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By Ralph W. M. Lai, D. W. Fuerstenau

This paper presents the results of a study of the principles which control the distribution of ultrafine particles between an oil phase and an aqueous phase. Alkyl sulfonates were used to control the wettability of fine alumina particles and to stabilize the water-isooctane emulsion system in the extraction process. The effects of sulfonate chain length, sulfonate adsorption, pH, and oil-water ratio on the recovery of solids in the oil phase were investigated. Higher extraction was found under conditions which yield higher hydrophobicity and large interfacial area of the oil-water emulsion. Today there is considerable interest in developing methods for the recovery of fine particles from disseminated ores. One such method might be the extraction of fine particulate solids from aqueous suspensions into an oil phase, and one example of a successful industrial process based on oil-water distribution phenomena is the emulsion flotation process used in concentrating manganese ore.' The oil agglomeration process of Farnand, Smith, and Puddington has been suggested for concentrating tin ore. Patents 3-4 for oil flotation processes extend back to that of William Haynes in 1860. The basis of all these processes is directly related to the stabilization of emulsions with solid particles. The first extensive study of oil-water emulsions stabilized by finely divided solids was made by Pickering. Later, Briggs,6 weston, 7 Chessman and King,8 and Leja and Schulman9 experimentally demonstrated how solid particles control water-oil and oil-water systems. Hildebrand10 suggested that fine particles can stabilize an emulsion because the fine particles are partially wettable by both oil and water, that is, that the contact angle must be finite. Takakuwa and Takamori 11 recently applied emulsion inversion to the study of collector adsorption in flotation systems. At the Royal School of Mines, Shergold and Mellgren12 are currently carrying out a comprehensive study of the extraction of fine particles into an organic liquid phase. In the present study of the liquid extraction or oil flotation of ultrafine particles, the recovery of hydro-philic alumina particles of 0.1-µ average diameter was determined after separating an isooctane-water mixture (emulsion) into its two phases. Alkyl sulfonates of different chain lengths were used to change the wettability of the alumina and to effect emulsifi-cation of the oil-water mixture. The effects of the oil-water volume ratio, sulfonate adsorption, and pH on the recovery of the fine particles were investigated. Since the surface charge on an oxide such as alumina is determined by the adsorption or interaction of H+ and OH- with the surface, pH control is extremely important. Furthermore, since the zero point of charge (zpc) of alumina13-14 occurs at pH 9 to 9.4, major adsorption effects with anionic collectors in these systems will occur below pH 9. The results of the foregoing investigation are discussed in terms of the recovery of the fine particles, the oil-water ratio, contact angles, surface tension, the adsorption of sulfonate onto the solid surface, and the emulsifica-tion of oil. MATERIALS AND EXPERIMENTAL METHODS Materials: The particulate solid used in all the experiments was Linde "A" alumina, a high-purity, readily available form of a-alumina. The surface area of the alumina, as evaluated from measurements of stearic acid adsorption from benzene, was 14.5 sq m per gm, based on a value of 20.5 sq Å for the cross-sectional area of stearic acid.13 All aqueous solutions were prepared from triply distilled conductivity water. Other materials included high-purity crystals of sodium alkyl sulfonates, isooctane, and, for pH adjustments, reagent grade hydrochloric acid and sodium hydroxide-Because sulfonic acids are strong acids, they are

Jan 1, 1969

By Gordon H. Geiger, John M. Svoboda

One mechanism of metal penetration into mold aggregates by cast steels is vapor state mass transport. In order to further understand and quantify this mechanism, the steady-state diffusion of metallic vapors was studied at 1250" to 1600°C in controlled oxygen pressure atmospheres by measuring the weight loss from a metal bath whose vapors were allowed to diffuse through a porous aggregate compact held at constant temperature. Mass transport rates substantially greater than those predicted from the assumption that the vaporizing species was the elemental metal vapor were observed. Vaporization rates were found to increase with an increase in the oxygen partial pressure in the gas atmosphere with maximum vaporization occurring at oxygen partial pressures just below those in equilibrium with a liquid oxide layer at the given temperature. When the liquid oxide layer was present, no vaporization was observed. Metal carbonyls were ruled out as the vapor species involved because of their thermodynamic properties. The species with the enhanced volatility were deduced to be gaseous metal-oxygen molecules, probably the polynuclear oxides (FeO)2 and (Mn0)2. Diffusion followed the ordinary diffusion mode, and Knudsen diffusion is not important in normal foundry molds. The interdiffusivities of the metallic vapors and the mold atmosphere, through the porous aggregates, were measured. The effective interdif-fusivity of the vapor species and mold atmosphere through the aggregate may be expressed as follows: Deff,12 - — where E is the void fraction of the aggregate and 7 is the "tortuosity factor". Aggregate material had no effect on diffusion rates, and the only relevant parameter was the void fraction. Values for 7 ranged from 3 to 6 for normal foundry aggregates with 4 being considered a good representative value. An area of interest in high-temperature metallurgical processes which has received little attention in the past is the diffusion of metal vapor species in porous aggregates. Research into the metal penetration phenomenon' in foundry molds has shown that a major penetration mechanism is the vapor transport of metallic species into the porous foundry sand molds, followed by condensation of metallic films on the sand grains. Considerable study of the vaporization of metallic species has been reported in the literature, and the vapor transport properties of many metallic species have been determined.2'3 Many instances have been observed where the vaporization behavior could only be explained by the existence of a metallic species with a vapor pressure greater than the elemental metallic species. These species were identified or, in some cases, presumed to be carbonyls,4,5 hydroxides,6-9 or vaporous oxides.10-16 The diffusion of gases through porous aggregates has received considerable attention in the literature pertaining to catalysis, although primarily at low temperature, and more recently in the literature concerned with ore reduction.17-22 The following experiments were devised and carried out in order to determine the nature of the metallic species involved in the metal penetration phenomenon, and the effective diffusivities involved. EXPERIMENTAL APPROACH Steady-state diffusion was selected for experimental convenience. The experimental systems used, shown in Figs. 1 and 2, consisted of a porous aggregate specimen contained in an impermeable alumina tube held above, and just separate from a metal bath. The entire system was held at constant temperature and pressure in a furnace with a controlled oxygen partial pressure atmosphere. After a brief period of nonsteady state behavior, a steady flux of metal vapor through the porous aggregate will develop due to the concentration gradient of metallic vapor in the gas phase. The flux of metallic vapor from pressure may be neglected because there is no pressure gradient. There is no flux from convection because there is no net flow of gas within the metal-aggregate system, and thermal diffusion is negligible compared to the flux from ordinary diffusion. If the material being studied is allowed to vaporize until steady-state behavior is attained, the experimental results may be analyzed using Fick's First Law.

Jan 1, 1970

Arizona Bureau of Mines and College of Mines and Engineering, University of Arizona, Tucson, Ariz. Lists of the maps and bulletins available will be sent upon request to G M Butler, Director, Arizona Bureau of Mines, Tucson, Ariz Bulletin 119, A resume of the geology of Arizona, by N. H Darton, is sold for $1, postpaid Fourteen other bulletins, any five of which may be had free of charge (additional numbers may be purchased for 10 cents each) are available as follows - 106, A geological reconnaissance of the Tucson and Amole Mountains, by Olaf P Jenkins and Eldred D Wilson, 114, Fluorspar, by M A Allen and G M Butler, 120, Gold and copper deposits near Payson, Arizona, by Carl Lausen and Eldred D Wilson, 122, Quicksilver resources of Arizona, by Carl Lausen and E D. Gardner, 123, Geology and ore deposits of the Courtland?Gleeson region, Arizona, by Eldred D Wilson; 125, The mineral industries of Arizona, by J B Tenney, 126, Asbestos deposits of

Jan 1, 1933

By A. T. Corey, J. H. Henderson, M. R. J. Wyllie, C. H. Rathjens

The results of three-phase relative permeability tests on nine water-wet consolidated Berea sandstone samples are presented as composite ternary diagranls showing isoperms of oil, water and gas. Capillary pressure control was exercised over the flow of gas and oil in the presence of water. The water saturations ranged from 17 to 71 per cent pore volume. A method of calculating both the oil and water permeabilities of a three-phase system from the easily measured gas relative permeability is presented. EXPERIMENTAL PROCEDURE AND RESULTS A renewed interest has been shown in three-phase relative permeability as a result of recent developments involving underground combustion processes, steam injection, and other multiphase displacement processes. The experiments and results described here involved simultaneous flow of oil and gas in consolidated Berea sand with brine present as the wetting phase. Gas and oil relative permeabilities were measured on nine cores with CaC12 brine present as the wetting phase in saturations ranging from 17 to 71 per cent. The average residual liquid saturation of the cores was approximately 20 per cent. In order to make certain that brine was the wetting phase, the test cores were saturated with brine before contact with hydrocarbons. As an added precaution to avoid having oil displace brine from the wetting position as a result of changing wettability, each core was only used twice, i.e., first with a fixed percentage of brine and then for a gas-oil permeability determination with no brine present. The results, therefore, are presented as composite ternary diagrams representing the flow tests on nine individual cores having very similar properties. All tests were made using a modification of the capillary pressure techniquc described elsewhere. The effective oil permeability was measured before gas was introduced using a very small pressure gradient (a few centimeters of oil). This determination was made without selectively wet barriers in contact with the core. The cores were then placed between capillary barriers and gas-oil relative permeability curves obtained. The capillary barriers had been made water repellent with a silicone treatment. In determining gas-oil-water relative permeability in this fashion, control was exercised over the capillary pressure existing between the gas and oil. No control was exercised over the pressure difference existing between the oil and water. Athough an equal pressure gradient was applied to the gas and the oil phases, this pressure gradient does not exist in the water phase. Since the pressure gradient across the core was always much less than the displacement pressure of the fully saturated core, the pressure gradient can have caused only a very slight distortion of the oil-water interfaces. This slight distortion of the oil-water interfaces had a negligible effect on the validity of the oil permeabilities measured. The oil permeability, measured in the presence of water but with no gas present, was in every case equal. within experimental error, to the gas permeability of the gas-oil system when the oil saturation was the same as that of the water. Gas and oil relative permeabilities were plotted as a function of total liquid saturation. It was found that the gas relative permeability curves obtained on cores with brine present were identical with those obtained on the same cores with no brine present. The denominator for calculating oil relative permeabilities was the permeability found by extrapolation to infinite mean pressure (A la Klinken-berg). Fig. 1 illustrates gas-oil relative permeability results obtained on a typical core. The solid permeability curves represent the experimental data. The dashed oil relative permeability curve was calculated using the relationship;

Jan 1, 1957

By G. M. Ritcey

Sulphuric acid leaching has been up to the present, the most popular of the leaching routes. Oxide ores are usually leached with sulphuric acid directly by dump leaching, as practiced at the Bagdad or Bluebird Mines in Arizona, or by vat leaching as done at Inspiration Mining in Arizona. Upgrading of the low-grade oxide ores by dump leaching followed by cementation of the copper from solution by scrap iron has been replaced by the leaching-solvent extraction-electrowinning route which results in a high purity product at the mill site at reduced production costs compared to previous practice. High-grade oxide ores, vat leached with H2SO4, can contain, for example, 25 g Cu/l and 25 g H2S04/,l, or higher concentrations of both, and are presently fed directly to electrorefining plants. Advantages of coupling solvent extraction-electrowinning with the low cost dump leaching instead of using cementation, are as follows (1): a) the production of high purity electrolytic copper rather than cement copper;

Jan 1, 1978

By S. L. Crouch, C. Fairhurst

The general term "coal mine bump" refers to the sudden and violent failure of in-situ coal. Coal bumps occur in most countries where coal is worked by underground methods. They are related to geological factors and mining techniques. Coal bumps can be characterized as unstable releases of energy associated with yielding that occurs with progressive mining. Unstable releases of energy occur when the coal is able to absorb less energy than is released by the surrounding rock mass during the yielding process. At any stage of mining, the amount of excess energy so released is governed by the mining geometry, the overburden stress, the elastic properties of the rock mass, and the stress-strain characteristics of the seam material. If the coal in the vicinity of the working face is crushed, the peak abutment pressure occurs at some distance into the intact portions of the seam, and mining takes place in essentially destressed coal. With subsequent mining, additional yielding occurs, excess energy may be released, and the peak stress is again shifted into the solid. This process continues until the mining geometry is such that the zone of peak stress is effectively surrounded by yielding coal, at which point it can be anticipated that further mining will produce dramatic redistributions of stress and be accom¬panied by large releases of energy. On this basis, the differences between several alternatives for mining a given block of coal may be pronounced.

Jan 1, 1975

By S. T. Yuster

An analysis has been made of the factors responsible for tilted fluid contacts in petroleum reservoirs. The factors are static and dynamic with the former being controlled by those variables responsible for the capillary rise of fluids, and the latter include rate of formation tilt and hydraulic circulation. The explanation that rate of formation tilt may be responsible for tilted contacts appears untenable. The role of some of these factors in the migration, fractionation. accumulation and possibly the prospecting for oil is indicated. INTRODUCTION While it is generally considered that the segregation of gas, oil, and water in a petroleum reservoir results in approximately horizontal planes separating these phases. there are factor; which modify this simplified picture to a very great extent. Some of these factors are static. and the departure of the fluid interfaces from horizontal may represent a static equlibriun. Some of these factors may be dynamic and the interface positions may be non-equilibrium and represent a steady .state condition. Of course combinations of these two situations may also exist. The reasons most commonly given for this behavior are hydraulic circulation of fluids, change in character of the formation, and a rate of tilt of the formations more rapid than the rate at which the fluids may re-establish an equilibrium. Russell's Principles of Petroleum Geology' contains an extensive discussion of tilted fluid interfaces and their importance in the migration and accumulation of petroleum. Russell cites examples of tilted water tables at Lance Creek, Wyo.; Rock River, Wyo.: Cut Bank. Mont.; Cushing, Okla.: and Graham; Okla. Also given was the Wasson Field of West Texas which has saucer shaped oil-water and gas-oil interfaces with the saucer being deeper in the case of the oil-water contact. The Bradford Field in Pennsylvania has a tilted water table. San Ardo. Coalinga None and some other California field.; have tilled contacts. A recent paper by King Hubbert discuses the effect of hydraulic circulation of the water underlying the oil in a given stratun and it- implications in the accumulation of and drilling for the oil. The foregoing would indicate that tilted fluid interfaces are not uncommon and that it would be of importance to underbtand the forces which are responsible. Further. it would be of interest to examine certain idealized models of situations which may cause tilting with the thought in mind of deriving relatinnships between the important variables. These relationships may only hold exactly for the model* assumed but the results may apply semi-quantitatively to actual formations and at least indicate trends. The discussion will be divided into the effect of static factors and the effect of dynamic factors. STATIC FACTORS It has already been mentioned that one reason given for tilted contacts is a variation in formation properties. Specifically this is a change in the pore size of the formation capilaries. If the internal surface of the reservoir is preferetially wet by water, capillarity will cause the water 10 rise to a greater extent above the free water table in a small capillary than in a large one. Consequently the water-oil contact will be higher in the lower permeability sands than in the higher permeability sand.;. The free water table may be defined as the position the oil-water interface would take if capillarity were absent. Since the phenomenon is the capillary rise of water in an oil environment, a derivation of this shold give a relationship between the variables. Fig. 1 is an idealized model of the situation with a uniform bore circular capillary ubstitttting for the tortuous non.circular formation pore. The upward force.; on the column of water will be equated to the forces downward to give the equilibrium situation. forces upward = force downward where r is the radius of the capillary in ceritimetera. a is the interfacial ten4on oil-water in dynes per centimeter, 0 is the

Jan 1, 1953

C. Q. PAYNE, New York, N. Y. (written discussion*).-The method adopted by Mr. Lennox is a very interesting test of the practical application of Mr. Gates' crushing-surface diagram to a greet variety of gold and copper ores. His method of dealing with the material below 200-mesh is also a distinct contribution to the subject, although, as he suggests, it seems likely that some microscopic measurement of this material may be advisable before the mesh reciprocals of its group particles can be dealt with as accurately as can those coarser than 200-mesh. In examining the general results shown in Table 3, it is somewhat puzzling to perceive why Calumet &, Hecla jig tails should show a crushing resistance 3 - times greater than that of the ore from the Ray Consolidated copper mine. The latter is, I believe, an altered. Pinal schist

Jan 10, 1918

By Carl G. Hogberg

DURING recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. PRINCIPLES OF IRON DESULPHURIZATION IN FURNACE Although investigations of the blast-furnace process have not clearly revealed the detailed mechanism of iron desulphurization within the furnace, they have been sufficiently extensive to permit a postulation of the following general principles: I. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurization is relatively narrow, being confined to a vertical distance extending approximately from tuyere level to the iron-slag interface in the hearth.1 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.2 Coke ash is released as the coke burns in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By John F. Shaw

The Denver Mining Research Center headquartered at Denver, Colo., is typical of the new research units recently activated as a result of increased emphasis by the U. S. Bureau of Mines on research concerned with metal and nonmetal (except mineral fuels) ore extraction. The Denver Center, together with the recently established Minneapolis Research Center and the Offices of Mining Research at Reno and Spokane, and the older, well-known Applied Physics Research Laboratory at College Park, Md., share the responsibility for the comprehensive mining research program. The Denver Center specializes in two areas of research: (1) The development of engineering principles and mathematical techniques applicable to exploration, development and operational problems in mining, and (2) the study of rock mechanics as applied to ground control. The first area presently includes three categories: research on methods of ore sampling, mine-systems analysis, and applications of statistics to problems of mineral exploration. The second area emphasizes research in two main categories: laboratory investigations designed to develop a fuller understanding of how rock be- haves under the loads imposed by mining, and field investigations to evaluate stress-strength relation- ships in full-scale, operating mines.

Jan 3, 1962

By Alan J. Strauss

The Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. This paper reviews the properties of the pseudobinary solid solutions formed by these compounds, including the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and energy band structure. Particular emphasis is placed on the Pbl-xSnxTe and Pb1-xSn,Se alloys with rocksalt structure, because of current interest in these malerials for generating and detecting infrared ,radiation. ThE Group IV elements germanium, tin, and lead form nine 1:1 compounds with the Group VI elements sulfur, selenium, and tellurium. Some of the physical and electronic properties of these compounds, including their melting points1-8 and energy gaps,4'9-12 are listed in Table I. Four compounds (SnTe, PbS, PbSe, and PbTe) have the cubic rocksalt (Bl) structure. At room temperature GeTe has a rhombohedra1 structure closely related to the B1 structure, into which it is transformed at about 400°C. Four compounds (GeS, GeSe, SnS, and SnSe) have the orthorhombic B29 structure. In samples which have not been intentionally doped with impurities, the electrical conductivity is due primarily to electrons or holes produced by the ionization of donor or acceptor lattice defects associated with deviations from stoichiometry. Undoped samples of PbS, PbSe, and PbTe may be either n type or p type, depending on whether they contain excess lead or an excess of the Group VI element, respectively, but only p-type samples of the other compounds have been reported. This paper will review the properties of the pseudo-binary solid solutions formed by the nine 1:l compounds. The topics to be considered include the extent of mutual solid solubility, temperature-composition phase diagrams, transport properties, deviations from stoichiometry, optical properties, and band structure. Particular emphasis will be placed on the Pb]-xSnxTe and Pbl-xSnxSe alloys with B1 structure, which are promising materials for generating and detecting infrared radiation in the 8 to 14 µm atmospheric window and beyond. MUTUAL SOLID SOLUBILITY The extent of mutual solid solubility in the pseudo-binary systems has been investigated for fourteen of the eighteen ternary systems (in which the two terminal compounds have a common element) and for nine of the eighteen quaternary systems. In most cases, X-ray diffraction measurements made at room temperature were used to determine the structure and lattice parameter(s) of the phase(s) present in samples of various compositions prepared by freezing from the melt. In many investigations, including the extensive studies of Krebs and co-workers,13'14 the samples were annealed at elevated temperatures before X-ray measurements were made. In some cases, metallographic examination and thermal analysis have also been employed. The results for the ternary and quaternary systems are summarized in Tables II and III, respectively. (The original references should be consulted for the annealing temperatures.) The solubility of one compound in the other is at least 5 mol pct in all cases, and is often much larger. Complete solid solubility has been observed in all systems so far investigated in which the terminal compounds have the same structure, although in the PbS-PbTe system complete solubility is limited to elevated temperatures. Thus complete solid solubility occurs in five systems where both compounds have the B1 structure (SnTe-PbTe, PbS-PbSe, PbS-PbTe at temperatures above 805°C, PbSe-PbTe, and SnTe-PbSe) and in three where both compounds have the B29 structure (GeS-SnS. GeSe-~n~e-, and SnS-SnSe), as well as in two involving GeTe and a compound with B1 structure (GeTe-SnTe and GeTe-PbTe). On the basis of thermal analysis data, complete solid solubility at sufficiently high temperatures has also been reported for the GeSe-GeTe2 and SnS- pbS22 systems. This seems unlikely, however,

Jan 1, 1969

By H. L. Luo, P. Duwez, C. C. Chao

BY rapidly cooling alloys from the liquid state, it is possible to obtain solid solutions beyond the equilibrium concentrations, provided that the components are miscible in the liquid state. Typical such cases include CU-Ag,1 Pt-Ag,2 CU-Rh,3 nickel-base alloys with silicon, germanium, and tin,4 and cobalt-base alloys with silicon, germanium, tin, aluminum, and gallium.5 In the present note it is shown that terminal solid solutions can be appreciably extended in A1-Mg alloys. The alloys whose compositions are given in Table I were prepared by induction melting in tantalum crucibles under an argon atmosphere. Both aluminum and magnesium were 99.99 pct pure. Weight losses after melting were less than 0.2 pct for the aluminum-rich alloys and less than 0.4 pct for the magnesium-rich alloys. From these weight losses it was estimated that the compositions of the ingots after melting were accurate within 0.3 at. pct for aluminum-rich alloys and within 0.5 at. pct for magnesium-rich alloys. As indicated in Table I, the compound AuCd10 in which there is an ionic contribution to the bonding. The authors thank Dr. J. H. Westbrook of the Research Laboratory, General Electric Co., for arranging the supply of materials and for his interest. This investigation was supported by the U.S. Atomic Energy Commission under Contract AT(30-1)-1002, Scope I. some of the alloys were also chemically analyzed and the results confirmed the limits of uncertainty based on weight losses. Rapid quenching from the liquid state was achieved by techniques previously described.8,7 The principle of these techniques consists of propelling a small globule of liquid alloy (about 20 mg) onto a copper substrate. The thin foils easily detached from the copper substrate were analyzed by X-ray diffraction using a Debye-Scherrer camera 114.6 mm in diameter and either nickel-filtered copper Ka or iron-filtered cobalt Ka radiation. Since the back-reflection doublets were resolved, the wavelengths used in the computatioas were CuKal = 1.54050A and CoKa1= 1.78892A. Lattice parameters were obtained by extrapolation of the Nelson-Riley function, and the tables compiled

Jan 1, 1964

By David C. Grant, Erich W. Tiepel

In situ mining is a process for recovering uranium from relatively small or low grade ore bodies. The process involves passing a lixiviant and oxidant, typically NH4HC03 and H202, through a uraniumcontaining ore body. As the solution progresses through the ore body, the uranium is oxidized from the plus four to the soluble plus six state. The bicarbonate complexed uranium laden solution is removed from the ore body and the uranium recovered in an above-ground processing plant. During the leach process lixiviant cations may be sorbed on the ore host, if the host contains exchangeable clay minerals. This report examines the implications of this clay interaction on ground-water quality, the various available in situ mining restoration methods, laboratory procedures for simulation and development of those methods, and the results of using the restoration methods in the field. Various restoration methods, including ground-water sweeping, clean water recycle, and chemical restoration are presented and discussed. The use of ore characterization, agitation leach tests, and column tests to study cation sorption and desorption, and thus, to identify and evaluate restoration methods is discussed. Ore characteristics identify the clay type and clay content, which allows the estimation of the magnitude of the cation sorption by that ore. The chemical effects of clay exchange and of chemical restoration can be examined using agitation leach experiments and packed ore column tests which also provide information on the physical effects. The agitation leach test is a relatively rapid means of determining the sorption and desorption characteristics of an ore. Unlike agitation leach tests, column tests can be used to assess the influence of solutions on permeability, on precipitation problems, and on other chemical changes. The effectiveness of using restoration methods, which were developed and tested in the laboratory, are examined by presenting field restoration data from several mining sites.

Jan 1, 1979

By A. H. Bromly

The small agricultural village of Santa Barbara, in the State of Guanajuato, has been the center of spasmodic tin-mining operations during recent years. The deposits, so far as I know, are unique, and a few brief notes may be of interest. Santa Barbara, about 12 miles west of San Felipe station on the Mexican National Railway, and at an elevation of 2,400 m. above sea-level, is situated in a flat valley extending east and west, and bounded north and south by broken rugged hills rising about 330 m. above the general level of the valley. Tin-mining operations have been conducted at the Queensland mine, near this village. A small concentrating-mill was erected and attempts were made to smelt the ore in reverbera-tory furnaces. The country-rock of the district for many miles is rhyolite of great thickness. There are some local variations due to differences in cooling, or subsequent alteration or impregnation; but throughout the whole district the principal constituents of the rocks remain the same, viz., free silica, orthoclase-feldspar and sanidine. The latter is especially marked. The crevices and joints of the rock are frequently filled with calcedonic and opalescent quartz. The ore-formation at the Queensland mine is of an unusual nature, consisting of cracks in the rhyolite which have been filled with clay. This phenomenon is largely developed over a width of from 80 to 100 m., in which the principal fissuring follows an approximate direction of north and south. The average dip ranges between 70 and 80 degrees. Some of the fissures hold sufficiently true for a time to afford the impression that they are due to dynamic causes, or earth-movement. This may be true of some of the north by south fissures; but considering

Jan 1, 1906

By H. C. Hardison

The Yates pool, Pccos County, Texas, has greater potential capacities than any other field in the United States. This field is notable for the large return it yields on capital invested, for low production costs and for the orderly and conservative manner in which it was developed and continues to be operated. The proven area is 20,000 acres and there are 392 producing wells, or approximately 1 well to 50 acres. The theoretical daily potential is 5,250,000 bbl. as determined by l-hr. open-flow gages. Individual well gages vary from a few barrels to 8500 bbl. per hour, and well depths range from 1000 to 1800 ft. The greater part of the production is from a very porous limestone, and by agreement no productive well has penetrated the lime more than 225 ft. The forces driving the oil from the formation to the surface are hydrostatic head, expanding gas or a combination of the two. The degree of effectiveness of either depends upon the structural position of, and porosity encountered in, the individual wells. Approximately 95 per cent. of the wells in the field flow naturally. The pipe line outlet of the field at the present time is 100,000 bbl. per day, which is less than 2 per cent. of the daily potential. Difficulties and Principles of Probation It became evident during the first year of the development of this field that operators would have to devise a scheme to allocate pipe line runs equitably among their different properties. When the idea of proration was first inaugerated, the matter of spacing wells was given consideration. This was given up through fear of legal difficulties. Storage was also a question that was given considerable thought, and a plan was finally developed which went into effect Oct. 1, 1927. It was decided that the oil runs should be prorated according to the total potential capacity of all the wells which the several operators had in the field. The potential capacity of the wells was measured by a l-hr. open-flow gage. All runs to storage by an operator were deducted from his daily allowance.

Jan 1, 1931

By Kenneth Cottingham

The number of wells drilled in Ohio in 1943 was slightly in excess of the number drilled in 1942. Compared with the average annual completions for the five years preceding, the year 1943 was short 11 per cent, hut the average initial volume of gas wells was considerably improved. In 1942 the average initial open flow per gas well was 668 M cu. ft., whereas in 1943 the average was 913 M cu. ft. Although no large gas-producing areas were discovered during the year under review, some 30 small pools were found in 17 of the counties of eastern Ohio. These new pools averaged about 300 acres each, and most of them were not extensions but were separate pools adjacent to older production. The Clinton sand furnished most of these discoveries, although six were from the Berea, one was Newburg, and three were shallow sands. No discoveries were made outside former producing counties, and there was no new development the Trenton area of western Ohio. The number of oil wells decreased from 181 drilled in 1942, to 170 in the year 1943. The production of Pennsylvania-grade oil increased 7644 bbl. The total Corning production, however, decreased 91,325 bbl. The present price of Corning-grade oil, $1.31 per bbl., is too low, in the opinion of the operator, to justify exploration. Until something is done in correcting the price level of Corning grade, the production probably will continue to decline. The oil industry in Ohio is making a concentrated effort toward increased production and improved methods of recovering Pennsylvania-grade oil, and a.s this report is written a research and engineering program is being formulated for the benefit and information of the various producers of that grade in Ohio.

Jan 1, 1944

By Kenneth Cottingham

The number of wells drilled in Ohio in 1943 was slightly in excess of the number drilled in 1942. Compared with the average annual completions for the five years preceding, the year 1943 was short 11 per cent, hut the average initial volume of gas wells was considerably improved. In 1942 the average initial open flow per gas well was 668 M cu. ft., whereas in 1943 the average was 913 M cu. ft. Although no large gas-producing areas were discovered during the year under review, some 30 small pools were found in 17 of the counties of eastern Ohio. These new pools averaged about 300 acres each, and most of them were not extensions but were separate pools adjacent to older production. The Clinton sand furnished most of these discoveries, although six were from the Berea, one was Newburg, and three were shallow sands. No discoveries were made outside former producing counties, and there was no new development the Trenton area of western Ohio. The number of oil wells decreased from 181 drilled in 1942, to 170 in the year 1943. The production of Pennsylvania-grade oil increased 7644 bbl. The total Corning production, however, decreased 91,325 bbl. The present price of Corning-grade oil, $1.31 per bbl., is too low, in the opinion of the operator, to justify exploration. Until something is done in correcting the price level of Corning grade, the production probably will continue to decline. The oil industry in Ohio is making a concentrated effort toward increased production and improved methods of recovering Pennsylvania-grade oil, and a.s this report is written a research and engineering program is being formulated for the benefit and information of the various producers of that grade in Ohio.

Jan 1, 1944

By R. S. Goodrich, G. S. Ansell

The microstructure of three Al-Al2O3 SAP-Type alloys (containing 2.0, 3.0, and 5.7 wt pct alumina, respectively) was studied utilizing transmission electron microscopy. These alloys were fabricated from aluminum powders by powder-metallurgical techniques, cold-rolled into thin strips, and recrys -tallized. Thin foils suitable for an electron-transmission study were then prepared from the strip material by electropolishing. The microstructure of these alloys is shown to consist of small (0.1 mean diameter) plate -shaped alumina particles finely distributed in an aluminum matrix. In the higher-oxide content alloys the platelets are somewhat larger and more irregular in shape. The distribution of oxide particles is not uniform and there is an increasing tendency toward clumping SINCE the discovery by Irmann1 that aluminum alloys produced by compacting, hot pressing, and extruding fine aluminum powders possess remarkable high-temperature mechanical properties, the Al-A12O3 SAP-Type alloys have been utilized extensively as model dispersion-strengthened alloys in both experimental and theoretical invest igations.2-8 The use of the SAP-Type alloys as model dispersion-strengthened alloys implicitly assumes that their microstructure has been completely delineated. This is, however, not the case. with increasing oxide content. In all the alloys studied, the mean center-to-center spacing of particles was quite small (0.2 u) due to the very fine oxide debris present. Selected-area diffraction of the specimen identified the oxide as either y Al2O3 or y' Al2o3. The re crystallized MD-5100 alloy exhibited a mean grain diameter of only 0.7u, while the grain size of the other alloys was several hundred microns. Severe pinning of the grain boundaries by oxide particles was rarely observed, and the grain boundary triple points in the small-grained MD-5100 alloy were often particle -free. Diffraction contrasts visible around the particles are attributed to elastic strain fields set up by differential thermal contraction during cooling from the recrystallization anneal. Early investigation demonstrated that optical metallography did not possess sufficient resolution to observe the microstructure of the SAP-Type alloys.' Later, extensive use was made of replication techniques to study the microstructure by means of electron microscopy.7-9 These studies indicated that the SAP-Type alloys consist of a dispertion of irregular Al2O3 platelets, approximately 150A thick 9 and a micron or so on edge,9 distributed in a matrix of commercial-purity aluminum. These oxide platelets tend to be oriented in the aluminum matrix, with their largest dimension parallel to the extrusion direction. 8,9 A study employing polarized-light techniques1' indicated that the grain size of a series of as-extruded SAP-Type alloys was several microns in diameter, while the grain size after re-crystallization was several millimeters in diameter. A more recent study 12 utilizing surface-replication techniques examined the particle morphology,

Jan 1, 1964