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LIMA (PERU) Established May, 1952 (Official year begins in June) Luncheon meetings third Wednesday monthly Ernesto A Baertl, Chairman Arthur C Hall, Chairman-elect Raymond R Beard, 1st Vice-Chairman Edgardo Portaro, 2nd Vice-Chairman Walter E King, Secretary-Treasurer Av Santa Cruz 331 San Isidro, Lima, Peru Alberto E Brazzini, Asst Treasurer Daniel M Rodriguez, Asst Secretary Robert P Koenig, '56, Section Delegate Arthur C Hall, Alternate Section Delegate

Jan 1, 1955

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship' to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,' using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager's extenbion of Fick's first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964

By S. J. Matas, R. F. Hehemann, R. H. Goodenow

The hot-stage metallographic method has been employed to determine radial growth rates of upper and lower bainite. Lower bainite appears to grow as individual plates that increase in both length and thickness while upper bainite grows as sheaves of closely spaced plates or needles. A discontinuity in the temperature dependence of the growth rate appears to be associated with the transition from upper to lower bainite and stepped quenching experiments suggest that lower bainite will not continue to grow when the temperature is raised to the upper range. Thus, a single process does not appear to control the growth of both upper and lower bainite. A tentative model based on the forces acting on a dislocation interface is proposed to account for the slow growth of bainite. It has been recognized since the early studies of Davenport and Bain that a close relationship exists between the martensite and bainite transformations in steels. However, diffusion of carbon during the transformation has lead to considerable controversy concerning the reaction mechanism.1-7 Many studies4,5,7-9 have emphasized the structura and kinetic aspects of the bainite reaction and, in particular, the difference observed between the two forms of bainite—frequently termed upper and lower bainite. A kinetic difference between the two types of bainite has been revealed in the activation energy determined from the overall reaction;4,5 however, many difficulties arise in an interpretation of these activation energies since a number of temperature dependent factors contribute to the kinetics of the overall reaction. The displacive surface relief10 accompanying the bainite reaction permits a separation of the nuclea-tion and growth contributions to the reaction and allows the kinetics of the growth process to be examined. Several investigations of this type have been conducted; however, they have been restricted to the low temperature range.3'6'11 Here, bainite plates are observed to grow slowly in both length and width. The present investigation extends such studies to include the upper bainite range. MATERIALS AND PROCEDURE Materials. The composition of the steels studied in this investigation are presented in Table I. The range of composition permitted a study of the effect of carbon content on the growth rate of upper bainite in the 9 pct Ni steels and consideration of both upper and lower bainite in the higher carbon steels. These steels were received as hot-rolled rounds and were forged to approximately 1/2 in. thick plates for preparation of metallographic specimens. In order to produce an essentially zero carbon steel, Steel A was decarburized in wet hydrogen at 1550°F for 15 days with the result tabulated as Steel AD. Experimental Procedure. In order to study the slow growth of the displacive transformation product, a commercially available Leitz hot stage was modified to permit heating of the specimen by its own resistance in a manner similar to that employed by other investigators.6 The furnace chamber was maintained at a pressure of 2 to 3 X 10-5 mm Hg prior to austenitizing at 2000° ± 12° F for 5 min. Samples could be cooled from the austenitizing to the transformation temperature in approximately 15 sec and the progress of transformation was recorded with a 9 cm by 12 cm single frame camera or a 16 mm movie camera. RESULTS AND DISCUSSION Growth Characteristics. The general growth characteristics observed in this investigation were analogous to those reported previously.3,6,11 Typical growth sequences for the high temperature and low temperature forms are illustrated in Figs. 1 to 5. In both temperature ranges, bainite plates increase in length at slow, temperature dependent rates until interrupted by a grain boundary, another plate, or

Jan 1, 1963

[Alphabetic Section (Page 729): The letter following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute o f Metals K-Council o f Economics]

Jan 1, 1961

By George D. Graffin.

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3550°C at a triple point under 1250 psi. It sublimes between 3300-3500°C at 14.7 psi. At 3726°C a second triple point occurs at approximately 100,000 atmospheres. Thermal oxidation in the presence of oxygen begins at 300°C and the rate increases with temperature. The three forms of carbon (charcoal, graphite, and diamond) are distinguished by chemical and physical tests. The specific gravity of charcoal is 1.3 to 1.9, of graphite 2.266 g/ cm3 (crystal density), and of diamond 3.5. Graphite has a hardness of 1 to 2 (Mohs' scale). Natural graphite can be divided into three classes: disseminated flake, crystalline vein (fibrous or columnar), and amorphous. Flake graphite is a lamellar form found in metamorphic rocks, such as marble, gneiss, and schist. Each flake is separate, having crystallized as such in the rock. Crystalline vein graphite is found in the form of well defined veins or as pocket accumulations along the intrusive contacts of pegmatites with limestones. The graphite of such deposits is of two types, foliated and columnar. The important Sri Lanka (Ceylon) deposits are vein type. Amorphous graphite is commonly found as minute microcrystalline particles more or less uniformly distributed in feebly metamorphic rocks, such as slates and shales, or in beds consisting practically entirely of graphite. The latter usually are metamorphosed coal seams and carry as much as 80-85% graphitic carbon, while the former, being altered carbonaceous sediments, commonly range from 25 to 60%

Jan 1, 1983

By M. F. McCarty, R. S. Olson

New organic flocculants of high-molecular weight are replacing lime, glue, and starch in liquid-solid separation. Of these synthetic materials, poly-acrylamides are outstanding. Polyacrylamides form a class of compounds varying widely in composition and activity. Separan 2610, one of the first of these flocculants' released to the mining industry in 1954, is described' as a high-molecular weight polymer of acrylamide with or without a copolymer material and with some replacement of amide by carboxylic groups. MECHANISM OF FLOCCULATION In practice, flocculation makes solids settle faster and filter better. But two opposing factors control it. The random motion that causes particles to collide favors Van der Waals' forces, which hold the particles together. The effect of zeta potential opposes this contact, and particles are mutually repelled. Flocculation can be achieved by reducing the magnitude of the zeta potential; this is the mechanism of flocculation by lime addition. The way in which polyacrylamides accomplish flocculation is not fully understood, but the action is undoubtedly comp1ex and probably varies considerably depending on the system. To begin with, the active groups of these compounds have an extremely high affinity for solid surfaces, probably by hydrogen bonding." Initially some active groups of the molecule attach themselves to the solids with a large portion of the molecule extending into the solution. Two particles can become tied together by long flocculant molecules in the following ways—by bonding between the active groups of two flocculant molecules on different particles, or by an extended molecule from one particle attaching itself directly to the surface of the other particles." These flocculant bridges prevent the particles from moving apart through random motion, but when such motion moves them together other active groups on the flocculant bridge bond to the solids, holding them in the closer position. This process is repeated until the particles are close together. Although bridging is probably a major flocculation mechanism, it is not the only phenomenon involved. Relatively neutral acrylamide flocculants reduce the magnitude of the zeta potential by increasing the viscosity of solution in the immediate vicinity of the solid surface which contains the mobile counter ions of the double layer. In other words, it moves the shear surface which bounds the zeta potential out into the solution containing counter ions which tend to neutralize the zeta potential. This effect is probably more pronounced during the initial adsorption period, before the flocculant molecules are pulled close to the solid. In some cases the slight charge of the polyacry-lamide molecule tends to neutralize a zeta potential. However, this is not a primary flocculation mechanism, as evidenced by the fact that the polyacrylamides will flocculate solids with either positive or negative zeta potential. Adsorption of polyacrylamide flocculants by a solid is substantially an irreversible reaction. Since the flocculant molecule is attached to the particle surface by many active groups of high bonding strength, desorption would require the simultaneous breaking of many bonds—an unlikely occurrence. UNIQUE PROPERTIES The irreversible adsorption of certain polyacrylamides, the flocculant's high affinity for solid surfaces and its rapid adsorption make it effective, but these unique properties require special techniques to achieve maximum flocculation. If flocculants of this type are added to a pulp as a relatively concentrated solution, the solids in the

Jan 1, 1960

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By M. E. Straumanis, R. P. Shodhan

LATTICE parameters of molybdenum of various purities are summarized in Table I. The latter shows that the parameter fluctuates between 3.1467 and 3.1475A. The room-temperature expansion coefficient a is also not well-known as values from 4.90 to 5.20 x 10-6 can be found in the literature.=-' It, therefore, seemed appropriate to repeat the measurements under exactly controlled conditions, using high-purity Hilger molybdenum powder (containing 0.0015 wt pct of Fe, 0.005 of Si and traces of other elements) and a 99.95 pct pure Sylvania Electric preparation (containing Cr, Fe, Ni, Si, Sn, and C in amounts of 50 ppm of each and in still smaller amounts Cu, Pb, Mg, and Mn). Of course, both samples could have contained at least 0.01 pct of oxygen in form of a surface oxide. However, oxygen, because of its small solubility in molybdenum, does not influence its lattice constant.g The determinations were made in a cylindrical precision X-ray camera, 64 mm in diam, the temperature of which was controlled within *0.05"C, by inserting it into a special thermostat." To exclude the film shrinkage effect (after the development of the film), the asymmetric film placement method was used." Absorption corrections (e.g., by extrapolation)" were unnecessary because of the use of a thin Li-B-glass fiber (about 0.08 mm in diam) which was fastened to the sample holder of the camera and dusted with the fine molybdenum powder. Cum radiation of the wavelength 1.389350 kX was applied because it produced in 30 min the line (420) having a high Bragg angle of about 81.6 deg. The conversion factor of 1.00202 gave the results in angstroms. To obtain the expansion coefficient a, exposures were made at various temperatures t, see Fig. 1, on at least two films at each temperature. The films were measured with a componator and the lattice constants a were calculated. The expansion coefficient was found from: where a2s is the constant at 25°C and A is the change in a and t. The same equation (knowing a) was used to reduce all the constants obtained at various temperatures to that of 25"C, Table 11. The probable error S507p (at a 50 pct confidence limit) was calculated from the reduced constants:

Jan 1, 1969

By AIME AIME

SIR HENRY CORT HAROLD CARPENTER, F. R. S. professor of metallurgy at the Royal School of Mines, was presented with his Honorary Membership certificate in the A.I.M.E. on Oct. 18, at a luncheon in his honor in the Abraham Lincoln room of the Savoy Hotel in London. The presentation luncheon was attended by some thirty distinguished representatives of the academic and industrial British metallurgical world, all friends and acquaintances of Sir Harold. Frank W. Harbord and

Jan 1, 1938

By G. M. Ritcey, A. W. Ashbrook, E. G. Joe

Solvent-in-pulp extraction of uranium from acid leach slurries of flotation concentrates is described. Solvent extraction was carried out in a 10 in. diam pulsed-plate column. The extractant was a 0.1 M tertiary amine (General Mills Alamine 336) in a kerosene diluent containing isodecanol as an emulsion suppressor and third phase inhibitor. In pilot plant operation at the Beaverlodge mill of Eldorado Mining and Refining, Ltd., slurry feeds containing up to 35% solids were processed at a throughput rate of 13.5 tpd of dry feed. Uranium extraction obtained was as high as 98%. Amine losses to the raffinate were approximately 0.07 lb amine per ton of original dry feed. The Beaverlodge Mill of Eldorado Mining and Refining employs a carbonate leach for the extraction of uranium from the ore.',' Prior to carbonate leaching sulphides are removed by flotation to reduce reagent consumption. This flotation concentrate containing some uranium is then leached with sulfuric acid, filtered, and the uranium precipitated with magnesium hydroxide. The precipitate is then returned to the carbonate leach circuit. Although the tonnage of flotation concentrate treated by acid leaching is low, reagent costs are relatively high. Also maintenance costs on the acid leach filtration circuit were beginning to show significant increases. The choice of solvent extraction-in-pulp as an alternative to the present circuit was influenced by the following factors: 1) elimination of acid pulp filtration, 2) increase in overall recovery because of soluble loss elimination, 3) reduction of reagent cost (mill sodium carbonate solutions are used as strip), and 4) production of higher purity precipitate at the mill site. Because a solvent-in-pulp process would be difficult to test on a bench-scale, the Eldorado experience in the use of pulse columns,3-5 mixer-settlers,6 and solvent-in-pulp operations in particular7 was applied directly to the initial pilot plant carried out during the summer of 1965 and followed by the second pilot plant in 1966. The latter work, which is presented in this paper, determined the following factors for anticipated scale-up to plant production: 1) overall uranium recovery by this process, 2) tonnage throughput expected, and 3) solvent losses anticipated for the full-scale plant. The equipment used consisted of a 10 in. diam extraction pulse column and three mixer-settlers for scrubbing, stripping, and acid equilibration. All equipment was designed by Eldorado and much of the pilot plant was built at the mill site. PROCESS CHEMISTRY Feed to the acid leach plant consists of a sulphide flotation1,2 concentrate containing mainly pyrite, uranium and graphite, with a particle size of 90%

Jan 1, 1968

By John A. Hosking

The recent activity of numerous foreign mining companies in the once flourishing tin fields in Cornwall, England has resulted in renewed interest in the evaluation of hypothermal tin deposits. These deposits are mainly narrow tabular bodies and are usually steeply dipping. They exhibit thermal zoning the mineralization changing from lead/zinc through copper to tin with depth. The tin zone virtually never exceeds 1,000' in depth and the ore shoots within this zone tend to be erratic and localized. The grade which is presently considered to be economic is about 0.7% Sn. , this means a concentration of about l% cassiterite (the only economic mineral) which, being twice as heavy as the gange, represents only. 5% of the lode volumetrically. Within the lode, only one third may reach this economic grade and values within the shoots can range from 100% cassiterite to zero over a few inches. The enormity of the problem of evaluating such a deposit has not been fully appreciated by the companies involved whose experience has, for the main part, been in larger and more predictable ore bodies. This paper attempts to put these problems into perspective and out- lines the useful applicatations of statistical and computer techniques. It also stresses the need for enlightened interpretation of data by men familiar with the problem and that even in this day and age, educated, intuitive deduction should not yet be relegated to the limbo of alchemy and witchcraft.

Jan 1, 1969

[Alphabetic Section (Page 689): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute of Metals K-Council o f Economics]

Jan 1, 1961

By Martin Rubenstein

CdS crystals have been grown from a number of metallic solvents such as bismuth, tin, lead, and cadmium. Etching studies have shown that plastic deformation occurs if the crystals are not removed from the solvent prior to the solidification of the solvent, on cooling. The deformed crystals show a umique exciton fluorescence as a function of edge dislocation density. If one grows the CdS in the eutectic alloy of the above four metals (commonly called Wood's metal) the crystals can be removed from the solvent with hot water and no plastic deformation occurs. In this paper, the liquidus solubility measurements of CdS, as a function of temperature, are presented. The data were obtained using a high -temperature filtration technique. CADMIUM-SULFIDE crystals have been grown from a number of metallic solvents1 such as cadmium, bismuth, tin, and lead. Liquidus solubilities of CdS in cadmium,2 bismuth,3 and tin4 have already been measured. Crystals of CdS, in all four metals, have been grown by solution growth: 1) by cooling a saturated solution and 2) by a solution transport method.1'"1 CdS crystals grown in these four solvents have a few characteristics in common: 1) 1.8°K photolumines-cent emission consisted mainly of the radiative recombination of the bound exciton commonly known as I,, 2) slip lines which could easily be seen by the naked eye, and 3) edge dislocation densities in the order of l05 per cu cm.1 It was decided that these slip lines and the high edge dislocation densities were caused by a plastic deformation of the CdS crystals. It was felt that this plastic deformation did not occur during the growth of the crystals nor during the cooling of the solution, but did occur when the solvent which was in contact with the crystals froze. If these assumptions were valid, the slip lines and the high number of dislocations could be reduced or eliminated by removing the crystals from the solvent before the solvent froze. Since crystals of CdS had already been grown separately in such solvents as bismuth, lead, tin, and cadmium, it was felt that crystals could be grown in a eutectic mixture of these four metals. In this work a eutectic (or near eutectic) mixture of bismuth, lead, tin and cadmium in the proportion 50, 26.5, 13.5, and 10 wt pct, respectively, was used to grow CdS crystals. Such a mixture has a melting point of about 70°C and is close in composition to the alloy commonly known as Wood's metals. If the crystals could be grown from this mixture of solvents, and if hot water (>75°C) could be used to separate the crystals of CdS from the metallic solvent, it was hoped that CdS crystals could be grown with little or no plastic deformation which had been ob- served when crystals were grown from these solvents uncombined. CdS crystals were grown from this low melting eutectic mixture of bismuth, lead, tin, and cadmium using the solvent transport method. CdS powder and the appropriate amount of metals were sealed in a quartz tube under a pressure of about 5 X 10-6 torr. This ampule was then placed in a vertical position in a furnace. The temperature was raised to about 900°C. The furnace was designed so that the top of the liquid column within the ampule was between 10° to 40°C higher than the bottom of the liquid column. These temperatures were measured on the outside of the quartz ampule. The ampule was maintained at temperature for 7 to 14 days (depending on the temperature at which transport was taking place) and then the furnace temperature was lowered until the temperature was about 125°C. The ampule was then removed from the furnace, placed in water maintained at about 90°C, and opened in this 90°C environment. The crystals could then be removed from this two-phase liquid (Wood's metal and water) by mechanically picking them out. Alternatively, the crystals could be quantitatively removed by adding an excess of mercury to the mixture of metals, crystals, and hot water. The hot solution of metals and the hot water could be evacuated using a small diameter tube connected to a vacuum. Small amounts of mercury and water could be removed by heating the crystals in vacuum. Crystals prepared using this technique showed no evidence of slip. However, some of these crystals did show edge dislocation densities as high as l04 per cu cm. Some few selected crystals showed no dislocations. Single crystals of CdS were grown as large as 5 by 5 by 0.5 mm. The ampules for the growth of these crystals were 13 mm O.D., 11 mm I.D., 150 mm! LIQUIDUS SOLUBILITY MEASUREMENTS The CdS starting materials was G.E. 118-8-2 powder which was fired in H2S at 1000°C, and then a vapor transport technique5 was applied to produce a "sound" mass of CdS. The Wood's metal was prepared by weighing out bismuth, lead, tin, and cadmium in the proportions of 50, 26.5, 13.5, and 10 wt pct, respectively. The bismuth, cadmium, and lead were from the American Smelting and Refining Co. (ASARCO) and all had purities of 99.999+ pct. The tin was 99.9999 pct spectroscopic grade from the Vulcan Materials Co. The appropriate mixture was placed in a quartz tube, evacuated to a pressure of 5 X 10-6 torr, melted to a liquid, cooled to room temperature under this same vacuum. This ingot was then placed in another quartz tube, evacuated to 5 x l0-6 torr, and sealed off under vacuum. The ampule was then horizontally placed in a furnace. The temperature was raised to 600°C, and over a period of several hours the ampule was vigorously shaken several times. The ampule was then removed from the furnace, and the metallic liquid was

Jan 1, 1970

By W. G. Sinclair

The North Texas district incorporated in this paper corresponds with the Railroad Commission's District No. 9, and includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Jack, Knox, Montague, Wichita, Wilbarger, and Young.† Table I,Oil and Gas Production in North Texas District, has been changed to conform with the nomenclature of pools designated by the Commission in order to facilitate compilation of the data, since most of the companies operating in the area are coming more and more to recognize one central authority in the matter of naming each new oil pool. No effort is being made to discuss the structural characteristics of the region, since it is generally known by oil men that most of the oil and gas comes from Pennsyl-vanian, with some of less importance from the Mississippian and Ordovician. Development during 1944 There were 1550 wells drilled during 1944, an increase of 450. Of this number, 677 were completed as oil wells, and 11 as gassers. Production increased 1,505,025 bbl., making the year's total 43,172,005 bbl. of oil having an average gravity of 40". Development generally, however, was somewhat disappointing. The 47 new pools, extensions, or new pay horizons in old fields, had a combined initial production of only 19,146 bbl. It is estimated that these wells added approximately 10,000,000 bbl. to the reserves. The largest single addition to the reserves was in the Caddo conglomerate in the Hildreth pool, Montague County. During the year, 66 wells were completed as the result of three extensions, I to 136 miles west, northwest and north of the field. Young, Archer, and Clay were the most active counties. Eleven new potential - oil fields were developed in Young County, nine in Archer and nine in Clay. Outlook for 1945 In spite of the fact that exploration as a whole was disappointing in 1944, prospects for increased development are bright for 1945. At the close of last year, 2.1 geophysical crews were operating in the district, which, together with the Ohio Oil Company's No. I W. R. Ross, a wildcat Strawn discovery in King County, 1 1/2 miles beyond the west boundary of district 9, stimulated a lease play extending over four counties. Two of them, viz., Foard and Knox, are in the area incorporated in this report. Acknowledgments The writer is indebted to Mr. C. W. Hanley, Zone Agent of the North Texas District, and Mr. William M. Lourcey, head of the Land, Leasing and Scouting Department for the Gulf Oil Corporation, both of Fort Worth, Texas, for permission to prepare this paper.

Jan 1, 1945

[Alphabetic Section (Page 1): The letter immediately following the member's name indicates grade: M-Member, A-Associate, J-Junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary Divisional affiliation: A-Mining & Exploration F-Coal B-Minerals Beneficiation G-Petroleum C-Iron and Steel H-Industrial Minerals D-Extractive Metallurgy J-Council o f Education E-Institute o f Metals K-Council o f Economics]

Jan 1, 1961

By Pierre J. Goossens

The coastal Cordillera around the Panama basin is made up of a Cu-rich tholeiitic volcanic belt representing either immature, late Mesozoic, island arc, or oceanic ridge. The same belt is exposed (uplifted) along the western slope of the Cordillera Occidental of Ecuador and Colombia. Ni-lateritic, Cr-podiform, and Pt-(Au) placer deposits are formed there after or within ultramafic bodies of oceanic association. Younger calc-alkaline igneous activity provided the mechanism for porphyry copper and associated ore formation. This Cu (+Mo) mineralization occurs along a narrow belt exposed by the erosion of the volcanic cap. Ag-Pb-Zn(-Au) and Hg volcanogenic mineralizations occur within the calc-alkaline belt, but slightly eastward and only above the copper belt. To the east and in the Venezuelan Andes, Paleozoic and older sediments, volcanics, and metamorphics contain volcanogenic massive sulfide, Pb-Zn, Au, and Cu sedimentary and vein deposits, and sedimentary iron ore and phosphate. The Cenozoic Cu, Ni-Pt-Cr and a portion of Ag-Pb-Zn, Hg, and Au mineralizations occur within or just above the oceanic basement whereas the eastern- most Cenozoic Ag-Pb-Zn mineralizations occur within and above a pre-Cenozoic sialic basement. This continental crust is the northern extension of the Peru-Chilean Andes where no oceanic crust has been preserved, however. Cenozoic metallogeny and subduction relationships are unclear in the Northern Andes. Yet strong structural volcanogenic ore controls exists apparently due to deep strike-slip movement between two plates.

Jan 1, 1977

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Nicholas J. Grant, Olaf Troili, John Chipman

IN recent studies of the factors which affect the rate of desulphurization and its equilibrium, it became apparent that certain concurrent reactions were operative which had a significant effect on desulphurization. This is emphasized in the experiments of Hatch and Chipman1 and of Grant, Kalling, and Chipman' by the slow approach to a final state of equilibrium which is in marked contrast to the initial rapid transfer of sulphur from metal to slag. Since the removal of sulphur is of such profound importance in iron and steelmaking, it appeared necessary to investigate the reactions responsible for this behavior. It is now known that the presence of iron oxide in the slag interferes seriously with the principal reaction of blast-furnace desulphurization: CaO (slag) +-S + C - CaS (slag) + CO [l] The interfering reaction is most simply expressed as: CaS (slag) + 0 = CaO (slag) +-S 121 and a small concentration of oxygen (or FeO) is sufficient to hold a considerable amount of sulphur in the metal. It has been shown by Grant, Kalling, and Chipman2 that the addition of MnO to blast-furnace slag slows the removal of sulphur from the metal. This effect overshadows the contribution of MnO to basicity and is ascribed to its oxidizing power. It will be shown in this paper that SiO, also has sufficient oxidizing power to interfere with blastfurnace desulphurization. This is, of course, only one of its several effects. Primarily it is an acid and therefore reduces the concentration of excess lime. But when silicon is reduced to the metal the oxygen to which it was previously bonded becomes in part available for reaction 2. The proof of this statement is found in the following experiments. Experimental Procedure and Results Utilizing the same procedure and apparatus described by Grant, Kalling, and Chipman' five additional heats were made using slags IV and 11, the starting compositions of which were: slag IV—40 CaO, 10 MgO, 35 SiO,, 15 A1,0,; and slag 11—50 CaO, 10 MgO, 25 SiO,, 15 Al3O3. An important difference between these heats and those previously reported was that silicon to the extent of 1 to 4 pct was added to the present heats whereas the starting silicon content was formerly about 0.2 pct. Table I shows the slag and metal analyses for heats 82 to 87, and Table I1 shows the silicon addi- tions made to the charge. These additions are based on 400 g of metal and 400 g of slag. All heats had 1.65 400pct S charged before the cold slagadditions. The temperature was maintained at 1525°C. Rate of SiO, Reduction: Fig. 1 shows the silicon content of the metal in contact with slag IV at 1525°C as a function of time. Heat 70 from the work of Grant, afunctionKalling,of and Chipman is included as the lowest starting silicon. It will be noted that eeven with 4 pct Si in the starting metal, there is an increase in silicon content with time. Heat 84 is apparently approaching silicon equilibrium very slowly. Heats 70 and 82 with very much lower slowly.starting silicon show a more rapid initial rise in startingsilicon content but do not reach equilibrium during a long holding period. Fig. 2 shows 3 different initial silicon contents for Fig.2shows3differentheats 73 (from Grant, Kalling, and Chipman) 86 and 87, in contact with slag II, the most basic slag. Heat 73 is increasing in silicon with time, whereas heat 87 with an initial silicon content of 3.7 pct shows a decrease with time. Heat 86 shows a very close approach to equilibrium. The rate of transfer of silicon from slag to equilibrium.metal is very slow in all of those heats, even those which are initially far from equilibrium. ____

Jan 1, 1952

By R. S. McFarland

OKLAHOMA, in 1924, recorded the largest single increase of any state; the total oil production for the year being 176,206,397 bbl. (Oil & Gas Jnl.), which gives an increase over 1923 of about 9 per cent. Oklahoma ranked second in total amount, California being first, and produced almost 25 per cent. of the total production of the United States. This gain in production is accounted for entirely by the rapid development, deeper drilling, and efficient management of productive areas known at the beginning of the year, for, due to the small number of wells drilled, few new pools were discovered and developed up to any important stage during the year. Three major pools, Burbank, Tonkawa and Cromwell, furnished 37 per cent. of the total production. Burbank led by a wide margin, having the largest production of any single pool; there was a steady increase in production until September. The close. development of the pools in Okfuskee, Seminole, and Hughes Counties, together with the new deep-sand production at Tonkawa and increased drilling operations in Osage County, accounted for the big increase shown during the year. In January, 1924, the shutdown movement and curtailment of production in Hewitt and Tonkawa, which had been effective during the year of 1923, were stopped. The shutdown movement and curtailment of operations in 1923 does not give a fair comparison with 1924, as undoubtedly a great deal more oil would have been produced in 1923 had it not been for these measures. The sensational developments during the year, which were certainly beyond the prediction of the oil industry, were the Cromwell field, which started the year with 10,478 bbl. for January and increased rapidly to 1,267,032 bbl. for. December, and the discovery of the Wilcox productions below 4000 ft. in the Tonkawa field in May, which by the end of the year had produced 11,650,000 bbl. In this connection, it can be safely said that 1924 was a banner year for the Wilcox sand series; it has been estimated that between 40,000,000 and 50,000,000 bbl. of the production for the year came from this sand. Although numerous Wilcox pools were opened throughout the state, the big Wilcox production came from. the Tonkawa and Stroud pools. Oklahoma's deepest well, the Kingwood Oil Co. No. 1 Barnett in the northwest corner of the northeast quarter of the southeast quarter of Sec. 7 T. 7 N. R. 10 E., Hughes County, was abandoned in January, at 5281 ft. with numerous good shows recorded, which have stimulated-further drilling in the locality.

Jan 3, 1925