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By Reginald S. Dean

Manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. Lixiviants of ammonia and ammonium carbamate permit ready extraction of manganese from reduced ores and the manganese in such solutions may be precipitated by heating to transform the carbamate to carbonate. THE widespread occurrence of manganese in low grade oxide and carbonate ores not amenable to mechanical concentration has led to extensive investigations of hydrometallurgical methods for producing a pure manganese compound suitable for further treatment. Manganese carbonate is the preferable compound. This product when fully crystalline and of not too fine crystal size is easily filtrable and stable in air. It can be converted to other compounds such as the oxides by heating in air or can be reacted with acids for producing salts. A useful hydrometallurgical process must produce relatively concentrated solutions that can be purified easily, reagents must be cyclically used, and heat requirements must be small. Neither the ammonium sulphate nor sulphur dioxide leaching processes that have been tested extensively fulfill these requirements. Other heretofore proposed processes have obvious limitations and have not been tried on a large scale. The present process is based on the discovery by the writer of a new group of aqueous manganese-ammonia complex solutions highly concentrated in ammonia, which permit rapid solution of manganous oxide to concentrations of 80 to 100 g Mn per liter and from which a fully crystalline, easily filtrable manganese carbonate is precipitated by the addition of carbon dioxide and partial ammonia removal. Although the process may be carried out with many ammonium salts, commercial advantages dictate the use of ammonium carbamate, which is obtained when CO2 is passed into concentrated aqueous solutions of ammonia. If the carbamate is used, the only reagents, ammonia and CO2, are volatile and may therefore be recovered from solutions and residues by heating, thus eliminating washing and extensive evaporation. Impurities are controlled easily as most metal oxides are either insoluble in the lixiviant or fail to precipitate with the manganese carbonate. Others are controlled by sulphide addition. The process has been tested extensively on a small scale on a wide variety of ores, including Three Kids, Artillery Peak, Cuyuna, and Chamberlain, as repre-

Jan 1, 1953

By Carl O. Thieme

INDUSTRIAL specialization has rapidly created a demand for new and better alloys. A more thorough understanding of the requirements of specific industries and the discovery of processes by which it has been made possible to utilize certain metallic elements in larger quantities, together with greater purity in most virgin metals, has resulted in a great increase in the number and variety of alloys. This increase in the number of elements entering into non-ferrous alloy manufacture has increased the contamination in secondary metals, as received by the smelter. In order to successfully refine scrap of a much more complex nature it has been necessary for the smelter to install new equipment and to constantly search for new methods of refining as well as to improve the methods already in use. In some instances it is largely responsible for specialization in the secondary metal industry. It is usually necessary to remove the contaminating impurities in scrap or eliminate to a degree not objectionable, no matter how introduced. In order to know what metals or elements are of an objectionable nature, the smelter must make a study of the effect of single elements and combinations of elements on many of the physical and mechanical properties, such as strength, ductility, color, hardness, casting soundness, etc. The smelter of secondary metals must be able to utilize scrap materials of all kinds, for, sooner or later, most fabricated metal parts and the waste products formed during the process of manufacture find their way to the smelter. In addition, the smelter, in contracting for salvaged material from the producer, gets some undesirable and unusual materials. The value of secondary metals and the importance of their recovery has increased in recent years and it is no longer sufficient to recover the base metal only, such as copper from copper-bearing material, but it is essential that other elements present be recovered and converted into useful form. This paper will deal not with the smelting and refining or separation of impurities from secondary metals but an attempt will be made to show the increased value of metal scrap when properly segregated and in a less contaminated condition. There are five principal reasons for contamination in secondary metals: New and unusual alloys, productive methods,

Jan 1, 1928

By Reginald S. Dean

Manganous oxide is readily soluble in concentrated ammonia solutions containing ammonium salts. Lixiviants of ammonia and ammonium carbamate permit ready extraction of manganese from reduced ores and the manganese in such solutions may be precipitated by heating to transform the carbamate to carbonate. THE widespread occurrence of manganese in low grade oxide and carbonate ores not amenable to mechanical concentration has led to extensive investigations of hydrometallurgical methods for producing a pure manganese compound suitable for further treatment. Manganese carbonate is the preferable compound. This product when fully crystalline and of not too fine crystal size is easily filtrable and stable in air. It can be converted to other compounds such as the oxides by heating in air or can be reacted with acids for producing salts. A useful hydrometallurgical process must produce relatively concentrated solutions that can be purified easily, reagents must be cyclically used, and heat requirements must be small. Neither the ammonium sulphate nor sulphur dioxide leaching processes that have been tested extensively fulfill these requirements. Other heretofore proposed processes have obvious limitations and have not been tried on a large scale. The present process is based on the discovery by the writer of a new group of aqueous manganese-ammonia complex solutions highly concentrated in ammonia, which permit rapid solution of manganous oxide to concentrations of 80 to 100 g Mn per liter and from which a fully crystalline, easily filtrable manganese carbonate is precipitated by the addition of carbon dioxide and partial ammonia removal. Although the process may be carried out with many ammonium salts, commercial advantages dictate the use of ammonium carbamate, which is obtained when CO2 is passed into concentrated aqueous solutions of ammonia. If the carbamate is used, the only reagents, ammonia and CO2, are volatile and may therefore be recovered from solutions and residues by heating, thus eliminating washing and extensive evaporation. Impurities are controlled easily as most metal oxides are either insoluble in the lixiviant or fail to precipitate with the manganese carbonate. Others are controlled by sulphide addition. The process has been tested extensively on a small scale on a wide variety of ores, including Three Kids, Artillery Peak, Cuyuna, and Chamberlain, as repre-

Jan 1, 1953

By G. L. Chierici

Starting from Muskat's theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

By W. L. Phillips

The plastic properties of lithium fluoride and magnesium oxide under compression were investigated in the temperature range 25° to 1000°C. At the higher test temperatures, the critical resolved shear stress and the rate of work-hardening of both materials decreased. At the same time, the number of stress lines decreased and the individual stress lines became wider. The density of dislocations decreased for a given strain the higher the test temperature for lithium fluoride. The decrease in the critical resolved shear stress as a function of temperature could be fitted by the equation 7 = Toe-KT. THE influence of temperature on the stress-strain curves of a variety of metal single crystals has been studied for a wide range of temperature.1"5 In general, it has been found that both the critical resolved shear stress and the rate of work-hardening decrease rapidly with increasing temperature and fall to a value of essentially zero well before the melting point is reached. AS the test temperature is increased, the density of slip lines has been found to decrease, while the width of the individual lines increases. Recently, Gallagher,' Graf et al.,7 and Pate1 and Alexander8 have found that single crystals of germanium and silicon, which have a covalent bond, can be plastically deformed at elevated temperatures. In compressing germanium it has been found that the strain-hardening coefficient decreased very rapidly as the temperature was increased. The coefficient did not tend to zero, however, as the melting point was approached. The plastic properties of ionic crystals at elevated temperatures have not been extensively investigated. In the only work previously reported Tamman and salge9 and Theile10 have shown that the yield point of sodium chloride single crystals tested in tension and compression decreased slowly with increasing temperature, falling to zero at the melting point. As the temperature was increased, they found a substantial increase in the amount of plastic deformation that could be sustained before fracture; and at temperatures above 400°C in tension tests there was an obvious necking which produced local extensions of up to 3000 pct. The purpose of the present work is to extend the knowledge of high-temperature deformation to the ionic crystals, lithium fluoride and magnesium oxide. The following were investigated: 1) The gross shape of the stress-strain curve at several temperatures. 2) The change in the critical resolved shear stress as a function of temperature. 3) The appearance of slip bands and the density of dislocations as a function of strain and temperature. EXPERIMENTAL TECHNIQUES The lithium fluoride and magnesium oxide used in this investigation were purchased from the Harshaw

Jan 1, 1961

By J. Clayton Nichols

The principal mines of this region are 7 miles SE. from Gusa, and about 4 miles in a direct line from the seacoast. Gusa is a small town on the north coast of Mindanao, 4 miles east from Cagayan, the capital of the province of Misamis. The mines are reached by steep, narrow trails over ridges varying in altitude from 1100 to 1600 feet above sealevel. The whole region is covered with a thick growth of tall grass, except a few spots on the sides of some of the hills, where there are patches of timber and jungle.

Jan 1, 1902

By W. M. Rutherford

A knowledge of the limits of miscibility between reservoir oil and possible injection fluids is required for selection of the optimum miscible-injection fluid. Limits of miscibility can be estimated from the results of equilibrium phase-behavior experiments. They can also be determined by means of displacement experiments conducted in a high-pressure sandpack. This paper describes the equipment and procedure which have been developed for determining miscibility conditions by stable displacement. A systematic series of displacements of a West Texas reservoir oil was carried out. The results indicate that, at constant pressure, miscibility is a function only of the pseudocritical temperature of the injection gas. This fact, together with improved experimental methods, makes the displacement technique a rapid, reliable means for determining miscibility conditions. In conjunction with the displacement experiments, phase diagrams were constructed for the oil with dry gas and propane and with dry gas and ethane. Phase behavior of the methane-ethane-propane system was determined at 110°F. The experimental work demonstrates the feasibility of using ethane-rich gases to reduce cost and pressure requirements for miscible displacement. INTRODUCTION In recent years, interest in the miscible displacement of oil by light hydrocarbon mixtures has been high. Many pilot and a few field scale projects have been started.1 These projects have made use of various methods for achieving miscibility: (1) the LPG-slug process, (2) the enriched-gas-drive process and (3) the high-pressure gas-drive process. Some field projects have been successful; the results of others are debatable. In general, projects which have performed best have involved the injection of an appreciable fraction of a pore volume of miscible material. Economical application of miscible displacement depends strongly on the cost of the miscible-injection fluid. If an appreciable fraction of a pore volume of material is required for successful application of these methods, a precise knowledge of the minimum requirements for miscibility in terms of composition of injection fluid is essential. Therefore, reliable experimental methods for determining miscibility conditions are important, and a procedure for estimating these conditions from the composition of the reservoir fluid is highly desirable. The subject of this paper is the problem of determining conditions which result in miscible displacement of oil by light hydrocarbon mixtures. Miscibility conditions can be estimated by means of equilibrium experiments conducted in a PVT cell, or they can be determined by means of high-pressure displacement experiments. This paper describes the equipment and procedure which have been developed for the determination of miscibility by high-pressure displacement experiments. These methods have been applied to the displacement of a West Texas reservoir oil with mixtures of dry gas, ethane and propane. In conjunction with the displacement experiments, triangular phase diagrams have been constructed for mixtures of the oil with dry gas and propane and with dry gas and ethane. The effect of injection-gas composition on conditions for miscible displacement in high-pressure sandpacks and cores has been the subject of several published papers.2-5 The experimental methods used in these investigations were such that displacements were unstable, and the effects of fingering and/or gravity layover are clearly evident in the results. Miscibility conditions were probably correct in spite of the instability phenomena, but the experiments evidently were time-consuming, and limited data were reported. Systematic high-pressure flow studies which would support a correlation of miscibility conditions have not been reported; however, Wilson5 has proposed the use of pseudocritical temperature of the injection gas as a parameter and Benham, et al,6 have based a miscibility correlation on observed and calculated equilibrium data.

MANY are the salts produced. by Nature in various regions and parts of the world, as Pliny shows in his History. Likewise, many are the differences among things that are salty and from which salt can be extracted, as, for instance, all the lyes from any kind of ashes and the urine of all animals. But because these are not things that give men the useful elements necessary to life, I shall omit speaking of them in detail with the exception of some of the more notable ones, and I shall tell you that I find that men proceed in only two ways in order to have a sufficiency for their needs. One is that of extracting it from the salty waters of the sea itself, or from springs, with a certain technique [34v] adapted to the places, either by congealing or by evaporation; and the other is that of mining it from the earth. The latter salt is clear and beautiful, and it is mined from mountains, already made by Nature in the form of stone without the aid of art. All these salts have more or less efficacy* according to the fineness or coarseness of their earthy elemental mixture, and according to the provinces and places where they are found generated. All are of an earthy

Jan 1, 1942

By W. D. Potter, E. T. Peters

Single-crystal films of boron have been prepared by thermal reduction of purified BCl3 with subsequent deposition of boron onto oriented silicon substrates. The structural properties of films prepared under various experimental conditions have been determined by light microscopy and "grazing-" angle electron-diffraction analysis. An orientation relationship is proposed for silicon and a-rhombo-heclral boron which can be described as: (111)Si (112)B; [110]Si [110]B ElEMENTAL boron is known to have a high energy gap* and consequently has potential value as a high- *Energy gaps of 1.35 to 1.55 ev1-3 and 2.0 ev4 are reported for ß-rhombohedra1 and a-rhombohedra1 boron, respectively. temperature semiconductor.5 Exploitation of this property, however, has been hampered by the unavailability of pure, single-crystal boron. Two recent symposia6,7 have treated the subjects of purification, crystallization, crystal structure, and properties of boron and provide a foundation for further investigation in these areas. The structure, lattice constants, and observed ranges of stability for four reported polymorphs of boron8°12 are listed in Table I. The rhombohedral structures are generally accepted as true polymorphs whereas the tetragonal structures are believed to be transient. Most currently available single crystals of boron are grown by Czochralski and floating-zone methods. Unfortunately, these crystals generally contain numerous defects and are highly strained as a result of the polymorphic transformations and thermal contractions which accompany cooling. Recently, Armington, Potter, and Tanner13 have reported the formation of single-crystal films of boron on silicon single-crystal substrates through thermal reduction of BC13 by hydrogen. Boron E. T. PETERS, Junior Member AIME, is Senior Scientist, ManLabs, Inc., Cambridge, Mass., and W. D. POTTER is Research Chemist, Air Force Cambridge Research Loboratories, L. G. Hanscom Field, Bedford, Mass. formed at temperatures near 1000°C was identified as the a-rhombohedra1 form, consistent with expectation. The present paper describes a continuation of this work with specific reference to characterization of the structural features of the deposited boron films. The ultimate goal of this program is to produce large-area single-crystal films of a-rhombohedra1 boron to be used for electrical and optical studies by other workers. PREPARATION OF BORON FILMS The experimental procedure of preparing thin films is similar to that described by Theuerer14 for the epitaxial growth of silicon by thermal reduction of SiC14 and has already been described as applied to the preparation of boron thin films.13 Briefly, a mixture of BCl3 vapor and dry hydrogen is passed over a heated silicon substrate. Thermal reduction of the BC13 allows deposition of boron on the substrate. The substrates were {111}-oriented, single-crystal silicon. Square specimens 0.63 cm on an edge by 0.1 to 3.0 mm thickness were prepared by

Jan 1, 1965

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By C. A. Mezger

These districts are limited approximately on the north by the railroad from Salisbury to Ashville, and comprises the counties of Alexander, Catawba, Burke, Rutherford, McDowell, Cleveland, Lincoln, Polk and Henderson in North Carolina, and Greenville, Spartanburg, Union and York in South Carolina. The occurrence of monazite at Amelia Court House, in Virginia, belongs evidently to the same geological system, as its distance from the Alleghenies corresponds with that of the above-mentioned districts, and all the stratification runs parallel with those mountains.

Jan 1, 1896

By E. D. Glass, R. C. Hessing

The volume of gas in storage reservoirs may be compuled from estimates of hydrocarbon pore volume and gas density. However, both are dificult 10 estimate accurrately. Further, no adequate method has been presented for estimating reservoir performance during operation for Volumetric gas-storage reservoirs. Normally, gas-storage reservoirs exhibit small pressure gradients in the area conr(zilliitg the storage wells, even under conditions of maximum injection or withdrawal. A zone of low permeability usally surrounds, and is in communication with, tile permeable zone which causes the storage reservoir to exhibit a definite pressure lag, as evidenced by lack of pressure stabilization after extended periods of shut-in. An analysis is presented for determining pore volume and gas in place, and for predicting future reservoir behavior of such reservoirs. The mathematical development is presented and a solution is shown for an operating storage reservoir. INTRODUCTION Depleted gas reservoirs arc often used for gas storage. The reservoir usually contains a permeable area in which numerous storage wells arc located. The permeable zone permits high deliverability and injectivity with relatively small pressure loss. However, pressure equilibrium may not be attained even after long periods of shut-in because of the fact that the permeable zone is in communication with an adjacent tight section. Most of these gas-storage reservoirs are sand lenses, such as ancient beaches or offshore bars. The areal geometry of these reservoirs is normally such that flow in the tight zone will be approximately linear, and the solutions presented here should apply. DISCUSSION For purposes of this paper, a gas-storage reservoir is considered to consist of a volume of permeable rock in communication with tight rock, all of which is surrounded by an impermeable barrier. Pressure gradients across the permeable zone are small due to low flow resistance and well density. Hence, the permeable zone is considered to be at a uniform pressure which is only a function of time as gas is injected or withdrawn. The tight zone is considered to be linear with uniform permeability and porosity, and the pressure in the tight zone is a function of both position and time. l'wo solutions for flow in this system are used to define the reservoir and determine its properties. The first solution is for an infinite linear tight zone in communication with the permeable zone. The expression for constant gas-withdrawal rate is Eqs. I and 2 ore superposed to account for varying rates of production or injection and are used to fit gas-storage field reservoir history. The solution for the infinite case, Eq. 1, is first applied to field data for early times following a shut-in period. Constants BDa and c are ohtained by a least-squares fit of pressure and rate data. After the pressure wave from gas injection or withdrawal reaches the external boundary of the tight zone, the infinite solution will no longer apply and pressure behavior should be more nearly represented by Eq. 2 for a gas reservoir in communication with a finite linear tight zone. The values of the constants found from curve-fitting Eq. 1 to the early time data may then be used in Eq. 2 that only the coefficient- L containing the unknown

By A. S. McLatchie, R. A. Hemstock, J. W. Young

Much attention has been given in the past few years to methods of increasing the recovery of oil from proven reserves. Numerous laboratories have made investigations to evaluate the possibilities of increased oil recovery by high-pressure injection of dry gas, injection of a propane slug followed by dry gas, solvent flooding. and by the injection at relatively low pressures of gases enriched with ethane and propane. Several years ago, Whorton and Kie-schnick' published the results of laboratory studies on high-pressure gas injection which showed that, in the case of light oils, recoveries could be considerably increased by sweeping the reservoir with dry gas at pressures in excess of 3,000 psig. The increase was attributed by those authors to the vaporization of oil at the invading gas front and viscosity and solubility effects produced at the front by the invading gas. Later, Stone and Crump' presented the results of a series of displacement experiments in which a light under-saturated crude oil was displaced from sand-packed columns with unusually high recoveries when the displacing gas was a rich condensate or a dry gas enriched with ethane or propane. They also conducted similar experiments at higher pressure on heavy undersa tu rated crude oil, although in this case the increase in recovery was not as great as in the case of the light oils. In both cases, viscosity reduction and swelling of the by-passed oil behind the invading gas front were believed to be responsible for the more favorable recovery of the original oil in place. Within the past year, other investigators", ' have presented the results of laboratory studies of miscible slug and solvent flooding recovery processes. This paper describes the laboratory methods developed for evaluating benefits to be obtained by enriched gas drive in specific reservoirs, and presents the results of several displacements of crude oils which possess a wide range of physical properties. The displacements were conducted at reservoir conditions of temperature and pressure. The apparatus used in the following experiments consisted of a sand-packed tube which served as the model reservoir, a cylinder of injection fluid, and a mercury pump. The stainless steel tube, 8 ft long and 0.53 in. I- was packed with a graded quartz sand. The high-pressure pump discharged mercury into the bottom of the injection fluid cylinder at a constant rate as low as 1 cc/hr. The average porosity and permeability of the sand column were 34.6 per cent and 3.25 darcies, respectively. In each case the tube was charged by the displacement of salt water by the reservoir oil under consideration. Recently a project was initiated to evaluate oil recovery by enriched gas drive from three oil reservoirs. Samples from a fourth reservoir (in this case high-viscosity oil) were studied with a view to obtaining recovery information of general applicability to low-grade, high-viscosity crudes. The oils from these four reservoirs exhibited a wide range of physical properties, and the reservoir conditions of pressure and temperature simulated in the laboratory represented several typical field conditions under which enriched gas drive might be employed. One of the reservoirs selected for laboratory displacement experiments produced an intermediate-gravity crude (29.6" API) by solution gas drive and a weak water drive. A low recovery in the range of 10 to 20 per cent was anticipated. Four displacement experiments were made to determine the effect of injection gas composition and initial gas saturation upon recovery of oil from the laboratory model. Two types of reservoir oil were used in these experiments. In the first run, a desaturated crude with a bubble point of 395 psi was charged to the tube. In the three subsequent runs, a simulated original reservoir oil was charged at 2,000 psi and produced by solution gas drive to 300 psi before beginning gas injec-

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By S. Kado, G. Derge, L. Yang

Self-diffusion coefficients of silver in molten silver have been measured by means of the capillary-reservoir method in the temperature range 1002" to 1105°C. The results can be .represented by the equation D = (7.10 i 0.06) X 10-4 exp [(—8150 ± 1130)/RT]. The heat of activation agrees within the limit of experimental uncertainty with that for the viscous flow. The validity of the Eyring and the Stokes-Einstein equations are examined on the basis of the self-diffusion coefficients obtained and the known viscosity data of molten silver. MEASUREMENT of the self-diffusion coefficient of silver in molten silver was made in the temperature range 1275° to 1378°K, using the capillary-reservoir method and &"' as the radioactive tracer. The experimental arrangement is shown in Fig. 1. Silver of 99.99 pct purity (fine silver), was melted and degassed in vacuum in a graphite crucible situated inside a McDanel vacuum jacket. The crucible (4 in. tall and 1 in. ID) was protected both at the top and at the bottom with graphite shields and contained about 220 g of silver. The sample holder was a piece of graphite rod (1 in. long and 1/2 in. diam) with 4 capillaries drilled longitudinally into it. The holder was screwed onto a long graphite rod (12 in. long and 74 in. diam) which was connected to a steel disk hanging on a nylon string through a glass pulley. The steel disk kept the sample holder at the center of the McDanel tube and was heavy enough to overcome the buoyancy when the holder was lowered into the molten silver. By turning a handle connected to the pulley through a tapered glass joint, it was possible to raise or lower the sample holder without breaking the vacuum. Two such arrangements were constructed, sitting side by side in 2 Kanthal furnaces. One with non-radioactive silver in its crucible was used for the diffusion run and the other with radioactive silver in its crucible was used for filling the capillaries. To fill the capillaries with radioactive silver, the sample holder was degassed first and then lowered into the radioactive molten silver in vacuum. Purified argon gas was then admitted into the system to push the liquid silver into the capillaries. After cooling in argon, the filled capillaries were polished on emery paper to expose the top of the rod and used immediately as samples for the diffusion run which was carried out at the same temperature as that used for filling the capillaries. During the diffusion run, the samples were degassed in vacuum and lowered slowly into the nonradioactive molten silver before purified argon was admitted into the system. After a predetermined period of time, the samples were raised out of the melt and cooled in argon. The temperature of the melt was measured before and after the run with a chromel-alumel thermocouple inside a McDanel protection tube. Another chromel-alumel thermocouple attached to the outside wall of the McDanel vacuum jacket was used to indicate any fluctuation in the temperature of the furnace during the run, which was found to be less than ± 2°C for the longest run made (93 min). The temperature gradient inside the molten silver was found to be negligible. No significant difference was observed in the results obtained whether the melt was stagnant during the run or was stirred by raising and lowering the sample holder slowly a few times a minute for a distance of about 1/4 in. inside the melt.

Jan 1, 1959

By T. J. Koppenaal

The surface slip line structure has been investigated by optical microscopy during the easy glide deformation of Cu-A1 single crystals as a function of composition, testing temperature and prior thermal treatment. The slip line structure in alloys of 2.5 or less at. pct Al is similar to pure copper, while alloys of 5 or more at. pct Al show slip tracings typical of a brass. Cross slip is observed in the "a-brass type" crystals and the amount of this type of slip increases rapidly with aluminum content. The cross slip tendency in 14 at. pct Al crystals is signicantly higher when tested at 150°C as compared to 4.2" and 77°K. In addition, cross slip is more pronounced in this alloy in the furnace cooled condition than when quenched from 450°C. The cross slip behavior is analyzed in terms of existing models for this type of deformation. In two previous investigations, reports of yield points1 and solid solution strengthening2 in Cu-A1 single crystals have been given. This paper enlarges upon the brief description of the slip line structure discussed in these reports. Since the easy glide slip line pattern of copper changes markedly with the addition of -30 pct Zn (-brass),3 a study of slip lines as a function of solute additions in Cu solid solutions should help to explain some of these differences. In addition to composition variables, slip lines have also been studied as a function of testing temperature and prior thermal treatment. PROCEDURE The slip line observations were made on single crystals of 0.5 to 14 at. pct Al using a light microscope. Details concerning the preparation and basic testing procedure are given elsewhere.' Prior to testing, each crystal was homogenized at 900°C for 24 hrs, furnace cooled, and electrolytically polished in a 60 pct phosphoric acid solution. The strain rate was-5 X 10 sec-I in each case. Unless otherwise stated, all observations reported upon here were made during the early stages of easy glide. RESULTS AND DISCUSSION The maximum magnification generally used was 1000X, and slip lines could be resolved down to about 105 cm (1000A). This resolution is appreciably less than obtainable with electron microscopy replica techniques where the replication can resolve slip lines down to about 40 A. Thus, while many qualitative features could be studied, the type of quantitative data obtainable with an electron microscopy replica study could not be made. Crystals containing 0.5 and 2.5 at. pct Al deform much like pure copper exhibiting a high density of fine slip lines that cover the entire gage length of the specimens. Fig. 1 shows the surface slip line pattern in a 2.5 at. pct A1 extended 0.01 shear strain at room temperature. Crystals having 5 to 14 at. pct A1 showed appreciably coarser slip lines that were generally concentrated at one end of the gage length. During easy glide these coarse slip lines propagate along the gage length in a manner similar to that observed in a-brass single crystals by Piercy, Cahn, and cottrel14 and refered to by them as a Lüders band propagation. Fig. 2 shows a typical area of these coarse slips in a 14 at. pct A1 crystal after a room temperature shear strain of 0.01. Two slip systems were apparently active. Using a method described by Cullity, the angles, between the specimen axis and the normals of the primary and secondary slip planes were determined to be 50 and 84 deg, respectively. 'From the Laue photograph, was 52, 81, 66, and 30 deg for the primary, cross, conjugate, and fourth slip planes, respectively. The secondary active plane in Fig. 2 is thus established as the cross slip plane, and the operative slip system is evidently the cross slip system, e.g., slip

Jan 1, 1963

By K. H. Nimerick, B. E. Scott, F. J. Beafore

A unique freeze conditioning agent (FCA) which functions by forming structurally weak ice rather than suppressing the freezing point of water has been successful in alleviating frozen coal problems. Frozen coal treated with FCA has been quickly unloaded at temperatures below -17.8OC (O°F). Other applications of FCA include deicing: conveyor belts, idler, idler arms, and other moving parts that have been impeded by ice.

Jan 1, 1980

By J. H. Frye, R. M. Treco

One of the chief hindrances to an understanding of the hardness of solid solutions is the sparsity of suitable hardness data. There is great need of a large body of hardness data obtained from many different alloys of high purity by identical testing methods and corrected to correspond to a single grain size. A considerable amount of such data has been obtained by means of the Meyer analysis on copper-rich and silver-rich solid solutions. There are enough of these data to permit comparison of numerous alloys at equal solute concentration in these two solvents, but only in a few cases is it possible to construct hardness-concentration curves for any given alloy. Therefore additional hardness work on most of these alloys is desirable. The primary solid solutions of silver with cadmium, indium, tin, or antimony as solute are of special interest, since all elements are from the same period of the periodic table and since, as shown previously,l the hardening effect of equal percentages of these solutes is proportional to the lattice expansion produced by them. This paper presents the relation between hardness and concentration in the silver-antimony system from very dilute to nearly saturated solutions of antimony in silver. Experimental Procedure Alloys were made from silver, 99.99 per cent pure, and antimony, 99.975 per cent pure. Silver and antimony were placed in graphite crucibles that had an ash content of less than 0.7 5 per cent. These metals were melted and allowed to solidify in a vacuum, which, after melting was corn- . plete, was usually equivalent to 3 mm. of mercury. A high-frequency furnace was used. The ingots so obtained were worked and annealed to lessen segregation and to control grain size. Annealing was done in evacuated and sealed glass tubes. Hardness measuremeuts on specimens from these ingots were by means of the Meyer analysis.394 Using a 4-mm. ball, impressions were made under seven loads from 25 to 400 kg. The diameter of impression made under each load was measured. This enabled calculation of the constants in the well-known formula of Meyer. L = adn where L = load, d = diameter of impression, a = a constant, n = a constant The Meyer hardness is defined as P = L/i(1/4pd2) or P = 4adn-2/p Meyer hardnesses corresponding to d = I and to d = 4 are of especial interest, since the first corresponds to comparatively slight 'plastic deformation and the second to the maximum plastic deformation producible by penetration of the ball. These

Jan 1, 1945

By Klaus Emicke

The paper describes the lead refining process operated at Norddeutsche Affinerie (N.A.). Incoming materials are different grades of lead with varying percentages of impurities: Cu, Te, As, Sn, Sb, Bi, precious metals. The facilities are designed for charge-wise operation. After drossing, generally Te, As, Sn and Sb are removed substantially by the Harris Refining Process using fused NaOH. A certain selectivity during refining is achieved by controlled addition of NaNO3. Another refining step is decopperizing by means of elemental sulfur. Complete separation of Te, As, Sn and Sb is accomplished by chemical methods in a leaching plant. A Howard Press is used in the Parkes Process for desilverizing. After vacuum dezinking in kettle, Bi is removed, if required, by means of Ca and Mg. In an end refining step Ca, Mg and Zn are removed by having the lead melt treated with NaOH and NaN03. The refined lead as such, or in the form of special alloys, is cast by an ingot casting machine into 50-kg ingots. Zinc which is used as a precipitant in the Parkes Process is recovered by distillation from the high grade Ag-Zn-Pb crystals in Faber du Faur retorts while the Pb/Ag alloy is fed to the cupellation furnace. Ca and Mg are removed from the Ca-Mg-Bi crystals formed in the course of Bi removal, and the Bi-bearing lead is cast into anodes. The electrolytic lead refining facilities at N.A. are operated largely for the purpose of separating Pb and Bi. These facilities are also used particularly for the refining of Bi-bearing lead which had gone through the above process, but from which Bi has not been removed by Ca and Mg.

Jan 1, 1970

By D. E. Furman

The thermal coefficients of linear expansion for several stainless steels have been determined over the temperature range from —300° to 1000°F. The steels studied include types 301, 304, 316, 347, 310 and 330. This wide selection of compositions allows an insight into the effects of austenite stability and alloy content on the expansion characteristics. THE recent increased use of materials in low temperature applications has created a field for which the properties of austenitic iron, chromium, nickel alloys are particularly suited. Tensile and impact values of stainless steels at subzero temperatures have been made available in the technical literature but, as yet, little information has been published with respect to expansion characteristics. In order to supply this need, a study was made of several of the more common compositions. Those selected were types 301, 304, 316, 347, 310 and 330 stainless steel. Both the mean and instantaneous coefficients of linear expansion were determined over the temperature range from —300°F to 1000°F. Procedure The materials used were commercial grades with the exception of type 301 which was made in a 10# high frequency furnace. The compositions are listed in table I. All steels were given an anneal at 1950°F for 30 min and water quenched prior to machining the expansion specimens. Expansion readings were taken on specimens 0.250 in. in diam by 4.000 in. long with a fused quartz tube expansion apparatus similar to that described by Hidnert and Souder.1 Temperature measurements were made with a chromel-alurnel thermocouple calibrated for use at subzero temperatures. A bath of propane was used for temperatures from —300° to —100°F and one of alcohol from —100°F to room temperature. These baths were contained in large mouthed Dewar flasks and cooled to the desired temperature levels by passing liquid nitrogen through glass cooling coils placed in the flasks. The baths were stirred constantly for temperature equalization and were heated by immersing metal rods which were replaced frequently enough to give a heating rate of approximately 150°F per hr. A resistance wound furnace was used for heating from room temperature to 1000°F and throughout this range rates of about 450°F per hr were maintained. The furnace was designed so that the temperature gradient over the specimen was within 5°F. In most instances, the expansion readings were taken during heating from —300° to +300°F at

Jan 1, 1951