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By R. A. Fitch, J. D. Griffith

A performance calculation method was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods. of improving their efficiency. The calculation method is based upon the division of reservoirs into multiple independent zones or strata. Comparison was made with some experimental floods and with a field project to obtain some measure of the applicability of the method. Two aspects of miscible flooding were considered: (I) the displacement of a miscible front through a reservoir, and (2) the distribution and utilization of the solvent volume injected to maintain miscibility. Calculations and experihental observations indicate that alternate gas-water injection behind a miscible front significantly improves miscible flood performance, both within a single stratum and in a multistrata reservoir. Calculations were made on the extent to which miscibiliry is maintained by a given solvent volume in a stratified reservoir. Two alternate criteria for determining the optimum volume of solvent for injection are discussed. The preinjection of a small volume of water ahead of the solvent is suggested as a method of obtaining more efficient utilization of solvent. Calculations and experiments were made to investigate the effects of water preinjection. INTRODUCTION Miscible fluid displacement as a possible means of recovering oil has been the subject of extensive research and numerous field tests over the past several years. This work has brought out both favorable and unfavorable features of the miscible recovery methods. Many tests have shown that a miscible fluid can displace all of the oil contacted, leaving no high residual oil saturation, as is characteristic of immiscible displacements. The miscible methods have proven dificult to control, however, as evidenced by early breakthrough of the displacing fluid and poor sweep efficiency in several field projects. It became apparent early in the investigation of miscible displacement that the development of improved techniques and better methods of control would be required to extend the range of applicability to any significant portion of our petroleum reservoirs. The purpose of this study was to consider the problem of designing miscible floods to obtain better performance. A performance calculation was used in conjunction with experimental studies to develop means of predicting and interpreting miscible floods and to explore possible methods of improving their efficiency. Two aspects of miscible floods were considered separately in this study and the results are presented in two parts. The first part concerns the manner in which the miscible front is displaced through the reservoir. In these calculations the condition of miscibility between the reservoir oil and the displacing fluid is assumed. In the second portion the distribution and utilization of the preinjected solvent in maintaining rniscibility is considered. This portion dealing with solvent utilization applies only to the enriched gas or LPG slug processes. CALCULATION METHOD AND EXPERIMENTAL STUDIES COMPUTATIONAL MODEL The calculations for expected reservoir performance are based upon the multi-strata concept of reservoir properties. The method assumes multiple, independent strata (no crossflow between strata) and explicitly includes variations in patterns, injectivity, areal sweep and displacement efficiency. Lateral variation in permeability within the strata (for example, directional permeability) may be considered in the calculations, provided the variations are similar in all strata. The calculations based on this model furnish the rates of injection and rates of production of both oil and the displacing fluid for the composite system of strata. To carry out calculations on the mathematical model described, information is required on the performance of the displacement process under consideration in a single stratum element of the pattern to be used. In particular, for a given pattern and displacement process, data are required relating injectivity and composition of the produced stream to the volume of fluid injected. Data on the variations in areal sweep must also be available if it is desired to track the areal sweeps in the multi-strata model. These data may be obtained from experimental work such as model studies or other suitable methods. This representation of reservoir properties is, of course, an approximation and may be inappropriate in some cases. But the representation is not an arbitrary one since most oil reservoirs are essentially successive layers of sediment with the net producing pay zone often comprising but a fraction of the gross formation thickness. The fact that permeabilities measured in the vertical direction are frequently but a fraction of the horizontal permeability adds some evidence to the validity of this model. This type cal-

Jan 1, 1965

By Barbara A. Thompson

A previously reported high-resolution method for the location of boron-rich areas in metallurgical and biological specimens was been adapted for general use on a routine basis. The rnetlzod utilizes neutron activation and autoradiograpizy. Alpha-particles emitted by boron nuclei upon neutron capture are recorded on a photographic emulsion. The resulting a-particle tracks show the location of boron-rich areas. Experimental techniques, interferences, and limitations of the method are discussed in detail. The method is most useful where there is marked segregation of boron. In this type of sample, the segregation can be observed when the nominal boron concentration is as low as 0.0006 pct. THE positive identification and location of boron-rich areas in metals is frequently of great interest in metallurgical work. Unequivocal identification is often difficult to make by conventional metallo-graphic methods. Recently, a method has been described which accomplishes this objective by neutron activation and autoradiography.l-3 The method can be described briefly as follows. Upon neutron capture, a -particles are emitted by boron nuclei according to the following reaction: ,Blo + n - ,a4 + 3Li7 + 2.4 mev The energy is dissipated as kinetic energy of the products. By irradiating a boron-containing sample in contact with a photographic emulsion and subsequently developing this emulsion, a-particle tracks are obtained whose location corresponds to the location of boron-rich areas in the sample. Two factors combine to make the reaction extremely specific for boron. The first is the unusually high (755 barns) cross section of boron for thermal neutron capture. The second is the higher neutron energy required to produce (n, a ) reactions in essentially all other nuclei except lithium. These two factors make the method specific for boron by six to seven orders of magnitude when a predominantly thermal neutron source such as the Brookhaven reactor is used. The reported limit of detection of this method is of the order of 0.01 pct B., The present work was originally undertaken to determine whether this limit could be lowered by use of a thinner emulsion. However, initial experiments showed that in order to use the method at all, it was necessary to reestablish the optimum experimental conditions in terms of the available irradiation facilities. It is the purpose of this paper to describe these experimental conditions in detail, to discuss the factors influencing sensitivity, and to evaluate several techniques for increasing sensitivity. EXPERIMENTAL A) Preliminary Experiments—The first measure-ments were made using samples of crystal oriented silicon steel containing various concentrations of boron. In the later experiments, samples of various high-temperature alloys such as M-252, hcoloy 901, Nichrome V, and so forth, were used. Faraggi, et al.,2 reported that the lower limit of sensitivity in this type of sample was about 0.01 pct B using nuclear emulsions of 50- u thickness. but that it should be possible to extend this limit by the use of thinner emulsions. Accordingly, we first used Kodak Auto-radiographic Stripping Film (Permeable Base) which has an emulsion thickness of only 5 µ. This was mounted on the metallographic specimens according to the technique described by Boyd.4 The emulsion remained in contact with the metal surface throughout exposure and development. Since the emulsion is transparent after development, the autoradiograph and metal surface can be viewed simultaneously and any correlation between film blackening and structure of the metal can be made directly with no problems of realignment. Because the silicon steel is readily attacked by moisture alone, it was necessary to apply a protective coating to the metal surfaces before mounting the emulsion. The coating was made extremely thin in order to absorb as few a-particles as possible. Boyd4 and Gomberg5 have discussed various plastics used for this purpose; however, none was sufficiently impermeable to prevent chemical attack of the steel during the developing process. This attack resulted in the production of gross chemical artifacts in the emulsion. It was, therefore, necessary to use the method of Wolfsberg and John6 as follows. A very thin (approximately 1 µ) coating of Plexiglas II was applied by dipping the sample in a 2 pct solution of Plexiglas II in dichloroethylene. Then, because the emulsion will not adhere to Plexiglas 11, a thin coating of Parlodion was applied in a similar manner using 2 pct Parlodion in iso-amyl acetate. No protective coating was necessary with the high-tem-

Jan 1, 1961

By Frank H. Macpherson

Few people realize the tremendously important part that Saline and Pulaski Counties in central Arkansas have played in the winning of the war The present favorable war situation might have been very different if we had not had the bauxite produced during the past two years from these two small areas, a total Of about 15 square miles. As a general statement, it can be said that the Arkansas bauxite deposits are, individually, relatively small, irregular in thickness, somewhat scattered and, therefore, compared with coal or iron-ore or open-pit copper deposits, relatively ill adapted to a rapid and drastic expansion in output. A few years ago it would have seemed an impossibility for these two counties to produce over six million long dry tons of bauxite in one year. However, with the cooperation of the operators, that is what happened in 1943, when the state of Arkansas achieved the seemingly impossible with a production of 6,020,684 1 long tons (dried equivalent) of bauxite ore during the calendar year, compared with an average annual production of 323,7252 tons in the period 1931 to 1941. It became apparent early in the year '94' that the united States soon might be drawn into the war, and, therefore, that an immediate study of the domestic metal situation was necessary. Aluminum is by far the most important metal used in the manufacture of aircraft and many other implements of war and it was evident that there would have to be a tremendous increase in the domestic production of bauxite, which is practically the only present source of this metal. AS more than 95 per cent of the known bauxite reserves of the United states was in Arkansas, careful preliminary studies were made in that state by representatives of the united States Bureau of Mines, the United States Geological survey and the War Production Board in the summer of 1941 Reserves in other states also were studied. The result of these studies was a recommendation by the War Production Board that mining in the bauxite.producing areas of Arkansas be geared for maximum production, in order to supply sufficient ore for this country's war requirements and, if necessary, to supply the war needs of Canada as well. The annual goal of eight million long tons (dry weight) set for Arkansas by the war Production Board was exceeded in 1943, when in August the output reached a rate equivalent to more than 8,300,000 long tons, dry basis. Because of the comparatively small tonnage of bauxite reserves, Congress appropriated funds for an extensive drilling program to be carried out by the Bureau of Mines in cooperation with the Geological Survey. Drilling began in May 1942 but owing to delay in delivery of drills, and trucks upon which the drills were mounted the program did not get into peak operation until early in 1943. By the end of July 1944, the Bureau of Mines records indicated an addition to the Arkansas reserves of 10,000,000 long tons (wet basis) in place,

Jan 1, 1946

By Norman Carmichael, John Kiddie

The problem of transportation in the Clifton-Morenci district of Arizona has been one of peculiar difficulty and consequently has been an important factor in the cost of mining and treating the ores produced. From the crude beginning made over 50 years ago, many changes have been necessary to keep pace with the increased output of copper. A heavy-duty haulage system has developed on the original 20-in. track gage to meet the existent metal-mine conditions. Topography The transportation difficulties of this district may be readily appreciated from the relief map shown in Fig. 1. The northern half of the district is high mountainous country and there is a general but irregular drop toward the southern part, where the country, although still rugged, is in reality a great sloping plain. This is cut by numerous ravines from which the waters, in the rainy season, discharge into the channel of the San Francisco River. A chasm, 1000 ft. deep, has been eroded through the center of the district by Chase Creek, which is flanked by high irregular mountain masses, notably Copper Mountain, American Mountain, Coronado Mountain, and Markeen Mountain. The latter rises 2300 ft. above the bed of the creek, The San Francisco River has also cut a deep channel, though it is somewhat broader than Chase Creek. Eagle Creek traverses the extreme southwest portion of the area, where it has carved picturesquely through vast volcanic flows. Faulting has left its mark upon the topography of the district by adding to the irregularities caused by erosion. Strong faults occur at the Coro-

Jan 1, 1924

By S. H. Ash

More than 100 minerals are mined and processed in the U. S. Management and labor have negotiated wage-scale agreements that have balanced wages and affected cost of labor in such a manner that comparisons can be made of transportation costs. Transportation of materials underground has become of vital importance. This report describes underground haulage methods and equipment, presents cost analyses, and discusses future plans for underground transportation in metal mines. It does not cover hoisting in shafts or slopes by cage, skip, or cars. Advancements have been made by the metal mining industry in lowering transportation costs in several mines, making it possible to mine orebodies or portions of orebodies not considered economically recoverable a few years ago. Numerous reports have been written on transportation at metal mines; this report covers recent haulage at some representative mines throughout the U.S. The term metal mine is used to include all noncoal mines from which up-to-date information was obtainable.

Sep 1, 1956

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By T. D. Tiemann

The chemical and mineralogical composition of Caribbean bauxite ores are described. Extraction of alumina by several processes from both Haiti and Jamaica bauxites is discussed and data presented. IMMENSE deposits of bauxite occur in the Caribbean islands of Hispaniola and Jamaica in the high plateau lands and have been excellently described by 0. C. Schmedeman.' The bauxite occurs as deposits in catchments or etched depressions in Tertiary limestone believed to have been deposited in the Eocene and Oligocene periods.' In appearance both the Haiti and Jamaica bauxites resemble a relatively high iron clay and have indeed been mistaken for such.' They are very soft and friable and disperse readily on vigorous agitation in water. The color range in general is light brown to red. Chemically, the outstanding characteristic of the bauxites is the low silica and high ferric oxide content. The extremely low silica makes them particularly valuable for the production of alumina in the Bayer plant since silica is responsible for the loss of both alumina and soda chemically combined as XNa,OYSiO2,ZAl2O2. The ferric oxide, only traces of ferrous iron are present, offers no interference in the production of high grade alumina. Typical oxide analyses of three types of ore are given in Table I2 and a list of the elements occurring in spectrographic quantities in Table 11." The size of the individual particles in the ore makes successful petrographic examination extremely difficult. The ores contain some relatively coarse grains of heavy minerals such as ilmenite, magnetite, and rutile, but other than occasional crystals of a few microns, the greater portion of the minerals are submicroscopic in size and approach colloidal dimensions. The mineralogic composition of the ores has been investigated by X-ray and differential thermal analysis.' These investigations indicate that the predominant mineral phases present are gibbsite (A1203.3H2O), boehmite (Al2O3.H2O), hematite (Fe2O3), and goethite (Fe2O3-H2O). There is no evidence of the occurrence of diaspore (Al2O3.H2O) in either the Haiti or Jamaica ores, but some type of "amorphous" alumina may be present in some of the bauxites of Jamaica." The temperature stability regions in the alumina-water system have been investigated and are given in recent literature. In the temperature range where the hydrated forms are stable, as determined by hydrothermal bomb methods," ibbsite is the stable phase to 155°C (311°F), boehmite from 155°C (311°F) to 280°C (536oF), and diaspore from 280°C (536°F) to 450°C (842°F). Although quite similar in many characteristics, the Haiti and Jamaica ore show a divergence in mineralogic composition that is reflected in the extractability of the alumina described in later paragraphs. Two principal differences occur in mineralogic composition. The iron-bearing mineral in the Haiti ores is predominantly hematite, while in the Jamaica ores goethite is predominant.4 Directly related to the extraction of alumina are the two minerals, gibbsite and boehmite. Boehmite is relatively high in the Haiti ores and in some of the less soluble Jamaica ores, while gibbsite predominates in the ores in Jamaica amenable to the American Bayer process of extraction. Pedersen and Related Processes In general, all processes for the extraction of alumina involving sintering or fusion of bauxite ores with limestone, soda ash, or a combination of limestone and soda ash followed by leaching, are based on the formation of alumina compounds that. yield alumina soluble in the subsequent leach. The principal idealized reactions in respect to alumina and silica for the three types of processes are as follows: Soda Ash Sinter: A12O3 + Na2CO3 = Na2O-Al2O, + CO2 SiO2 + Na2CO3 = Na2O . SiO2 + CO2 A12O2 + SiO2 + Na2CO3 = Na2O.Al2O8. SiO2 + CO2 Leach (with excess water): H2O + Na2O-A12O3 = 2 NaOH + A12O3 (insolution) H2O + Na2O-SiO2 = 2 NaOH + SiO2 (in solution) Soda Ash— Limestone Sinter: Na2CO2 + A12O3 = Na2O.A1203 + CO2 2CaCO3 + SiO2 = 2CaO . SiO2 + 2CO2 Leach (with excess water): Na2O' A1208 + H2O = 2NaOH + A13O3 (in solution) These latter reactions are the basis of the sinter process currently used for the recovery of soda and

Jan 1, 1952

By Norman B. Pilling, George P. Halliwell

The effects of lead and tin up to maximum contents of about 0.1 per cent. each, in the presence of oxygen between 0.04 and 0.30 per cent., have been studied. Tin is retained efficiently in the oxidized condition, whereas lead is not. An approximate relation between the lead-oxygen and tin-oxygen contents is deduced which, if observed, permits the presence of these elements without detrimental effect. Excess of lead beyond this limit affects ductility and rolling properties adversely and an excess of tin correspondingly diminishes the conductivity. It is shown that copper carrying a combined lead and tin content of several hundredths per cent., yet fully equal in quality to electrolytic wirebar, may be produced under commercial conditions. Tin is not normally found in more than bare traces in current grades of American electrolytic copper, and lead is rarely found to more than a few thousandths per cent. In the electrolytic refining of copper these metals do not present great difficulty in separation and their presence in any considerable amount in copper that has been refined by this method need not be tolerated. On the other hand, the effect of these elements is not entirely academic, as a considerable tonnage of scrap copper liberally contaminated with them has been reclaimed by the fire-refining process into metal with a residual lead and tin content of several hundredths per cent., yet having excellent working properties and fully equal in quality to current grades of electrolytic wirebar. Such copper has been found entirely suitable for use in the manufacture of electrical apparatus. In the absence of oxygen, tin is known to depress the conductivity rapidly, and lead to impair ductility and the rolling properties, yet the effects of these metals on commercial grades of copper—i. e., copper containing from 0.03 to 0.10 per cent. of oxygen—apparently has not received systematic attention. Occasional reference is made to the fact that in the presence of oxygen lead may be tolerated, yet Addicks says,1 in regard to overpoling: "The unstable condition can be controlled by adding certain substances, notably lead, in small quantities, but as mere

Jan 1, 1926

By W. A. Doble

Opinions differ as to whether the water-wheel almost universally known as the Pelton type belongs to the impulse, the tangential, the reactive, the jet or the percussion class, or to a cross between two or more of these classes. The fact is, that for an almost infinitesimal part of a second the axis of the jet of water strikes the bucket of this wheel at a true tangent to its base-line. The percussion of the water, striking the bucket, imparts an impulse to the wheel, causing rotation; and generally the bucket is so shaped that the direction of the jet is

Jan 1, 1900

By B. M. Larsen

A discussion based on three commercial furnace tests and electrical analogue calculations is presented. It shows that while regenerator efficiency is mainly dependent on loading or relative amount of heat exchange surface plus the heat transfer coefficients as effected by flow velocity, the actual air preheat temperature can be high or low, largely independent of regenerator efficiency, mainly due to the diluting or unbalancing effects of cold air leakage into various parts of the furnace system. THERE are many signs of a renewal of interest in the heat regeneration aspect of the open hearth process, among them being the recent paper by Marsh,' the introduction of auxiliary checkers in the stacks of the Isley furnace design, and a number of recent installations of two-pass checkers in new and old furnaces. However, there are also signs of yielding to the usual temptation of oversimplifying a problem. Faced with the job of obtaining better draft on a furnace, for example, a good designer always recognizes that focusing attention on some one factor, such as height of the stack or capacity of the exhaust fan, does not make his problem any easier; rather he must look at the whole system, including such items as valve resistances, bends in the flues, and flow resistance in the waste heat boiler; then he must make his design in relation to the available draft so as to avoid any serious bottleneck in the system. Yet this example is really much simpler than the problem of air preheating, and again, the latter problem is not really made easier by concentrating on air temperature in uptakes and on the more obvious methods for making this air as hot as possible. Also to be considered are such things as the total amount of air needed theoretically for complete combustion at any selected fuel rate, together with that needed for oxygen absorbed into the bath and for burning the combustible gases given out from the bath, plus some excess air. Furthermore, how does this total air requirement relate to the regenerator efficiency at various loadings? How much of the total air equivalent in stack gases will come from preheated air passed through the whole length of the incoming regenerator and how much from air leakage into various zones of the whole furnace system? Does the effect of leakage air differ depending on whether it leaks into the ingoing regenerator, the furnace above floor level, the outgoing regenerator, or the stack zone? Over a number of years we have in this Laboratory experimented with methods for measuring hot gas temperatures; we have measured, approximately, the efficiency of a few regenerators on commercial furnaces and we have developed an electrical analogue' for calculations of regenerator efficiency. The whole problem is too complex to cover in one paper even with a more complete background of data than we possess, but we can attempt here to clarify certain aspects in a general way, hoping to assist specific plant studies on individual furnaces. Some of our earlier experience has been incorporated into chaps. 4, 19, 20, and 21 in the book "Basic Open Hearth Steelmaking,"" and on the assumption that this text is available to most readers, this discussion has been shortened by references to that book. The most recent design of a flowing-gas thermocouple which we are now using for measurement

Jan 1, 1955

By C. M. Loeb, T. E. Norman

The use of ball, rod and tube mills for grinding ore, cement and other materials has grown so rapidly during the past forty years that the world's annual consumption of ferrous grinding media for these mills is now estimated to be between one half million and one million tons per year. Ferrous grinding balls constitute the major portion of this tonnage. Obviously they represent suficient value to justify thorough studies of the factors governing their performance. The selection of grinding balls is governed principally by: I. Quality (wear resistance, impact resistance, soundness, and the like). 2. Sources of supply and delivered cost. 3. Grinding characteristics or efficiency in the ball mill. This paper deals principally with the quality of ferrous grinding balls. In the study of these factors certain data relative to the fundamental nature of ball wear in ball mills have been obtained. These data are also presented and discussed briefly. The Development of a Suitable Wear Test A study of the fundamental factors governing the quality of grinding balls has been hampered seriously by the fact that a competent test has, in the past, involvetd the purchase of several hundred tons of halls of a specific type which were then run in one or more ball mills for a period ranging from several months' to several years' duration. Often, during the period of test, it became necessary to change operating conditions or the character of the ore fed to the test mill with the result that the rate of ball consumption changed and the test figures became of little value. Under such circumstances, progress in the development of better grinding balls, has been necessarily slow. Economic factors and variations in the quality of balls produced by different sources of supply generally make it necessary for each mill operator to determine for himself the most suitable type of balls for his mills. In our own ball mill grinding operations at Climax, Colo., we were faced with this problem. After we had run a few large scale wear tests at considerable expense we decided to investigate the possibilities of a small scale wear test which would be capable of testing numerous types of balls within a relatively short time. The most important requirement of any test is, of course, that it give results which can be used to predict accurately the wear in full scale operations. It was known that Ellis and his associates1'2 had developed a method of testing grinding balls by small scale tests run at the Ontario Research Foundation. Ellis' method of testing was used as a starting point in our investigations. In the course of our tests a number of modifications of the original method were found to be desirable so that, by an evolutionary procedure, a method of small scale

Jan 1, 1949

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

THIS chapter and the one following deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the simplification of the first two ' laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the "heat balance" of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced, and we assume that the cause lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities of flow distribution, air leakage, etc., present in any real, open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained- by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot-metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million B.t.u. per net ton. of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million B.t.u., and the sensible heat in the preheated air at the port ends is 117 million B.t.u. so that the total heat input at the ports is 477 million B.t.u. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million B.t.u., but 120 million of this is supplied by the heat in the hot metal and by various heat--evolving reactions in the bath, so that only 75 million B.t.u. need be supplied to the bath by the flame.

Jan 1, 1944

By G. W. Healy, W. D. Forgeng, N. R. Griffing

The liquidus surface of the C-Cr-Fe system to 1900°C has been mapped from carbon solubility and freezing point measurements, metallographic observations, and published data. In the graphite field, the surface drops precipitously to meet a slope descending from the Cr3C2-C join through the mixed carbide fields to a meandering eutectic valley; this flows from the Cr-C to the Fe-C edge. On the low-cavbon side of the valley, the surface rises to the chromium corner. 1 HE purpose of this inquiry was to gain a more complete knowledge of the C-Cr-Fe liquidus surface. This required an extensive study of carbon and chromium-rich alloys which, in the past, have received the least attention. Sanbongi el al.1 measured the solubility of carbon in liquid alloys containing up to 25 wt pct Cr at temperatures of 1460" and 1545°C and found that it increased with chromium content and temperature. Lucas and wentrup2 also made solubility experiments in graphite crucibles, but at higher chromium contents in the range of 38 to 80 pct and at temperatures of 1550" to 1700°C; however, their experiments were relatively few, and the effect of temperature was not consistent. The present investigation included compsitions ranging from 0 to 94 pct Cr and 1.4 to 11.7 pct C at temperatures up to 1800°C. Saturation experiments in graphite crucibles, thermal analyses during freezing, and metallographic and X-ray diffraction studies were employed to obtain desired information which, together with published data from other investigations about the binary edges and the ternary system at lower carbon levels, made possible the construction of a comprehensive C-Cr-Fe liquidus surface. C-CR-FE LIQUIDUS SURFACE The derived ternary liquidus surface is shown in Fig. 1 where the solid curves are liquidus isotherms. The dashed curves and the binary edges are the liquidus field boundaries of the primary crystals, the arrows along these boundaries indicating their direction with decreasing temperature. Each intersection of three internal boundaries is the composition of liquid involved in four-phase isothermal equilibrium with the three primary crystals whose liquidus fields touch there. It may be observed that a total of six four-phase equilibria occur at melt temperatures. The general topography of the liquidus surface consists of a eutectic valley sloping down from the Cr-C edge at 3.2 pct C to the Fe-C edge at 4.25 pct C. The liquidus surface rises in two directions from the valley, one hillside terminating at the Cr-Fe edge while the opposing hillside rises toward the carbon corner out beyond the top edge of Fig. 1. Both hillsides are interrupted by intersections of surfaces or joints representing the liquid colmpositions of various three-phase equilibria. Seven primary crystals occur, namely a(bcc), ?(fcc), graphite, (Fe, Cr)3C capable of dissolving as much as 15 pct Cr, and three different chromium carbides in which iron is partially soluble by substitution for chromium. The composition ranges of the primary l~hases at melt temperatures are shown

Jan 1, 1962

By A. W. Peake, F. O. Prior

Considering the great advance in the development and application of electricity, it is not strange that eventually a big field for its use has been found in oil-field operations. So far as is known, the first electric drive in oil-field operations was in the Russian field of Baku in 1900. The first application in this country was made by the South Penn Oil Co. near Folsom, West Va. in 1903. In 1916, electric power was first used in the Burma fields of India for drilling and pumping. Between 1916 and 1922, The Empire Gas & Fuel Co. made the first large electrical installation in the Mid-Continent fields. But although the first application was made 27 years ago, it is only within the last 10 years that oil companies have begun to look upon its use with much favor. Within the last few years, there has been a steady increase in the use of electricity in the oil fields. The first application of electricity for oil-field operations in Wyoming was in the Lander field in 1919; the second was in 1924 in Salt Creek; and the third, and last to date, was made by the Continental Oil Co. in the Big Muddy field during 1926. Lander Field The electrification of oil-field operations in Wyoming was initiated by J. W. Steele, superintendent of the Producers & Refiners Oil Corpn., in the Lander field in 1919. At that time, 32 wells were being pumped from five band-wheel powers, with oil engines as the prime movers. Eight barrels of fuel oil were used for power per day and at the price of 90 c. per bbl. the fuel bill was $36 per day. It was decided to try a 15 to 35-hp. oil-field motor on one of these powers. Electric power was generated with steam at the old Wind River refinery station. This test was so successful that in 1920 all five powers were equipped with 15 to 35-hp. oil-field motors, the power being obtained from the Sinks Canyon hydroelectric station. Four of these powers pumped wells at an average depth of 1450 ft., and the fifth pumped wells at an average of 2100 ft. In 1920, the average production per day from the 32 wells was 325 bbl. The power bill on the

Jan 1, 1928

By H. N. Hall

Various factors must be considered in an engineering evaluation of gravity-drainage reservoirs. Among these are: (1) the effect of producing rate on total oil recovery; (2) the effect upon well productivity and ultimate recovery of the pressure level maintained during the producing life of the reservoir; (3) the economic advantage of full or partial pressure maintenance; and (4) estimate of the rate of gas production and injection and the possible purchase of gas under conditions of full pressure maintenance to ascertain compressor facilities needed. All of these factors can be evaluated only when a reliable method is employed for determining reservoir performance in gravity-drainage reservoirs. The purpose of this paper is to present a general method for calculating the performance of a gravity-drainage reservoir. This method is applicable for conditions of complete pressure maintenance, partial pressure maintenance and normal pressure depletion. Provisions are made to take into account variations throughout the reservoir of reservoir configuration, changes in permeability and fluid composition. Based on the method presented in this paper, an IBM 650 computer program has been developed. The past performance of an actual gravity-drainage reservoir producing under conditions of declining pressure and no gas injection was duplicated using this program. INTRODUCTION In tilted reservoirs the production of oil is influenced by drainage of oil from upstructure to downstructure locations. When this downstructure drainage of oil is sufficient to cause effective segregation of the gas and oil in a reservoir, the reservoir is usually classified as a segregation drive or gravity-drainage reservoir. (Discussion will be restricted to gravity-drainage reservoirs which have no encroachment of edge water.) The important feature in gravity-drainage reservoirs is the density difference between reservoir oil and gas. These phases tend to segregate in the reservoir with the result that in the gas cap the oil saturation is maintained at a higher level by drainage of oil from the gas-cap area. Oil can be produced from the oil zone at a low gas-oil ratio and reservoir energy is thereby conserved. The standard material balance in not adequate for predicting gravity-dramage reservoir performance because it does not take into account the difference in saturation above and below the gas-oil contact. Several authors'.' have presented methods for calculating the performance of gravity-drainage reservoirs in which reservoir pressure is maintained constant by gas injection into the gas cap. Using some simplifying assumptions, these methods can be employed with a desk calculator to give acceptable results. The problem of predicting the performance of gravity-drainage reservoirs under the conditions of declining reservoir pressure is many time more complex than that of constant pressure. fierefore, attempis to develop a method suitable for desk calculation have required excessively simplified assumptions. In the past several years, highspeed digital computers have become more widely available for reservoir engineering problems. These corn puters are well suited to problems such as the prediction of the performance of gravity-drainage reservoirs with pressure decline. Many of the simplifying assumptions necessary for hand computation can be eliminated so that a realistic approach to the gravity-drainage process can be made. CONCEPTUAL PICTURE OF OIL MOVEMENT IN GRAVITY-DRAINAGE RESERVOIRS Before attempting to develop an analytical treatment for conditions occuring in a gravity-drainage reservoir, a concept should be formed concerning the movement of fluids in the reservoir as oil is produced. A review of the literature'.' shows that it is customary to classify gravity-drainage operations into two categories—(1) with complete pressure maintenance, and (2) with declining pressure. The same line of reasoning will be followed in presenting the concept of the movement of fluids in the reservoir because it is easier to visualize the movement of fluids under conditions of complete pressure maintenance. After discussing complete pressure maintenance, an analogy will be made between that and the case of declining pressure. It should be kept in mind throughout that the final aim for the problem of solving gravity-drainage performance with digital computers will be to develop a general program for any kind of gravity-drainage reservoir. COMPLETE PRESSURE MAINTENANCE One feature which is generally common in gravity-drainage reservoirs is a gas cap located at the top of the structure. This is shown in Fig. 1(a). Fig. l(b) shows oil saturations that might occur through the reservoir. In the gas cap, oil saturation is lower than

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The kinetics of crack propagation in a hydrogenated high-strength steel at subzero temperatures indicated that cracking progressed in a discontinuous fashion. The delayed failure process thus involves a series of crack initiations rather than the continuous growth of a single crack. The incubation time required for the initiation of delayed failure was controlled by the diffusion of hydrogen. The activation energy for the process was 9120 cal per g-alom. As the test temperature was lowered the incubation time constituted a greater percentage of the total tinze to fracture, and al -50°F the incubation and fracture times were essentially coincident resulting in instantaneous, catastroplzic fracture. A unique feature of hydrogen embrittlement is the delayed failure process in which the material fails under the action of a sustained load even though it is capable of supporting a higher load for a finite period of time.')' Delayed failure of steel and titanium is characterized by an incubation time, preceding the initiation of a crack in a highly localized region, and the subsequent growth of the crack to ultimate failure.3-5 The kinetics of crack growth in hydro-genated high-strength steels have been studied through the use of resistance measurements and have an important bearing on the mechanism of delayed failure. Delayed failure is believed to be merely a facet of hydrogen embrittlement in which sufficient time is allowed during a test for hydrogen diffusion. The current theories employed to explain hydrogen em-brittlement can be grouped into two types. one6-8 explains the embrittlement on the basis of the pressure exerted by molecular hdrogen in lattice voids or defects while the other9-10 attributes the embrittlement to the influence of hydrogen in the lattice. The mechanism used to explain the nature of the crack kinetics in delayed failure is based on the stress-induced diffusion of hydrogen to the area of maximum triaxiality.3 When the hydrogen concentration in this region reaches a critical value, a crack is nucleated. This initial crack propagates instantaneously until stopped by the higher fracture stress of the adjacent material of lower hydrogen content. The continuation of cracking must then await the further diffusion of hydrogen to the new region of triaxiality near the base of the crack where another initiation will occur. From this mechanism it follows that crack propagation is nothing more or less than a series of initiations with limited fracture. The purpose of this investigation was to examine the kinetics of crack growth in an effort to determine whether or not the process was discontinuous. Studies of crack propagation were conducted at low temperatures to retard the diffusion of hydrogen which is presumed to be the rate controlling process in delayed failure. MATERIALS AND PROCEDURE Specimen Preparation—A commercial heat of air-craft quality SAE-AISI 4340 steel, designated as Heat G, was furnished by the Republic Steel Co. in the form of %-in. hot-rolled bars. The material had the following chemical analysis: Composition of 4340 Steel—G Heat C Mn Si Ni Cr Mo 0,395pct 0.82pct 0.29pct 1.76pct 0.85pct 0.25pct Notched tensile specimens with less than a 0.001 in. radius, Fig. 1, were used throughout the investigation. The specimens were heat treated to a 230,000 psi strength level according to the following sequence: a) Normalize bar stock at 1650°F for 1 hr, b) Stress relieve at 1200°F for 4 hr and furnace cool,

Jan 1, 1960

By Stuart S. Forbes

Changes and additions made to the Canadian Copper Refiners Ltd. electrolytic refinery between 1949 and 1955 are reviewed. The effect of high current density on current efficiency and section work is discussed. OPERATING and physical changes which have been made to the electrolytic tank house of Canadian Copper Refiners Ltd. suggest a review of present conditions. Previous papers1 a have described the general arrangement. Since then, expansion, closer anode spacing, and higher current densities have increased annual cathode capacity from 112,000 to 182,000 tons. A recent extension to the tank house, begun in the spring of 1954 and completed in August 1955, was undertaken to handle the monthly production of about 3,000 tons of anodes from Gasp6 Copper Mines. The anticipation of these additional receipts and large stocks of unrefined copper caused by the increase in custom smelting at Noranda made it necessary to increase production without immediately available additional cell capacity. Accordingly, from December 1954 through March 1955, the tank house was operated successfully at a current density of 24.0 amp per sq ft. Again, as of September 1955, one of the two tank house circuits is being operated at this high density. Although other refineries may operate at current densities higher than 24 amp per sq ft, none is doing so with anodes which contain silver and gold content as high as those being refined at Canadian Copper Refiners Ltd. General Arrangement The original building consisted of two parallel bays, each 660 ft long and 60 ft wide, with a 24 ft pump bay extending along the west side of the building. A previous expansion, completed in 1939, was to the west of the original building and consisted of two 60 ft parallel bays 240 ft long. The length of these two bays was extended in 1954 to 540 ft, adding one stripper and 12 commercial sections to No. 2 electrical circuit. Space is still available for an additional six commercial sections and one stripper section. Construction on these seven sections started in September 1955, and will be completed early in 1956. The tank house capacity will then be 206,000 tons of cathodes per year. In the two tank houses there is a total of 900 cells distributed as follows—commercial, 468; stripper, 36; total, 504 in the No. 1 tank house (No. 1 circuit): commercial, 360; stripper, 36; total, 396 in the No. 2 tank house (No. 2 circuit). Section arrangement consists of nine cells to a tier and two tiers or 18 cells to a section. Anodes, weighing 620 lb each, are cast with a Baltimore groove and are refined by the multiple system. Solution enters each cell through a bottom inlet at one end and overflows at the top of the opposite end. Rate of solution flow through the cells is controlled by valves at each section to 4.5 gpm. Electrical power to the tank house is now provided by nine 675 kw motor generator sets. Each set consists of a 135-12 v 5000 amp dc generator, driven by a 980 hp 2300 v synchronous motor. When No. 1 circuit is operated at 22,000 amp, five sets, at 4400 amp each, are connected in parallel. As the maximum allowable current on No. 2 electrical circuit has recently been set at 18,000 amp, only four sets are connected in parallel on No. 2 circuit. A tenth set, now being installed, will be reserved as a spare, for use in either circuit as required. Recent Changes In 1949, the annual capacity of the tank house was increased from 112,000 to 132,000 tons by closing the

Jan 1, 1957

By F. Lynwood Garrison

It is not intended to make in the present paper any deduction or to formulate any theories from the results obtained by experiments. The further expenditure of considerable time and labor would be required to obtain a sufficient basis for positive assertions as to the microscopic structure of the different varieties of iron and steel, and the structural changes which take place in them. It is therefore my purpose at this time to offer simply a synopsis of the general results arrived at in a few months' work, a brief description of apparatus used, and a few hints as to the preparation and preservation of the material which it is intended to investigate. The study of the microscopic structure of iron and steel is not altogether new. Some attention has been given it in both England and Germany. But the foreign publications on the subject have thus far been confined, so far as I am aware, to two papers, one by Herr Martens, of Berlin, contributed to the Verein zur Befoerderuny des Gewerbfleisses and the other a lecture by Dr. H. C. Sorby of Sheffield. Dr. Sorby, it seems, was induced to investigate the subject as bearing on the structure of meteoric iron ; and the results he obtained are certainly very interesting. At the Boston meeting of this Institute, in February, 1883, Mr. J. C, Bayles called attention to the subject in a neat and exceedingly interesting paper, in which the work of Messrs. Martens and Sorby was summarized,* and original suggestions were added. It is at present difficult to say what will he eventually the practical value of the microscope, thus employed, in the sciences of engineering. The role which it seems most likely to play is that of' an adjunct to the testing-machine, and not (as some have supposed) a rival to the chemical laboratory. That it will be a most valuable accessory seems, to say the least, highly probable. I need hardly go at length into the details of preparing the material for examination. Mr. Bayles has described the process in such a plain and comprehensive manner that if his instructions are

Jan 1, 1886

By H. Tabachnick, N. Hedley

The extraction of gold and silver from ores with alkaline cyanide solutions is well known. Cyanide solutions are also good solvents for many base metal minerals, particularly most of the copper minerals. Leaver and Woolf,1 who determined the solubilities of copper minerals in 0.10 pct sodium cyanide solution, showed that malachite, cuprite, chalcocite, and bornite are readily soluble in cyanide; least soluble are chalcopyrite and chrysocolla. The Mining Chemicals Laboratory of American Cyanamid Co. has studied the possibilities of using cyanide solutions for leaching base metals. In this article the authors present the results of their experiments with cyanide leaching to reduce the copper content of a zinc concentrate from 0.050 pct to the desired specification of less than 0.02 pct. Zinc Ore Sample: The sample of commercial zinc ore used in this investigation to produce zinc concentrates was ball mill feed ranging from 1/2 in. to fines. The ore was crushed to —10 mesh and riffled into 600-g charges for zinc flotation. Analysis revealed 4.54 pct Zn and 0.005 pct Cu. Examined microscopically, the ore consisted essentially of cream-colored sphalerite and carbonate gangue. It contained a small amount of pyrite, partly tarnished. The only copper mineral identified was chalcopyrite, mostly smaller than 20µ, some of which occurred as attachments on sphalerite. Flotation Procedure: Batches of zinc concentrates were made as required according to the following general procedure. A 600-g charge of —10 mesh ore was ground for 4 min at 60 pct solids in a laboratory steel rod mill. Screen sizing showed it to be all —35 mesh with 42 pct —200 mesh. The pulp was transferred to a Fagergren laboratory flotation machine, diluted to 25 pct solids and conditioned for 5 min with 0.6 lb per ton CuSO4, . -5H2O. It was then conditioned with 0.10 lb per ton Sodium Aerofloat promoter and floated for 5 min with pine oil as frother and creosote as froth stiff-ener. The pH during flotation was 8.5. A typical analysis of zinc concentrate subjected to leaching is 44.41 pct Zn and 0.051 pct Cu. The ratio of concentration was close to 10 to 1. Leaching Procedure: Aero Brand cyanide, technical calcium cyanide analyzing 49.5 pet NaCN equivalent, was used for all cyanide leaching tests. For each test three rougher concentrates floated as described were combined (total weight close to 180 g) and the water content adjusted to 150 ml. The percent solids in the pulp was thus 55. After a weighed amount of cyanide flakes had been added, the pulp was agitated on rolls for a given period, then filtered and washed. Filtrate and washed concentrate were assayed for copper content. The procedure for ammonia leaching was similar to the cyanide process. A series of tests was run in which the effects of ammonia as a solvent for copper in the zinc rougher concentrate were investigated. In each test 180 g of zinc rougher concentrate was leached with 150 ml of ammonia solution. Various strengths of ammonia and times of leaching were investigated. The results are shown in Table I. It is apparent that ammonia was a poor solvent for copper in the zinc concentrate; 60 min of agitation with a relatively strong NH:, solution extracted only 2 pct of the copper. CYANIDE LEACHING TESTS Effect of Solution Strength: The solvent effects of 0.125, 0.187, and 0.250 pct NaCN equivalent solutions were compared for leaching periods of 15 min. Residue and filtrate were assayed for copper content. The copper content of the filtrate plus wash was calculated back to the original volume of cyanide solution (150 ml). The effects of cyanide strength are given in Table II, It will be noted that 15 min leaching with 0.25 pct NaCN equivalent solution extracted 74.6 pct of the copper in the zinc concentrate. The leached product assayed 0.013 pct Cu, appreciably below the required specification of 0.020 pct. Effect of Leaching Time: Portions of zinc concentrate were leached with 0.25 pct NaCN equivalent

Jan 1, 1961