Search Documents

By Samuel Daniels

In this paper are given the mechanical properties, determined by the Engineering Division, Air Service, U. S. A., of the 94 per cent. aluminum, 5 per cent. copper, 1 per cent. silicon alloy as sand-cast and as heat-treated commercially to Air Service Specification No. 11,300. This particular alloy was tested both in the cast and in the heat-treated condition. Tension and tension modulus values were obtained from machined and from un-machined test specimens; while data for shear, compression, impact, torsion, and for Brinell and Rockwell hardness were found from machined bars. Specific-gravity tests were made on sanded, un-machined specimens. The metallography of the alloy is useful as a control to heat treatment and presents some interesting peculiarities in regard to the two iron-bearing compounds. THE demand for an aluminum alloy, suitable for sand castings, that may be heat treated to meet requirements of high strength, ductility, shock and corrosion resistance, and ready machineability has led to the commercial development of a proprietary material that contains from about 4 to 5 per cent. of copper, 1 per cent. of silicon, and such impurities as iron, up to a maximum of 0.75 per cent., and manganese, in quantity usually less than 0.1 per cent.1 Magnesium is not generally present, for it tends to nullify the beneficial influence of the added silicon by forming magnesium silicide. The function of the silicon is to minimize casting difficulties and, structurally, to favor the precipitation of (insoluble) iron-bearing skeletons rather than the needles, which prevent full realization of tensile properties from heat treatment by stimulating intergranular fracture. The amount of silicon necessary to counteract the ill effect of iron is equal to or slightly more than the content of iron; the excess of silicon over this ratio, under certain conditions of heat treatment, enters with CuAl2, the principal hardening constituent, into solid solution and contributes somewhat to the strength of the alloy without appreciably impairing its ductility. The schedule of heat treatment of this alloy depends on the design (cross-sections) of the castings and on the nature of the tensile properties desired. Essentially, the process consists in heating the material at about-950° F., quenching in oil or in cold or boiling water, and artificially aging

Jan 7, 1925

By Jacob T. Wainwright

AS a means for increasing the efficiency in modern blast-furnaces by supplying to them blast of a much higher temperature than is now possible, the writer offers as a suggestion a modification in the construction of regenerative hot-blast stoves. Stated briefly, the plan proposed is to pre-heat both the gas and the air for its combustion in a manner similar to that generally adopted in Siemens openhearth furnaces. After thus carrying the temperature of the stove to a point much higher than that common in hot-hlast stoves, the cold blast passes through it. Without entering into the details relating to the reversing valves and the system of flues, the general plan may be outlined as follows, referring to the accompanying drawings: The valves are so placed in heating up the stove that the blast-furnace gas enters at B, Fig. 1, and the cold air for combustion at A. Ascending in flues, F and E, respectively, combustible gas and air meet and mix in the combustion-chamber, I. Flowing through K, they descend through the flues, G and H, escaping through the chimney. In this manner the walls of the combustion. chambers, I and L, are highly heated, and the right-hand side of the stove is carried to a higher temperature. By reversing the valves, blast-furnace gas enters at C and cold air for combustion at D. Both are pre-heated in their ascent through the flues, G and H. They burn in the combustion-chamber, L, and the hot gases of combustion, flowing through K, I, E and F to A and B, heat the left-hand side of the stove. In this manner the stove is carried to a temperature greater than that of those now generally in use, in which air and gas are burned without preliminary pre-heating. In the plan proposed, that side of the stove will, of course, be relatively cooler through which cold air and furnace-gas last passed in its ascent to its combustion-chamber. After having sufficiently heated the stove in the manner outlined, the cold blast is admitted through all the flues, A, B, C and D. It ascends through the highly-heated regenerative material to the chambers at the top and descends through the flue, P, Fig. 2 (dotted

Jan 1, 1889

By Paris V. Brough

This paper, which describes the practice of milling custom ore, in addition to that produced under company and lease operations in the Tom Reed mines, is one of a series 'being prepared by the Bureau of Mines. ACKNOWLEDGMENT Acknowledgment is made to W. B. Phelps, managing director, and Jack Zwinge, superintendent, far permission to publish, a-ad to G. E. Jarpe, the present mill superintendent, for his assistance in preparing the paper. LOCATION The mill is in Oatman, adjacent to the Benjamin Harrison shaft of the Tom Reed Gold Mines Co., in the foothills on the western slope of the Black Mountains, western Mohave County. The railroad shipping point is Kingman, Ariz., 25 miles northeast of Oatman. Paved highway U. S. 66 passes by the mill. The altitude is approximately 2,700 feet.

Jan 1, 1937

By G. L. Gates

The Bureau of Mines studied the scales formed in producing wells in the Wilmington field, California. The scales were primarily barium sulfate and resulted from the mixing of injected sea water and formation waters; there was excess sulfate in the injection water and the formation waters contained appreciable barium. After breakthrough, the produced brines were supersaturated with barium sulfate. Laboratory tests indicated that barium sulfate precipitated quickly When the supersaturated brines were agitated with crystals of barium sulfate and fairly rapidly when more sulfate solution was added. Precipitation occurred slowly on standing or under nonturbulent conditions. Both the apparent and equilibrium solubilities of barium sulfate in these brines were determined and compared with equilibrium solubilities in distilled water and sodium chloride solutions.

Jan 1, 1965

By James L. Hendrix

This paper is intended to give the reader an update on the work being done at the Mackay School of Mines about the fate of cyanide on precious metals mill tailings waste. During the last two years several tailings impoundments have been sampled and analyzed for total and free cyanides. From our sampling program we are beginning to learn valuable information concerning the fate of cyanides in precious metals mill wastes. Included in this paper is a detailed description of our sampling and analytical techniques. Also, some of the data obtained from five sites are given.

Jan 1, 1986

By R. R. Klimpel

The industrial processing of ores containing precious metals such as gold is generally very mining site specific, e. g. McQuiston and Shoemaker (1985), vanZyl et. a1. (1988), Fuerstenau and Hendrix (1990), and Hausen et. a1. (1990). The variety of various mineral processing techniques employed is extensive and includes size reduction, size classification, gravity separation, roasting, cyanidation, chemical and/or bacterial leaching, ion exchange and/or solvent extraction, and froth flotation. Gold occurs in the earth's crust on the average in very low concentration estimated by various sources to be between two and five parts per billion. For a specific ore deposit to be considered as an economic source of gold, generally a concentration of near one part-per million (one gram / Mton) or more is required. From a mineralogical viewpoint, gold often occurs in its native or free form. However, it can also occur as gold compounds of telluride, antimony, and selenium contained within either sulfide minerals such as pyrite, arsenopyrite. and pyrrhotite or, to a less extent, within silicate, oxide, and carbonate minerals. In many locations, alloying of gold with silver is found. The optimal processing method for recovering gold is determined by many factors such as the mineralogy of the gold bearing minerals as well as the associated mineralogy of the gangue minerals, the type of liberation profile of the gold bearing minerals upon' size reduction, and the particle size of the gold itself. Free or native gold particles can vary in size from the extreme of large nuggets to very finely disseminated gold associated in a complex sulfide mineral matrix. Typically free gold particles of several hundred microns or larger are efficiently recovered by one or more of a number of gravity based techniques due to the large specific gravity differential of gold (19.3 to 15) versus typical gangue minerals (5 to 2.7). When gold is associated with a sulfide (usually pyrite) matrix, historically most industrial plants involving size reduction and subsequent liberation have operated in a size range of 50 to 80 percent less than 75 microns. Grinding finer than this has been normally not economical unless the ore has a high gold content in the feed ore.

Jan 1, 1998

By McElroy. G. E.

"INTRODUCTION The ventilation of development faces in mines for diluting gas or dust concentrations and, in hot mines for providing air-motion cooling effect, by fan pipe units discharging high-velocity streams of air close to the face, is an important phase of mine ventilation. The effectiveness of such units depends largely on the air-flow distribution between the pipe discharge and the face, a subject on which little definite information is available. A study of the air flow from grills into rooms 3/ has provided some basic data, but under conditions no different from mine fan-pipe installations in development ends that the data are of doubtful application to mine installations, owing to differences in air-flow conditions.The purpose of this report is to present and discuss the results of an initial series of tests of a general investigation designed to yield definite laws and design data for the discharge of fan-pipe lines in mines. This series was planned to yield preliminary data on the effects of velocity of discharge, size and shape of pipe, and adjacent walls on the air-flow distribution. Tents were made on 10-inch pine with seven different end conditions and one change of wall condition. Changes in size and shape of discharge wore made by short transformation pieces directly at the discharge end, with the result that effects due to contraction and expansion of the flow, which proved to be of much greater importance than was expected, totally obscured any normal effects due to size and shape. The results of this series of tests, therefore, relate to 10-inch pipe with various discharge designs and are so reported."

Aug 1, 1940

By James H. Jolly

Although zinc in the environment is generally considered to be beneficial or benign, excessive amounts can cause deterioration of environmental quality and toxicity problems for some plants and animals. High amounts of zinc in the environment are often associated with anthropogenic activities, mainly those involving zinc production and consumption and those related to the use and disposal of zinc-containing products. To obtain some upper limit parameters on the historical quantities of zinc chat may have entered the U.S. environment from anthropogenic sources, the Bureau of Mines conducted a materials flow study of zinc from the earliest beginning of the domestic industry through 1990 and for the year 1989. For comparative purposes a generalized historical materials flow of zinc for the world was also prepared. The United States was the world's leading producer and consumer of zinc in the 1850-1990 period. In that period, U.S. mines and smelters produced 15% and 20%, respectively, of world output, and U.S. zinc consumption accounted for about one-fourth of the world total. Maximum zinc losses into the environment related to the above production, consumption, and disposal of end use products total about 63 million tons. Dissipative uses and landfill disposal have accounted for about 73% of the potential zinc losses to the environment, followed by mining and smelting 22%, and manufacturing, 5%. At the end of 1990, contained zinc in useful end-products in the United States was estimated to be about 23 million tons. In 1989 slightly more than 1 million metric tons of zinc in new zinc-containing products were added to the domestic pool of zinc in use but in the same year, an estimated 0.9 million tons was dissipated and discarded, indicating only small net gains to the zinc pool of use annually.

Jan 1, 1992

By C. Özgen Karacan

This study presents the results of core-log analyses from the exploration boreholes, the analyses of face advance rates, and the results of downhole monitoring studies performed in gob gas ventholes for calculation of changes in hydraulic properties in the longwall overburden at a mine site in southwestern (SW) Pennsylvania section of Northern Appalachian Basin. In the ?rst part of the study, coal measure rocks in overburden strata were analyzed and the locations where possible fractures and bedding plane separations would occur were evaluated. In the second part, the hydraulic conductivities were computed by two different slug test analyses methods using the water level changes measured in gob gas ventholes as longwall face approached. Hydraulic conductivities were analyzed with respect to the changes in overburden depth, the locations of the borehole, and mine face advance rates. These data were used to interpret the potential productivities of the gob gas ventholes as a result of fracturing and changes in hydraulic conductivities. The general results showed that the probability of fracturing and bedding plane separations in the overburden increase between strong and weak rock interfaces. Also, the probability of bedding plane separations increases as the interface is close to the extracted coal seam. Evaluation of slug tests showed that the hydraulic conductivity developments in the boreholes and their potential production performances are affected by the underground strata and the roof materials. In situations where the roof material is stiff and thick, the development of high permeability fractures around the borehole will be less. Results also indicated that borehole location with respect to face position affects the fracturing time and permeability evolution as well. Greater overburden depths generally cause earlier fracturing as longwall face approaches, but eventually result in lower hydraulic conductivities and potentially less effective boreholes. Increasing mining rates also resulted in generally lower hydraulic conductivities in the overburden. The results of this study were intended to improve the interpretation of gob gas venthole performance and to provide better siting of these boreholes.

Jan 1, 2009

By S Hapugoda

Iron ore oxide and oxyhydroxide minerals such as haematite (eg various types of martite and microplaty haematite), different forms of goethite, magnetite, hydrohaematite and kenomagnetite were analysed using optical microscopy, scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) techniques, to determine the type and proportion of deleterious elements present and the chemistry of associated gangue minerals. The aim was to characterise elements potentially deleterious for agglomeration and steelmaking, eg sulfur, phosphorus, aluminium and silicon and correlate their distribution with mineral texture and association, to provide feedback on downstream processing performance and product quality.Examples of characteristic mineral associations are shown from various genetic styles of iron ores, including magnetite banded iron formation (BIF), BIF-derived martite-goethite and skarn-type magnetite ores.A number of examples are presented demonstrating the benefits of the use of combined techniques of reflected optical microscopy, SEM and EPMA data to reliably identify ore and gangue minerals and their associations in different types of iron ores.

Jul 11, 2011

By J. J. Wallaert

The decreasing supplies of natural gas and low-sulfur crude oil available for electric power generation in the United States will unquestionably shift the emphasis to nuclear and coal fired steam power plants in the immediate future. Failure to do so will ensure our dependence on mid-east low sulfur crude oil comprising some 70% of the known world reserves, and imported liquid natural gas. By contrast, the United States has 43% of the known world reserves of anthracite, bituminous and semi-bituminous coal and 48% of all known coal reserves of the world including lignite. It is evident, therefore, that coal is alive and well and will continue to be a significant energy source for the production of electricity for many years. Of course, concern for our environment and the development of new technologies will ultimately curtail the utilization of coal for the generation of bulk power, but information released by the National Electric Reliability Council and the Federal Power Commission is worth repeating. In the year 1972 the total capacity of generating units in the United States was 379,552 Mw of which 149,974 Mw, or 39.5% of the total, was produced by coal fired steam turbines which consumed 344,700,000 tons of coal. New capacity additions planned or in construction show that in the year 1981 our total generating capacity will be 843,503 Mw, of which 257,995 Mw, or 30.6% of the total, if from coal only. Translating this increase into terms meaningful to the bulk material handling industry suggests that ten years from now the utility industry will require 590,000,000 tons of coal per year - a monumental task - if we are to sustain our current demand rate for power.

Jan 1, 1973

By Thomas Camus

"STATE OF THE ART The current situation of ground prediction in TBM is of great concern for tunnelling contractors, and the subject has been quite widely addressed over recent years, for instance by the French Eupalinos 2000 programme, which tested a variety of technological approaches. A number of interesting projects were executed, such as the SOUND and OnSITE projects, part of the German Geotechnologien programme: these projects are focused on seismics, while other techniques such as radar are not considered. Little information and even less industrial applications have been released apart from lab simulations and numerical modelling. A number of field tests in different configurations have been carried out for compression waves, but the results were often not reliable or convincing, and therefore little has been reported in open literature. The advances seem somewhat promising as far as hard rock tunnels are concerned, but ignore the problem raised by concrete lined tunnels such as those bored by a TBM in soft ground. In such tunnels, sending and receiving seismic waves reliably through the lining (and the grouting behind) is quite illusory. A careful analysis of the seismic prediction research results show that the main problem is the source which is poorly controlled and poorly coupled (for instance in concrete lined tunnels, or in approaches that use the TBM cutter head vibrations as a source). Generating waves perpendicular to the tunnel axis is also a problem: aligning with the tunnel axis makes more sense. Radar (Ground Penetrating Radar - GPR) has been used in geotechnical surveys for decades, and also for tunnel inspection. Attempts have been made at using it on a TBM (for example in Japan by Taisei) but mainly using off-the-shelf GPRs, which are not adapted to work in the specific environment of a TBM (because of its huge mass of metal, to start with). Very few results have been published, probably due to the somewhat disappointing performance of such implementations. At present, no TBM has a GPR incorporated in its cutter head that is able to predict ground characteristics while drilling. Another characteristic and drawback of most current methods is that they require dedicated periods of time during which other tunnel construction activities must be stopped. Due to the duration of such operations this leads to performing ground prediction on a weekly basis only, and therefore to a requirement for an investigation range of 100 metres approximately (in order to cover the TBM advance over the coming week). This is not achievable with boreholes made from the TBM, even less if a reasonable accuracy is required, as is usually the case."

Jan 1, 2016

By J. Shen

Direct methanol fuel cells have been the subject of considerable research in the last decade. Performance levels realized in cells, stacks, and systems show that this technology is a promising power source for a wide range of portable applications. A direct methanol fuel cell (DMFC) operates directly on a methanol fuel stream typically supplied as a methanol/water vapour or as an aqueous methanol solution in liquid feed DMFCs. The fuel streams in DMFCs are usually recirculated in order to remove carbon dioxide and to re-use the diluent and any unreacted fuel in the depleted fuel stream exiting the DMFC. The concentration of methanol in the fuel circulation loop is an important operating parameter because it determines the electrical performance and efficiency of the direct methanol fuel cell system. The methanol concentration in the circulating fuel stream is usually measured continuously with a suitable sensor, and fresh methanol is admitted in accordance with the signal from the sensor. There are many factors to consider in developing a methanol sensor suitable for DMFCs. These factors include sensitivity, cost, size, simplicity, reliability, longevity, concentration range, and dynamic response. In particular, reliability and low cost should be addressed. Methanol concentration sensors measure methanol concentration by means of detecting the variations of physical/chemical properties of the solution. In this work, methanol concentration sensors based on electrochemistry, electric-capacitance measurement, infrared sensing, ultrasound sensing, and other techniques are reviewed to discuss their advantages and disadvantages.

Jan 1, 2005

By S. Seetharaman

A mathematical model has been developed to evaluate the viscosities of melts at high temperatures. The viscous flow in liquid is described by the equation, {n = Aexp(AG*/RT)} based on the absolute reaction rate theory. The Gibbs energy of activation,{ AG* } is considered to be a function of the temperature as well as the composition of the melt. The model has been applied successfully to various metallic and slag systems from unary to quaternary. On the basis of this model, a relationship has been suggested to relate the Gibbs activation energy of viscosity to the Gibbs energy of mixing in binary metallic melts. The viscosities predicted from available thermodynamic data in the case of a number of binary metallic systems using this correlation show satisfactory agreement with the reported experimental values.

Jan 1, 1994

By Kenneth P. Michalek, James E. Kelly, Jonathan A. Dantzig

"Many investigations have been reported regarding the simulation of continuous casting with emphasis on in-mold heat transfer. These analyses have been limited, however, because they require either estimation or measurement of the characteristic heat transfer between the ingot and the mold. In this paper, a self-consistent model 'is presented for calculating the heat transfer between a solidifying continuous casting and the mold, in the context of the continuous casting of steel. Using both thermal and stress analyses, the air gap formed during continuous casting is calculated and used to compute the heat transfer coefficients. Iteration between the thermal and stress analyses is used to determine a self-consistent solution. IntroductionThe continuous casting process for steel is illustrated schematically in Fig. 1. Molten steel is tapped into a tundish from which it flows at a controlled rate into the continuous casting mold. The initial shell of the casting forms in the mold by transfer of heat from the metal through the mold wall to the cooling water. The remainder of the casting is solidified by application of water sprays, and/or radiation cooling below the mold.Heat transfer in the mold portion of the process is important because it controls the formation of various defects which are deleterious to subsequent processing. Examples of defects formed in this region are surface irregularities, such as cold folding and oscillation marks, and more serious defects, such as longitudinal or transverse cracks. A more catastrophic problem which may occur is a breakout, in which the shell ruptures and molten steel is discharged in an uncontrolled way."

Jan 1, 1986

By F. Crundwell, N. Steenekamp

"The leaching of sulphide minerals generates a significant amount of energy. There are three systems that might be used to remove this energy. These are: cooling coils, quench water, and flash recycle. Flash recycle is the recycling of slurry from the autoclave to the feed tank. Heat is removed in this arrangement when the slurry at elevated temperature and pressure is flashed to atmosphere, releasing steam. The slurry is returned to the autoclave at lower temperature, resulting in cooling. The cooling is directly proportional to the steam released from the recycled slurry. Design equations and results for the flash recycle system are presented. A fourth proposal for removing heat is to recycle slurry from the back of the autoclave. These four alternatives not only remove the heat, but also have an effect on the leaching efficiency. Amongst the four alternatives, design calculations indicate that the flash recycle option is the optimal solution in terms of leaching efficiency and heat removal, and recycling product from the back of the autoclave is the worst. In spite of its efficiency in terms of heat removal and leaching, the implementation of the flash recycle system is limited to a few operations in the platinum industry.INTRODUCTIONIn considering ways to improve leaching operations, focus is placed on the chemistry, on the kinetics, the agitation and perhaps even on the gas mass transfer conditions. Attention is less frequently placed on the removal of energy from these reactors and how this might limit performance.The pressure leaching of sulphides releases a significant amount of heat. For example, the reaction for the leaching of chalcocite, Cu2S, given by"

Jan 1, 2012

By Donald H. McLaughlin

THE activity and enthusiasm of pioneers still prevail among workers in applied geophysics1.- Within the year, new devices have .been tried out, instruments and technique have been improved and the methods of application to commercial problems have been increased in many ingenious ways. There is still great need for more skillful interpretation of results in terms of geology, but oil the whole geophysical prospecting is making encouraging progress toward finding its proper place and function in engineering and geological practice. Spectacular successes continue to be reported, particularly .from the Gulf Coast, where the race for salt domes has not slackened, and encouraging results have been giined elsewhere in the mapping of structures in the search for oil. In the mining field, however, it can hardly be claimed that the same measure of success has been obtained, for brilliant efforts worthy of wide recognition have been overshadowed to some eatent by the unfortunate outcome of surveys undertaken unwisely without recognition of the limitations of the work. Consequently, hopes were aroused that could not be fulfilled, and it must be admitted in an impartial survey that there are a few regions, chiefly in the far north, where the standing of geophysical prospecting is somewhat doubtful and where the course of public opinion regarding it shows a certain similarity to the history of the market during the past few months. Reliable work, however, is steadily going 011 and it can confidently be expected that the methods will eventually be regarded in many regions as an essential part of the technique of securing geologic data needed for intelligent exploration.

Jan 1, 1930

By Christopher Mark

"Many problems in rock mechanics are limited by our imperfect knowledge of the material properties and failure mechanics of rock masses. Mining problems are somewhat unique, however, in that plenty of real world experience is generally available and can be turned into valuable experimental data. Every pillar that is developed, or stope that is mined, represents a full-scale test of a rock mechanics design. By harvesting these data, and then using the appropriate statistical techniques to interpret them, mining engineers have developed powerful design techniques that are widely used around the world. Successful empirical methods are readily accepted because they are simple, transparent, practical, and firmly tethered to reality.The author has been intimately associated with empirical design for his entire career. But where his past papers have described the application of individual techniques to specific problems, the focus of this paper is the process used to develop a successful empirical method. A six-stage process is described:1. Identification of the problem, and of the end users of the final product2. Development of a conceptual rock mechanics model, and identification of the key parameters in that model3. Identification of measures for each of the key parameters, and the development of new measures (such as rating scales) where necessary4. Data sources and data collection5. Statistical analysis6. Packaging of the final productEach of these stages has its own potential rewards and pitfalls, which will be illustrated by incidents from the author’s own experience. The ultimate goal of this paper is to provide a new and deeper appreciation for empirical techniques, as well as some guidelines and opportunities for future developers."

Jan 1, 2015

By B. Anameric

The pig iron nugget process is gaining in importance as an alternative to the traditional blast furnace. Throughout the process, self-reducing?fluxing dried greenballs composed of iron ore concentrate, reducing-carburizing agent (coal), flux (limestone) and binder (bentonite) are heat-treated. During the heat treatment, dried greenballs are first transformed into direct reduced iron (DRI), then to transition direct reduced iron (TDRI) and finally to pig iron nuggets. The furnace temperature and/or residence time and the corresponding levels of carburization, reduction and metallization dictate these transformations. This study involved the determination of threshold furnace temperatures and residence times for completion of all of the transformation reactions and pig iron nugget production. The experiments involved the heat treatment of self-reducing?fluxing dried greenballs at various furnace temperatures and residence times. The products of these heat treatments were identified by utilizing optical microscopy, apparent density and microhardness measurements.

Jan 1, 2007

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965