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By M. Bourgon

The conductivity of liquid copper sulfide has been measured as a function of the mole fraction of sulfur in the melt at three temperatures: 1170°, 1250°, and 1300°C. The results show that a) the conductivity of copper-rich Cu,S is independent of the sulfur pressure in the furnace, and b) the conductivity of sulfur-rich copper sulfide increases rapidly with sulfur pressure. Assuming that the band theory is applicable to liquids leads to the conclusion that copper-rich copper sulfide is an intrinsic semiconductor, in which case electrons act as carriers. The activation energy for conduction in this case has been calculated to be 0.7 ev. On the other hand, sulfur-rich copper sulfide behaves as a p-type semiconductor, positive holes being responsible for conduction. IN order to elucidate the structure of Liquid copper (1) sulfide, Derge, Pound, and Osuchl have studied the electrical conductivity of this compound as a function of temperature. Their results showed that the conductivity is rather high, of the order of 100 ohm" cm", and that the temperature coefficient of conductivity is positive. This high conductivity seemed to indicate electronic rather than ionic conduction. This conclusion was checked further by Derge, Pound, and Yang,2 who measured the current efficiencies of copper sulfide melts at various temperatures. In all cases, the current efficiency was found to be nil, indicating the absence of appreciable ionic contribution to the conduction in

Jan 1, 1958

By B. J. Dotson, P. N. McCreery, R. L. Slobod, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By P. N. McCreery, R. L. Slobod, B. J. Dotson, James W. Spurlock

A core sample porosity-check program is described. A number of laboratories participated in the investigation. which comprised measuring the porosities of ten selected natural and synthetic core samples. Each laboratory employed its own method (or methods) of measurement. These included Boyle's Law, water-saturation. and organic liquid-saturation methods. Brief descriptions of each method employed are given. In general, the measured values of porosity were in reasonably good agreement. The average deviation of porosity from the mean or average values for the group of samples was ±0.5 porosity per cent. The results of these measurements are compiled and presented in graphical form. INTRODUCTION The total hulk volume of a porous sample is derived from the sum of two volumes, the void or pore volume and the solid* or grain volume. The porosity fraction of the sample ia defined as the ratio of the void volume to the bulk volume. Multiplication of this ratio by 100 converts it to per cent porosity. Distinction is made here between total porosity and effective porosity. The former includes all void space, both interconnected and isolated, while the latter includes only those voids which are interconnected. This investigation deals only with the effective porosity.* Numerous cases had been noticed in which there appeared to be appreciable discrepancies in the results of porosity determinations on core samples. Differences of as much as 10 to 15 porosity per cent had been reported from different sources

Jan 1, 1951

By T. Tanaka, H. Kiuchi

The combination of the following two exothermic reactions was studied with the purpose of recovering H2 from H2S formed in acid leaching of sulfide ores, direct reduction of metal sulfides with H2 or desulfurization of crude oils: In the kinetic study of the recovery of H2, the reaction rate was measured by the two methods of single-stage and circulation blowing of H2S through molten Pb in the temperature range of 550 to 750°C. The experimental results showed that the rate determining step is in the chemical reaction itself and also that this reaction is accelerated markedly by the addition of a trace of Ni, which may be responsible for the catalytic action of Ni dissolved in molten Pb. In the experiments where Pb metal was produced, PbS was oxidized in a stream of atmospheric N2 containing 0.5 to 20 vol-% 02 or in the same 02 partial pressures as in N2 though under reduced pressures in the temperature range of 400 to 800°C. It was found from these experiments that the formation of PbSO4, basic sulfates and PbO are suppressable to yield Pb metal alone above 750°C and for 02 concentrations of less than 1 vol-%. Vapor of PbS was thought to take an important part in the Pb formation mechanism, and the probability thereof was demonstrated thermodynamically.

Jan 1, 1978

By T. F. Archbold, R. E. Grace

The use of interference colors is the simplest experimental way to determine the approximate film thicknesses of oxides formed on liquid metals. A large amount of data under various conditions can be obtained easily and quickly. The oxidation of liquid lead has been studied by several investigators,1-5 but all of these studies have been on thick oxide scales. The purpose of- this work was to investigate the range 0 to 2000A film thickness. By using electron diffraction, Jenkins concluded that the surface of the film on molten lead is yellow orthorhombic PbO with the (110) planes parallel to the surface. This was confirmed by Shimaoka and Yamai7 who also used electron diffraction from the melting point of lead to 730°C. The rate of oxidation of pure liquid lead in air was measured in the temperature range 453" to 643°C by observing the rate of formation of interference colors on static lead baths. Approximately 170 g of lead (99.999 pct) was placed in a refractory dish having a working surface of 13.8 sq cm. This crucible was placed in a deep-well resistance furnace open to the atmosphere. The times at which the various interference colors appeared, after wiping the molten metal surface clean, were determined at 453", 533°, 600°, and 643°C. Elapsed times were determined with a stopwatch and all colors were estimated by eye. Bath temperatures

Jan 1, 1959

By Frank Nicholson

Copper ore was first noticed in Ste. Genevieve County in 1563. The diswvery mas made by a German farmer named Simon Grass, who had occasion to make a road from his farm down the hill into the neighboring valley, and while so engaged noticed pieces of a green-colored mineral, some of which he collected. Not knowing the character of the ore he had found, and supposing it to be valua ble for its brilliant green color only, he carried a piece with him into the town of Ste. Genevieve and showed it around the various bar rooms as a curiosity. No special attention was paid to the matter until nine years later, when Mr. 0. D. Harris sent a specimen of the ore to Dr. Theodore Fay, of St. Louis, for analysis. This analysis, which was the first ever made of Ste. Genevieve copper ore, showed the specimen to contain : Copper,. .........17.75 per cent. Zinc,..........3.21 " Iron........... 24.50 " Sulphur ..........1.09 " Organic matter, silica, carbon, and oxygen,. .. 53.45 " 100.00 " From this analysis it is evident that the sample was taken from near the surface, and was probably recognized by its green color. The almost entire absence of sulphur proves it to be an oxidized form. There is on file, at the office of the Ste. Genevieve Copper Works, a paper* giving three arsays of the ore made in 1875 by Henry B.

Jan 1, 1882

By V. Damiano, M. Herman

CELLULAR substructure observed in metal crystals grown from the melt. has been studied extensively'-' and is attributed to the existence of a constitutionally supercooled zone in the liquid ahead of the solidifying interface. The mathematical description of this process has been given in terms of the concentration of solute in the liquid phase, the rate of solidification, and the temperature gradien.t in the liquid as the only variables.5 This technical note presents some evidence of 1) the effect of crystal orientation on some aspects of cellular growth, and 2:) the degeneracy of these cells into dislocation arrays. The zinc single crystals used in these studies were alloyed with cadmium sufficient to produce the constitutional supercooled cellular substructure. Crystals containing 0.05 pct Cd exhibited substructure formation for a growth rate of 10 cm per hr and a temperature gradient of 15°C per cm in accord with the theory. The growing liquid-solid interface was examined after we liquid had been decanted away in a fashion similar to that described by Rutter and Chamers.' The cellular substructure was also observed after polishing and etching the surface directly behind the decanted interface with a solution of HNO, and water. Fig. 1 is a photomicrograph of a typical polished and etched surface revealing substructure, the cleavage plane, and twins. The crystal has been grown with its basal plane parallel to the direction of growth and the plane of the micrograph is per-

Jan 1, 1960

By F. W. Robinson

THE temperature coefficient of electrical resistance of pure metals is high and therefore the resistance increases rapidly with rising temperature. In 1871, Siemens suggested the use of this property as an accurate means of temperature determination. Owing to practical difficulties, particularly the contamination of the metal and consequent permanent change in its resistance and its resistance-temperature relation, this method fell into disrepute as a practical standard until revived later by Callendar and Griffiths, and subsequently by Holborn and Wien, all of whom showed that the earlier difficulties were not inherent in the method but incident to the mode of protection of the resistance coils. Following .the work of these investigators, the problem of temperature measurement by this means has been the subject of careful study and has now assumed an importance second only in practical adoption to the thermo-electric method. It is generally recognized, both here and in Europe, that the standard temperature scale should be the thermodynamic as it permits the evaluation of high temperatures on the basis of the radiation laws of Stefan and Bolzmann, of Rayleigh, and of Wien and Planck, on a scale consistent with that obtained by means of the gas thermometer at low temperatures. Lord Kelvin showed that only. a very small correction, amounting to about +0.7° at 1000° C.-almost within the limits of experimental errors-is necessary to adjust the constant-volume nitrogen thermometer to the ideal thermodynamic scale.

Jan 9, 1919

By John P. Norton

Microcrystalline silica has been mined in Illinois from the Clear Creek Formation since the turn of the century, especially in the area around Tamms in Alexander County, in the southernmost part of the state. This silica is consumed mainly by the abrasives and coatings industries, but is also sought after for many filler/extender uses. Production has grown with the economy with several new applications overshadowing traditional markets in recent years. Many of these applications are directly or indirectly related to energy saving factors. As a result of the "energy crisis" and "resin crunch," fillers have received a great deal of renewed attention as a desirable way of stretching the available resin supplies. With feedstocks in short supply and shortages existing in the entire petrochemical industry, the use of bulk materials to improve and extend existing resin is becoming an every increasingly important facet of plastics and coatings technology. Silica is the choise of fillers in applications where inertness, hardness, and low absorption are necessary characteristics. Microcrystalline silica has the additional advantage of being relatively easy to grind because the crude ore is a friable rock composed of tiny crystallites, many less than 0.1 u in diameter. Grinding represents a significant energy input in the production of silica flours. With energy costs increasing rapidly, comparable grades of silica flour made from microcrystalline silica have advanced less in price and it is expected this trend will continue in favor of the microcrystalline silica.

Jan 1, 1978

By Robert W. Zimmerman

POROUS SOLID COMPRESSIBILITIES There are four different compressibilities associated with porous solids, each relating the fractional change in either bulk volume or pore volume with the change in either pore pressure or confining pressure. These will be referred to as Cbc, Cbp, Cpc, and Cpp, with the first subscript denoting the relevant volume, and the second subscript denoting the relevant pressure. They are defined as: [ ] Note that minus signs are included in two of the definitions so that each of the compressibilities will always have a positive value. In general, each compressibility depends on the elastic moduli of the matrix material, the porosity, and the exact geometry of the pores. Taking the latter factor into account calls for separate analysis for each different pore shape, which of course can only be attempted for a few relatively simple cases. But lower bounds for each of the four compressibilities can be found, independant of pore structure, in terms of only the porosity (0) and the elastic moduli of the matrix material (any pair chosen from K, E, G and V). The first step is to find relationships between the four compressibilities, starting with the following observation: If a porous solid made of a linear elastic, isotropic and homogeneous matrix material is subjected to uniform hydrostatic pressure of magnitude P on its external and all of its internal (pore) surfaces, the state of stress in the solid will be exactly the same as that which would occur

Jan 1, 1982

By C. A. Lemke

THE ores now milled at the Midvale concentrator of the United States Smelting, Refining & Mining Co. come mostly from ;the company's mine in the Bingham district, about 18 miles west of Midvale. Custom ores from this same district and from other western mining districts are also milled at times. The Bingham ores consist of galena, pyrite, chalcopyrite, and sphalerite in a gangue of quartz, quartzite, limestone, and porphyry. The percentage of chalcopyrite is small, usually about 0.5 per cent., while the galena, pyrite, and sphalerite combined constitute about 60 per cent. of the total ore. These three minerals vary considerably' in amount and, at times, all three are somewhat oxidized. The ores also contain gold and silver, the former being mostly in the pyrite while the latter is generally with the galena. The crystallization of the economic minerals varies from fairly coarse to extremely fine. The ores are carried to Midvale by the Bingham & Garfield and the Los Angeles & Salt Lake railroads or by the Denver h Rio Grande Western railroad, in 50-ton, steel, full dump cars. The milling problem is to recover the silver-bearing galena, the gold-bearing pyrite, and the chalcopyrite in a product suitable for the lead smelter and containing the least possible amount of gangue and sphalerite and then recover the sphalerite in a product suitable for a zinc smelter. The minerals are recovered partly by water concentration and partly by water concentration combined with electrostatic treatment.

Jan 9, 1925

By J. C. Mertz, C. H. Mathewson

Accurate knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these components. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccuracies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in consideration of the uncertainties thus made apparent, presents new X-ray data obtained with the first three members of this group. Copper-phosphorus System Heyn and Baurl found that in slowly cooled alloys phosphorus forms a solid solution with copper up to about 0.175 per cent. Huntington

Jan 1, 1937

By L. L. Hirsch, W. M. Parris, P. D. Frost

IT has been established that titanium alloys con- taining sufficient amounts of ß-stabilizing elements, such as iron, chromium, or manganese, can be age hardened.' Adenstedt, Pequignot, and Raymer2 showed that age hardening occurred in a Ti-15 pct V alloy at room temperature after it was quenched from a temperature in the ß-phase region. During a recent investigation of the heat-treating characteristics of binary Ti-Mn and Ti-Cr alloys at Battelle, further evidence of low temperature aging was found. Appreciable hardening occurred in some of these alloys at aging temperatures as low as 212 OF (100oC). Indeed, the brief heating period employed for mounting metallographic specimens in bakelite resulted in hardening. It was felt that further information on this low temperature aging phenomenon would be of general interest in view of the large amount of work currently being done on titanium alloys. The alloys examined in this investigation were arc-melted in a water-cooled copper crucible as 3/4-lb ingots. Du Pont Process A sponge was used as a base material. The arc-melted ingots were forged at 1700" to 1800°F (927" to 982°C) and hot rolled at 1450°F (788°C) to 14 gage (0.064 in.) sheet. Small specimens were heated in argon at 1742°F (950°C) for 30 min and quenched in various liquid media or air cooled. They were then mounted in a room-temperature-setting resin and given a metallographic

Jan 1, 1954

By Frank M. Randall

The Buick mill is located at the site of the old Buick general store, approximately 4 miles south of Bixby, Missouri on route KK. It is a part of the operations in the area now called the "New Lead Belt". The ore body lies at an elevation of 270 feet above sea level, and is fairly flat lying, becoming slightly deeper toward the south. The mineralization is due to the secondary deposition of galena, sphalerite, chalcopyrite, pyrite, calcite, dolomite and some localized drusy quartz in a country rock of dolomitic limestone. The galena is fairly coarse grained with some large crystaline structure, and some oxidized surfaces. The sphalerite is fine grained- small crystals containing Cd (about 0.7%) and Ag (about 10 oz per ton) in solid solution. The chalcopyrite is fine grained, fine crystals that are sometimes massive in nature. The mine plan is a modified room and pillar system. Broken ore at the mine face will be transported to several different ore passes by rubber tired load-haul-dump units. Ore passes will drop the ore to a rail haulage level some 90 feet below the mining level where bottom dump cars will deliver it to a 42 in. Nordberg gyratory crusher. Two 12 ton capacity skips in balance carry the ore some 1,200 feet to the surface. The hoist is equipped with automatic controls for loading, hoisting and unloading.

Jan 1, 1970

By A. Boltax

The effect of cold work on the electrical and magnetic properties of solution-treated and aged Cu-Fe alloys was studied. The electrical resistivity of solution-treated and of aged Cu-1.7 wt pct Fe samples increased by up to 25 and 140 pct, respectively, follozcing a 55 pct reduction of area. The principle contributions to the increase of resistivity of the solution-treated and aged samfiles are examined. Measurements of the .saturation induction, coercive force, and stacking fault Probability are also reported. 1 HIS paper is the second in a series which examine the behavior of the electrical and magnetic prop- erties of Cu-Fe alloys. The first paper1 was primarily concerned with the effects of thermal treatment whereas the present paper examines the effects of cold work on solution-treated and aged Cu-Fe alloys. The effects of cold work on the transformation of the coherent fcc iron precipitate to the ferromagnetic form2 and the coercive force and remanence3 have already been described, but the unusually large increases in resistivity (up to 220 pct) which occlir with cold work have not been reported previously. EXPERIMENTAL METHOD The methods used for alloy preparation, heat treatment, and electrical and magnetic measurements are described elsewhere.1 The specimens, initially 4-in. lengths of 0.0625-in. diam wire, were cold worked by swaging in hardened steel dies. Following each reduction, the samples were etched lightly in hydrochloric acid to remove surface con-

Jan 1, 1962

By G. J. Wolga, W. W. Tyler, A. C. Wilson

THE physical properties of uranium have been reviewed by Katz and Rabinowitch.1 Their review includes thermal conductivity data for ternperatures above 375°K. Recently, Mendelssohn and Rosenberg' have published data on the thermal conductivity of uranium from 2" to 20°K. Our measuremerits indicate the temperature dependence of the thermal conductivity in the temperature interval from 20" to 300°K. Electrical resistivity and thermoelectric power were measured on the same sample. The material studied was normal uranium which had been heated at 700°C in a lead bath for 10 min and then quenched in a water bath held at 50°C. From this material a rod M in. in diameter and 2 1/2 in. long was machined. Two 0.040 in. holes were drilled into the rod 1 3/4 in. apart. Copper-constantan thermocouples for temperature and potential measurements were soldered to copper pins which were pressed tightly into these holes. Details of the equipment and experimental techniques used in making the measurements have been described elsewhere." Fig. 1 shows micrographs of a section of the sample studied. Fig. la was taken with unpolarized light and shows impurity inclusions, probably uranium carbide. Fig. lb, showing the same field, was taken with polarized light and gives some indication of the grain size and twinning within the grains. Experimental Results Thermal conductivity and electrical resistivity data are shown in Fig. 2. Table I shows values of

Jan 1, 1954

The following is an incomplete list of members and guests who called at Institute headquarters `during the period Aug. 10, 1918 to Sept. 10, 1918. Amil A. Anderson, Hill City, S. D. A. A. Holland. H. G. S: Anderson, Hurley, N. Al. Paul S. King, Wilmington, Del. Louis A. Barton, Capt., Engineers, U. S. A. Herbert G. Officer, Washington, D. C. K. Baumgarten, lst Lieut., U. S. R. A. B. Parsons. Charles W. Boise, Belgian Congo. Robert R. Pollock, San Francisco, Cal. Henry C. Carlisle, The Pas, Manitoba. Frank A. Smith, Edgewood, Md. J. Ross Corbin, Boyertown, Pa. Edward C. Thompson, Kennett, Cal. S. Le Fevre, Forest Glen, N. V. Malcolm M. Thompson, Morsemere, N. J. Harold P. Ford, Cleveland, 0. Lester C. Uren, Berkeley, Cal. William L. Hogg, Waynesboro, Va. Harold W. Aldrich has been appointed assistant general superintendent of the Inspiration Consolidated Copper Co. at Inspiration, Ariz. Capt. Percy E. Barbour, formerly with the New York State Troopers, has been granted a leave of absence from the Department for the period of the war, by the Governor, and has been appointed Captain in the Engineer Corps, U. S. A. He served on the Mexican border in the New York State National Guard. A. C. Barke, formerly with the United States Smelting, Refining and Mining Exploration Co., has accepted a position with the United States Fuel Co. at' Salt Lake City, Utah.

Jan 10, 1918

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do's or the H'S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.' In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,' the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.' Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.' The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.'' Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

By George W. King

The yield strength of a dispersion-hardened W-3.8 vol pct Tho,alloy, in both the recovered and recrys-tallized condition, was investigated and cornpared with that ofrecrystallized pure tungsten over the temperature range of 325" to 2400°C. It is deduced that the Orowan mechanism is obeyed in the recrystallized alloy. In the recovered alloy, a further enhancement of the yield strength results from the retained substructure which is stable up to temperatures in excess of 2700°C. Temperature and strain rate cycling tests were also performed, and the apparent activation energy for the deformation process was derived. This activation energy, - 3 ev, for the recovered and also the recrystallized alloy was about the same as that for re crystallized pure tungsten. However, the activation volume of the recovered alloy, -10-2 cu cm, was about an order of magnitude lower than that of the recrystallized alloy or pure tungsten. This fact accounts for an enhancement oj- the temperature dependence of the yield stress of the recovered alloy. A dislocation velocity exponent of about 4 to 13 was deduced frorn the strain rate cycling tests , which is in good agreement with values reported for tungsten single crystals. VARIOUS theories have been developed to explain the enhanced yield strength of a metal containing a dispersed second phase of small hard particles. These theories are thoroughly reviewed by Kelly and Nicholson.' The theoretical models can be separated into two types. The first type assumes direct interactions between moving dislocations and dispersoids. One of the most widely investigated models for this mechanism is the bowing out of dislocations between the dis-persoids and their subsequent pinching off in order to bypass the obstacles. This is the well-known Orowan mechanism.' The second type is an indirect effect of the dispersion because of its ability to stabilize to high temperatures the substructure introduced by cold working. In this instance, the increment in the yield strength is expected to be inversely proportional to the square root of the subgrain diameter. In the present work, a quantitative study was made of the strengthening effect caused by a thoria dispersion in a recrystallized W-3.8 vol pct Thoz alloy over the temperature range 325" to 2400°C. The results are compared with the increment predicted for the Orowan mechanism based on the calculations by ~shb~.~ In addition, the alloy was tested in the recovered state so that any additional strengthening resulting from the substructure produced during fabrication could be measured. The respective contributions can be separated in this manner, provided that the particle size distribution of the dispersion remains the same in both the work-hardened and the recrystallized state. Particle size distribution measurements showed that this condition was met in the present work. I) EXPERIMENTAL PROCEDURES A) Material Production and Fabrication. The alloy investigated is essentially the same as that reported much earlier by ~effries,~ who also found the strength of tungsten to be improved by the thoria dispersion. The procedure for producing the alloy consisted of mechanically blending a thorium nitrate solution in proper concentration with tungsten oxide (WO3) powder, followed by hydrogen reduction to metal powder. After reduction, the dispersed second phase is present as thoria (Thoz). The pure tungsten powder used for comparison was produced in the same manner except that the thoria doping step was omitted. The powders were consolidated by cold pressing and self-resistance sintering in hydrogen. The resulting ingot had a cross section about 0.6 sq in. and a density about 93 pct of theoretical. The ingot was swaged to 0.174-in.-diam rod at temperatures varying from 1650°C initially to -1200°C near final rod sizes. Two intermediate recrystallization anneals were employed during fabrication. Analysis of the swaged rods is reported in Table I. B) Electron Microscopy Techniques. Carbon extraction rrPxcas prepared by a technique reported by ~00' were used to quantitatively evaluate the thoria particle size and distribution. Electron nlicrographs of extraction replicas were taken at 20,000 times but were then enlarged two to three times in printing. The areas photographed were randomly selected. A Zeiss Particle Size Analyzer (Model TGZ3) was used to count and measure the sizes of all particles present on the print. About three thousand particles were counted in determining a distribution curve. Electron transmission microscopy was used to determine the effect of annealing on the substructures of the materials. Thin foils were produced by a two-stage thinning process. The rods were first ground on emery paper to ribbons about 10 mils thick and then a jet of 5 pct KOH was used to electrolytically reduce a portion of the cross section of the ribbon. Final perforation was achieved by immersing the specimen in a 5 pct KOH solution and electrolytically polishing at a current density of about 0.3 amp cm-'. The foils were examined with a Hitachi HU-11A electron microscope. C) Tensile Testing. Tensile testing was performed in an Instron Testing Machine equipped with a radiation-type vacuum furnace which operates at about 1O"S torr at temperatures as high as 2400 °C. The same furnace was used for annealing the tensile specimens.

Jan 1, 1970

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te' forms on cooling at 829°K by a peritectic reaction.' Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l'' It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~'~ The heats of formation of InSb at 78", 273', 298", and 723°K have been measured5-' and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968