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By Laurence C. Hicks

Consideration of the past work on the subject of the diffusion of chromium into iron suggested that additional information might be given by the use of X-ray spectroscopy in following the concentration changes through the diffusion zone. Grube and Fleischbeinl packed rods of electrolytic iron in a mixture of alumina and chromium. These specimens were heated in an atmosphere of purified hydrogen for varying lengths of time. After treatment the specimens were examined metallographically and showed the usual structure, consisting of a border of radially oriented columnar grains ending in a sharp boundary line. Reference is made to the fact that etching with certain reagents will attack only the material inside the border of columnar growth and also to the fact that polishing seems to develop a ridge at the position of the boundary between the etched and unetched areas. By chemical analysis of thin layers turned off on a precision lathe, the authors were able to obtain depth-concentration curves. These curves, reproduced in Fig. 1, show that in most cases a pronounced change of slope occurs, corresponding to the position of the boundary of the columnar grains. In a laler paper Grube extends his work to other systems which show the same characteristics.~ He concludes that the reason for the break in the curve is that a hindrance of diffusion occurs at the place where the regularly oriented grains of the diffusion zone meet the random grains of the interior portion, on the assumption that the diffusion velocity in one direction in a grain may be greater than in another direction, and that the grains in the diffusion zone orient themselves so as to give the maximum diffusion rate. Kel1ey" points out that Grube has failed to note that the boundary line does not consistently cross all grains and

Jan 1, 1934

By E. V. Potter, H. C. Lukens

The volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.² Both sets of data show a minimum solubility between 500' and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. Therefore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. Apparatus and Method The apparatus and method were essentially the same as those described in the previous work,' as shown in Fig. I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transi- . tion points determined under such conditions were less accurate. Absolute Solubility Procedure ad Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1947

By B. N. Webber

During World War II the Pocos de Caldas bauxite deposits of Minas Gerais in Brazil yielded some 60,000 tons. Since then they have maintained a small but almost continuous production. Known for many years, the deposits have been reconnoitered by a number of geologists,1-4 but no dimensional study has been possible because there have not been enough exposures to show clearly the depth, bedrock, and habit of occurrence. The deposits are somewhat unorthodox in their occurrence mainly on steep slopes of mountainous terrain. Although the parent rocks are a sequence of alkalic intrusions that bauxitize readily under the proper conditions, bauxitization has not been the dominant weathering process in the area. It is limited to certain localities where important volumes of bauxite have formed by laterization of several rock types, each yielding a distinctive type of bauxite. Bauxitization may be observed in several stages and in both direct and indirect cycles of formation. The deposits are unique in being of demonstrably recent age, so that the conditions under which the bauxite formed are essentially those of the present time. The bauxitization sequence is postulated in Fig. 1. Pocos de Caldas district is situated at approximately 21" 50' south latitude and 46" 30' west longitude in southwestern Minas Gerais, near its boundary with the state of Sao Paulo. It lies within the Eastern Plateau physiographic province of Brazil, occupying a prominent highland area that rises some 2000 ft above the surrounding country. The central portion of the Pocos de Caldas highland is characterized by gently undulating topography, with generally sluggish drainage, and is surrounded by a rim of hills rising above 1000 ft above it. In cross section the highland resembles a truncated cone with a depressed central area. The rim has been sculptured into a more prominent and abrupt topographic pattern than the central area, and streams that are of low to moderate gradient in the central plateau plunge over the rim in a spectacular series of cascades and falls. GEOLOGIC SETTING The Pocos de Caldas highland owes its physiographic expression mainly to the differential erosion of a complex intrusion of alkalic rocks into gneiss and sandstone. Erosion was guided somewhat by faulting. The highland is almost circular, and its limits, except in one locality, coincide with the periphery of the intrusion. The alkalic intrusions largely control its shape and extent, aided by some subsidence through faulting of the central portion. The mountainous rim of chilled phase, the later intrusions, and the indurated intruded rocks have resisted erosion more effectively than the central portion of the intrusion, which is composed of more coarsely crystalline alkalic rocks that form a central basin in the highland. Gneiss and sandstone are found coincident in elevation with the topographically highest intrusions. BAUXITE TYPES Most of the bauxite, which varies in physical type, is on the top and steep slopes of the northern rim. The only alumina mineral is gibbsite, definitely crystalline but iron-stained unless of secondary origin. Clay particles occurring with the bauxite are kaolinite. Some types of bauxite are an index to their origin. There are four general physical types of bauxite or bauxite laterite: 1) Surface Rubble: This partly nodular and partly fragmented type, usually less than 3 ft thick, results from surface weathering of massive bauxite or may form by superficial enrichment of nodular bauxite with a clay matrix when the interstitial clay is removed by surface runoff.

Jan 1, 1960

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.' Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe's treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.' This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963

By C. D. King

THE key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades' of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the coal washer at Clairton made it possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of 100 per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. I and No. 2 blast furnaces at Rankin, Pa., Carnegie-Illinois Steel Corporation. CLAIRTON BY-PRODUCT COKE PLANT AND COAL WASHER The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width. These ovens also differ in height and length. The present coal washer has a daily capacity of- approximately 14,000 tons, leaving 16,800 tons to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used on all the remaining ovens. The customary arrangement is

Jan 1, 1943

By L. W. Kempf, K. R. Van Horn

Plastic deformation of most commercia1 metals within a sufficiently low temperature range results in profound changes in structure and properties, of which the causes and effects are not completely understood. One of these effects is the presence of internal residual stresses and strains, which ordinarily do not appear to require specific consideration in most structural applications but which may be quite undesirable in particular instances. For example, in heavy sections that require considerable machining before assembly, residual stresses may be undesirable because of the distortion they cause when their balance is disturbed by machining or otherwise. In addition, the distribution of stresses may be such that it acts in the same direction as the applied load, thus bringing about premature failure or reducing the load-carrying capacity of the member. One source of residual stress in metal structures is the plastic deformation that may occur during rapid cooling from relatively elevated temperatures, as in the cooling of a casting in the mold or the quenching of a heavy section from elevated temperatures during heat-treatment. These residual stresses are usually undesirable because their direction of operation and magnitude cannot be controlled well enough to permit utilization of the changes in properties of the metal that they may bring about. The most convenient manner of controlling such residual stress is by proper selection of the cooling rate or by reheating to a temperature at which plastic flow can take place, resulting in relief of the residual stresses and strains. Both of these methods of control, however, may cause a reduction in the optimum properties obtainable from the previous operation. A compromise must be struck, and if it is to result in the best possible combinations of properties, specific information must be available regarding the magnitude of the stresses and the rate at which they are affected by variations in cooling rate or in reheating temperature. The complete quantitative estimation of residual stress in complicated metal shapes is exceedingly difficult, if not impossible. In simple sections, however, relatively quantitative analysis may be applied and useful cstimations of stress distribution may be made. This paper is concerned largely with the rate of relief, upon reheating, of internal residual stress in simple aluminum-alloy structures. Since even with simple structures quantitative estimation of residual stresses is laborious and costly, an attempt was made to find other means of collecting data upon which commercial heat-treatments might be based. Incidentally, a few data were collected bearing on the problem of relaxation of aluminum alloys. Determination of Residual Stresses The magnitude and distribution of residual stresses in simple aluminum-alloy shapes rapidly cooled from elevated temperatures has been discussed in a previous paper.' Fig. I reproduces some of the data

Jan 1, 1942

By Pedro L. Lizaur

INTRODUCTION The degree of success of an association between parties in establishing a new venture ultimately depends on three factors: a. the venture's underlying economic strength, which is based on the complementarity of the comparative advantages brought by each party to the negotiating table; b. the ability to reach an agreement which satisfies each party's objectives and constraints; and, c. the capacity to design and implement a funding structure which is consistent with the project economics. A thorough assessment of the venture's profitability and associated risks under alternative technical and economic scenarios is the basis for a sound "go" or "no go" decision. In-depth evaluation of the risks and rewards to each of the parties involved under alternative legal and financial structure must be the foundation for a long lasting "how to go" decision. The allocation of risks and rewards should be consistent with the objectives and constraints of all parties and the sharing mechanisms, established in the contract, should be flexible to assure the long-term stability of the agreement. Rapidly changing economic conditions during the last decade have had a dramatic impact on the envisaged allocation of risks and rewards between host countries and private investors. The effects of these changes, and the fact that the relative strengths of the parties involved may shift during the life of a project (e.g. before and after major capital investments have been made), have forced the renegotiation of a multitude of contracts. Therefore, the present and future stability of an economic agreement would depend not only on the originally designed provisions, but also on provisions which allow for the automatic adjustment of rewards to project sponsors under a variety of future economic situations. A pre-condition for the allocation and quantification of risks and rewards is the definition of standards of measurement used by each of the parties. This is critical in international negotiations when one of the parties represents the national interests of a country. The understanding and use of different standards for the measurement of rewards for risk taken between a government and private enterprise facilitate the negotiation of a satisfactory agreement. This is possible because certain trade-offs between the negotiating parties may have different relative values. STANDARDS OF MEASUREMENT OF REWARDS FOR RISK TAKEN The negotiating process takes a step forward when the parties are able to focus on their interests, explore different alternative solutions and then base results on a set of objective standards. Unfortunately, the parties frequently put more effort into "staking out" and defending positions, than into understanding their intrinsic interests. Moreover, when one party, such as a governemnt owned corporation, represents a country's national interests, the negotiation process increases in complexity. Private firms focus on commercial profitability, using discounted cash flow techniques such as NPV, IRR, or ROE. In contrast, the government is also concerned with the project's impact on the local socio-economic environment. Without entering into a discussion of alternative economic development theories and approaches, there exist several possible measures that could be pragmatically utilized by each party in evaluating the socio-economic impact of a project. The more complete measure is the National Profitability (NP). The NP is a discounted cash flow procedure similar in structure to IRR or NPV but in which the project's financial cash inflows and outflows and discount rates are adjusted to take into consideration the local conditions. The NP is calculated on an unlevered basis and all taxes and duties are removed from the project

Jan 1, 1985

By E. C. Bitzer

The primary object of the work described in the following pages was to simplify the equipment in the separating circuit of the heavy-media process by substituting a spiral classifier for the separatory cone. Mechanical considerations were the leading attraction and the best that was hoped for on metallurgical performance was that the new vessel would give results equal to those obtained by conventional equipment. Tests have demonstrated in commercial operation on iron ore that the mechanical advantages of the spiral separator are about as predicted; also, the metallurgical performance is superior to the cone on the ores treated. Treatment of iron ore involves the separation of two products: a concentrate that sinks and a float product that contains true float material plus a controlled division of interfering middling. The middling material is heavier than the average specific gravity of the separating medium. Recent work with the spiral separator on Tri-State zinc ore showed that the middling material had to be recovered as concentrate because this fraction contained the bulk of the zinc in the ore. It has been demonstrated that it is possible to make three products with the new separator on an ore such as this: a float tailing, a float middling, and a high- grade heavy sink product. It appears from this last work that the new separator has definite mechanical and metalluigical advantages over any type of separating cone for treating feed that contains large amounts of material of a specific gravity close to that of the separating medium. However, either type of separator should perform equally well, metallurgically, on feed that is free of middlings. Each series of experiments with the spiral separator has required additional work to fully develop the possibilities of the machine. For this reason the paper is divided into chronological parts. History of Development A drag-type classifier was first proposed as a substitute for the cone separator by Butler Brothers technicians during the initial tests with galena medium at Crosby, Minn., in 1937. The desire for finding a substitute for the cone arose from trouble with interfering middlings and certain operating disadvantages of the cone. The possibility of using a spiral classifier was also suggested at this time by Emmett Butler and C. J. Abrams. However, inability to satisfactorily recover fine galena, which was used as a medium, terminated all development work at Crosby. During the winter of 1937--1938 investigation started on magnetic medium with concurrent development of the inverted or closed-top cone, which was found necessary to eliminate iron-ore middlings with the float product. About

Jan 1, 1949

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By Walter R. Hibbard, Harold Margolin

The effect of ten ternary additions on the aging of a Cu-Ag alloy was measured by X ray, microstructure and hardness. A supersaturated copper-rich transition structure was found. The effect of the ternary element was related to differences between transition and precipitate lattice parameters and analogies with solution and strain hardening. IN addition to the prerequisite of diminishing solid solubility with falling temperature, the theory of coherency hardening1 proposes that the principal source of hardening during precipitation is strain caused by coherency between the matrix and precipitate. For a given system greater coherency hardening would result from lengthening the period of coherent growth and/or increasing the number of nuclei, other things remaining equal. However, the hardness change during aging is a function of a number of phenomena in addition to coherency hardening, such as dispersion hardening, loss of coherency, solute depletion, matrix recovery or recrystal-lization, coalescence, and their relative time sequences. The present investigation was undertaken to study the effect of ternary additions on the age-hardening of Cu-Ag alloy. For this purpose a series of alloys were made containing as ternary constituents Mg, Al, Si, P, Mn, Ni, Zn, As, In, and Sb. These elements were added to a master 5 wt pct Ag in Cu alloy in such amounts as to obtain alloys listed in Table II containing the following approximate atomic percentages: 96 pct Cu, 3 pct Ag, 1 pct ternary addition. A 97 atomic pct Cu, 3 atomic pct Ag alloy was used as a comparison standard. There have been numerous investigations of age-hardening in Cu-Ag alloys2-lo but few of ternary Cu-Ag alloys. Pfister and Weist" found that 1 wt pct Ni reduced the solubility of Ag in Cu above 600 °C and that the rate of precipitation was slower than in polycrystalline Cu-Ag alloys of similar silver content. More recently Hodge, Jaffee, Dunleavy, and Ogden12 investigated the effect of ternary additions of Mg, Li, P, Cd, Zn, Zr and Be on strength properties of Cu-Ag alloys. Mg, Cd, and P were found to increase strength in the aged and cold-worked condition. Experimental Procedure Charges weighing 7.5 lb were melted in a closed carbon crucible under a reducing atmosphere* of nitrogen and hydrogen. A Durville-type casting procedure with a hot-top arrangement was used to obtain a sound casting, 2x2x43/4 in. Prior to rolling and annealing of the ingots, a trial solution anneal of rolled sections of the hot-top portions indicated that at 780°C melting was avoided except for the Cu-Ag-Sb alloy. This alloy could not be produced as a single phase within the limits of temperature control. i 3" to 5oC, since melting occurred at 64O °C, and below this temperature precipitation was

Jan 1, 1952

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952

By Henry Doherty

FOR many years more money was spent in the search for and the production of gold than the gold that was produced was worth. The same thing is now true of petroleum. More money is spent for the search and. production of petroleum than the market value of the petroleum produced. The first thought concerning this statement will be that men would not embark in a business in which more money was expended than the value of the product produced. Few people realize that more money is spent in the oil business than the market value of the oil produced. This would not stop the spending if they knew it. Everybody knows that more money goes into a lottery than comes out of it, yet the instinct for gambling is so widespread and so easily excited that lotteries are forbidden by law. The hope of winning the grand prize is what lures men on. The search for and production of oil has become a more frenzied game than the search for gold ever was. THE OIL BUSINESS PAYS NOW BUT THE PUBLIC WILL PAY FOR ALL ETERNITY The public could sit back and enjoy all of this, knowing they were being supplied with petroleum products at less than their real cost, if it were not that our most valuable and least plentiful natural resource is being dissipated at an alarming rate, which is constantly increasing. Here is an industry that for many years has not been governed by natural laws. The so-called laws of individual and mass psychology play a more important role than natural physical and economic laws. Even the law of supply and demand works only in the most remote way in this industry. The oil production business as a whole is now paying the price for this folly; but the public will pay the price for all eternity. The seriousness of this matter, as an outstanding national problem, has been under consideration by many men for a long time, but nothing has been done to conserve our petroleum resources and prolong the supply, although very important steps have recently been taken to make this possible.

Jan 3, 1925

By Roscoe E. Bell

BETWEEN 1945 and 1948 the author made studies of the western phosphate industry and its potentialities. These included an appraisal of the opportunities for western development of the industry, studies of production costs, of market potentials, of transportation economics, and of industry location. This paper will be directed toward pointing up the factors which have an important bearing on the establishment of fertilizer plants in the western area. Industry Location Factors: There are, of course, an infinite number of possible organizational setups which might require consideration. However, the phosphate industry is simple enough so that studies of the most probable alternatives can be made conveniently. The salient factors which require special consideration in such a study are: (I) the location of the raw materials, (2) the location, size, and character of the present and potential markets, (3) the location of energy sources and materials required for fertilizer processing, (4) the location and capacity of present manufacturing facilities, (5) the cost of assembling the materials and energy needed in manufacturing, and (6) the cost of distributing the manufactured product. Raw Material Supplies: Rock phosphate is the raw material for the manufacturing of phosphate fertilizer. In the United States the important known deposits of this material are located in three general areas (fig. 1). The western deposits, comprising about 60 pct of the nation's supply, are in the four-state area—Idaho, Wyoming, Utah, and Montana. The Florida deposits comprise roughly 38 pct of the national supply. The Tennessee deposits, comprising about 2 pct of the national supply, have been the most important source until recent years. The western deposits, which are virtually undeveloped, have not been used to any extent to meet the nation's need for phosphate rock and phosphate fertilizer. Fertilizer Markets: The large national markets for fertilizer are in the midwestern and eastern United States (fig. 2). The principal far-western markets are along the Pacific Coast, especially in California. Until recent years the western markets have been extremely limited, whereas the markets in the eastern United States have long been established and manufacturing facilities have been provided to meet these needs (fig. 3). In recent years the western markets have expanded very rapidly, continuing to grow throughout the war years and postwar period at a similar rate. The question always arises as to whether this is a temporary war-swollen market which will shrink back to its original size as soon as the present agricultural price levels drop. In order to answer this question consideration must be given to the character of the market (fig. 4). I have considered seventeen western and midwestern states in the western market area where transportation costs from the western deposits are equal to or lower than those from Florida. They include all states west of a line drawn through Chicago, Kansas City and the western boundary of New Mexico. In the mewar period this was a small market totaling only 37,000 tons of P,O, annually. The 1946 total for this same area was approximately 200,000 tons. Considerably more fertilizer would have been used in 1946 had adequate supplies been available. Estimates of future markets are difficult to make, but we do have some indices that are useful. The

Jan 1, 1951

By A. J. Lyon

The stability and permanence of any structural material used in aircraft are of paramount importance. The spontaneous hardening, or age-hardening, which takes place in some of the aluminum alloys under ordinary conditions of temperature and atmosphere, is accompanied by an increase in tensile strength and proportional limit and a decrease in elongation or ductility. Within the last few years the introduction of a number of strong and ductile casting alloys led to a study by the Materiel Division, Air Corps, of the permanence of the physical properties in several of these alloys. It has been found that even though some alloys have good properties directly after casting or heat treatment, they are not satisfactory for stressed parts that require a combination of strength and ductility. It has also led to the conclusion that all alloys that can be hardened by artificial aging—heating in a temperature range below 170" C. (340" F.)—will harden spontaneously if allowed to stand for a sufficient length of time. It follows that, in aircraft work where the factors of safety are limited on account of the necessity of keeping the weight of the structures as low as possible consistent with their safe operation, the properties of the alloys in the stable or final condition should be used as a basis for design rather than the properties obtained on the material directly after casting. The work of Wilm in Germany, Hanson and Gayler at the National Physical Laboratory in England, and Merica, Jeffries, and others in the United States, has shown that the spontaneous hardening is characteristic to a greater or less extent in all aluminum-base alloys in which the solubility in the solid state of the alloying constituents decreases with the temperature. It has been shown that, by heating to a temperature as near as possible to the melting point of the material and soaking at that temperature for a sufficient length of time and then quenching or cooling rapidly, a maximum amount of the soluble constituents can be retained in solution and the condition of maximum hardening effect upon aging can be obtained. Also, in ordinary sand and chill castings, without heat treatment, a sufficient amount of the alloying constituents is held in solution to cause important changes in the final physical properties.

Jan 1, 1929

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By F. Wartenweiler

Much has been written on milling and cyanidation as practiced on this gold field, therefore the purpose of this paper is to record its development only briefly and to describe in more detail the contemporary state of the science and art of this branch of metallurgy. It is a pleasing task, because a steady evolution is to be recorded. Definite trends influenced the development. Some have the stamp of original thought and observation; many have been achieved from a logical sequence of planned experimentation and research; while others have resulted from the drive of sheer necessity. The large scale of operations and capital outlay has compelled conservative progress. Banket ORe For a better understanding, a review of the characteristics of the ore may not be out of place. The Witwatersrand gold ore is named "banket" from the similarity of the oxidized outcrop ore to the Boer almond cake of that name. The inter bedded orebody is commonly called "reef." It is a conglomerate composed of various sizes of pebbles, principally non-gold-bearing white quartz, which constitute about 70 per cent of the bulk, within a matrix of cementing material consisting of fine-grained quartz, sericite, chlorite and chloritoid and containing the precious metals and mineral sulfides. Argillaceous components in the mil pulp may be as high as 32 per cent. Of the sulfide minerals, pyrite and pyrrhotite are predominant. Most base-metal sulfides are present, but sporadically and generally only found in highly concentrated mill products. In the latter, osmiridium is recovered in varying amounts; from 1 oz. in 3000 tons to 1 oz. in 10,000 tons of ore. Most of the oxidized ore has been mined, so milling is confined principally to the sulfide ore. A typical analysis of sulfide ore is: silica (SiO2), 86.76 per cent; pyritc (FeS2), 2.75; ferric oxide (Fe2o3), 2.65; alumina (Al2o3), 6.91; lime (CaO), tr.; magnesia (MgO), 0.70; sp. gr., 2.7. Milling grade at present price of gold (137 shillings per ounce) varies from 3.5 to 8.5 dwt., with one mine milling ore as high as 16 dwt. The

Jan 1, 1935

By Rush Greenslade

The oil and gas lease is the basic contract of the oil and gas industry; it is the foundation stone upon which the producing industry, particularly, is based. As the industry is precarious and highly speculative, the foundation contract should be of the utmost integrity and certainty. But right there an anomaly exists; the oil and gas lease is the most obscure, most uncertain, doubtful contract in the realm of law today. That is a condition that must be considered when taking oil and gas leases, and when buying, selling, and holding them. It may fairly be asked why should this industry rest upon so insecure a foundation. Why should not the oil industry rest upon the contract that is the basis of all industry, the warranty deed? There are many contributing reasons, but the principal one is business expediency. The Anglo-Saxon idea of ownership of land is that every land owner owns from the center of the earth to the sky—all that is above and all that is below—consequently the oil and gas are owned by the person who owns the surface. That idea is not exactly true with reference to oil and gas, for many states have adopted the doctrine that oil and gas are like wild animals; they are fugacious and migratory and belong to the man that traps them. But, except for that doctrine, we believe that oil and gas are owned by the owner of the surface, wherein we differ from the Latin-American countries where the mineral rights are owned by the government. The United States was settled largely by homesteading. The owners of land were, in the main, farmers, who did not have the means or the faith to drill for oil or gas. The operators or speculators did not want to buy the land on the mere possibility of finding oil; hence a compromise resulted by which the land owner gave the speculator or the operator what he called an oil and gas lease, or a right to go upon his land and drill for oil and gas. What is supposed to be the first oil lease placed on record reads as follows: Agreed this 4th day of July, a.d. 1853, with J. D. Angier of Cherrytree township in the county of Venango Pennsylvania that he shall repair up and keep in order the old oil springs on land in said Cherrytree township, or dig and make new springs, and the expense to be deducted out of the proceeds of the oil, and the balance, if any, to be

Jan 1, 1924

By F. W. Jessen, F. W. Rols-Hausen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By William D. Klopp, Joseph R. Stephens

Chromium alloys were coated with silicon, alumi-nuw, and boron by pack cementation. None of these simple coatings provided adequate nitridation/oxida-tion protection for a Cr -0.17pct Y alloy substrate as shown by a substantial Increase in the ductile -brittle transition temperature after air exposure for 100 hr at 2100°F. Iron-modified silicide coatings afforded good protection, holding the transition temperature of air-exposed specimens to 350° F compared to 200° F for uncoated unexposed specimens and 800°F for un-coated exposed specimens. Additional attractive cant-binations of modi-tying elements included Fe-mo, Fe-Mo-W, Fe-,Mo-W-Ti, and V-Mo-W-Ti. THE desirability of increased operating tempera-tures as a mcans of improving the performance of ad-vanced air breathing engines has resulted in emphasis on the development of materials with high operating temperature capabilities. Chromium, because of its relatively low density (7.19 g per cu cm), high melt-ing point (3410°F), and adequate strength upon alloy-ing, is a candidate material for turbine buckets and stator vanes of advanced air breathing engines. How-even, chromium is not without severe limitations, the major one being susceptibility to nitrogen embrittle-ment upon exposure to air at high temperatures.1,2 For example, a 25-hr air exposure of a Cr-5 pct W* * All compositions in wt pct. alloy at 2100°F produces a 600°F increase in the duc-tile-brittle transition temperature.' Although dilute alloying with such elements as yttrium, lanthanum, arid thorium3,4 or strong nitride formers5 has been shown capable of reducing nitrogen embrittlement, it is apparent that some additional form of surface protection, such as coatings or claddings, will be required for long time service in air breathing engines. Studies of aluiminide6 and silicide7 coatings and of nickel-base claddingsl on chromium alloys to date have suggested that these protection systems are inadequate. Of the aluminidc systems Studied,6 a simple aluminum and an Fe-Al coating on a Cr-5 pct W-0.1 pct Y alloy showed the lowest air exposure weight gains. However, the air exposures raised the ductile-brittle transition temperature of the coated specimens to above 1600°F from an initial level in unexposed specimens of about 500°F. A second in-vestigation for protection of Cr-5 pct W-0.1 pct Y employed gas pressure bonded alloy foils as protective claddings.1 An aluminized Ni-20 pct Cr-20 pct W alloy plus an unalloyed tungsten barrier layer gave the best performance with air exposure lives based on appearance and weight gains of over 600 hr at 2100°F. However, the bend ductile-brittle transition tempera-ture was increased to at least 1000°F after 100 hr at

Jan 1, 1970

By Bruce F. Grant, Stefan F. Szasz

During 1947, a Sinclair research team was assigned to investigate thermal methods of oil recovery. The assignment was recommended by a survey of possible research approaches to increase the amount of oil that ultimately can be recovered from oil producing reservoirs. The use of heat to stimulate oil production rates by the melting of paraffin deposited in well bores can be traced back to within one or two decades of the drilling of the Drake well. The application of heat on a larger scale has been discussed by generations of oil producers. Shortly after the turn of the century, one intrepid operator is reported to have injected steam into a Pennsylvania property. After a few weeks, he apparently became discouraged and terminated his experiment. Subsequently, the literature contains references to several well-developed techniques for supplying heat to a producing well bore to melt paraffin or to reduce the viscosity of oil contained in the formation immediately around the well bore.1.?.3.4 Some early references discuss procedures to furnish heat to the reservoir,5,6 with the injection well as the heat source, thus obligating the process to maintain the entire rock mass at a temperature above that at which the desired improvement in oil recovery would occur. Another approach to reservoir heating was reported by a group of Russian technologists in 1935.7,8,9 They definitely demonstrated that combustion can occur within the porous structure of an oil-bearing sandstone. Their field experiments, however, relied less on combustion within the rock than on heat furnished by combustion of oil supplied to the injection well bore. Ignition of the air-oil mixtures in the well bore was found very difficult, and the field tests were carried on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well, on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well. The Brundred Oil Corp. reportedly obtained combustion in the sand immediately around the injection well bore, but the experiment was abandoned because of interference with normal production schedules. Injection capacity of the experimental well was greatly reduced by firing. The well was reshot and pieces of sand showing partial fusing of the quartz matrix were recovered. To the authors' knowledge no other field experiments utilizing combustion techniques for formation heating were undertaken prior to 1948, although the patent literature evidences continued interest in formation heating."'," CONCEPT OF COMBUSTION-SUPPORTED HEAT WAVE The references cited were in agreement that heat applied to a reservoir would increase recovery, but there

Jan 1, 1955