or commercial nitrogen, that is, approximately 96 pct nitrogen, 2 pct hydrogen 2 pct CO, also dehydrated, would be used to provide a protective atmosphere for the resistors and to flush out more soluble gases from the molten copper. The operation of a small unit producing approximately 1000 lb of copper per hr has shown that the commercial nitrogen will allow the production of tough pitch electrolytic copper when the metal is transferred from the meltdown unit contemplated to a special type induction unit where the oxygen absorption and temperature can be controlled. Standard practice in treating low grade scrap brass has been to oxidize the zinc by blowing air through the molten metal. This operation results in the recovery of approximately two-thirds or less of the zinc content of the brass in the form of an impure zinc oxide having only a fraction of the value of the zinc in metallic form. The balance of the zinc is lost to slag, fume and drosses. Fig 1 shows the revised flow sheet of the process for the treatment of scrap brass. For this application and as shown on the flow sheet a low frequency induction furnace has been substituted for the Wilkins-Poland type as a melting unit. This type of furnace has been found the most suitable for the purpose as will be shown by the following discussion. Serap Brass The melting of refinery scrap brass preparatory to distillation presents a melting problem quite different from the usual melting of brass mill scrap for recasting because refinery scrap is a heterogeneous mixture of alloys each having different melting and boiling points, and coated with a variety of corrosion products and foreign materials. In addition, brass and copper plated pieces of sheet iron, stainless steel, ceramic materials, and others are present that do not melt except at temperatures above the boiling point of the liquid bath. In the previous paper it is noted that difficulty was encountered in the melting of refinery grade scrap brass without excessive loss of zinc by volatilization and that 5 to 10 pct razorite flux was used to alleviate this condition. While this flux was successful in preventing the excessive loss of zinc by volatilization it interposed a low heat conductivity layer between the source of heat and liquid charge and resulted in lowering the melting rate of the furnace. This same problem presents itself in all types of furnaces in which the metal is heated by radiation and conduction from above the charge. It has been found in melting this type material that the melting rate per hour or per square foot of hearth area

Jan 1, 1950

By F. F. Poland

S. ROLLE*—As one who has been privileged to read Mr. Poland's paper before its publication, I wish to express high praise for it and the record which it gives of the work done by the Research and Development Department of Revere Copper and Brass Inc. in developing a satisfactory furnace for the recovery of metallic zinc from secondary metals by distillation. I have also had the opportunity of studying the operation of the furnace when running on scrap brass at the Detroit plant of Revere, and I can therefore say from knowledge gained first-hand that the unit is efficient and economical when used in conjunction with distillation. However, when I read what Mr. Poland has to say in reference to the possibility of using the furnace for melting copper cathodes for the production of oxygen-free and tough-pitch copper shapes, I am constrained to be somewhat skeptical. No doubt the furnace can readily be modified so as to make it possible to melt cathodes, but that is only a part of what is required to produce refinery shapes. Because of its construction the atmosphere in the furnace is highly reducing and even without protective gases such as nitrogen the copper cathodes which are

Jan 1, 1950

By Edna A. Dancy, Gerhard J. Derge

Jan 1, 1963

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680' to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,' however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated' dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski's measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving' a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski's result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski's shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur' are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955

By W. F. Hergert, L. H. Banning

Experimental production of Al-Si alloys, containing from 33 to 55 pct Al, by direct reduction of aluminum silicates in a three-phase arc furnace is described. Advantages of a smelting technique utilizing hogged wood waste as part of the reductant and for temperature control are discussed. WORK on the problem of producing aluminum by smelting has been in progress since the middle of the eighteenth century. Early work met with little success and in 1782 Lavoisier, an eminent French chemist, expressed the belief that alumina could not be reduced by carbon. It was almost a century later when the Cowles brothers developed a process for the production of aluminum alloys by reducing alumina coincident with the reduction of other metal oxides. In practice, the other metal oxide was usually copper. In 1907 it was first shown that alumina alone could be reduced by carbon at a temperature of 2200°C. The metal produced was volatilized and lost or recombined with the oxides of carbon formed in the reaction.' For a number of years after the Cowles brothers abandoned production of Cu-A1 alloys because their product was not commercially competitive with the aluminum produced by the Hall process, there was little interest in thermal reduction processes. After World War I interest in such processes was renewed and a number of patents were issued on processes for the production of A1-Si alloys.' , "he function of the silicon in these processes was the same as the function of the copper in the Cowles brothers process, namely, to prevent the reduced aluminum from recombining with the oxides of carbon and to promote absorption of the aluminum vapors set free at the high temperature required for the reduction reaction. The advantage of using silicon in place of copper for this function is that silicon has a higher boiling point (2600"C) than copper (2310"C) and its oxides, combined with aluminum oxides, occur in nature in almost unlimited quantities. No A1-Si alloys have been produced commercially in the United States, as far as is known. However, considerable experimental smelting of aluminum silicate materials has been done by the TVA at Wilson Dam, Ala.' The most extensive development and commercialization of the electrothermal production of A1-Si alloys took place in Germany before and during World War II.V he furnaces used in the

Jan 1, 1956

By K. J. Brondyke, P. D. Hess

Two processes have been developed for improving the quality of molten-aluminum alloys before casting. The Filtration Process. which involves passing molten metal through a packed bed of granular filter material, is a rapid means of removing finely divided particles. It has the most potential in those instances where removal of inclusions is of primary importance. The Combination Fillration-Inert Gas Fluxing Process inuolzles introduction of an inert gas so that it will diffuse countercurrent to metal flow through the filter bed of granular material. Dissolved hydrogen is removed from the metal in addition to removal of finely divided particles. The Combination Process is most useful where both inclusion removal and attainment of conistently low-hydrogen-content metal are important. Metal treated by the Combination Process is of higher and more uniform quality than heretofore attainable with prolonged chlorine fluxing. Costs of the Combination Process can, for the most part, be offset by savings derived from high recoveries and increased production of superior-quality products. IMPROVEMENT in the quality of molten-aluminum alloys is secured generally through the use of some fluxing practice in a crucible, holding furnace, or ladle involving either gaseous or solid fluxing media. Typical fluxing agents may include the gases nitrogen, argon, or chlorine used either singly or as mixtures and the solids aluminum chloride or hexachloroethane. Regardless of the fluxing means used, the primary objectives are the adequate removal of both metallic and nonmetallic inclusions and reduction of hydrogen content to an acceptably low level. The ultimate goal is to produce ingots and cast products of high quality free from inclusions and porosity. The development of ultrasonics for measurement of internal quality, tightening of quality controls, and the application of the aluminum alloys to new or different commercial fields have been responsible for an ever increasing demand for improvement of quality of both cast and fabricated products. This demand for high quality has not been restricted to any single type of product. On the contrary, the demand encompasses about the entire variety of products including those for fabrication, those to be machined, buffed, or finished for decorative purposes, and those for critical applications where both surface and internal quality is of utmost importance. In many instances products acceptable in the 40's would now be scrapped as unacceptable by these higher present-day standards. With this ever increasing demand for higher quality, it became apparent at Alcoa that conventional means of melt treatment were inadequate in many instances and new approaches were necessary. Consequently the research program was intensified with attention focused on metal treatment during transfer in order to reduce the furnace processing time to a minimum in an effort to attain the desired results at a minimum of additional expense. As a result of this intensive research program which covered numerous variations and adaptations of conventional methods in addition to new methods of melt treatment, several new processes were developed, two of which will be described here. The first of these, a method of melt filtration, was patented in February, 1959.l The second process involving combination filtration—inert gas fluxing was patented in June, 1962. 2 Other melt-treatment processes developed during this period of investigation were patented as listed.3 FILTRATION PROCESS General Description. The Filtration Process, which involves passing molten metal through a packed bed of granular filter material, is a rapid method of effectively removing finely divided particles. It is an impingement-type filter; hence the size of the particles removed from the metal are considerably smaller than the interstices of the

Jan 1, 1964

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit 'flash' chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om'nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.' One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.' By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By Molly Gleiser, John Chipman

The standard free energy of formation of WC was obtained from determination of the equilibrium WC + CO2 = W + 2CO between 1215° and 1266°K. Its uallie is -8340 * 300 cal Per mole over the above range of temperature. AS a part of a program devoted to measuring the stabilities of the carbides, a study was made of the free energy of formation of tungsten carbide, WC. The homogeneity range of this compound is very small,' and it is generally accepted and is dealt with here as a stoichiometric compound. The heat of formation, ?H°f, of WC has been accurately measured by Huff, Squitieri, and snyder.2 The only attempt, however, to measure the free energy of formation of this compound was made by Schenck, Kurzen, and wesselkock3 who brought tungsten carbides into equilibrium with H2 and CH4. Unfortunately their results are not sufficiently accurate nor consistent enough to permit the calculation of free energies. METHOD Heating mixtures of tungsten and carbon powders in hydrogen for 4 days at 1050°C led to formation of some WC without any trace of W2C. It was deduced, therefore, that at least below this temperature W2C will not be formed during experiments with mixtures of tungsten and WC. This was subsequently shown to be correct. The method chosen was the measurement of the equilibrium of the reaction

Jan 1, 1962

By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

By G. H. Turner, R. C. Bell, E. Peters

Zinc oxide activities in a typical lead blast furnace slag have been calculated from plant operating data. These activities were used to assess the probable effect of fuel composition, oxygen enrichment, and air preheating on the efficiency and capacity of the slag-fuming operation. THE physical chemistry of zinc fuming has been examined with three objectives in mind: 1—to predict conditions favorable to increasing furnace capacity, 2—to predict the changes required to fume zinc more economically, and 3—to explain reported differences in the efficiencies of various slag-fuming plants. This study, made at ail in the plants and laboratories of The Consolidated Mining and Smelting Co. of Canada Ltd., developed from a program undertaken some three years ago on behalf of the AIME Extractive Metallurgy Div. subcommittee on slag fuming. Lead metallurgists first became interested in the recovery of zinc from lead blast furnace slags in 1905 and 1906. An excellent review of the early experimental work has been made by Courtney,' who described blast furnace, reverberatory furnace, and converter methods of fuming zinc from slag. Some of the investigators did not appreciate the importance of reducing the zinc oxide content of the slag to metal in order to fume it, since they tried compressed air blast without fuel in their earliest attempts. However, by 1908, the importance of reducing the zinc was established.' In 1925, the Waelz process for the recovery of zinc oxide from oxidized zinc ores was developed in Germany.' This process was not readily adaptable to lead blast furnace slags because of the difficulty in handling fusible charges in a kiln. What appears to have been the first slag-fuming operation as it is known was commenced by the Anaconda Copper Mining Co. at East Helena, Mont. in 1927." The first Trail furnace was completed in 1930, and this was followed by the construction of several other slag-fuming plants. During the period in which slag fuming has been extensively employed, little development of the chemistry of this process as a whole has taken place. Several good papers on the petrography of lead blast furnace slags have been published,""= but these studies could do little more than establish the forms in which lead and zinc occur in the initial charge and final products of the slag-fuming operation. In recent years, zinc-smelting problems have been ap- proached from a thermodynamic point of view. Maier has published an excellent thermodynamic treatment of zinc smelting." The important thermodynamic properties of zinc and its compounds have been determined and checked by other investigators.' However, to the best of the authors' knowledge, no thermodynamic treatment of the fuming of zinc from slag has been published. A thermodynamic study of any process requires that the essential chemistry of that process be known. In slag fuming there appear to be some differences of opinion as to whether the active reducing agent is elemental carbon or carbon monoxide. Furthermore, some observers have noted that high volatile coals appear to be more efficient than low volatile coals, indicating that hydrogen is also an important factor in the reducing efficiency of a fuel. That both hydrogen and carbon monoxide are effective reducing agents for the zinc oxide content of lead blast furnace slags can be demonstrated readily by introducing these gases into a slag bath held in a neutral vessel at 2100°F (1150°C). Elemental carbon also will reduce zinc oxide, but it is improbable that much free carbon is available for reduction of zinc, as the reaction between the finely powdered coal and air should be largely completed before the solid coal particles reach the slag. Some large-scale fuming experiments using gaseous hydrocarbons have been carried out by other investigators, but, as far as is known, these have not been developed yet into operating processes. The thermodynamic treatment in this paper is based on the following reactions: 1—to supply the thermal requirements C+V2O2- CO [1] C + 0,-CO, [2] H2+ ~z0,-H,O 131 and 2—to reduce ZnO ZnO + CO + Zn + CO, c41 ZnO + H, e Zn + H,O. [51 The furnace-gas composition also is controlled by the equilibrium constant of the familiar water-gas reaction H,O + CO + CO, + H2. C6l In order for the thermodynamic calculations to be quantitatively applicable, it is necessary that the chemical reactions to which they are being applied

Jan 1, 1956

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2'3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By Robert D. Pehlke, Arden L. Bement

A mass transfer coefficient for the removal of hydrogen from liquid aluminum by inert flush degassing has been determined experimentally at 700°C. A mathematical model has been derived, assuming transport control, which adequately describes the experimental data. The removal of hydrogen is shown to increase with decreasing bubble size, and with increasing flow of flushing gas. The presence of hydrogen in liquid metals in amounts which exceed the solid solubility at one atmosphere hydrogen pressure is highly undesirable, causing unsound ingots or castings, or resulting in difficulties during further fabrication. The removal of hydrogen from liquid metals can be accomplished by several methods, the principal two being vacuum treating and inert flush degassing. The design of a process involving either of these techniques is based on the mass transfer coefficient for hydrogen between the liquid metal and a hydrogen-dilute gas phase. In an effort to extend our knowledge in this area, an investigation of the rate of removal of hydrogen from liquid metals by inert gas flushing was undertaken. In view of the difficulties encountered with gas porosity in the casting of aluminum and aluminum alloys, and because of certain experimental advantages, liquid aluminum was selected for the study. PREVIOUS INVESTIGATIONS The removal of gases from liquid metals, particularly steel, has received considerable attention in recent years, The first definitive work of a theoretical nature was presented by Geller1 who considered the case where equilibrium exists between purging gases and metal bath during flushing, and also deviations from this ideal case. Hulme2 has surveyed a number of experimental studies and discussed some of the practical limitations of removing dissolved gases from molten metals. More recently a number of studies have been reported on degassing of steel melts by flushing with an inert gas.3'4 Considerable work has also been reported on aqueous and organic liquid-gas systems, and an excellent summary prepared by Hovis.5 The treatment of liquid aluminum by a flushing gas to remove dissolved hydrogen has been known for several decades.6 A number of gases have been used for this purpose, including nitrogen, argon, and chlorine, or mixtures of these gases. Tikkanen and Erkko7 have studied the relative density changes of aluminum castings poured from melts degassed with chlorine, nitrogen, and mixtures of the two gases. Their

Jan 1, 1962

By Herbert H. Kellogg

Graphs representing the standard free-energy of formation as a function of temperature for 21 fluorides are presented, along with estimated values for the standard free-energy of formation of 20 atedadditional fluorides. A few of the many possible uses of these data in metallurgical calculations are discussed, including the fluorination of oxides, sulphides, metallurgicaland chlorides, and the reduction of metal fluorides. RECENT papers which have presented free-energy data for oxides, sulphides, chlorides, carbonates, sulphates, and silicates in the form of free energy vs. temperature plots,1-5 have found important uses in teaching and metallurgical development work. This method of presentation of thermo-dynamic data serves to make available in readily usable form thermodynamic constants which are scattered throughout the literature, and to show by graphical means the stability relations which exist between the compounds of a given type. It is certainly desirable to have these free-energy-temperature diagrams for as many types of compounds as are of present or potential use in metallurgical processes. Thus, even though there are but few uses of metallic fluorides in extractive metallurgy today, the potential uses of fluorine processes are of great importance and serve as the principal justification of this paper. Recent developments in the production of fluoro-carbons have resulted in vastly improved methods for the production and handling of fluorine and corrosive fluorides, with consequent reduction in costs.".' The extractive metallurgist should no longer overlook possible fluorine processes when development of a new process for a relatively high unit-price metal is being considered. In a previous paperv he author outlined in some detail the importance and use of free-energy data in metallurgical calculations and also discussed the properties of a standard free-energy vs. temperature diagram. The same method of presentation is adopted in this paper, and the reader is referred to the earlier work for explanations of the use of free-energy data. Thermodynamic Data This paper presents standard free-energy vs. temperature diagrams, Figs. 1 and 2, for those fluorides for which the major thermodynamic constants are known. In the calculations of the standard free-energy of formation (AGO), values of the enthalpy of formation at 298°K (?Ho,) were taken from "Selected Values of Thermodynamic Constants"8 most of the values of standard entropy at 298°K (S°298) were taken from "Selected Values"," but in a few cases the values given by Kelley9 ere preferred; data for the Phase changes came from "selected Values" and several of Kellley's publics- tions;0-12 and most of the specific-heat data were taken from Kelley.l0 The appendix gives a detailed list of the sources of the data. As explained in an earlier paper,6 he accuracy of some of the standard free-energy relationships is not high. An error of +1 kcal at 1000°C is expected in most of the curves of Figs. 1 and 2. The error may be as high as +3 kcal in some of the curves. Rather than attempt to estimate the reliability of each curve, the source of the data used is reported in the appendix, and the reader may compare these data with newer values as they become available. Figs. 1 and 2 fail to show values for the fluorides of many important metals. In most cases this is because the entropy of the metallic fluoride is unknown. For preliminary calculations it is often useful to have available the best estimate of an unknown datum, rather than no information at all. With this in mind, Table I lists estimated standard free-energy values for a number of important metallic fluorides not included in Figs. 1 and 2. The values reported in Table I were, calculated by Brewer et al.13 and are based on estimated entropy values. The estimated uncertainty of the values for each fluoride were calculated from the uncertainty values given by Brewer1' for ?H°, and the entropy function.

Jan 1, 1952

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By Donald Ingvoldstad, Harold E. Lee

AT Bunker Hill the original charge storage and preparation system was installed in 1917 to accommodate lead-silver gravity mill products. Only minor tonnages of wet fines such as vanner and flotation concentrates were received. Charge flux and diluent requirements were .provided by an ample supply of siderite middlings and coarse lime-rock. While oversize material was crushed through ¼in., the use of roll crushers in series resulted in a more or less granular, free-running charge of adequate porosity. Under such conditions, receipts could be proportioned directly from receiving bins, and suitable blending was obtained by passing the resultant layered composite through a small Stedman disintegrator. This elementary system served well for production and smelting of an extremely lead-rich sinter, in the low column blast furnace. Here sinter physical quality is less critical, and appreciable quantities of raw flux and oxidized ore may be charged directly to the blast furnace without seriously impairing furnace capacity. Prior to 1938 the relative proportions of zinc receipts were low and extraneous flux requirements at a minimum. However, subsequent war-inflated zinc demands brought marked increase in fine concentrate and slimy zinc leach residue receipts and an abrupt introduction to smelting a more refractory zinciferous charge. The higher temperature demands of the more refractory zinciferous charge required a higher smelting column and the higher column, in turn, rendered the blast furnace less receptive to improperly prepared feed. Inadequate presinter processing facilities prevented the production of acceptable sinter, and blast furnace production declined to 50 pct of former capacity. In view of a prevailing contention among lead metallurgists as to the deleterious action of high zinc slag on blast furnace capacity, it was natural to overstress this factor and to concentrate on possible changes in furnace design. Another interpretation was that primary correction should be sought through expanded sintering facilities. This divergence of opinion, together with the extreme material shortages of the 1940's, delayed corrective

Jan 1, 1957