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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

By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By J. R. Stone, G. D. Storm

Design features and operating methods of ASARCO's new unit for the continuous melting and casting of tough pitch copper at Perth Amboy are described. Preliminary studies made for determinitzg economic feasibility and design details are also presented. Cathodes are preheated with oil and melted in an electric furnace at 40-ton per hr rate, from whence the molten copper is fed simultaneously to the wire bar casting wheel and the continuous casting of cakes and billets. In the early 1950's the copper refining furnaces at ASARCO's Perth Amboy plant reached a point where major expenditures would have to be made for replacement of the furnaces and the auxiliary equipment. The problem was whether to continue with the standard reverberatory furnaces or to consider continuous melting in electric furnaces. Reverberatory furnaces have been used for years in the copper industry and for some 50 years at the Perth Amboy plant. Reverberatory melting practice, however, imposes certain restrictions. First, labor costs are high, usually requiring three shifts per day. Secondly, they operate on a batch basis, the conventional operation being a 24-hr cycle including

Jan 1, 1961

By J. W. Byrkit

Design features and operating methods at the new Ajo smelter are described in detail. Successful operation of a novel method of handling and charging wet concentrates to a deep bath type reverberatory furnace contribute to the daily production of 200 tons of anodes with good results from the standpoint of both metallurgy and economy. THE New Cornelia Branch of the Phelps Dodge Corp. is located at Ajo, Ariz. Large scale mining operations were started at Ajo in 1917, when a 5000 ton leaching plant was put in service to treat the copper carbonate ore that overlaid the sulphide ore-body. In 1924 a 5000 ton flotation plant was built to treat the sulphide ore and the leaching operation was abandoned a few years later. Changes in practice and additions to plant facilities have resulted in a gradual increase in the milling rate which now approaches 30,000 tons daily. Prior to the erection of the Ajo smelter, flotation concentrate was shipped by rail to Douglas, Ariz, where it was treated in the Phelps Dodge smelter. Construction of a one reverberatory furnace smelter to produce an average of about 200 tons per day of copper anodes at Ajo was started early in 1949. Initial heating of the reverberatory furnace was begun on June 21, 1950. Charging the furnace was started on july 8, and the first anodes were cast on July 14. Neither the anode furnace nor the reverberatory furnace has cooled since the initial firing. Fig. 1 is a photograph of the new smelter. Built primarily to eliminate the '300 mile haul of concentrate to the Douglas plant, the new smelter was designed to treat the Ajo concentrate, with a minimum of capital investment. A novel, and relatively simple, method of concentrate handling and furnace charging made unnecessary the installation and operation of expensive storage facilities and reclaiming equipment, and obviated the necessity of holding in storage large quantities of copper-bearing materials. (Patents are pending in the United States and abroad on the Ajo process.) In the selection and arrangement of equipment, consideration was given to the full utilization of all smelting facilities, reducing the amount of idle equipment to a minimum. The layout of the smelter is shown in Fig. 2. The important problem of internal transportation was minimized by arranging the reverberatory furnace, converters, and anode furnace in a compact group and providing storage bins inside the smelter building, within reach of overhead cranes, for fluxing materials and other supplies needed in the daily operation. This can be seen in the sectional view of the smelter given in Fig. 3. Incorporated in the design were many innovations in smelting equipment intended to facilitate operations and effect economies in maintenance expense and manpower requirements. Table I gives operating data of the entire plant. Metallurgy The metallurgical practice at Ajo is based essentially upon the use of a single, deep bath reverberatory furnace for smelting wet concentrate, without concentrate storage facilities. The large reservoir of slag and matte maintained in the furnace serves to equalize, to some extent, the day to day variations in the nature and grade of concentrate and permits

Jan 1, 1954

By T. E. Evans, C. T. Baroch

ZrB2 was produced in batches of 4 to 6 Ib by interaction of ZrO2, B4C, B203, and carbon at around 2000°C in a simple graphite resistance furnace. Techniques of production are discussed and the final design of a suitable furnace is described in detail. Several other borides were made by the same technique and the process appears to have possibilities for commercial production. N seeking out new hard and refractory com- pounds, many researchers have turned to the investigation of the borides and excellent papers have been published on the properties of these compounds. Few papers, however, have appeared on the techniques and problems concerned with the production of these high temperature substances. This report describes progress made in developing a method for preparing zirconium diboride, ZrB2, on a pilot plant scale. The literature of the borides and other refractory hard metals recently has been reviewed, annotated, and classified so completely' that it is needless to attempt such an outline here. It is enough to say that three borides of zirconium have been reported: ZrB, ZrB2, and ZrB12.2 ZrB2 is the most stable of these and is especially stable in the presence of carbon up to and including its melting point of around 3000°C. Like most borides, it can be prepared in several ways. It can be prepared by synthesis of the elements, but these are expensive and difficult to produce in a high state of purity. Obviously, production directly from the oxides would have decided economic advantages. In electrolytic production such as that of calcium boride,:' the product is recovered as a sludge mixed with electrolyte; and separation of product from adhering electrolyte and regeneration of the electrolyte is an involved and difficult process. The work on borides was started on a small scale in 1948. Late in 1949, Naval Ordnance expressed a specific interest in ZrB2 and the project then centered on this compound. After the usual experimental work necessary in a new field, ZrB2 of good quality was produced by heating mixtures of B4C, ZrO2, B2O3, and carbon to a temperature of about 2000 °C in a resistance-type electric furnace. Over 100 lb was made for experimental use tests, and the method of production probably could be expanded into a commercial operation. A similar process has been described by Kieffer and coworkers.' The main chemical problems were the development of proper charges to insure complete reduction of the elements, determination of the proper temperature range at which these reductions took place, and adoption of techniques necessary to pre- vent inclusion of such impurities as carbon and nitrides. The mechanical problems consisted of developing a simple practical furnace that would attain the high temperatures required and permit use of a controlled atmosphere when necessary and determining of suitable refractories. Both problems were solved by designing a crucible resistance furnace. Crucible Resistance Electric Furnace Attempts were first made to produce ZrB2 in an electric arc furnace, but such a furnace would not provide the degree of carbon control required for producing clean graphite-free borides, so it was decided to try working in a crucible. Obviously, the furnace would have to be constructed of graphite, as the temperatures required are too high for other refractories or heating elements. Crucibles were made by hollowing out segments of graphite electrodes, which were fitted with a cover and clamped between two electrodes so that the current passing through the thin wall of the crucible would generate heat, using the principle of the Helberger crucible furnace."? Preliminary tests with this type of furnace were encouraging and led to the furnace design shown in Fig. 1. The essential components were a thin-walled graphite crucible resting on a graphite block, which formed the lower electrode assembly, and a top electrode assembly swung from a pipe column making contact with the top of the crucible. The space around the crucible was filled with graphite prepared from waste electrodes crushed to about ¼ in. This packing had excellent insulating properties, both electrically and thermally, and could be removed easily and quickly from around the crucible by means of an industrial vacuum cleaner. The largest resistor crucibles were machined from 8 in. electrode stock and were 26 in. long, with a side wall Yi in. thick and a 1 in. bottom. Temperatures were determined optically by sighting down a 1 in. hole drilled longitudinally through the top electrode and the crucible cover. Sealing this hole at the top was a water-cooled brass sight-glass assembly, shown in Fig. 2. An opening was provided for a light flow of helium to keep the sight opening clear of smoke, and a glass prism above the sight glass changed the line of sight to the horizontal for easier reading. More recently, the prism and optical pyrometer were replaced by a photoelectric recording pyrometer. At first the charges were placed directly in the resistor crucible but this meant that everything had to be withdrawn from the furnace every time the charge was emptied. Later, smaller crucibles were made up that could be placed inside the resistor

Jan 1, 1956

By Sandford S. Cole, John S. Breitenstein

The recovery of over 80 pct of the vanadium values in titaniferous magnetite from Maclntyre Development,Tahawus, N. Y., was accomplished by an oxidizing roast with Na2O3-NaCI addition. Process description is given for leaching of roasted ore and precipitation of V2O5 and Cr2O8 from leach liquor. THE exploration and development of the Mac-Intyre orebody at Tahawus, N. Y., by the National Lead Co. provided a source of vanadium. Analyses of various composite sections of the drill cores of the MacIntyre orebody were made to establish whether or not the vanadium was constant throughout. Ten drill cores were sampled as 50 ft sections, crushed, and a portion magnetically concentrated. The head and concentrate were analyzed for total iron and vanadium. The results on the concentrates indicated that the vanadium is associated with the magnetite and maintains a close ratio to the iron content. The nominal ratio of 1:25:140 of V: TiO2:Fe was found to exist in the concentrates. Typical value for the vanadium in the magnetite both from laboratory concentration and mill production is 0.4 pct. The recovery of vanadium from the magnetite was investigated in 1942 to 1943. The research program encompassed both laboratory and pilot-plant work on sufficient scale to provide adequate data to establish the feasibility of a full scale plant. The recovery of vanadium from various ores has been reported in the literature and has been the subject of many patents. The literature dealing with recovery from titaniferous ore by roasting is quite limited. Roasting with alkaline sodium chloride, sodium chloride or alkaline earth chlorides, and sodium acid sulphate have been claimed in various processes as effective means.1-8 The reduction of the ore, followed by acid leaching, was another method proposed.'-' "he use of various pyrometallurgical processes for recovery of vanadium in the metal or in the slag has also been extensively investigated, but the results had little application to the problem."-" The separation of vanadium values from subsequent leach liquors and vanadium-bearing solution has been the subject of a considerable number of papers and patents. The most practical is by hydrolysis at a pH of 2 to 3 by acidifying a slightly alkaline solution. Data on solubility of V²O5 and V2O4 in water and in dilute sulphuric acid indicated a solubility of 10 g per liter in water.'" Laboratory Results Magnetite Analysis: Adequate stock of magnetite was provided so that the laboratory and pilot-plant operation was on ore representative of the mill production. The ore was analyzed chemically and examined by petrographic methods to ascertain whether the vanadium was present in combined state or as an interstitial component between grain boundaries. No evidence was obtained which would indicate that the vanadium was in a free state as coulsonite.15 The analysis of the ore was as follows: Fe²O³, 47.4 pct; FeO, 29.1; TiO,, 10.1; V, 0.40; and Cr, 0.2. The screen analysis of the ore on the as-received basis was: -20 +30 mesh, 28.8 pct; —30 +40, 18.9; -40 +50, 9.7; -50 +60, 15.1; -60 4-100, 5.9; -100 + 200, 11.2; -200 +325, 3.7; and -325, 7.2. Roasting Conditions: The prior practice indicated that a chloridizing roast with or without an alkaline salt had been effective on other titaniferous magnetites. On this basis roasts with additions of sodium chloride, sodium carbonate and mixtures thereof were investigated varying the roasting temperature between 800" and 1100°C. Since the ore had shown no segregation or concentration of vanadium, the influence of particle size on the freeing of vanadium by the reagents during roasting was determined. The initial work was on silica trays in an electric resistance furnace with occasional rabbling of the charge. Subsequently, the roasting was carried out in a small Herreshoff furnace to establish the influence of products of combustion on the recovery of the vanadium. The laboratory tests showed that this ore required an alkaline chloridizing roast, in conjunction with a reduction in particle size to less than 200 mesh. When roasted in air at 900 °C with 5 pct NaCl and 10 pct Na2CO³, over 80 pct recovery of the vanadium was attained as a water-soluble salt. The presence of alkaline earth elements gave detrimental effects and care had to be exercised to avoid any contamination of the ore or roast product by such materials. The solubilization of vanadium under the various conditions is given in a series of curves in Figs. 1 to

Jan 1, 1952

By H. J. Tschirner, L. P. Davidson, R. K. Carpenter

HE electrolytic zinc plant of the American Zinc Co. of Illinois, at Monsanto, was expanded in 1943 to a capacity of 100 tons of slab zinc daily. This capacity was not attained because of inability of the leaching plant to deliver an adequate amount of solution for electrolysis. Changing the leaching method so that the acid was added to the roasted zinc material reversed the usual procedure and made it possible to attain the desired capacity. The conditions which prevented satisfactory work before this change and the difficulties which arose in reversing the usual leaching procedure are described. The "reverse" leach operation as now practiced is carried out as follows: All the calcine to be leached is fed continuously to a slurry mixing tank. About one third of the acid to be used is fed to the tank with the calcine. The slurry is discharged continuously to a Dorr duplex classifier in closed circuit with a Hardinge mill. The classifier overflow is pumped to any of six leaching tanks where the leach is completed. A finished leach is discharged through Allen-Sherman-Hoff pumps to Dorr thickeners, from which the overflow goes to the zinc dust purification and the underflow to vacuum filters. This change in leaching procedure from the usual one of adding calcine to a large amount of acid made it possible to provide an adequate amount of purified solution to the electrolyzing division and at the same time filter and dry all the residue produced. Operating savings in reagents and better metallurgical recoveries were also important benefits. The original flowsheet of the leaching plant provided leaching, sedimentation of the insoluble residue, and purification of the neutral zinc sulphate solution with zinc dust. The thickened residue was filtered and washed. The purification cake of excess zinc dust, precipitated copper and cadmium, and any insoluble residue was filtered off on plate-and-frame duplex classifier. Settlement in the thickeners was inadequate and the suspended solids in the thickener overflow gave rise to filtration difficulties after the zinc dust purification. Further, the filtration and washing of the leach residue was poor, and it became necessary to pump a large amount of unwashed or poorly washed residue to storage ponds outside the plant building. Two causes of the poor settling and filtration were determined: Soluble silica and ferrous iron in the calcine treated. The latter was a result of poor roasting and with more experience ceased to be a major problem. The silica was a normal constituent of the feed and the working out of the problem became a matter of controlling its solubility. The obvious method to render the silica insoluble was by intensive roasting. This, however, met with total failure as such roasting resulted in silicates, probably zinc, soluble in the 13 pct acid used for leaching. Attempts were made to coagulate the fine gelatinous slime with addition agents. Glue, lime, starch, beef-blood serum and others were tried without success. All the suggested tried-and-tested means of operating the thickeners gave no consistently good results. Variations in leaching time, in addition of calcine to the leaching tanks, "conditioning" of the pulp by prolonged agitation, immediate discharge of the leach upon completion to avoid breaking up flocs were all tried and given up as ineffective. Byron Marquis, of Singmaster and Breyer, worked with the plant staff on a beaker scale until a leaching procedure was developed which gave consistent results and a promise of overcoming the difficulties which had plagued the plant operation. It was suggested that the difference in solubility of silicates and zinc oxide in sulphuric acid could be made use of in a leaching method where the acidity was controlled carefully. Such control is possible when acid is added to a slurry of calcine. This process reverses the normal procedure of adding calcine to a vessel of acid, hence the term "reverse leach" was applied. In this way, the overall acid concentration can be kept very low. In the tests made, it did not exceed 0.05 g per liter free sulphuric acid. Numerous advantages were realized when no silicates were taken into solution and later precipitated as a bulky gel. The gel had made reasonable thickening and filtration of the leach pulp and practical drying of the residue impossible. When the gel was eliminated, thickening rates were increased as much as five times. The volume of residue after thickening represented about 10 pct of the total leach pulp and had been as high as 95 pct when the gel was present. The thickened pulp was filterable and the filtered cake was dried readily after washing. The zinc extraction from the calcine was slightly lower. This was more than compensated for by the increase in zinc recovered in solution from zinc which had been trapped in the gelatinous residue. The amount of copper recovered was lower. However, the amounts of other impurities, such as arsenic, antimony, and germanium, taken into solution were lower. This was particularly true of antimony. Since the inception of reverse leaching, no concentrates have failed to yield solutions free of antimony even when present in the calcine to the extent of 0.2 to 0.3 pct. Oxidation of ferrous iron is a problem of reverse leaching. Ferrous hydrate does not precipitate at pH 5.3 to 5.4 where a leach is finished. The usual oxida-

Jan 1, 1952

By Werner Schwartz, Wolfgang Haase

Lead sulfide concentrates, which may include other lead concentrates, are sintered on an up-draught sintering machine without the addition of any diluting agents or fluxes. Subsequently they are melted in an oil- or gas-fired rotary furnace. The sintering and melting processes are based upon the following roast-reaction: PbS + 2 PbO = 3 Pb + SO, PbS + PbSO, =2 Pb + 2 SO, For obtaining a lead bullion free from sulfur, the sintering process is carried out in such a way that the sinter product contains a small amount of excess oxygen above that to react with the sulfides. At the end of the melting process, when the reactions are finished, the remaining small amount of oxide residues is reduced with coal to which a certain percentage of soda ash (about 1 pct of the lead bullion) is added. For the lead smelting process described neither coke nor fluxes—except soda ash—are required. This process is being utilized by a European smelter successfully and with a high lead recovery. The consumption figures for the smelting of 100 tons per day of lead concentrates are indicated. The lead content of the lead concentrates from modern ore dressing plants ranges from 65 pct to above 80 pct. In most lead smelters of the world these concentrates are smelted in a blast furnace. For blast-furnace smelting the concentrates have to be desulfurized and agglomerated by sintering. A requirement for the perfect operation of a down-draught sintering machine and of a blast furnace is a maximum lead content in the feed of 40 to 45 pct. For this reason, some lead concentrates have to be diluted by adding return slags, limestone, and possibly iron oxide and sand. As an example, 100 tons of lead concentrate with 72 pct Pb would contain 13.5 tons of gangue (including the zinc). To produce a perfect sinter with 42 pct Pb it would be necessary to add 70 tons of flux and return slag, more than five times the original weight of the gangue, to the sinter mix and blast-furnace charge. A correspondingly large amount of coke would be required in order that all of these materials reach the heat of formation and the melting temperatures of the slag (1200" to 1400°C) inside the blast furnace. The roast-reaction process presents a possibility for lead recovery without dilution of the concentrates. In this process the concentrate mixed with coal is placed upon a Newnam-hearth and air is blown through nozzles into the heated mix. AS a result metalllic lead and a relatively great amount of so-called .'Grey Slag" with a lead content of 25 to 35 pct are formed. The slag is sintered to eliminate sulfur and, after addition of the requisite fluxes, treatt:d in a blast furnace. Owing to the poor recovery of lead from the hearths and to the unavoidable heavy hand-work plus the risk of poisoning this process is utilized in very few 112ad smelters today. Since in mxny countries of the world coke is expensive and difficult to obtain, it appeared feasible to use the principle of the roast-reaction by modern sintering and melting methods with recovery of the lead in electric, or oil, gas, or coal-fired furnaces. Two processes are utilized on an industrial scale: A) Lead smelting in the electric furnace of the Bolidens Gruv A/B in Sweden, as described by S. J. Walldcn, N. E. Lindvall, K.G. Gorling, and S. Lundquist. B) The self-fluxing lead smelting of Lurgi Gesell-schaft fiir Chemie und Huttenwesen m.b. H., Frankfurt a M, Germany, which is described in this paper. In the Boliden process referred to above the sinter mix is pelletized by enveloping return fines with layers of flue dust, limestone powder, and dried galena concentrate. The roasting and agglomeration are carried out on a down-draught machine, and a slight excess of sulfur is left in the sinter product. During the smelting in the electric furnance the roast-reactions occur and a slag poor in lead and a sulfur bearing lead are formed. This latter is subsequently oxidized in a converter to obtain lead bullion and dross. The Lurgi-process achieves the maximum possible extent of the roasting reaction on the sintering machine. The wet flotation concentrates are blended with return fines (lead content 70 to 80 pet), any existing flue dusts and lead slimes—but without the

Jan 1, 1962

By Karl F. Peterson, H. K. Najarian, Robert E. Lund

PRIMARY products of the Josephtown smelter are zinc metal of various grades, lead-free zinc oxide pigments, cadmium metal, and sulphuric acid. Zinc concentrates of domestic and foreign origin are blended and desulphurized at the roaster plant. The equipment includes five, 12-hearth Herreshoff roasters and two modified Trail-type suspension roasters. The sulphur dioxide containing gases from the roasting operation are diverted to a four-unit contact acid plant for the manufacture of sulphuric acid. The roasted calcines are agglomerated by sintering on Dwight-Lloyd-type sintering machines; the sinter is crushed and sized within required limits; and the sized sinter is smelted in vertical shaft-type electro-thermic furnaces. Of the 13 electrothermic furnaces of various sizes now in operation, four are designed to produce American process zinc oxidc of various specifications; and the remaining nine furnaces are equipped with vacuum-type condensers and produce zinc metal. Papers describing the general smelting practice at Josephtown have been published by AIME. Since both High Grade zinc metal and lead-free zinc oxide pigments are produced direct from the electrothermic furnaces without need for subsequent refining, the elimination of impurities such as lead and cadmium has to be accomplished during roasting and sintering operations. To effect the producing of both High Grade and Prime Western zinc products, the roasting and sintering operations are on two separate circuits. A High Grade circuit produces finished sized sinter low in lead, cadmium, etc., for the High Grade furnaces; and the Prime Western circuit produces finished sinter destined for the furnaces producing Prime Western metal. Sintering at the Josephtown smelter differs in many important respects from the sintering practice in smelters operating horizontal retort zinc furnaces. Requirements of the electrothermic smelting furnaces define the physical characteristics of the sinter, while the chemical composition of the sinter is controlled according to the grade of metal and oxide to be made as final products. Three principal objectives in the sintering process at Josephtown smelter are: 1. To transform the zinc calcine from the roasting operations into a hard, yet porous agglomerate that will not crumble in the smelting furnace. 2. Crushing and sizing of the sinter to obtain a proper screen analysis which is normally —% in. down to +1/4 in. particle size. 3. To eliminate, particularly in the High Grade circuit, as much of the impurities such as sulphur, lead, and cadmium as possible. The sintering plant as originally built in 1930 was equipped with three standard 42 in. x 44 ft Dwight-Lloyd sintering machines. Each machine was equipped with a 15x60 in. sintering corporation fan driven by 150 hp, 900 rpm synchronous motor through a magnetic clutch and capable of delivering 30,000 cfm of air at 15 in. of water and 150°F. Each sintering machine was driven by 7½ hp dc motor with controllers for varying the speed of the machine from 8 to 32 in. per min. The pallets were cast iron and the grates of the herringbone type. The charge was mixed in a 4 ft diam x 8 ft Stehli pugmill and transported by belt conveyor, elevator and tripper conveyor to a small bin over each machine. Shortly after the start of operations the following changes were found necessary: 1. The herringbone grates which plugged very quickly and were difficult to keep clean were replaced by straight, narrow cast-iron grate bars running at right angles to the travel of the pallets. These grate bars are held in place by a center bar extending across the pallet on the 24 in. dimension and by removable retaining plates which form the sides of the pallets. 2. Mechanical grate knockers were developed in conjunction with new grate bars for continuously and automatically cleaning the grates. 3. As the cast-iron pallets cracked, they were replaced with cast-steel pallets. In 1938, the capacity of the sinter plant was increased with the installation of two 42 in. x 22 ft machines which were brought from the company's Herculaneum lead smelter. With a circulating load of some 250 to 300 pct, production of finished sinter on the 42 in. x 44 ft machines at this time amounted to about three tons of sized sinter per machine hour. In 1945, one of the 42 in. x 22 ft machines was replaced by a 60 in. x 44 ft machine of our own design. In 1948, as part of the plant-wide expansion program, the sinter plant not only was expanded but also divided into two separate plants; namely, Prime Western and High Grade circuits. The sinter destined for furnaces producing Prime Western zinc metal is made in a new plant comprising two 60 in. x 44 ft Dwight-Lloyd-type sintering machines, each having a 45,000 cfm Sturtevant fan at 18 in. water static pressure and served by an 8 ft diam x 12 ft long rotary charge pclletizer and auxiliary crushing and sizing equipment. The sinter destined for furnaces producing High Grade zinc metal and zinc oxide pigments is produced in the old sinter plant which was expanded to accommodate four of the 60 in. x 44 ft sintering machines, replacing the old sintering units. In the High Grade sinter circuit, two units of the 60 in. x 44 ft machines are used as preliminary soft sinter machines; and the remaining two units of the 60 in. x 44 ft machines are used to make finished hard sinter. Purification Theory Partial elimination of lead and cadmium in the sintering of zinc ores is common knowledge. However, by some manipulation and by taking advantage of the double circuit, it is possible to make zinc sinter which is nearly free of contaminators. Lead

Jan 1, 1952

By E. T. Turkdogan, P. Grieveson

Molten silver is equilibrated with silicon nitride at 1400°C in nitrogen + hydrogen gas mixtures, and from the solubility data the activity coefficient of silicon is found to be 1.76 at silicon concentrations below 1 pct. Using this value, and that available from the silicon cmbide solubility measurements, together with those derived from the phase equilibrium diagvam, the activities of silver and silicon are estimated for the entire composition range. The main feature of the activity data is that there is a pronounced positive deviation from ideality. The activity of silver in molten silver containing up to 5 pct Si was determined by Schadel, Derge, and Birchenall1 by measuring the vapor pressure of pure silver and of the alloy over a temperature range of 850º to 1050°C. They deduced from their results that there is a positive deviation from Raoult's law and that the activity coefficient of silver increases with decreasing temperature. However, as pointed out by Kubaschewski and Catterall,2 their activity coefficients are much too high, giving silver activities greater than unity. At a later date McCabe and Birchenal13 showed that the previous vapor pressure data on silver4 were high by a factor of about 1.3; presumably a similar error must have occurred with the vapor pressure measurements on the Ag-Si alloys. The activities of silicon and silver calculated by tager' from the phase diagram and by Gibbs-Duhem integration, respectively, show a positive deviation from Raoult's law for silicon activity and positive and negative deviations for the silver activity. According to these computations, at infinite dilution of silicon ygi = 1.12 at 1420°C. d'Entremont and chipman6 measured the solubility of silicon carbide in molten silver at unit carbon activity; the equilibrium silicon content is found to be Nsi = 0.017 ± 0.002 atom fraction for 1420°C. Using the data of Grieveson and Alcock7 for the free energy of formation of silicon carbide from pure silicon and graphite, the activity of silicon for unit activity of carbon and of silicon carbide is asi = 0.0308 at 1420°c; therefore for the above solubility data on silver, YSi = 1.81, which is somewhat higher than that given by Hager. Use is often made of silver alloys in the measurements of activities of solutes in metals where silver has a very low solubility; in fact, Ag-Si and Ag-A1 alloys have been used in the past for such purposes. In an attempt to gain more thermodynamic data on molten Ag-Si alloys, measurements have been made in the present study on the solubility of silicon nitride in molten silver; the results on these solubilities are given in this paper together with a detailed discussion of activities of silver and silicon. SOLUBILITY OF SILICON NITRIDE The standard free energy of formation of silicon nitride is known with a reasonably high degree of accuracy. According to the measurements made by Hincke and Brantle8 and by Pehlke and Elliott,' the following are the free energy data for the standard states of solid Si3N4, liquid silicon, and Nz at 1 atm pressure:

Jan 1, 1963