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By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

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

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

Jan 1, 1963

By R. Schuhmann Jr., P. J. Ensio

As a first step in a study of the physical chemistry of copper-smelting slags, experimental measurements were made of the oxygen pressure of simple iron-silicate slags in equilibrium with solid iron. The experiments consisted in bubbling CO2-CO mixtures through the slags in iron crucibles and in finding the equilibrium ratios of CO2 to CO. From the data, activities and partial molal heats of solution FeO and SiO2 in the slags were calculated. THE ternary system FeO-Fe,O,-SiO, is the simplest system which can represent adequately the important chemical properties of the slags formed in matte smelting and converting. Accordingly, the experimental study of slags in this system was started as the first step in a general research program on the thermodynamics of copper smelting. A recent paper by one of the authors' outlines this general research program and shows in some detail how information on thermodynamic properties of iron-silicate slags, especially information on oxygen activities, is essential to a full understanding of the chemistry of copper smelting. The FeO-Fe,O,-SiO, system also is the basis of slags produced in other processes, such as acid steelmak-ing processes, and is important in relation to the behavior of silicious refractories. In addition, data on the physicochemical properties of iron-silicate slags should contribute to a general understanding of the nature of slags, since at present such data for all kinds of slags are relatively meager. The principal quantitative information already available on iron-silicate slags consists in Bowen and Schairer's constitution diagram for slags in equilibrium with metallic iron,' Darken and Gurry's complete and precise thermodynamic study of the Fe-0 system,",' and Darken's study of the phase equilibria in the Fe-Si-o system. From the results of this previous work, it was clear that a complete thermodynamic study of ternary iron-silicate melts was a major undertaking which would have to be broken down into parts, including the working out of the ternary equilibrium diagram as well as extensive activity measurements on slags. The experimental measurement of oxygen activity, using CO-CO, and other gas mixtures as yardsticks of oxygen activity, was the basis of Darken and Gurry's study of the Fe-0 system. From the experimental measurements of oxygen activities over a large range of temperatures and compositions, they were able to calculate the activities of other species such as Fe, FeO, Fe,O,, etc., and also the other important thermodynamic properties in the Fe-0 system. At the start of the present investigation, it appeared that the same approach would be fruitful for the study of iron-silicate melts. Also, the experimental measurement of oxygen activities seemed particularly attractive because oxygen activity itself is a quantitative measure of oxidizing or reducing power, which is an important variable in copper-smelting slags. The slag compositions in equilibrium with yFe appeared most suitable for the first investigation of this kind, for the following reasons: 1—Good constitution data2 were available. 2—An iron crucible could be used, thus affording a simple solution to the refractory problem without introducing contarnination. 3—With Fe activity fixed, at unity with respect to a standard state of solid Fe, measurements of 0 activity could be followed by simple calculations of activities of FeO and other Fe-0 complexes and of SiO,. 4—This starting point afforded several possibilities for cross-checking with previous work,

Jan 1, 1952

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

By R. W. Mancantelli, J. R. Woodward

IN 1947 a large low grade deposit of uranium was located in the northwest corner of Saskatchewan, in the Beaverlodge property of Eldorado Mining & Refining Ltd. Most of the values occur as thin seams and as coatings on other minerals, and the ore, which is light and friable, is not amenable to the usual gravity methods of concentration. The acid leaching process developed to retreat the company's Port Radium tailings was also impractical, as the percentage of carbonates is high and the percentage of sulphides relatively low. Construction of the mill building and installation of equipment, both scheduled for 1952, awaited selection of a satisfactory ore dressing process on or before Oct. 1, 1951. An extensive research program on dressing of ores from the Ace mine therefore was undertaken by the Mines Branch in Ottawa, a research team at the University of British Columbia, and an ore dressing group at the company's Port Hope refinery. Pilot plant operations were conducted at the Ottawa plant of Sherritt Gordon Mines Ltd. under the general direction of C. S. Parsons, consultant on metallurgy and ore dressing for Eldorado. In mid-September, having compared results of the several research programs, Dr. Parsons recommended a process employing a carbonate or basic leach. He reported that, while the chemistry of the process had been proved, engineering of the flowsheet was incomplete, and he suggested that under normal conditions further pilot plant work at the Ace mine might be profitable. However, since this would involve a delay of 12 to 18 months in bringing the property into operation, he recommended that design of the concentrator proceed immediately. Concentrator capacity was determined by two considerations: 1) the amount of ore then available and 2) the expectation that continued improvements would be made in the ore dressing process as a result of the intensive research being carried out by the Mines Branch of the Department of Mines and Technical Surveys. As these improvements could affect both the chemistry and the en-

Jan 1, 1956

By A. W. Schlechten, R. F. Doelling

Parkes' process crusts were vacuum distilled using a shortened Pidgeon retort. Zinc was effectively removed below 800°C and recovered as a zinc sheet easily stripped from the furnace liner. Lead dasdistillationazinc required about 950°C and the resulting lead condensate tillationtended to stick to the thin metal liner. Final purity of residue is limited only by nonvolatile metals such as copper. THE successful commercial application of vacuum distillation for the removal of zinc from lead, as described by W. T. Isbell,' raises the question of whether or not a similar method can be used for other metal separations. Preliminary laboratory experiments on the vacuum distillation of Parkes' crusts by one of the authors' gave such encouraging results that it was decided to make a series of tests with large scale equipment to determine the results that might be expected in plant operation. The pilot-plant test results are reported in this paper. The great advantages of vacuum dezincing are its simplicity, the relatively low temperature of operation, and the fact that the zinc is recovered in the metallic state ready for use again in the desilveriza-tion of lead bullion. These same advantages and others would be realized from the vacuum distillation of the zinc-lead-silver crusts made in the Parkes' process. Zinc readily will distill over at temperatures of 800" to 900 °C as contrasted with the 1200°C or more used in the Faber du Faur furnace. Furthermore, the recovery of zinc as metal is practically perfect since there is no loss by oxidation or fuming. If the vacuum distillation is continued and hastened by raising the temperature to around 1000°C, the lead will distill over at an appreciable rate and deposit in a warmer zone of the condenser. This lead will contain a small amount of silver, but it can be returned to the desilverizing kettles and there is not the chance of loss that there is in disposing of the rich litharge from cupelling. The lower temperatures required will mean a saving of fuel and less wear on the equipment. One further point is that the vacuum distillation could be run on a small scale practically continuously, so as to avoid the accumulation of large amounts of silver-rich material and the need of assembling a large crew for special cupellation runs. It should be pointed out here that the final purity of the silver residue will depend on the copper or iron content of the crusts, as these and other metals with low vapor pressure will not be eliminated. The idea of treating the silver-zinc-lead crusts from the desilverization of lead bullion by vacuum distillation is not a new one, but such experiments have not been reported, as far as can be determined. In 1912, T. Turner presented a paper3 before the Institute of Metals on the vacuum distillation of brass, and a member of the audience suggested that he try his method on Parkes' crusts. In 1935, W. J. Kroll, noted for his discovery of debismuthiz-ing lead by calcium additions, published a paper' on vacuum distillation of metals and pointed out possible applications in the lead industry. Principles of Separation The successful separation of two or more metals by distillation depends upon an appreciable difference in the effective vapor pressures of the metals in the alloy to be treated. The vapor pressures of the common metals have been determined with considerable accuracy; for example, at 800°C the vapor pressures of the individual metals which are of particular interest in this paper are about .as follows: Zn, 241 mm; Pb, 0.0553 mm; and Ag, 0.0000276 mm. Unfortunately,, data are not available on the activities of the components in the ternary system Zn-Pb-Ag, but it can be estimated that on the basis of the vapor pressures of the individual metals a good separation can be made by distillation. The preliminary laboratory tests previously mentioned' supported this assumption. The pilot-plant size vacuum distilling furnace is shown in Fig. 1. It consisted of an abbreviated Pidgeon retort, 5 ft long with an ID of 8 in., heated by six silicon carbide elements placed symmetrically

Jan 1, 1952

By F. Habashi

"A short account will be presented on the extraction of rare earths from monazite sand, bastnasite ore, and phosphate rock of igneous origin. This includes mineral beneficiation, leaching methods, fractional crystallization [of historical interest], ion exchange, solvent extraction, precipitation from solution, and reduction to metals. INTRODUCTIONOriginally, the term rare earths was only used for the oxides, R2O3, which are similar to one other in their chemical and physical properties and are therefore difficult to separate. Within the rare earth group, the elements scandium, yttrium, and lanthanum differ in their atomic structure from the elements cerium to lutetium (the lanthanides, Ln). Scandium occupies a special position with respect to this classification and its other properties, and therefore does not belong to either of these groups. The rare earth elements always occur in nature in association with each other. The isolation of groups of rare earth elements or of individual elements requires costly separation and fractionation processes owing to the great similarity of the chemical and physical properties of their compounds, which explains why the history of their discovery has extended over such a long period.The word “rare”, when used to describe this group of elements, originates from the fact it was thought that these elements could only be isolated from very rare minerals. Considering their abundance in the Earth’s crust, the term rare is now inappropriate. These elements are lithophilic and are therefore concentrated in oxidic compounds such as carbonates, silicates, titano-tantalo-niobates, and phosphates.The abundance of the rare earth elements taken together is quite considerable. Cerium, the most common rare earth, is more abundant than cobalt. Yttrium is more abundant than lead, whereas Lu and Tm are as abundant as Sb, Hg, Bi, and Ag. For all practical purposes promethium does not occur in nature. It forms only in nuclear reactors."

Jan 1, 2012

By C. D. Anderson

A variety of processing technologies exist for recovery from both primary and secondary sources of rhenium. Currently, there are no known primary rhenium deposits, thus, the method in which primary rhenium is produced is dependent on the commodity of which it is a byproduct, e.g., copper, molybdenum, uranium, etc. In addition, focus on the recovery of rhenium from secondary sources, such as alloy scraps and catalysts, is continually growing. This paper presents a review of both primary and secondary processing technologies for the recovery of rhenium. Key Words: Rhenium, Ammonium Perrhenate, Extractive Metallurgy

Feb 27, 2013

By D. R. Spink

An historical background is presented to provide a basis for the lack of normally expected developmental effort over the first 20-25 years of viable zirconium production operations. This is followed by a description of developing technology, which is the result of years of research and piloting effort directed to the development of a more economical method to produce high-grade metallic zirconium. It is predicted that many of the process improvements described will have a significant impact on future zirconium production methods and consequently on future prices and markets.

Jan 1, 1977

By J. F. Mitchell, R. Bainbridge, E. A. Melvin

IN the fall of 1953, The Consolidated Mining and Smelting Co. of Canada Ltd. put into operation a completely new and modern plant for sintering the rather complex assortment of materials which comprise the feed to the Lead Smelter at Trail, British Columbia. This Lead Smelter is one section of an integrated metallurgical plant producing lead, zinc, silver, gold, cadmium and other metals. Since most of the incoming lead concentrate contains appreci- able zinc values, and most of the zinc concentrate similarly contains appreciable lead values, the cross-routing of residues or tails from the respective lead and zinc plants offers obvious advantages in recovery of metals, and has been practiced for many years. A disparity has existed, however, between the output of zinc plant residue and the capacity of the Lead Smelter to treat it, with the result that over the years a stock-pile of residue had been accumulating, and by the end of World War II had reached the formidable total of half a million tons. To treat this stock-pile, in addition to all current zinc plant residues and, of course, the regular quota of lead concentrates, became a prime objective of the Lead Smelter following World War 11. As zinc plant residue plays an important part in the operations to be discussed in this paper, some consideration of its

Jan 1, 1958

By Joseph B. Story, John T. Clarke

A modification, of the Kelvin bridge using an inductor was used to measure the conductivities of molten sodium chloride, calcium chloride, and mixtures thereof. A capillary-type four-lead fused quartz dipping cell was constructed. The effect of a small amount of potassium chloride on the conductivity of the melt was determined. IN the electrowinning of sodium and chlorine from sodium chloride in Downs cells, calcium chloride is added to the sodium chloride in an approximately equimolar amount to permit cell operation at a lower temperature. This lower temperature improves current efficiency and ease of operation, but decreases voltage efficiency by decreasing the electrical conductivity of the melt. A knowledge of the electrical conductivity of the Downs cell melt is necessary to the understanding of Downs cell operation, for the IR voltage drop across the melt is responsible for a significant part of the electrical power consumed by the cell. The work of previous investigators on fused sodium chloride-calcium chloride mixtures was reviewed from the standpoint of consistency with the results of others on the conductivities of the pure constituents. The electrical conductivity of pure fused sodium chloride has been established with accuracy by Van Artsdalen and Yaffe,1 by Edwards, Taylor, Russell, and Maranville,2 and by Lee and Pearson.3 It has also been studied by a number of other investigators.4-13 The best values for calcium chloride are believed to be those of Lee and Pearson,3 since the sodium chloride and potassium chloride conductivity values given by them check the best literature values. A number of other investigators have also reported values for calcium chloride.'-"."' Electrical conductivity data for fused sodium chloride-calcium chloride mixtures have been reported by Sandonnini,12 Vereshchetina and Luz-hnaya,18 Ryschkewitsch,11 Barzakovskii,5 and Alaby-shev and Kulakovskaya.15 Sandonnini reports no data at temperatures lower than 850°C. The conductivity values reported by Vereshchetina and Luz-hnaya, by Ryschkewitsch, and by Barzakovskii for pure sodium chloride and for pure calcium chlor- ide vary somewhat from the literature values believed to be best and the sodium chloride-calcium mixture data of these authors and of Alabyshev and Kulakovskaya (who give no data for the pure compounds) show significant variations. In view of these facts, it seemed that an investigation of the electrical conductivities of fused sodium chloride-calcium mixtures would be worthwhile. Apparatus Bridge System—The bridge used,in this investigation is diagrammed in Fig. 1. In general, the elaborations of this bridge over the simple Wheatstone bridge were for the purposes of a) eliminating lead resistances or making them accurately measurable, and b) eliminating major capacitative and inductive effects or balancing them against each other. Lead resistances in the lower arms of the bridge were kept as low as possible by making the leads short and of low resistance wire. This could not be done in the cell arm of the bridge because of the remoteness of the cell from the other bridge components and because of the high-resistance nickel or chrome1 wires used in the cell. Since maximum sensitivity is attained when the resistances of the four arms of the bridge are equal, 50-O resistors were used in the lower arms of the bridge when fused salt conductivities were being measured, and 1000-O resistors were used when the cell was being calibrated with normal aqueous KCl solution. The cell resistance was of the order of 50 ohms with fused salts and of the order of 1000 ohms with normal aqueous KC1 solution. The resistors used were non-inductive and accurate to 50.05 pct (General Radio Co. Types 500-C and 500-H). The lead resistance between point A in the cell and point E at the measuring resistor was eliminated by using the kelvin bridge principle; that is, the voltape drop across the lead from point A to point E was divided between the cell arm of the bridge and the measuring arm of the bridge in proporation to the resistaxes in the lower arms of the bridge.

Jan 1, 1958

By L. J. Howell, R. C. Sommer, H. H. Kellogg

WORK described herein was undertaken with the aim of determining some of the physical-chemical properties of electrolytes suitable for the electrodeposition of pure zirconium metal. In this paper the phase diagram, vapor pressure, and activities in the melt are considered. In a companion paper,' the electrolytic conductivity of some of these melts is reported. The melts studied were mixtures of NaCl and/or KC1 with ZrC1,. Chloride melts were chosen for study because 1) if the electrolyte is to be useful for industrial electrodeposition of zirconium, the chlorides will be preferred to the relatively costly bromides and iodides; 2) fluoride melts were being studied in another laboratory (Horizons Inc., Cleveland); and 3) melts containing oxygen, in any form, are unsuitable for preparation of pure zirconium, because of the great affinity of this metal for oxygen. Unlike electrodeposition from aqueous solution, the fundamental behavior of fused-salt electrolysis is poorly understood. In most cases, such basic electrochemical information as the phase diagram of the melt system, activities in the melt, conductivity, the nature of the current-carrying ions, the equilibrium electrode potentials, and the overvoltage behavior of the electrodes is unknown to the researcher who would develop a new electrodeposition process employing a fused salt. This research project was designed to supply information about some of these basic physical-chemical properties so that an intelligent choice of electrolyte for electrodeposition studies could be made. Experimental The experimental difficulties-encountered in this work result from the properties of zirconium metal and ZrC1,. ZrC1, is a solid which sublimes at 334°C. It is rapidly hydrolyzed by moist air to HC1, ZrOCl,, and ZrO,. Unusual precautions were exercised in this work to prevent hydrolysis of ZrC1, and rigidly to exclude oxygen, nitrogen, hydrogen, and carbon from the melts under study. These elements are known to react with and contaminate zirconium metal. All melts were studied in vacuum systems, i.e., in the presence of ZrC1, vapor only. Transfer of ZrC1, to or from the melts was accomplished entirely by vacuum sublimation. In this way, neither the melts nor the ingredients thereof were permitted to

Jan 1, 1958

By Ramin Motamed, Joseph A. W. Toth

Evaluation of the capacity of large-diameter drilled shafts using current load test methods present challenges when considering the magnitude of loads required to fully mobilize their capacities. Often, these full scale tests do not fully mobilize the capacity through side resistance. Therefore, the need for innovative solutions to extrapolate side resistance and interpret nominal capacity are of key interest. In this study, we evaluate three methodologies for extrapolating unit side resistance based on bi-directional load test data. Fellenius (2001) presented these methods for interpretation of pile capacity using static load tests. Our interpretations are based on the evaluation of 116 load tests. Unit side resistance was calculated and reviewed for each load test and categorized using three criteria of mobilization; (A) full, (B) partial and (C) linear. This study specifically focuses on load tests that showed fully mobilized unit side resistance behavior (Criteria A). The three methodologies were applied assuming Criteria (A) load tests were mobilized to 50% of their measured values. Subsequent comparisons of each extrapolation were then compared against the full measured values for each test and generally showed good agreement. INTRODUCTION It is widely accepted that conducting load tests such as standard top-down tests or bi-directional (i.e. O- cell) tests can help designers understand load-settlement behavior and the nominal resistance of drilled shaft foundations. These load testing methods provide the advantage of confirming design assumptions as well as improving the reliability of the foundation design. The potential cost savings from the application of these methods for mid to large size projects is self-evident. For example, in a recent project in Northern Nevada, an O-cell test on a 6.9 ft diameter, 114.8 ft length drilled shaft imposed an initial cost of $125k to the project, resulting in a 15% reduction on the total foundation cost; equivalent to $1.3 million in overall savings (Pease, 2014). However, the costs of implementing such methods on smaller projects can be prohibitively expensive (Hagerty et al, 2016). Despite the clear advantages of drilled shaft load testing, the current practice is not without limitations. Performing load tests on large-diameter drilled shafts with high capacities is a challenge considering the significant loads required to fully mobilize the capacity of such foundations. In some cases, the feasibility of these tests is impractical because the associated initial cost is not guaranteed to outweigh the final savings. As a result, large scale load tests are sometimes ruled out from the design phase of projects. Furthermore, in the majority of load tests the magnitude of loads applied are specifically selected to not approach failure, so the shafts can be used in the future foundation system (i.e. production shafts). This practice of field testing restricts our knowledge of the true capacity of the drilled shaft at failure; hence the nominal resistance remains unknown.

Jan 1, 2018

By J. Drimmer

The past several decades have seen the rapid expansion of multinational mining companies? exploration and production activities around the globe. This trend has resulted from a number of factors, including increased demand for resources as a result of worldwide economic growth, the diminishment of known and proven reserves, rising commodity prices, technology improvements, and the liberalization of investment regimes in developing countries with significant natural resources. With those opportunities, however, come associated risks and significantly increased legal compliance obligations that may be imposed by various bodies. That includes domestic regulations, as well as foreign civil and criminal laws with extraterritorial reach. A failure to adhere to those laws can have dire consequences, including substantial monetary fines and penalties, severe damage to a company?s reputation, and even jail time for individual company employees.

Jan 1, 2010

By Gabrielle Luana Jimenez

Aparelhos eletroeletrônicos como computadores e televisões são constituídos por telas de cristal líquido, que ao se tornarem obsoletos são classificados como resíduos, e dispostos em aterros sanitários. Entretanto, na composição das telas de cristal líquido há metais de valor agregado, como o índio (In). Com a fundamentação no processo de reciclagem de telas de LCD, este estudo propõe a recuperação e quantificação desse metal que é encontrado na forma de ITO (óxido de índio e estanho). Para tal feito, foram empregadas rotas hidrometalúrgicas, tendo como principal etapa a lixiviação. Como parâmetros de controle, os ensaios de extração sólido-líquido foram realizados em temperaturas que variam de 50 a 80°C. Com isso, foi obtido resultado de extração do índio em cerca de 60% em massa, nas condições de 60°C e após 4 horas de lixiviação.

Aug 17, 2017

By Alexandre Silva Guimarães

A extração por solventes sinérgica dos metais cálcio, magnésio e níquel, presentes em soluções aquosas sulfúricas em níveis de concentração similares aos dos licores industriais HPAL (High Pressure Acid Leaching), foi avaliada neste trabalho empregando-se os extratantes comerciais Cyanex 272 e Cyanex 301. O uso de Cyanex 301 (10%v/v) sozinho não se mostrou eficiente, em decorrência do baixo percentual de extração e da baixa seletividade entre os metais. Quando misturado ao Cyanex 272, porém, observou-se a possibilidade de remoção seletiva de magnésio, deixando cálcio e níquel em solução. A melhor condição operacional foi obtida utilizando-se 5-10%v/v de Cyanex 301 e 20% de Cyanex 272, na faixa de pH entre 5,4-5,7, na qual se extraiu aproximadamente 70-80% de magnésio, 15-35% de cálcio e 10-15% de níquel.

Aug 16, 2017

By Alexandre Silva Guimarães

Investigou-se a extração seletiva de Ca e Mg do licor sulfúrico concentrado de Ni visando sua purificação. Observou-se que a mistura sinérgica dos extratantes D2EHPA + ácido naftênico apresenta maior afinidade na extração de Ca em pH = 5. Comportamento oposto foi verificado pelo extratante Cyanex 272, cuja preferência de extração é pelo Mg para 5 = pH = 6. A cinética de extração de Ca e Mg é rápida atingindo o equilíbrio em menos de 6 minutos. A purificação do licor de Ni requer a utilização de 2 circuitos de extração em operações estagiadas. No primeiro circuito, Ca pode ser removido do licor empregando-se o sistema orgânico D2EHPA (10% v/v) + ácido naftênico (20% v/v). O pH ótimo é 3,5, no qual foram extraídos 72% de Ca (ßCa/Ni = 40) em uma contatação. No segundo circuito, o licor deve ser submetido a uma extração de Mg pelo Cyanex 272 (20% v/v). O pH operacional propício é 5,5 com extração de 66% de Mg (ßMg/Ni = 16, uma contatação). O licor purificado de Ni pode ser encaminhado à etapa de eletrorrecuperação almejando-se a obtenção de Ni metálico.

Oct 30, 2017

Coal has been mined in the central Appalachian coalfields of southern West Virginia, western Virginia, and eastern Kentucky for more than a century. The dwindling reserve base consists in large part of coal that would have been considered unmineable by earlier generations. Nearly every current operation is working on a property where coal has been extracted in the past, from seams either above, below, or both. NIOSH is conducting research aimed at helping mine planners prevent hazardous conditions due to multiple seam interactions. To-date, more than 300 case histories have been collected from underground mines, mainly from central Appalachia. This paper focuses on several of the more challenging situations that have been encountered, including: • Room-and-pillar development 20 ft (6 m) beneath full extraction workings at a depth of 1,000 ft (300m) of cover (Virginia) • Pillar recovery 45 ft above full extraction workings at 900 ft (270 m) of cover (Virginia) • Near-simultaneous room-and-pillar mining with pillar recovery with 40 ft (12 m) of interburden and 1,500-2,000 ft (450-600 m) of cover (Kentucky) • Longwall mining directly beneath main entries in overlying seams (West Virginia) • Some of these operations have been highly successful in overcoming the challenges, others less so. The lessons learned from their experience will help ensure that these and similar difficult reserves can be mined safely.

Coal has been mined in the central Appalachian coalfields of southern West Virginia, western Virginia, and eastern Kentucky for more than a century. The dwindling reserve base consists in large part of coal that would have been considered unmineable by earlier generations. Nearly every current operation is working on a property where coal has been extracted in the past, from seams either above, below, or both. NIOSH is conducting research aimed at helping mine planners prevent hazardous conditions due to multiple seam interactions. To-date, more than 300 case histories have been collected from underground mines, mainly from central Appalachia. This paper focuses on several of the more challenging situations that have been encountered, including: • Room-and-pillar development 20 ft (6 m) beneath full extraction workings at a depth of 1,000 ft (300m) of cover (Virginia) • Pillar recovery 45 ft above full extraction workings at 900 ft (270 m) of cover (Virginia) • Near-simultaneous room-and-pillar mining with pillar recovery with 40 ft (12 m) of interburden and 1,500-2,000 ft (450-600 m) of cover (Kentucky) • Longwall mining directly beneath main entries in overlying seams (West Virginia) • Some of these operations have been highly successful in overcoming the challenges, others less so. The lessons learned from their experience will help ensure that these and similar difficult reserves can be mined safely.

Jan 1, 2006