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By Nicholas J. Grant, Rolf Nordheim, Bill C. Gissen

The system Cb-Re was examined in detail utilizing pure metals, careful melting techniques, and heat treatments. Metallographic and X-my methods were utilized for phase identification. In addition to soli-dus determinations, the composition limits and mode of formation of the intermetallic compounds 0 and X were determined. The binary constitution diagram Cb-Re has been the subject of a number of investigations.'-7 Two intermetallic phases have been described and tentative diagrams have been proposed. It was the aim of this investigation to obtain a complete and more accurate diagram through the use of purer alloys and improved techniques. The diagram worked out by Knapton7 was published after our experiments were concluded. EXPERIMENTAL METHODS The starting materials were Re powder of 99.95 pct purity, supplied by the Chase Brass and Copper Co., and Cb rondelles of 99.6 pct purity, supplied by the Electro Metallurgical Co. Typical analyses are given in Table I. The alloys were prepared from compacted Re powder and Cb rondelles; for critical compositions master alloys were used. The melts varied from 5 to 50 g and were melted nonconsumably in an Heraeus arc furnace, under ti-tanium-gettered laboratory grade argon. It was necessary to invert the buttons and remelt, followed by crushing and further remeltings, the number of which depended on the nature of the fracture of the alloy. The weight of each alloy was carefully checked after each melting operation. It was found that significant weight losses occurred only when loose Re powder was used. These losses amounted to a maximum of 3 wt pct in such instances, but did not occur after the charge was once molten, regardless of the composition. Typical loss of weight after 4 remelts, including crushing, amounted to 0.2 wt pct. Oxygen pickup during successive melting cycles did not appear to be significant, since the weight gain values never exceeded 0.01 wt pct. Control of the composition of the alloys was not too difficult; however, the problem of homogenization was a far greater one. Optimum alloying conditions were finally achieved by a combination of master alloy production and repeated crushing and remelting cycles. The compositions of the alloys utilized to determine the constitution diagram are listed in Table 11. The weight balance method was used ultimately as the sole analytical method, since repeated checks indicated that it was accurate to 0.2 pct, if the weight losses were small. The results were double-checked by a metallographic study of the homogeneity of the samples, since this was presumed to be the more serious factor. Heat treatments at 1200°C or lower were accomplished by sealing the specimens in Vycor tubes, heating in a Globar furnace, followed by air cooling. This was considered to be an adequate quench because of the very low temperatures involved. For temperatures of 1200" to 1900°, alloys were homogenized and heat treated in a tungsten-filament resistance vacuum furnace. From 1900" to 2750" a tantalum-tube resistance furnace was utilized, operating under a vacuum of 105 mm Hg. The temperature measurements up to 1200" were made by means of platinum-platinum 10 pct Rh thermocouples, with an accuracy of 5°C. For temperature measurements greater than 1200°C, optical pyrometers were used. They were calibrated against a standardized instru-

Jan 1, 1962

By P. W. Billwiller

Abstract The Britannia Mining and Smelting Company, Limited, have replaced diamond drills with percussion drills and tungsten: carbide bits for most of their blast hole drilling operations and have thereby reduced ore breaking costs. Two-inch Carset bits .are used, with one-inch hexagonal Atlas Chippewa alloy steel in 3-foot .and 6-foot lengths. Locally made couplings of Atlas SPS 245 alloy steel connect the rods. The machines used are 31½-inch automatic leyners with lugged or anvil block chucks. For drilling holes below the horizontal, the lugged machines with special adapter rods made from 114- inch solid round Atlas SPS 245 are required. These rods are lugged at one end and a water hole is drilled for six inches into the other end. Over this rod is placed a water swivel which permits the water or air to be sent directly into the steel. A decreased cost per foot, increased footage per shift, and the use of standard equipment and crews are some of the main advantages of tungsten carbide drilling over diamond drilling. Introduction Long-hole drilling with percussion drills and sectional steel was introduced in several American mines some twenty-five years ago. It did not prove very successful, however, because the rapid gauge loss in steel bits necessitated the use of very large starter bits. This in turn rapidly fatigued the straight carbon-steel then in use, made it difficult to maintain the couplings, and resulted in a slow drilling rate. The introduction of the tungsten carbide insert bit and alloy drill still has changed this picture and opened real possibilities for the application of percussion drills to blast-hole drilling. If this type of bit had been perfected ten years ago, much of the research work and experimenting done to apply diamond drills to ore breaking would have gone toward developing the application of the tungsten carbide bit to this problem.

Jan 1, 1950

By W. J. Kroll

This report on the bibliography of zirconium has been confined to those publications and patents that appear to be useful in the commercial development of the metal, both the malleable and the nonmalleable. The methods of production have been stressed and special attention has been given to the alloys. Compounds of importance, like the oxide and chloride, for the manufacture of the metal or of the alloys have been considered. The use of the oxide in refractories anal in the glass and porcelain industries has been omitted. The present survey is critical; that is to say, an attempt has been made to evaluate the effectiveness of suggestions made in the literature. The exhaustive work of Marden and Richy, Bureau of Mines Bulletin 186, published in 1921, has been taken as a base to start from with the intention of bringing the subject up to date with material published in the last 24 years. During this time there was considerable 'advance in the preparation of the metal and Its alloys, and in the development of new uses. On the other hand, there was little progress in the methods of decomposing the ores, so that the chapter on this latter phase is necessarily short.

Jan 1, 1946

By M. Somppi, Z. Yamak

"Gold producers invest significant effort in mining, processing, and creating an intermediate gold doré product. Nonetheless, equal effort should be extended to the final handling and processing of the doré bar, and managing the high-purity gold produced at the fine-gold toll refiner. This detailed attention to bullion handling and refining provides rigor and confidence that the mine site is achieving, through fair and controlled methodology, the most appropriate value for the final product. With the above in mind, the following study explores the importance of preparing a set of site best-practices for bullion handling and specifically, detailing the peculiarities of sampling methodologies and the impact on assays.INTRODUCTION Gold and silver handling practices are common place at mine sites and refineries. The practices include but are not limited to smelting, ingot casting, weighing practices, and secure transportation. Proper handling and processing of the bullion material ensures that the mine site is achieving the true value of the final product. Various handling aspects can critically impact the perceived value of the bullion. A few of these particulars include weight tracking, scale recertification and calibration, refining and melting practices, melt temperature measurement, sampling, pouring, bar cleaning, furnace technology and crucible selection, and assaying. Nevertheless, this report discusses and focuses on the importance of proper sampling and molten-metal temperature measurement and their potential impact on the final doré bar value. Refining or re-melting operations achieve a proper measure of the precious metal content of its bullion when the sample accurately represents the whole bar. At first this task appears seemly straightforward, however, taking a representative sample can be challenging and is also one of the most important tasks for valuing gold during the settlement stage at the precious metal refinery. Various bullion sampling methodologies exist; including: dip sampling, granulation, drilling, cutting, and vacuum pin sampling. The Royal Canadian Mint (2009) indicated in their technical review of refinery operations that pin sampling is one of the best methods for cases where representative sampling and accuracy are required, e.g. to determine the payable metal content. Pin sampling consists of inserting a sealed glass vacuum tube (Figure 1) into the molten metal; when the molten metal contacts a purposely-designed weak portion of the glass, the seal breaks and the metal is suctioned into the hollow centre (Figure 2)."

Jan 1, 2018

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By B. L. Landrum, P. B. Crawford

The rise of a new laboratory model for studying tran-sient fluid flow problems, is described. The theory of he model is based on the analogy between the equa-ions which describe the flow of compressible fluids in porous media and the conduction of heal m solids. The "thermal model" is used to study the Iransient Pressure distributions during fluid displacement in five Standard well patterns. The studies indicate quantita-ively how die pressures change with lane at any poit in the reservoir. It was found that, in general, the equipressure contours are more radial about the wells early in the program than after steady-state conditions are established. In addition two studies of fractured five-spot patterns are presented to illustrate the opplicability of the model for a wide range of reservoir conditions. INTRODUCTION In reviewing the oil recovery techniques involving fluid displacement it was found that a very considerable quantity, if not all of the fluid within the pattern, mav be displaced (during a time-dependent or transient period rather than the usually applied steady-state conditions. Since the oil is displaced during a transient period, it was believed desirable to study the nature of the transients for several of the commonly used fluid displacement patterns. A literature review indicated fairly complete studies of the streamlines and isopotentials for steady-state: yet few data were available on the transient displacement process. Several simulated steady-state multiwell displacement programs were carefully mapped by Foster and Lodge on an electrical conducting sheet as early as 1875, hut the more recent work of Muskat provides the best source for steady-state phenomena having direct petroleum production applications. In order to study the transient phenomena a new lab-oratory model was developed which is based on the similarity of the equations that describe the flow of fluids and the conduction of heal. The equations describing heat flow were developed early in the nineteenth century. Regorous solutions tor most transient problems are in gcneral complex and usually limited to fairly restricted houndary conditions.2 the thermal model may be used to obtain approximate solutions for many transient problems without some of the restrictions required for analytical solution. The application of the analogy between heat conduc-. tion in solids. electrical flow and fluid flow, in a porous media has long been recognised. Techniques originally developed for the solution of heat conduction prol?lems have in many instances proved useful in ohtaining solutions to fluid flow prohlcms. Ir is not surpri5ing then that a heat conduction or thermal model might bf usefull in sludying transient fluid flow. As an example ol the problems suitable for the study with the thermal model, transient pressure distributions during fluid displacement programs are studied for the five-spot, line-drive, staggered line-diibe. seven-spot 211 two fractured patterns. A model was constructed of an iron plate of geometry similar to the reservoir patterns under study. The principle of mirror images as suggested by Bryan was employed in shaping the model. A temperature differential was obtained by soldering two sections of copper tubing to the plate at points analogous to the well location in the field. Hot and cold water was passed through the tubing. The temperature distribution, analogous to the pressure distribution in the field. was obtained a a function of time from thermocouplcs distributed over the plate.

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The effect of machine stiffness on discontinuous flow and fracture of the 2024 aluminum alloy was studied in tension at 4.2OK. An increase of machine stiffness was found to decrease the amount of elongation and drop in load during discontinuous flow, thereby postponing fracture to larger strains and higher stresses. The possibility of utilizing stiffened tools in deformation processing to suppress shear fracture originating from unstable flow was indicated. The problem of nucleating discontinuous flow and the role of the effective mass of the system in discontinuous flow were also considered. AT low temperatures the plastic flow of metals is often discontinuous, with sudden load drops and elongations.1,3 Basinski1,4 has presented strong evidence that discontinuous flow, at least in aluminum alloys, occurs under nearly adiabatic conditions. During testing the load may drop suddenly and flow become localized when the thermal softening, due to heat generated in plastic straining, is greater than the strain and strain-rate hardening. This instability criterion is more easily satisfied at low temperatures because 1) the volume specific heat is reduced so that relatively large temperature increases are possible in straining, and 2) the flow stress is relatively temperature-dependent. The important role of adiabatic shear in ductile fracture processes has been emphasized,5-1 and consideration has already been given to the influences of thermal and mechanical properties on the tendency of a material to undergo adiabatic shear.17677 By focusing attention on how the mechanical loading system influences low-temperature discontinuous flow, additional insight into adiabatic shear and its effect on fracture may be gained. EXPERIMENTAL PROCEDURE Because of its low thermal conductivity, the 2024 aluminum alloy exhibits a highly consistent discon- tinuous-flow behavior at 4.2°K and was therefore chosen as the material for study. Machined specimens of 0.113 in. diam and 1.125 in. gage length were solution heat-treated at 490°C for 3 hr, quenched into cold water, and immediately immersed in liquid nitrogen until just before testing. Testing was done at 4.2°K by immersion in liquid helium at a crosshead drive rate of 0.03 in. per min. As normally used (hard-machine basis), the spring constant of the testing machine was k = 25,000 lb per in. By inserting beam springs in series with the specimen, this value could be lowered by a factor of about 100. Details can be found elsewhere.? As a result of variable machine stiffness, the actual strain rate ranged from about 3 x 10 5 to 3 x 10-4 per sec from one test to another, as well as within any one test. However, preliminary tests had established that the tensile curves were not altered significantly by this strain-rate variation. Fig. 1 shows a typical load vs plastic-elongation curve for a solution heat-treated 2024 aluminum alloy specimen pulled in the standard hard machine (k = 25,000 lb per in.) at 4.2"K. The elastic extension has been subtracted. Plastic flow proceeded smoothly from yielding at approximately 22,000 psi (load = 220 lb) to a strain of about 4 pct at which point the flow became discontinuous. The magnitude of the load drops as well as the plastic elongation per drop increased with increasing strain until the specimen finally broke abruptly. The load-elongation behavior of a sample tested with a relatively soft machine under otherwise identical conditions is given in Fig. 2. In general, there

Jan 1, 1964

By Norihisa Iida, Yutaka Koshiba, Tsutoipu Masui

"Mitsubishi Materials has many years of experience in the production of oxygen free copper (OFC) and its alloys with a fully continuous-casting process. Four grades of OFC, commercial, electronic, superconductor, and ASTM class I are available according to user needs such as stabilizer for superconductivity, magnetron, and ultra-vacuum systems. Along with Cu-Ag and CuSn, we offer OFC based copper alloys such ·as Cu-Cr-Zr, Cu-Fe-P, Cu-Ni-Si and others, that are suitable for lead frame and connectors. Within the maximum sizes of 260mm X 1050mm for cakes and 385mm diameter for billets, we are very flexible and can adjust the ingot size to customer’s requirements. Other products that we can supply are semi-finished products such as hot rolled sheet, ·forged blank, extruded rod and finished products like mold for continuous casting of steel, ring mold for non-ferrous casting and backing plate for sputtering target.IntroductionMitsubishi Materials Corporation developed mass produced high quality oxygen free copper and. high copper alloy ingots in the 1960's. We produce 60,000 - 70,000 tons annually giving us 22 - 23% share of the world's market.Our oxygen free copper and. copper alloys are produced with a fully continuous casting process using only high-grade copper cathodes from our Naoshima and Onahama refineries. The raw material is melted and cast in' a carefully controlled atmosphere resulting in a product with low impurities and excellent properties.Using a controlled atmosphere it is possible to produce high quality copper alloys including active elements like chromium (Cr), zirconium (Zr), titanium (Ti), and magnesium (Mg) which are difficult to produce using standard batch casting methods.Using our own cakes and ·billets we produce and supply worldwide wrought materials like molds for ferrous and non-femous casting. These products receive special patented thermo-mechanical· treatments resulting in high strength and excellent conductivity with low cost."

Jan 1, 2000

By J. A. Organiscak

Enclosed cabs are a primary means of reducing the silica dust exposure of equipment operators at surface mines. The National Institute for Occupational Safety and Health (NIOSH) has investigated various factor effects on enclosed cab air filtration system performance. Factors experimen­tally investigated were intake filter efficiency, intake air leakage, intake filter loading (filter flow resistance), recirculation filter use and wind velocity effects on cab penetra­tion (inside to outside cab concentration ratio). Adding an intake pressurizer fan to the filtration system was also investigated. Results indicate that the intake filter efficiency and recirculation filter were the two most influential factors on cab penetration .Use of a recirculation filter significantly reduced cab penetration over the intake air filter by itself due to the multiplicable filtration of the cab interior air. Cab penetration was also affected to a lesser extent by intake filter loading and air leakage. Adding an intake pressurizer fan notably increased intake airflow and cab pressure while providing only minor changes to cab penetration.

Jan 1, 2008

By P. Bakke

Following extensive R&D efforts, Hydro Magnesium has launched a new alloy series with remarkable combinations of properties. The AE alloy family is based on additions of aluminium and rare earth elements to control mechanical properties, including elevated temperature creep strength. By combining these alloying elements with manganese additions, high purity alloys with outstanding corrosion performance are defined. A basic philosophy behind the developments has been to simultaneously approach all the critical issues related to developing a commercial material. Apart from the obvious requirements for material properties, the critical issues relate to die casting performance, as well as alloy production, recycling and environmental compatibility. Some of the important elements related to alloy production and recycling are addressed in the present paper.

Jan 1, 2006

By S. J. Pearce

The need for a simple, very sensitive, and accurate method for the determination of benzene in blood and urine vas evident throughout a recent study of chronic benzene (C6H6) poisoning conducted cooperatively by the United States Bureau of Mines, The Barrett Company, and the producers of benzene. A combustion method which will be described in a later publication, and a previously described/ adaptation of Smyth's method were developed and used during that investigation. The adaptation of Smyth's method gave satisfactory results when dealing with exposure conditions that produced chronic poisoning in a comparatively few days, but it was time-consuming; and lacked the accuracy necessary for a study of the absorption, distribution, and fate of benzene in the body during exposure to threshold concentrations of benzene vapor in air. The combustion procedure was satisfactory from the standpoint of sensitivity but was cumbersome, intricate, time-consuming, and required the use of special and somewhat expensive Physical and chemical apparatus. Following the termination of this study of chronic poisoning, possibilities ides for developing better methods occurred, and these have been investigated by the Bureau of Mines with the aid of Relief Works Division personnel microcolorimetric method for the determination of benzene in air has been described recently.6/ The present report deals rich the adaptation of this new colorimetric method to the determination

Jan 1, 1936

By W. Dan Walker

In an effort to keep mine hoist accidents to a minimum and to impart to managers and workers the essential elements that enter into safe installation and maintenance of hoisting equipment, the Bureau of Mines presents this Information Circular as a guide. Hoisting of men and materials is an essential operation in many mines and has become so commonplace that some persons are likely to ignore day-to-day inspections or become lax in the operating phases. With proper maintenance and operation, hoists can be exceptionally safe. However, lack of strict attention can invite tragedy or costly shutdowns.

Jan 1, 1961

By R. V. Ramani

In this paper, the application of the concepts of reliability engineering to the evaluation of longwall system performance is illustrated with data from an operating longwall face. A number of cases are analyzed to highlight the impacts of longwall equipment, geological conditions and outby haulage on systems reliability and availability.

Jan 1, 1988

By P. R. Tisot

Knowledge acquired from this research contributes to a better understanding of the physical structure of Green River oil shale and provides fundamental data and concepts that may serve to improve oil-shale technology. This study by the Bureau of Mines indicates that oil shale is a highly consolidated organic-inorganic system with no significant micropore structure, pore volume, or internal surface. This system is a form of physical structure that precludes rapid diffusion of either gases or liquids. The mineral matter consists essentially of nonspherical particles that tend to follow a log-normal size distribution. An excess of 99 weight-percent of these particles have equivalent spherical diameters of less than 44 microns--75 weight-percent are from 2 to 20 microns, and 15 weight-percent are less than 2 microns. The surface area (3 to 5 square meters per gram) of these mineral constituents is mainly external surface. The mineral constituents contain some micropore structure--pore radii ranging from 10 to 100 Angstrom--with the pore sizes randomly distributed. Distribution of the organic matter within the inorganic matrix is essentially interparticle and not intraparticle. The organic matter within the micropores of the mineral constituents is less than 4 percent of the total. Estimates made from surface area data suggest that perhaps only a small amount of the organic matter is bonded either physically or chemically to the mineral constituents.

Jan 1, 1963

By Michael P. Amsden

"THE ECSTALL CONCENTRATOR is situated adjacent to Highway 101 and the Ontario Northland Railroad, 15 miles east of Timmins, Ontario. Ore is delivered to the concentrator by rail from the mine, which is 17 miles northwest of the plant. Power and fuel are obtained from the hydro and natural gas lines which pass close to the plant site. Water is obtained from the Frederickhouse River, 6 miles east of the concentrator. The main concentrator building is a large structure 500 by 640 feet by 90 feet high and contains facilities for fine crushing, crushed ore storage, grinding, flotation, tin recovery, concentrate handling and reagent handling. Located in the same building are the machine shop, warehouse, metallurgical laboratory, pilot plant, men's change room, sample preparation area and an assay laboratory. The general concentrator layout is shown in Figure 47. Originally designed to handle 9,000 tons per day, the concentrator now treats 10,000 tons per day. Two different ore types are processed by selective flotation in three individual circuits to recover copper, lead and zinc concentrates. In 1973, another circuit was added to recover pyrite and tin concentrates from the combined zinc tailings of the three main circuits."

Jan 1, 1974

By A. D. Fisher

This paper describes the future position of metallurgical coal, particularly as applied to Canadian reserves. Quality coking coal is declining in availability, but preheating practices may alleviate this situation to some extent. Two new processes are discussed in the paper - formed coke and direct reduction - and their coal specifications are outlined.

Jan 1, 1972

THE Synthetic Liquid Fuels Act (30 U.S.C., 321-325, and amendments) become law April 5, 1644, and a period of intensive research and development in this field was begun by the Bureau of Mines. As part of this program bulletins were published on a pressure hydrogenation,3 the Fischer-Tropsch synthesis,4 and oil shale.5 The Bureau also has published a short bibliography on coal gasification,6 mostly of a theoretical nature. Because coal gasification is prerequisite to Hither the Fischer-Tropsch or coal-hydrogenation processes, publishing this sizable, collection of technical information in this form will be valuable. The material is presented in three parts, as follows: I. United States Patents. II. United Kingdom, Australian, Canadian, and South African Patents. III. Belgium, French, German, Italian, and Swedish Patents. The domestic patents for this bulletin were collected between 1963 and 1955. Some of the Foreign Patents were collected at the same time and a few of them later in 1961. Part I was published in 1960; Part II was published in 1962.

Jan 1, 1964

By G. E. McElroy

Tae purpose of this paper is to present types of charts adapted to aid in the graphic solution of fan-performance problems of selection and operation, and to urge the adoption of similar charts by the National Association of Fan Manufacturers as standard forms for presenting fan-performance data. As matters now stand, it is difficult for the average engineer to solve such problems because a laree number of variables are involved, and performance data are not presented in a manner that permits their direct application to many problems encountered in practice. The performance of any centrifugal machine is determined not only by the machine itself but also by the fluid-flow system on which it operates. Actual performance of centrifugal fans is therefore e matter of the type, size, and speed of fan, on the one hand, and of the relation of pressure to quantity of flow, as determined by the physical condition of the airway system, on the other.

Jan 1, 1936

By G. E. McElroy

[The purpose of this paper is to present type: of charts adapted to aid in the graphic solution of fan-performance problems of selection and operation, and to urge the adoption of similar charts by the National Association of Fan Manufactures as standard forms for presenting fan-performance data. As matters now stand, it is difficult for the average engineer to solve such problems because a large number of variables are involved, and performance data are not presented in a manner that permits their direct application to many problems encountered in practice. The performance of any centrifugal machine is determined not only by the machine itself but also by the fluid-flow system on which it operates. Actual performance of centrifugal fans is therefore a matter of the type, size, and speed of fan, on the one hand, anti of the relation of pressure to quantity of flow, as determined by the physical condition of the airway s: stem, on the other.]

Jan 1, 1936

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956