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By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By R. W. Kraft, L. D. Graham

The process of' spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of' thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By M. J. Marcinkowski, A. Szirmae, R. M. Fisher

Room -temperature hardness measurements obtained from single and polycrystalline samples of a 47.8 at, pet Cr-Fe alloy which were aged for various times al 500°C show a two-fold increase over that of the unaged alloy after annealing for 1000 hr. A detailed examination of the deformation markings in the neighborhood of the hardness imbressions reveals that twinning becomes an increasingly more important mode of deformation as aging proceeds. this observation is shown to be inconsistent with the Proposals that the transformation is eve of order-disorder On the other hand, the results are in agreement with previous observations of Fisher et al. of a coherent chromium-rich precipitate which forms in an iron-rich matrix as a result of a miscibility gap in this alloy system as proposed by Williams . Using the coherent precipitate hypotlzesis as a model, a detailed analysis of the various possible strengthening contributions to both the slip mid twinning stresses is made. In the case of' slip, lattice friction within the chromium-rich phase and the chemical energy associated with the interface between the two phases contribute about 60pet to the total strength. The contributions from coherency strains and modulus differences are thought to contribute the remaining 40 pet of the strength but are difficult to evaluate because of uncertainties regarding the flexibility of the dislocation line. All of the factors have nearly the same or else a smaller effect on the twinning stress in the aged alloy. Twinning is never observed in the unaged alloy because the twinning stress is much higher- than that for slip. With increased aging times, the various contributions to the total stress for both twinning and slip increase, but most of those for slip increase much more rapidly, so that, in the fully aged alloy, it surpasses the stress for twin propagation. When a twin is nucleated by the chance occurrence of an internal stress concentration during a test, the subsequent twin burst results in a low hardness reading. FeRNTIC Fe-Cr alloys from about 15 to 80 at. pet Cr content show considerable change in properties such as hardness, electrical resistivity, saturation magnetization, and so forth, after aging in the vicinity of 500°C.* The most marked change is a large increase in hardness accompanied by a sharp decrease in ductility, so the phenomenon has often been referred to as the 475°C (885°F) em-brittlement problem. Changes in microstructure are rather subtle and most investigators have not been able to observe any X-ray diffraction or metal-lographic changes during aging. There is little doubt that the phenomenon is inherent to the Fe-Cr binary system and is not directly related to the formation of a phase. Two distinct schools of thought have developed during the past decade concerning this problem. Masumoto, Saito, and sugiharal have concluded, from their own specific-heat measurements, that atomic ordering occurs in this temperature range. Pomey and Bastien2 have also attributed the changes in physical properties with aging in the neighborhood of 500°C to atomic ordering. In addition, Takeda and Nagai3 claimed to have found X-ray verification for superlattices corresponding to the compositions FesCr, FeCr, and FeCr3. However, all known attempts to observe superlattices in Fe-Cr alloys using neutron diffraction, which should be much more sensitive, have been unsuccessful. These have been reported by Shull et al.4 for 25 at. pet Cr, williams5 for 75 at. pet Cr, and Tisinai and samans6 for a 28.5 at. pet Cr. steel. The second and more prevalent opinion ascribes the 475°C embrittlement phenomenon to the formation of a coherent precipitate due to the occurrence of a miscibility gap in the Fe-Cr system below about 550°C. This latter concept was first indicated by the results of Fisher, Dulis, and Carroll,7 who were able to extract fine particles about 200Å in diameter from samples of 28.5 at. pet Cr steels aged from 1 to 3 years at 475°C. The extracted material was found to be nonmagnetic, to have a bee structure with a lattice parameter between that of iron and chromium, and to contain about 80 at. pet Cr. Williams and paxton8 and williams5 confirmed these results and first explicitly proposed the existence of a miscibility gap below the a region in the equilibrium diagram. Alloys aged within this gap

Jan 1, 1964

By James A. Crookston, William D. Fitzpatrick

Committee C-8 of the American Society for Testing and Materials defines refractories as "material, usually nonmetallic, used to withstand high temperature," and it defines the term refractoriness thus, "in refractories, the capability of maintaining the desired degree of chemical and physical identity at high temperatures and in the environment and conditions of use.” The ability to withstand high temperatures is critical to classifying a material as a refractory. However, as the foregoing definition of "refractoriness" implies, the refractory material may be subjected to and is expected to resist not only high temperatures but a variety of other destructive forces incidental to its use. These include abrasion, impact, thermal shock, chemical attack, and high level loads at high temperatures. The various industrial applications of refractories represent an infinite variety of combinations and degrees of severity of these destructive forces, including high temperatures. Naturally, such a variety of application conditions leads to a need for a wide variety of refractory products to satisfy those conditions. The number of refractory products available is great enough that some form of classification is necessary to a discussion of refractories. Refractories may be classified in several ways, but the most suitable one is based on their general compositions and to lesser degrees on their physical condition and distinctive properties. The primary types of brick include aluminosilicate brick (fire clay and alumina), basic brick (magnesia and chrome ore, alone and in various combinations), silica brick, insulating brick, and special refractories (carbon, SiC, ZrO2, zircon, borides, and nitrides). Brick is, of course, preformed and usually is heat treated at high temperatures before use, but in some instances is unburned and/or chemically bonded, including the relatively new class of tar-bonded magnesia and/or dolomite brick. In addition to preformed refractories, another broad category includes the so-called specialty refractories, which are usually made in the same types as itemized for brick-bonding mortars and high temperature cements, hydraulic setting castables or refractory concrete, plastic firebrick, and ramming mixes. Refractory grains, such as fire clay and high alumina calcines, dead-burned magnesite and periclase, and dead-burned dolomite are also considered refractory products. Bricks are also classified on the basis of physical dimensions, as standard sizes and special shapes. The standard sizes are those which are of definite shape and design and are designated as 228.6 x 114.3 x 63.5 mm (9 x 4 ½ x 2 ½ in.) and 228.6 x 114.3 x 76.2 mm (9 x 4 ½ x 3 in.) straights and series. Bricks of nonstandard sizes are referred to as special shapes. These come about as a result of a particular need for a given furnace or for a particular application. Types and Classes of Refractories Fire Clay Refractories Classification: Fire clay refractories, as the name implies, are composed essentially of fire clay and/or calcined fire clay in varying proportions. The ASTM Standard Classification of Fireclay and High Alumina Refractory Brick, C27-70 (reapproved 1976), gives five classes of fire clay brick designated as super-

Jan 1, 1983

By I. R. Kramer

The stress associated with the surface layer was deter-minedfor iron and molybdcnum. These measurements show that the surface layer plays a very important role in the plastic deformation of bcc metals. From the relationship between strain arui the surface layer stress and the back stress imposed by the internal obstacles, it is Proposed that the term of of the Hall-Petch equation is related only THE large number of studies on plastic flow of bcc metals have failed to delineate clearly the nature of the obstacles influencing dislocation movement. Since there have been numerous articles which have reviewed the mechanisms proposed to explain various aspects of plastic flow of bcc metals (for example, conrad1 and Keh and weissmann2), no attempt will be made here to discuss their conclusions. However, it should be to the surface stress while the term Kfd is the stress required to move dislocations through internal obstacles. Further, it was possible to derive the well-known empirical equation C = , and it is shown that the terprz a is comprised of two terms: a term Cs associated with the surface layer stress and Ci related to internal dislocation obstacles. pointed out that in all of these publications it has been tacitly assumed that plastic flow occurred uniformly throughout the cross section of the specimen (except, of course, for the Luders band region), It has generally been further assumed that the nature and distribution of the obstacles opposing the motion of dislocations are of the same type throughout. The role of the surface layer in bcc metals has not, as yet, been considered even though its role in fcc metals has been shown clearly to be of primary importance.3-5 Investigations on fcc metals have shown that at the onset of plastic deformation a surface layer acts to

Jan 1, 1968

By L. L. McDaniel

Copper smelters of various kinds have operated in the Morenci district since 1872, but all have been abandoned with the exception of the present Morenci Smelter of Phelps Dodge Corporation, which was completed in 1942. During the five-year period starting in 1937, the Morenci ore body was prepared for open pit mining, pilot mill test work was carried out, and a complete reduction works, of which the Smelter is a part, was designed and erected. Actual construction work on the Morenci Smelter was started in the fall of 1940, and warming up of the units began on April 1, 1942. Charging of the reverberatory furnaces commenced on April 18, 1942, and the first anode copper was produced on April 26, 1942. The smelter was originally designed to handle the production of the Morenci Concentrator on a 25,000 ton per day program, but by the time the smelter was in operation, plans were already underway to increase the smelter capacity to handle the production of the concentrator which was being enlarged to 45,000 tons a day capacity as a war-time necessity. This extension to the smelter was completed and the new units were put in operation toward the beginning of 1944. The original smelter consisted of a smelter crushing plant, bedding plant, two direct-smelting reverberatory furnaces with two waste-heat boilers on each furnace, three converters, an anode department, a stack, and all of the usual accessory smelting equipment. The extension consisted of increasing the bedding plant from three to five beds, the reverberatory department from two to four furnaces, and from four to eight waste-heat boilers, and the converter department from three to six converters. A third converter aisle crane was added and additions were made to the flue systems and conveyor systems throughout the smelter; but no change was made in the smelter crushing plant or the anode department, and the same stack was used for all additional Smelter units. A blister casting machine was installed at that time in the south end of the converter aisle to handle excess and emergency production above the capacity of the anode department and in 1947 a converter aisle skull breaker and a lime burning plant were added as the final units for a complete plant. The choice of direct smelting over calcine smelting for the Morenci Smelter was made after careful study by members of the Western organization of Phelps Dodge Corporation and after test runs on direct smelting of Morenci concentrate had been made at the Douglas Smelter of Phelps Dodge Corporation. The Morenci furnace charge is made up of comparatively high grade concentrate with no ores of smelting grade available and with only flux, a small amount of copper precipitate and the usual amount of smelter secondaries to be smelted with the concentrate. The simplicity of direct smelting for this charge and the large amount of waste-heat steam available from direct smelting operations were factors influencing the decision to adopt direct smelting for Morenci. The design of the Morenci Smelter and the type of units selected followed best experience at the Douglas Smelter of Phelps Dodge Corporation. A description of the original smelter before operations started was given in an article in the May 1942 issue of Mining and Metallurgy. The purpose of the present article is to describe the enlarged Morenci Smelter, with a discussion of metallurgy and operating practice and to show tabulations of operating and metallurgical results obtained. Because of beginning operations during the early years of World War 11, many problems caused by labor shortage were encountered, but no major difficulties developed in starting the new plant. However, because of labor shortage, full scale Smelter production was not reached until the fall of 1946. Fig 1 shows a general plan of the Morenci Reduction Works. The arrangement of the smelter equipment is shown in Fig 2, a sectional view of the smelter is shown in Fig 3, and the smelter flow sheet is shown in Fig 4. Metallurgy The metallurgy of direct smelting, being more or less fixed by the character of the charge, is not subject to the control available in calcine smelting. Slags may be modified by the addition of suitable fluxes, but the grade of the matte is determined almost entirely by the iron:copper ratio of the concentrate. The direct smelting operation involves distributing the wet concentrate along the sidewalls and in the bath of a reverberatory furnace by means of some suitable feeding device and raising the temperature of the charge so that first the moisture is driven off, then the first-atom sulphur is eliminated, and finally the sulphide portion of the charge melts and runs into the bath, carrying with it the non-sulphide portion which has been partially fluxed to form a suitable slag. The fusion of the non-sulphide portion is completed by contact with the irony converter slag which is regularly being poured into the reverberatory furnace. The smelting rate of the charge is influenced by the mineralogi-cal composition of the sulphide portion of the concentrate and by the composition and amount of the non-sulphide portion including the fluxes added. The copper in Morenci concentrate is chiefly in the form of chalcocite, intimately associated with pyrite, and non-sulphide content is very low so that

Jan 1, 1950

SPEAKING generally, it may be said that leaching is the simplest method of recovering copper from its ores. Likewise it is perhaps the oldest method of treatment used by copper metallurgists of the modern era. Reliable records indicate that as early as 1752 cupriferous pyrite was leached in the famous Rio Tinto region in Spain. Though the manipulation was quite different from that in use today at Chuquicamata, New Cornelia, Inspiration, and Andes, it resembled that employed by Phelps Dodge at Bisbee, as described in Chapter XIV. Leaching consists of subjecting ore to the action of a liquid solvent or menstruum (usually an aqueous solution) which dissolves the major part of the soluble copper minerals. The resulting pregnant solution is drained off or otherwise separated from the residual ore; and the copper in the solution is then recovered by some appropriate means of precipitation. When sulphuric acid is the lixiviant, as is usual, the simplest procedure is to pass the copper-bearing solution through large troughs containing scrap iron. The iron displaces the copper in the solution, precipitating it as a slime coating the iron and varying in color -from bright copper to a dull black. This may be washed off at intervals, collected as a sludge, dried, and melted with a little fluxing material to produce reasonably pure copper. Usually, of course, the mud is sent to a smelter where most often its destination is the converter or reverberatory furnace. Modern practice uses precipitation on iron only as a complemental process to electrolytic precipitation or deposition, wherein the pregnant copper-bearing solution, acting as the electrolyte in a cell having insoluble anodes and copper cathodes, is depleted of the copper it contains. Cathode copper, 99.5 per cent pure, is produced ready for the market as refined copper, or for a simple process of melting, fire-refining, and casting in

Jan 1, 1933

By H. I-Lieh Huang, O. D. Sherby, J. E. Dorn

RECENT investigations1-4 have suggested that the total plastic strain, C, for high temperature creep under a given stress can be correlated by means of a temperature-compensated time, te- where t is the duration of test, e is the base of natural logarithms, aH is the activation energy for creep, R is the gas constant, and T is the absolute temperature. A typical set of data on which this deduction was based is given in Fig. la. Inasmuch as the e-in t curves for the various temperatures are identical except for their displacement along the In t axis where f and are appropriate functions. If the increase in creep rate with an increase in temperature is exclusively ascribable to a single process involv- ing thermal activation, (T) should equal RT and therefore it = constant [2] where ?= te Assuming the validity of this relationship, ? = ?2 at the same strain, or where the subscripts refer to two alternate test conditions.

Jan 1, 1957

By W. C. Knopf, G. Samsel

For several years International Minerals & Chem-ical Corp. has used a radiation method to assay potassium content of products from potash and feldspar beneficiation. The procedure is rapid, accurate, and inexpensive and is easily handled, if necessary, by nontechnical personnel. Data are presented to show the accuracies that may be expected if the technique is used for control of pilot plants or large-scale plants. Natural potassium is composed of three isotopes —K, K and K. Five other isotopes, artificially produced, have been detected. In natural potassium only the K isotope, with a half life of 1.4x10 years, is radioactive. Its modes of decay are beta and gamma rays, positrons, and x-rays. Only the more abundant beta rays, however, are important in radiation measurements using geiger tubes. Barnes and Salley' measured radiation of potassium salts in solution in 1943. Gaudin and Parnell2 first reported the use of solid salts arranged in a vessel surrounding the ß counter in 1948. Later, Scheel used the method to assay potassium content of various crude and finished potash salts. Experimental: Dip-type Geiger-Muller tubes (TGC-5) supplied by Tracerlab Co. were used in all radiation counting measurements. The tube was encompassed by a glass container about M in. larger in diameter than the tube. This container, which served as a sample holder, was closed at the bottom with a rubber stopper to facilitate removing the samples. Samples were not weighed, but about 40 g of sample were needed for each test. Electrical impulses from the tube were counted on either a Tracerlab scaler or a rate meter. To obviate the need for constant attendance, preset features were incorporated into the scalers, so that at a predetermined time or count the units were automatically deactivated. When rate meters were used, counting rates were read directly from instrument or from a recorder used in conjunction with the rate meter. Each tube was calibrated, according to the manufacturer's instructions, to determine the correct operating voltage to insure reproducible results. A linear calibration plot of percent K2O vs counting rate was also obtained for each tube by recording the counting rate plus background count of several standards of different K2O content chemically analyzed by the chloroplatinate method.' These standards were of approximately the same particle size distribution as samples to be assayed. Specific background count caused by cosmic rays and other surrounding radiation was checked periodically by counting a sample of pure NaCl. Fig. 1 is a representative calibration plot. Assays were determined directly from the standard plot or calculated by subtracting the background count from the counting rate, then multiplying by the slope of the line. Chemical assays of the test samples were made by the Sherril method," a flame photometric technique, or the chloroplatinate method. Data: The radiation assay method has been used for three years by International Minerals & Chemical Corp. in the laboratory and in pilot plants processing ores containing potassium. These dry concentration plants process sylvinite and langbeinite ores at Carlsbad, N. M., and feldspar ores at Top-sham, Maine. Sylvinite ore is predominantly a mixture of syl-vite (impure KCl) and halite (impure NaCl). Contaminants include sulfates, such as langbeinite (2MgSO - K2SO4), kieserite (MgSO H2O), poly-halite (MgSO4.K2SO, 2CaSO, . 2H2O), and slimes. Langbeinite ore is predominantly langbeinite and halite with small amounts of sylvite, sulfates other than langbeinite, and slimes. Several variables, in addition to correct calibration and standardization of tubes, were found to be important in obtaining reproducible results. Particle size distribution of standard samples should be

Jan 1, 1959

The following is an incomplete list of members and guests who called at Institute headquarters during the period June 10, 1918 to July 10, 1918. F. C. Alsdorf, Tucson, Ariz. Emory M. Marshall, Camp Raritan, N. J. Juan F. Brandes, Santa Barbara, Cal. Jacques S. Negru, Camp Niagara, Ont. .H. Smith Clark, Kansas City, Mo. Arvid E. Nissen, High Bridge, N. J. J. S. Cunningham, Charleston, W. Va. Richard G. Place, So. Strafford, Vt. W. G. Eberhardt, Tucson, Ariz. Frank H. Probert, Berkeley, Cal. M. Eldredge, Bombay,. India. Martin A. Roudabush, Osterburg, Pa. A. D. R. Galloway, Accra, W. Africa;. P. H. Royster, Minneapolis, Minn. F. Hanst, Harrisburg, Pa. J. L. Schueler, Peoria, Ill. B. B. Hood, Chrome, N.. J. Henry B. Smith, New Britain, Conn. Paul S. King, Wilmington, Del. W. G. Sommer, Peoria, Ill. E. D. Kinney, Anaconda, Mont. A. L. Toenges, Roanoke, Va. E. W. Kohl, Jr., Philadelphia, Pa. G. D. B. Turner, Butte, Mont. James W. Love, Knoxville, Tenn. A. T. Ward, Bellefonte, Pa. Edwin A. Austin, formerly with the Yukon Gold Co., is superintendent of the Elkoro mine at Jarbidge, Nev. John W. Beard is now with the Cia Minera de Penoles, Ojuela, Dgo., Mexico, via Mapimi. R. S. Bonsib has accepted a position with the United States Emergency Fleet Corporation as District Safety Engineer, San Francisco, Cal. Albert Burch has been appointed by the Bureau of Mines to encourage the mining of chrome. F. B. Caldwell is working for the U. S. Bureau of Mines, under Albert Burch, in the investigation of chromite deposits. W. A. Carlyle has taken over the duties (in addition to his own) formerly assigned to E. P. Mathewson with the British America Nickel Corporation, at Sudbury, Canada. R. M. Catlin received the honorary degree of Doctor of Science at the recent commencement of Rutgers College, New Brunswick, N. J. S. K. Dahl is giving up his position as mill superintendent with the Messina Mines, which have been suspended, and is returning to this country. Algernon Del Mar has become manager of the Techatticup mines, El Dorado Canyon, Nev. Robert Dye has succeeded D. L. Forbes as manager of the Teck-Hughes at Kirkland Lake, Ont., Canada. J. O. Elton, superintendent of the Anaconda company's electrolytic zinc plant at Great Falls, Mont., is doing special work with the U. S. Bureau of Mines. R. B. Caples takes charge of the plant in his absence. George H. Gibbs has resigned his position as engineer at Messrs. T. & 1. Bradley & Sons, Ltd., Darlaston blast furnaces, Darlaston, and is now located at "Belmont." Litchfield Road, Rushall, Walsall, England. William D. Gordon, for the past 7 years manager of The Mine & Smelter Supply Co. at El Paso, has been elected president of Camphuis, Rives & Gordon,. Inc., and has opened American headquarters for the company at 81 New Street, New York, N. Y. E. Harms, for the past 16 years inn charge of metallurgical operations of the Torreon, Mexico; lead and copper smelter, has resigned and is now located at El Paso, Tex.

Jan 8, 1918

By Chandler Morse

RENEWABLE VS. NONRENEWABLE NATURAL RESOURCES Nonrenewable resources, such as minerals, are the inevitable center of attention in discussions of depletion and exhaustion. Nevertheless, it may well be proper to regard some nonrenewable resources as not subject to exhaustion, and renewable resources may sometimes be treated as if they were finite stocks. Thus, the availability of nonrenewable resources is not and probably never will be known completely Chap. 2.5A, and therefore is not subject to firm predictions concerning exhaustibility. Moreover, because exploration and discovery are more or less continuous processes it is often appropriate to regard mineral supplies as flows, and to treat the estimated reserves as working capital, an inventory, continually depleted by use and augmented by discoveries.23 The aggregate economically exploitable stocks of a given mineral are seldom estimated (or estimatable) with precision, as Chap. 2.5A shows, and even when they are, forecasts concerning years of remaining life can be and often are falsified by changes in one or more of the multidimensional conditions of supply and demand; or the productive services formerly derived from an exhausted stock may continue to provided without material impairment by one or more substitutes b Conversely, the renewable resources are all subject to depletion when the rate of use exceeds the natural or induced rate of replenishment, and cases of exhaustion or near exhaustion, as through soil erosion, overcuttmg of forest lands, and overfishing, are rather common c Where exhaustion is a clear possibility the resource may either be exploited on a consciously adopted "sustainable yield" basis or be treated as an exhausting asset." In some cases, conscious treatment

Jan 1, 1976

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By Tkeoclore Marvi

IT is singular that an industry quite the antithesis of flying should record tremendous strides in the utilization of aviation through- out the entire depression period, .while in the same years private interests lagged and airplatie manufacturing plants closed to such an extent that he purchase of new planes of certain types was practically impossible. Though receiving little notice from aviation publications and national associations, this use of the airplane progressed by sheer merit. It saved money, conserved energies, and made minutes in the air the equal of weeks on foot or water. The advent of aviation into mining and petroleum operations dates back many years, yet it \vas not until the depression that this new facility of the mineral industry was put on its proper economic basis. There, by its possibilities for saving effort, time, and money, it takes its place equally with other great technical advances in nietl

Jan 1, 1934

By Eric K. Albert, J. Kiusalaas

The paper presents an overview of SPASID (Kiusalaas and Albert, 1983), a new computer program developed under U.S. Bureau of Mines funding for the prediction of surface subsidence caused by under- ground mining operations. The presentation, which is illustrated with two case studies, also re-evaluates the influence function method as a tool of subsidence prediction, arriving at some rather unconventional recommendations. SPASID consists of four modules that communicate through common data bases: (1) Preprocessor. This module prepares and maintains the database for the entire site. The database contains all the information about the site and the mine operation that is necessary for the computation of subsidence. (2) Subsidence Predictor. The influence function method is used to predict the surface displacements that occur in any portion of the site that occur between two given dates. The computations take into account the time lag between extraction and displacement, and the effects of pitching seams and incomplete compaction at the edges of panels. The program contains i not he's influence function and the Green's function of transversely isotropic elasticity theory. (3) System Identification. The purpose of System Identification is to determine the optimal values of the various parameters associated with the influence functions in the Subsidence Module. System Identification requires measurements of subsidence from a site with a sirnilar overburden structure. The values of the subsidence parameters are obtained by minimizing the discrepancy between the measured and computed surface displacements. (4) Postprocessor. The Postprocessor is a graphics facility for displaying the data generated by the other program modules.

Jan 1, 1984

By John G. Tate, George W. Nicolson, James L. Bruce

For more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.' From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. Description of Ore Bodies The shape Of the Ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions) extending from unknown depths below the bottom level at elevation 250 ft below sea level) to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the Ore body extended to surface and was Mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the Ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upper-side of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and Clay sedimentaries of Miocene and later age, The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-Stained by the descending meteoric waters, It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pet Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pet. on the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main Ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. 'This probably can

Jan 1, 1949

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand or magnetite, in water, and, (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended sand or magnetite pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous; vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the introduction of feed and withdrawal of products, 'so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary is get the recoveries and grade of product desired. Sizes usually cleaned are plus ¼ in. or plus 1/8 -in. in the United States and plus 1/16-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about 1/8-in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media processes is progressing rapidly and it is likely that equipment, media, and procedures will be developed to clean sizes down to 0.5 mm. efficiently and at low cost.

Jan 1, 1950

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947

By M. Muskat

A theory has been developed describing the behavior of wells and reservoirs producing by the action of bottom water drives. It is assumed that the pressures are maintained above the bubble point, and that the permeability to viscosity ratio of the water in the flooded zone is the same as for the oil in the oil-saturated pay. Accordingly, the treatment is based on the homogeneous fluid potential theory. The effect of the difference in density between the oil and water is neglected. .4fter deriving the proper potential distrihutions, the nature of the rise of the water-oil interface below the producing wells is calculated. The primary clean-oil-production phase is expressed in terms of the displacement efficiency, defined as the fraction of the pay flooded out by the rising water table at tlle time of first water entry. The variation of this displacement efficiency is calculated as a function of the well spacing, pay thickness, the ratio of the horizontal to vertical permeability, and the well penetration. The important parameter, other than the well penetration, is found to be the ratio of the well separation to the thickness of the oil pay multiplied by the square root of the ratio of vertical to horizontal permeability. It was found that the displacement efficiency continually decreases as this parameter increases, and for values of the latter >3.5, the efficiency varies inversely as the square of the parameter. It also increases with decreasing well penetration. Perhaps the most striking result of this phase of the analysis is the conclusion that in order to explain the delay in entry of water in wells producing by bottom water drives for periods longer than a few days normal production, with drawdowns large compared with the differential density head between the oil and water, it is necessary to assume that the vertical permeability is a very low fraction of the horizontal permeability. An analysis is also given of the production history after the water has broken through, on the assumption that the production mechanism and details of the flow distribution continue to be the same as during the phase of clean-oil production. As is to be expected, it is found that the water cut will increase at an accelerated rate as production proceeds. However, the initial differences between systems of different well penetrations or well spacings with respect to the total clean-oil production gradually decrease in terms of the variation of the water-oil ratio with cumulative production. In particular, by the time the water-oil ratio has reached values of the order of 5 or greater the cumulative recoveries will generally differ much less among various producing systems than their corresponding clean-oil recoveries. Introduction On the basis of elementary geological principles, one may classify effective water-drive fields in two groups. In the first, the entry of water into the oil-producing formation may be characterized as an edge-water encroachment. This term is used to suggest that the motion of the water proceeds largely in a direction parallel to the planes of stratification. This type of water intrusion occurs usually in thin producing zones and in strata lying along structural flanks of appreciable dip. In the second group—"bottom water-drive" fields—the water-oil interface lies in a plane of zero or slight inclination to the

Jan 1, 1947