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By H. C., Weed

THE Inspiration Consolidated Copper Co., located in the Globe-Miami district at Inspiration, Ariz., became a producer of copper in 1915. From 1915 until 1948, 116,278,000 tons of ore were produced from underground workings by the block-caving system of mining. In April 1948, open-pit ore production from portions of the ore body was started and earlier plans for block-caving in these areas were abandoned. The change was due to economic conditions. Prior to the war years Inspiration's costs of mining by block-caving methods were comparable to, or even below, the costs of some open-pit operations. By the end of the war these conditions were completely changed. Underground costs had risen steadily for labor and supplies. Difficulty was being experienced in finding competent underground men and underground development was almost hopelessly behind schedule. On the other hand, open-pit costs had been sharply reduced through the development of modern earth-moving machinery and plenty of labor was available for surface work.

Jan 1, 1950

Frank Clemes Smith, Deadwood, 8. D. (communication to the Secretary): The reading of Mr. Chance's interesting paper suggests a few ideas relative to his discussion of certain Black Hills gold-ores. Mr. Chance refers to his examination, in 1897, of " the (Carboniferous) limestone plateau-country which encircles the central area of the Black Hills," and says that " it had been generally assumed that the mineralization of this formation was confined to the northern area;" further, that he "found, however, a general mineralization, extending in zones or belts throughout the region," and that the ores, being more or less specially

Jan 1, 1900

By W. J. PRIESTLEY

WHEN during the war the Navy Department decided to build an armor-plate and gun-forging plant of its own at South Charleston, W. Va., one of the most important units of the equipment proposed was a 14,000 gross ton forging-press to be used for forging, bending, and rectifying battleship armor-plate and making hol¬low forgings for large caliber guns. A press suitable for doing this kind of work was put into operation in the fall of 1921 and was operated successfully on armor-plate and large forgings until the closing down of the ordnance plant following the Limitation of Armament Conference held in Washington, February, 1922. PURPOSE OF THE PRESS There are three methods by which armor-plate can be made, namely, hammering, forging, and rolling the ingot. Each method produces a different result in the mechanical working of the steel. The hammer was eliminated as impractical from an operating standpoint. The first armor-plate made in this country was worked under a hammer at the Bethlehem Steel Co., between the years 1891 and 1893, but was superseded by forging when the large press was completed in 1893. Harry T. Morris of the Bethlehem Steel Co. informs me that the 1.25-ton steam hammer began operations in 1891 and was in operation for about two years. The Carnegie Steel Co. and the Midvale Steel and Ordnance Steel Co. also forged armor-plate. Certain European manufacturers rolled the plates from large slab ingots, after removing the sink-head and giving the body of the ingot a light pass under a hydraulic press. While rolling accomplished more mechanical work on the surface of an armor plate, forging, on the other hand, resulted in a greater amount of work in the interior of the plate. Either type of equipment involved an enormous expendi¬ture, so it was deemed advisable to adopt the method which would make it possible to use the equipment for more than one purpose. Since g large rolling-mill could be used only for the single operation of rolling armor-plate, a press was decided on, for the reason that it might be designed so as to forge armor, as well as bend and rectify it, and also be used in the forging of ingots for large caliber guns, both in the form of hollow forgings and also solid shafts.

Jan 1, 1926

By T. J. Woods

This paper deals with the origin, definition and prevention of scabs on semifinished rolled-steel product. Mold coatings, which are considered essential in scab prevention, were found to be effective only in relation to the ingot surface of semikilled and killed steels and not necessary for the rolled product. That is to say, the scabs on ingots caused by having been cast in uncoated molds are eliminated in the soaking and rolling operations, therefore are not present on the rolled product. This fact, which is contrary to the average opinion, was established after extensive and thorough experiments had proved the ordinary conception of the origin of scabs to be incorrect. This subject may be of little or no concern to steel plants producing small ingots for the manufacture of small billets and bars, except as it may be of interest in showing why their surface troubles with scabs do not exist on the product of heats with normal pouring practice. But to the producer of large ingots to be rolled into slabs for large plates used in shipbuilding, it is a very important subject. Definition of a Scab The generally accepted opinion is that the individual scabs present on rolled products (as shown by Fig. I) are considered to have been individual splashes on the ingot surface. This opinion was found to be incorrect. Experiments showed that there were no individual scabs on the product that had appeared as individuals on the ingot surface. The single scabs seen are either pieces of a shell that is present near the bottom of all top-cast ingots, or a veneer that may be present on any part of an ingot improperly poured, as when the stream strikes the mold wall. This definition is based on a detailed study of scabs and their characteristics in which the following have been found true: Location.—On the product of heats poured without trouble, scabs, if present, are always on the product that corresponds to the bottom end of the ingot, and usually occur in clusters. This is true whether molds are coated or not. Shape.—There is no regularity as to shape, size or thickness. It is sometimes possible to separate a few pieces and place them together, like pieces of a jigsaw puzzle, indicating that at one time they had been united as one piece. If individual splashes were the origin of scabs, the foregoing would not be true. Instead, the splashes, which occur throughout the pouring of the ingots, would be present uniformly over the entire product and there would be considerable similarity in the shape and thickness of the scabs. Experimental Work Our experimental work was conducted on 200-ton heats of semikilled plate steel tapped into an oval ladle 15 ft. high. All ingots were top-cast direct into 24 by 54 by 82-in. molds, straight-sided, set on flat stools. Two separate studies were made about one year apart, each study extending

Jan 1, 1943

By T. J. Woods

This paper deals with the origin, definition and prevention of scabs on semifinished rolled-steel product. Mold coatings, which are considered essential in scab prevention, were found to be effective only in relation to the ingot surface of semikilled and killed steels and not necessary for the rolled product. That is to say, the scabs on ingots caused by having been cast in uncoated molds are eliminated in the soaking and rolling operations, therefore are not present on the rolled product. This fact, which is contrary to the average opinion, was established after extensive and thorough experiments had proved the ordinary conception of the origin of scabs to be incorrect. This subject may be of little or no concern to steel plants producing small ingots for the manufacture of small billets and bars, except as it may be of interest in showing why their surface troubles with scabs do not exist on the product of heats with normal pouring practice. But to the producer of large ingots to be rolled into slabs for large plates used in shipbuilding, it is a very important subject. Definition of a Scab The generally accepted opinion is that the individual scabs present on rolled products (as shown by Fig. I) are considered to have been individual splashes on the ingot surface. This opinion was found to be incorrect. Experiments showed that there were no individual scabs on the product that had appeared as individuals on the ingot surface. The single scabs seen are either pieces of a shell that is present near the bottom of all top-cast ingots, or a veneer that may be present on any part of an ingot improperly poured, as when the stream strikes the mold wall. This definition is based on a detailed study of scabs and their characteristics in which the following have been found true: Location.—On the product of heats poured without trouble, scabs, if present, are always on the product that corresponds to the bottom end of the ingot, and usually occur in clusters. This is true whether molds are coated or not. Shape.—There is no regularity as to shape, size or thickness. It is sometimes possible to separate a few pieces and place them together, like pieces of a jigsaw puzzle, indicating that at one time they had been united as one piece. If individual splashes were the origin of scabs, the foregoing would not be true. Instead, the splashes, which occur throughout the pouring of the ingots, would be present uniformly over the entire product and there would be considerable similarity in the shape and thickness of the scabs. Experimental Work Our experimental work was conducted on 200-ton heats of semikilled plate steel tapped into an oval ladle 15 ft. high. All ingots were top-cast direct into 24 by 54 by 82-in. molds, straight-sided, set on flat stools. Two separate studies were made about one year apart, each study extending

Jan 1, 1943

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By B. F. Peters, J. Gordon Parr, E. R. Macgregor

A SERIES of seven hypoeutectoid alloys, up to 18.2 atomic pct Mn, was made by the levitation melting technique. The loss of weight on melting was considered to be entirely due to volatilization of manganese, and compositions were computed on this basis. Filed samples (—200 Tyler mesh) were helium quenched from 1000°C after soaking for 5 min by a technique already described.' Quenched Alloys -Assessments of the amounts of a phase produced and the hardness of the quenched alloys are summarized in Fig. 1. The experimental techniques and calculations involved have been described previously. The amount of a decreases as manganese content increases, until at 10.6 pct Mn only a trace of a' is observed. Previous

Jan 1, 1957

By William G. Pariseau

The flexure of geologic strata, a phenomenon of interest to geologists and mining engineers alike, is examined as a sheet bending problem in Coulomb plasticity. Fonnulae for the distribution of stress, strain, and displacement increments; volume change; change in the length of the central surface; and power of dissipation, as well as for the neutral surface shift are given. Strains of any magnitude are considered. The analysis shows that deeply buried strata may bend and develop "tensile" cracks under generally compressive states of stress. It is also shown that bed separation and high capacity props are desirable in mechanized longwall mining, a result in keeping with operating experience. Although speculative at this time, the analysis provides a rational working hypothesis as regards the problem of strata flexure and control. | he purpose of this paper is to present an analysis of the flexure of geologic strata as a problem in the bending of a sheet of material failing in accordance with a Mohr-Coulomb criterion. The flexure of strata has an obvious academic interest to the geologist concerned with the mechanics of folding. It is of interest to the economic geologist as it relates to the structural control of certain types of ore deposits. It has an intimate association with mine subsidence phenomena, and is of concern to the mining engineer. Strata flexure is also the dominant feature of roof behavior about longwall workings. An improved understanding of strata flexure through a rational mechanical analysis thus appears desirable not only from the academic view but from the economic one as well. In the field, the most commonly observed feature of folding, subsidence, and longwall roof behavior is the permanent and therefore inelastic nature of the strata movement. Fig. 1 illustrates the physical disposition of strata in the vicinity of a longwall face. Inasmuch as most rocks (with the possible exception of certain evaporites) do not exhibit significant viscoelastic behavior, at least not over time spans of engineering interest, a plastic analysis is indicated. The analysis is meant to apply to strata whose deformation is dominantly that of bending such as might be expected in the remote roof about a longwall face.

Jan 1, 1970

By Gregoire Gutzeit

THE development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. GENERAL OUTLINE The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties-for instance, isotropism, anisotropism, color, cleavage, reflecting power-are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1942

By AIME AIME

A MODERN copper reduction works has both a genera1 chemical laboratory for control work and a research laboratory for the study of improvement of present processes and better working-up of by-products. The division of work in the general laboratory would naturally differ in different plants. The following statement to the writer from a chemist in one of the works will give a good idea of the type. of work in the general laboratory :

Jan 1, 1929

SINCE it seems to me that guns are of greater importance in the art of casting than any of the other things that are made by it, and that they require more foresight and care because they need many perfections, I wish now to repeat certain useful and necessary precautions in corroboration, for though I have already spoken to you of them in some detail, the power has not been granted me to pass with one breath completely through a subject with many parts. Therefore it will not be wearisome to you to hear the same thing told again, because it will not be without amplification of some pertinent points. For this reason I have prepared the present discourse, which I have called admonitions. The first of these concerns the making of the pattern upon which the

Jan 1, 1942

By C. Dinis da Gama

In order to reduce the complexity of mechanisms influencing rock. fragmentation by blasting a simulation approach is proposed, using the capabilities of microcomputer interactive graphics. Situations involving cratering end bench blasting are simulated, and both jointed and intact rocks can be subjected to explosive action, taking into consideration its breakage mechanisms. Size analysis curves relating rock distribution before and after the blasts are determined and compared with field data.

Jan 1, 1984

By R. E. Lund

Josephtown Smelter employs the St. Joe-developed electrothermic process for producing zinc metal and zinc oxide. The process uses resistance-type electric furnaces. Flow of current through the sintered ore and coke charge develops the energy required for smelting at the reaction sites. To produce zinc metal, the furnace off-Gases bubble through a large "U"-tube filled with molten zinc which condenses the zinc to liquid; the metal is then mechanically cast into slabs. To produce zinc oxide, the furnace vapors burn in air and the resultant powders are collected. The smelter comprises three distinct circuits. One circuit produces American Process zinc oxide and high grade metal; another circuit produces tailor-made alloys of controlled lead and cadmium content; the third circuit produces prime western zinc metal and feedstock which is refined into special High grade metal and French Process zinc oxide. The roasting circuit utilizes multiple-hearth furnaces for deleading the zinc concentrates; fluid bed and suspension roasters are employed for desulfurization. Sintering produces a hard, porous furnace feed. The flexible smelting process is adaptable to consuming various kinds of secondary material. Extensive residue treatment accomplishes high overall zinc recovery. Smelter by-products include sulfuric acid, cadmium, and mercury.

Jan 1, 1970

By S. K. Nicol, A. R. Swanson, J. C. Day

Addition of oil to a suspension of hydrophobic coal particles can influence its dewatering characteristics. An agglomeration process occurs in which coal particles are held together by negative capillary pressure at particle/oil/water contacts. Consequently, the units round which flow can occur are enlarged and this improves dewatering parameters such as drainage rate, solids recovery, and equilibrium moisture content. This paper discusses processes which attempt to use this principle, in terms of metallurgical and economic efficiency. The discussion is augmented by results of recent experiments on the effect of oil addition to centrifuges and vacuum filters.

Jan 1, 1980

By G. Carman Ridland

Front Range, Colorado: The majority of the rocks comprising the Front Range of Colorado are pre- Cambrian schists, gneisses, and intrusives which have been elevated to form part of the Southern Rocky Mountain physiographic province. The region is noted mainly for its production of gold and silver, but ores of tungsten, fluorspar, uranium, copper, and iron have been worked. Geological literature describes pitchblende and other radioactive minerals occurring at Jamestown, Boulder County; Central City, Gilpin County; and Lawson, Clear Creek County (fig. 1). These three adjoining counties cover most of the highly mineralized section of the Front Range which extends from James- town to Breckenridge. As far as the writer is aware, uranium has been found only in the portion north-east of Lawson.

Jan 1, 1950

By W. P. Frey

The briquet plant of the Lehigh Coal and Navigation Co., at Lansford, Pa., has previously been referred to.' It has passed the stage of experiment and now rests on a foundation practically and financially sound. The purpose of this' paper is to explain how success has been attained, and to set standards for the development of hard-coal briquetting which may eliminate future failures. All the conclusions are based on actual results, avoiding speculation and theory. Up to three years ago, the L. C. & N. Co. used coal-tar pitch as a binder in making hard-coal briquets. The plant operated with a monthly output of 300 to 600 tons and was unable to meet its own expenses. Naturally, no one was satisfied, especially as the ideals of a smokeless briquet were still unrealized. Then came the Dutch oil process, introduced in this country by the General Briquetting Co. of New York. This process uses as binder a small percentage of heavy residue of petroleum, which, being liquid, permits great economy of handling; it also did away with the most objectionable fumes of the former briquets. This oil2 is not absolutely smokeless; heating the fresh fuel to red heat liberates some low-volatile hydrocarbons, yielding a white smoke which is not objectionable. On the other hand, this oil adds to the briquet about 7 per cent. of volatile matter, giving the product a heating capacity equal to that of the best free-burning anthracite coal. The average silt used in the manufacture of these boulets averages 16.5 per cent. chemical ash, corresponding to 12,000 B.t.u. per pound of coal. The Hydrolene used as binder runs about 17,500 B.t.u. per pound, and approximately 7 per cent. of it enters into the mixture, hence 12,000 X 0.93..........................11,160 B.t.n. 17,500 X 0.07.......................... 1,125 B.t.u. Total.....................................12,385 B.t.u. per pound of briquets

Jan 1, 1918

Welfare endeavor in connection with both the metal and the coal mines of Utah has shown gratifying progress during recent years and both the operators and their employees are deserving of much credit for the efforts put forth to better living, working, educational and receational conditions in most of the mining camps of the state. In the older metal mining camps of Utah, where the towns are incorporated and independent of the mining properties operating in the vicinity, less opportunity is presented for the companies to exercise efforts looking towards improved welfare conditions than is the case of camps located on company ground and under the full control of operators.

Jan 1, 1925

By J. S. Lasater

Resu1ts of experinmental measurernents of heat capacities and thermal conductivities of some typical porous rocks are presented. Measured heat capacities agree closely with va1ues calculated front known chenlical . compositions of the rocks. On the basis of this agreement, heat capacitir.7 of fluid-satttrated rocks were calc~ililted. Therrnal conductivities of the rock samples were measured under varioits conditions of fluid saturation. From these data therrnal dif-fvsivities were calculated. A significant variation of thermal diflusivity with trnlperature is indicated. Knowledge of the thermal characteristics of fluid-bearing porous rocks has become increasingly important with the development of thermal oil-recovery processes. Reliable thermal data for petroleum reservoir rocks are not available and approximate values are generally assumed for reservoir calculations. 'The effects of temperature, pressure and fluid saturation on thermal properties of porous rocks have not been carefully studied. The purpose of the present work was to measure and report the thermal characteristics of some typical porous rocks. A group of eight sedimentary rock samples, including limestone, shale, sandstone and silt-stone, was selected for the study. Properties reported include heat capacities, thermal conductivities and thermal diffusivities. The effect of fluid saturation on these properties was also considered. Determinations of thermal properties require precise measurements which are time consuming and difficult to reduce to a routine basis. Methods have not been developed for measurement of thermal proper-ties under conditions of pressure, temperature, and fluid saturation, which may be encountered in thermal recovery processes. As one approach to these problems, some preliminary work on methods of estimating thermal properties from other more readily measurable characteristics of the rock-fluid system is reported. The samples selected for the studies were oilfield cores from within, or closely associated with oil-productive zones. Descriptions of individual samples are given in Table 1. Clay minerals present in the samples were determined by differential thermal analysis (DTA). Quartz content was estimated from DTA cooling curves. For all but the thermal conductivity tests, a representative 200-gm sample of each core was disaggregated, thoroughly extracted in diox-ane and oven dried at 100°C. The cleaned and dried sample was care- fully split into appropriate portions for the several tests. Chemical analyses of the samples were obtained to permit calculations of heat capacities by methods which are outlined later. Resuits of chenlical analyses are given in Table 2. Heat contents of the test samples were measured by a Runsen-type calorimeter. The heat content of the unknown sample is measured relative to the known heat content of platinum. The apparatus is referred to as a relative error type because of the comparative measurements, and has the advantage of canceling systematic errors. Experimental results are reproducible within 0.5 per cent. A temperature base of 298.16 K is taken for heat content measurements. Measurements were made at five temperatures (260, 440, 620, 800 and 980° F). It was necessary to preheal the sample above the maximum experimental temperature to eliminate volatile constituents. Assuming the weight loss on pre-heat, ing was mostly water, a correction to the observed heat content was made to account for the water originally present in the sample. This latter procedure was followed in the determination of calculated heat contents as will be described later. The apparatus and the method of measure-

By H. A. Dierks

PENNSYLVANIA's anthracite region lies in the heart of the richest and most densely populated area of the U. S. Nearly 70 million people live within a radius of 500 miles, in which 130,000 manufacturing plants employ more than 8 million workers. The region comprises some 3000 sq miles and contains 484 sq miles of coal measures, which folding and erosion have divided into four separate and distinct fields, known as the Northern, Eastern Middle, Western Middle, and Southern.

Jan 10, 1957

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965