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By R. J. Tailleur, M. Rosenberg

Oil well drilling muds prepared with lubricating aids such as oil, graphite or mica will not produce a sufficiently strong protective lubricant film for the bit bearing surfaces under high load conditions encountered in drilling operations. Consequently, the damage to the bearing surfaces resulting from the absence of such a film frequently results in a shortening of the drill bit life. Several different types of extreme pressure lubricating additives for use in muds have been developed. These arlrlitives are capable of providing a protective lubricating film for bearing surfaces subjected to high load pressures. A modified version of the Timken lubricant tester, an instrument commonly used for testing the extreme pressure lubricating properties of oils, is used for measuring and controlling the lubricating qualities of the mud. Comparison tests made in the laboratory with 55/8-in. tricone bits drilling on steel plates immersed in extreme pressure lubricating muds and conventional muds showed that the bearing life of those bits tested in the lrrbricating mud was three to four times greater than obtained with conventional muds. Drilling tests made with extreme pressure lubricating muds in West Texas increased over-all bit life three to fourfold, reduced drilling torque and wear on drill pipe and drill collars. INTRODUCTION Roller bit cones contain roller, ball and journal-type bearings that are subjected to very heavy loading during drilling operations in which the only lubricant available for these bearings is either water or drilling mud. These bearings must be able to operate satisfac- torily in order for the cutting structures on the surface of the cones to be fully utilized. Frequently, the bearings wear to the point that the cones freeze and the bit must be pulled before the cutting structures on the cones become worn. In some instances the bearings continue to turn with severe wear but the cones, which are held on the bit by the bearings, drop off; and this causes an expensive fishing job. In other instances the bearings wear to the point that the cones pinch in causing an undergauge hole and delays to ream the hole. The advantage of increasing bit bearing life is self-evident. Because of inability to control the internal wear of bits while drilling, it was felt that improvement of the lubricating qualities of the circulating mud would be helpful. However, the often-discussed lubricating property attributed to muds has been a rather vague and intangible one. The literature has implied that the oil-emulsion muds are more effective lubricants than non-emulsion muds. Actually, there has been no direct method of measuring the lubricating property of muds which would indicate that one mud was better than another; there has been no way to determine whether the lubricating property of any mud was adequate. Furthermore, in comparing lubricating properties of muds, two qualities should be considered—the coefficient of friction and the extreme pressure lubricating qualities. For example, graphite can reduce the coefficient of friction, but does not provide a strong enough lubricating film to protect bit bearings subjected to high loads. The primary object of the investigation reported herein was to find a method for prolonging the bearing life of drill bits; and considering the heavy loads used in drilling, it was felt necessary to find both a method of measuring lubricating properties under high load conditions and methods of establishing effective lubrication under these conditions. Extreme pressure lubrication deals with that realm of lubrication where metal surfaces are in rubbing contact with each other under very high pressures. These pressures may be quite high, as for example,

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".' More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid's viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-

Since its organization, in July, 1917, the War Minerals Committee of the Institute, of which William Y. Westervelt is chairman, has been studying important phases of the mineral industry and its relation to winning the war. From this has come a realization of the imperative need for more definite coordination than is possible without direction by some governmental agency. No privately controlled industry can have the detailed knowledge of war needs or the control of all its supplies and markets necessary to effect the adjustment of its activities for war purposes. Inevitable shortages of certain essential minerals confront us unless immediate steps are taken to stimulate and develop. the mining

Jan 2, 1918

By Arthur Fleischer

THE Kalunite process? for the production of metal-grade alumina from alumina-containing ores is applicable, considered from a general point of view, to any aluminous raw material that can be converted to potassium alum or equivalent normal alum. This result of modern technology has been the subject of a continuous study and development since 1929, on a laboratory and test-plant scale, with initial emphasis on the utilization of alunite as the raw material. The research and developmental program was carried out by the Kalunite Company and its successor, Kalunite, Inc., an affiliate of the Olin Corporation of East Alton, Illinois. The process is now approaching the time for a major test in its history with the completion of construction of a plant having a capacity of zoo tons of alumina per day in Salt Lake City for the conversion of Marysvale, Utah, alunite ores to alumina and potassium sulphate. The Salt Lake Alumina Plant is a Defense Plant Corporation project. PRODUCTION OF ALUMINUM The known existence of alunite deposits, especially in the Marysvale district, furnished the motive for the original inquiry into the utilization of this raw material for aluminum production. The deposits in this region were actively explored during World War I and utilized for the production of potassium sulphate, an essential fertilizer, of which a shortage of monumental proportions then existed. Up to the twentieth century for alunite is a mineral with an ancient history-it was used in Europe and in China as a source of potassium alum. It never had been used successfully in. this country as a source of oxide for reduction to metal. Although the known reserves of this ore, which undoubtedly will be greatly expanded with a commercial outlet for this ore, are recognized to be sufficient for only a part of the present-day needs of aluminum, it has a definite place in the aluminum industry. Academically it points the way for future raw materials. The aluminum industry has undergone a remarkable growth in the past few years as a result of defense and war requirements. Its expansion in many ways has been beyond belief and prediction, both in volume and location. This wartime status of the industry has accelerated the consumption of bauxite to such an extent, that a re-evaluation of the raw material reserves for the future peacetime industry and for eventual wartime reserves is seemingly of concern. The generally accepted picture of bauxite ore reserves in the United States, especially in raw material suitable for treatment by the Bayer process, focuses attention on other possible sources of raw material of metal-grade oxide. The perspective for the development of a suitable process may have changed in the interim

Jan 1, 1944

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.' Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.' They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.' He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.' They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.' The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 ' who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By N. M. Langdon

In considering the magnificent success of Mr. Gayley's bold experiment of applying dry blast to the blast-furnace, whereby a saving of 20 per cent. of fuel per ton of iron is effected, the question arises whether still further economy in fuel is possible, and, if so, how it is to be attained. The manner in which the heat generated in the furnace is utilized in the production of pig-iron may be determined, by the method of Bell and Gruner, for any furnace for which the necessary data are obtainable ; and the study of the operation, under various conditions, of a number of furnaces, for which such information has been worked out, should enable us to form some conclusion on the subject. The tables and calculations here given cover the operations of several furnaces reported in our Transactions ; also the two furnaces using natural and dry blast ill Mr. Gayley's experiment, for which the heat-equation has been worked out by Prof. Joseph W. Richards in his admirable discussion ' of Mr. Gayley's paper, The Application of Dry Air Blast to the Manufacture of Iron, and, finally, various hypothetical furnaces. The full list is as follows : A. Isabella furnace, with natural blast. B. Isabella furnace, with dry blast. The data stated for A and B in Table 111. are those given by Professor Richards, except that the heat-units are given for one unit of iron instead of 100 units, and some items of heat supplied, as stated by Richards, have been subdivided, the total being the same as given by Richards. (Columns A and B are introduced in Table 111. for comparison with C and D.)

Jan 1, 1910

By C. D. Rubert, W. J. Parton

LARGE quantities of fine anthracite with associated impurities are discharged with the waste water from the coal-cleaning plants in the Pennsylvania anthracite region. Furthermore, for many years this fine material has accumulated and formed silt banks. The difficulty of removing the impurities from the fine material and the lack of adequate markets are responsible for the waste of this material. In view of a larger demand for fine coal, mainly for pulverized fuel, the Lehigh Navigation Coal Co. Inc. decided to investigate the froth flotation process for recovery of fine coal from these waste solids. A test plant was constructed and operated for six months during 1942 in order to determine the practicability of recovering coal from the waste water of a cleaning plant (breaker) by froth flotation, and to obtain operating data for designing a commercial plant if the results were favorable. PRELIMINARY INVESTIGATION Before the pilot plant was constructed information was obtained by field and small-scale laboratory tests to serve as a guide in the design and operation of the pilot plant. Size and ash analyses of a representative sample of the material discharged in the wash water from a cleaning plant are given in Table I. [ ] The refuse content increases progressively as the size of the particles decreases. The larger particles (+35 m.) are low in ash content and could be marketed without cleaning. Since these solids are discharged from the breakers with 90 to 95 per cent water by weight, the first step in the recovery of the coal was that of reducing the quantity of water so that water in excess will not have to be handled. Furthermore, it was found that the removal of most of the minus 200 mesh high-ash material was desirable to permit the most efficient flotation of the coal. Classification tests were run and showed that a hydroseparator overflow rate of 12 ft. per hour was sufficient to eliminate much of the minus 200-mesh material while allowing the coarser material to settle and be thickened.

Jan 1, 1944

By Thomas T. Read

MINING, which is at least twenty centuries old, was at first, and long, wholly a practical art. Little more than two centuries have elapsed since the inception of the idea that general education and a knowledge of natural science would be of advantage to those engaged in the mining industry. Though schools of mining began to develop in Europe early in the eighteenth century the concept of educational preparation for technical conduct of the industry was slow in winning general acceptance in the industry itself. John Hays Hammond, in his autobiography, recalls that when he sought employment with a mining company after he had graduated from Yale and Freiberg he had to assure its executive, before being even considered for employment, that he did not consider that he had learned anything about mining. This was as late as 1880. Existence in the industry of a prejudice against education of the academic type is perhaps an explanation why inadequate provision has been made by the mining industry for the continuing education of technical employees after they enter employment, although engineering education prior to engaging in industry has now won general acceptance. I am familiar with the existence of "loop" courses for engineering graduates in metallurgical plants, of schemes for giving mining graduates "practical experience," and of the interest in vocational courses for workmen which sprang up in the period of labor shortage during and immediately following World War I (but which quickly died when the depression of 1921 again made experienced workmen available in sufficient supply), having been chairman of a committee appointed by the Mineral Industry Education Division to make a survey of existing provisions for post-employment training for engineers in our industry. The results of that survey, reported elsewhere, dearly indicate that it is inadequate as to amount; the aim of this paper is to present evidence for belief that it is also inadequate in quality. To avoid becoming too involved, no reference will be made here to post-employment vocational training for workmen, which is a subject differing so much from post-employment education for engineers as to require separate treatment. Neither will postgraduate education for metallurgical engineers be discussed, because a distinction must then be made between training for research work and for plant operation, whereas mining engineers engage almost exclusively in operations. Since the situation in the coal-mining industry has been discussed at several recent meetings, that also will be passed over, and what follows should be taken as a discussion applying exclusively to the metal-mining industry. PROFESSIONAL DEVELOPMENT In the operations field (both in mining and metallurgy) the work to which a beginner is assigned is seldom closely related to previous academic- education. The contrast is almost as great as between

Jan 1, 1941

By F. N. Koepel, L. A. Callaway

The property of the Andes Copper Mining Co. is in the central part of the Republic of Chile, Province of Atacama, about 75 miles to the eastward from the port of Chafñaral. At this point the Andean system is made up of two principal ranges, and the mine and metallurgical plant are both on the westerly slope of the outer or western range. Mean elevation of the mine is 10,500 ft., while at the plant the elevation ranges from 9445 to 9700 ft. A meter gage railroad extends from the company's port at Barquito, near Chañaral, to the reduction plant at Potrerillos. This road has a total length of 94 miles, of which 57.79 miles are owned by the Andes Copper Mining Co. and the remainder of the road is controlled by the State. Development of the Potrerillos mine and installation of the metallurgical equipment presented unusual difficulties due to the arid nature of the country, high altitude and remoteness of the location from any considerable center of population. As a primary step it was necessary that railroad transportation be provided in order that mine development and plant construction could go forward on an economical basis. Provision of an adequate supply of water for domestic and metallurgical uses involved the construction of approximately 178 miles of pipe lines, all of which have their sources at altitudes ranging from 12,000 to 14,000 ft. above sea level and traverse rough and difficult terrane. Water for metallurgical use is brought to Potrerillos from the Ola River, a stream originating in the high cordillera to the eastward from the property. It is delivered by means of a steel pipe line, 32 miles long, having diameters ranging from 22 to 36 in. Domestic water is supplied to the various camps through a system of pipe lines aggregating 146 miles in length, the Ola water being unfit for this purpose. These conductors gather water from numerous springs in the high mountains to the eastward from Potrerillos and deliver it to the mine, the reduction works and the port at Barquito. Extensive permanent housing facilities had to be provided as it was necessary to care for more than 3000 workmen and employees at the

Jan 1, 1934

By Chester Purington

PROBABLY no battleship of any great power save Japan could long remain in. the Pacific Ocean tinder present conditions, were it to depend for fuel supply on the hitherto developed coal or oil resources of any part of the adjoining lands in either hemisphere. This statement does not overlook the important but not inexhaustible oil fields of California, the bunker coals of British Columbia, nor the coals accessible and mined adjacent to Chinese water-ways. For both naval and merchant ships, however, modern practice seems to require high-grade Welsh or Pennsylvania bituminous even at great expense for transportation. Otherwise, we should not see British ships bunkering Welsh coal at Singapore nor the United States establishing a store of Pennsylvania coal at its naval base at Pearl Harbor, Hawaii. Compared with Atlantic coals, the best Miike and Nagasaki (Japanese) bunker coal, the Kailan coal of China, and the Welling-ton and Nanaimo coals of British Columbia, are dis-tinctly inferior, as one can soon learn from the chief engineers on Pacific liners. In addition to the coal used for steaming and bunker purposes, it is of increasing importance that an adequate supply of coking coal for metallurgical purposes should be made available at reasonable prices at industrial centers on the west coast of America, and at Japanese and Chinese coastal cities. The use of Chinese coking coals for smelting the iron of the lower Yang-Tse deposits is by no means so satisfactory as could be desired, while the poor quality. of Japanese coals for coking purposes is well known. If Russia, as seems not improbable, is to become a power on the Pacific in the course of the next few decades, she will doubtless develop an iron and steel industry in the Maritime Province, where an adequate and accessible supply of iron ore will necessitate a supply of coking coal.

Jan 9, 1923

By A. L. Benham, W. E. Dowden, W. J. Kunzman

The mechanism involved in creating a miscible fluid displacement of typical reservoir fluids through porous media by light hydrocarbon mixtures usually involves a number of mixing and separation stages in the contact area. This mechanism has been illustrated on ternary diagrams for miscible displacement of reservoir fluid by rich hydrocarbon gases. A relatively simple method has been devised for calculating the approximate conditions for a miscible displacement of reservoir fluid by rich, light hydrocarbon gases or by LPG mixtures. Miscibility is favored by increased pressures, decreased temperatures, light reservoir fluids and light hydrocarbon-displacing fluids rich in the heavier components. The conditions for miscible displacements of five typical reservoir fluids by various light hydrocarbon mixtures were determined for a range of temperatures from 70" to 260°F and pressures from 1,000 to 3,000 psia. A correlation of these conditions was obtained using the variables of temperature, pressure, C,+ molecular weight of the reservoir fluid, C,+ molecular weight of the displacing fluid, and mol per cent methane in the displacing fluid. This correlation has been applied to data appearing in the literature with very good success. A partial check of the correlation has been made using a step-wise procedure with a windowed PVT cell. INTRODUCTION The term, "miscible fluid displacement", may be defined as any oil-recovery displacement process where there is an absence of a phase boundary or interface between the displaced and displacing fluids. A water flood would not be a miscible fluid displacement, although cycling in a condensate reservoir would be. Another example is displacement of oil by gasoline. Not so obvious, however, are the conditions under which fluids (such as propane, mixtures of propane and methane, or other similar systems) will give a miscible fluid displacement of oil. There are four standard miscible-fluid-displacement processes being used for the recovery of oil from an "nderground reservoir—(1) high-pressure dry-gas miscible displacement, (2) rich-gas miscible displacement, (3) miscible slug using a slug of LPG followed by a lean dry gas under miscible conditions, and (4) gas driven-slug process using a slug of LPG followed by a lean dry gas under immiscible conditions. The first problem faced by the engineer designing a miscible displacement process is to determine the conditions for miscibility. A number of papers have included discussions of the process of obtaining miscibility in these processes.1-8 However, methods for calculating the conditions for miscibility have not been published. This paper includes a method for calculating the conditions for a miscible displacement of reservoir fluid by a rich gas (LPG diluted with methane or natural gas). In this paper, a rich-gas miscible displacement process is defined as an oil-recovery process in the reservoir. The cost of a rich-gas miscible displacement will be decreased by diluting the LPG with methane or natural gas as much as possible. Therefore, it is important to be able to predict the maximum dilution for miscibility. MECHANISMS The mechanisms for obtaining miscibility between a displacing mixture of light hydrocarbons and displaced reservoir fluid often involve a number of displacing and mixing stages. As stated previously, the cost of a rich-gas miscible displacement is decreased by diluting available LPG with natural gas. The problem is to predict the maximum dilution allowed while maintaining miscibility. To get a picture of the displacing and mixing stages, it is helpful to consider these complex hydrocarbon mixtures as pseu do-ternary systems. Graphical representation of a complex system as a pseu do-ternary system can be thermodynamically rigorous if enough variables are used to describe the character of each pseudo-component in one of the phases. However, even if the characterization of each pseudo-component is not complete, pseudo-ternary representation does serve to illustrate the mechanism for obtaining miscibility and can be used to make some general conclusions concerning the conditions for obtaining miscibility. A phase diagram for the ternary system, methane-

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult's law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener's paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult's law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener's paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By G. D. Cremer, J. J. Cordiano

Aluminum powder is a well-known article of commerce and in various forms has been marketed widely for use in paint, for pyrotechnic purposes and for exothermic mixtures. For a number of reasons, however, aluminum powder has not been employed extensively in powder metallurgy, although a great many proposals along this line have been offered. Aluminum and alumiuum-alloy powders oxidize readily upon exposure to air and the thin film of oxide (or hydroxide) thus formed is highly refractory, in that ordinary gaseous reducing agents such as hydrogen or carbon monoxide do not reduce the oxide to metal at temperatures below the melting point of aluminum. It has been thought that the presence of these films of oxide on aluminum particles would interfere markedly in powder metallurgical work and a number of suggestions have been made, either for preventing the formation of the film through the production of the powders in inert or reducing atmospheres, or for the removal of the oxide by means of powerful reducing agents, including "nascent" or atomic hydrogen released from metal hydrides. A second and more serious difficulty in the use of aluminum and aluminum-alloy powders in powder metallurgy resides in the fact that during compression such powders tend to adhere or cold-weld to the die walls, thus interfering with the formation and ejection of a compact. A third difficulty, which has been encountered only with aluminum-alloy powders, is their hardness when compared with elemental aluminum. Certain of these powders are susceptible to age-hardening, which further hinders the formation of strong green compacts. These conditions are particularly true of atomized aluminum-alloy powders. Even in the annealed condition, plastic deformation of alloy powders under pressure is low when compared with unalloyed powders. This fact, coupled with the lower corrosion resistance of the alloy powders. is probably the significant factor in our failure to obtain strong sintered pieces. Methods of Puoducing the Powder Many methods have been proposed for manufacture of aluminum powder, only a few of which are used commercially. Several of the more important processes include: (I) atomization of the molten metal; (2) mechanical pulverization and other types of comminution; and (3) graining, in which molten aluminum is stirred during freezing. For pigment and certain pyrotechnic uses aluminum flake powder is desirable, because of its greater proportion of surface to volume; and large quantities of such material are made by a procedure that involves stamping or ball milling. In making flake intended for use as pigment,

Jan 1, 1943

By G. D. Cremer, J. J. Cordiano

Aluminum powder is a well-known article of commerce and in various forms has been marketed widely for use in paint, for pyrotechnic purposes and for exothermic mixtures. For a number of reasons, however, aluminum powder has not been employed extensively in powder metallurgy, although a great many proposals along this line have been offered. Aluminum and alumiuum-alloy powders oxidize readily upon exposure to air and the thin film of oxide (or hydroxide) thus formed is highly refractory, in that ordinary gaseous reducing agents such as hydrogen or carbon monoxide do not reduce the oxide to metal at temperatures below the melting point of aluminum. It has been thought that the presence of these films of oxide on aluminum particles would interfere markedly in powder metallurgical work and a number of suggestions have been made, either for preventing the formation of the film through the production of the powders in inert or reducing atmospheres, or for the removal of the oxide by means of powerful reducing agents, including "nascent" or atomic hydrogen released from metal hydrides. A second and more serious difficulty in the use of aluminum and aluminum-alloy powders in powder metallurgy resides in the fact that during compression such powders tend to adhere or cold-weld to the die walls, thus interfering with the formation and ejection of a compact. A third difficulty, which has been encountered only with aluminum-alloy powders, is their hardness when compared with elemental aluminum. Certain of these powders are susceptible to age-hardening, which further hinders the formation of strong green compacts. These conditions are particularly true of atomized aluminum-alloy powders. Even in the annealed condition, plastic deformation of alloy powders under pressure is low when compared with unalloyed powders. This fact, coupled with the lower corrosion resistance of the alloy powders. is probably the significant factor in our failure to obtain strong sintered pieces. Methods of Puoducing the Powder Many methods have been proposed for manufacture of aluminum powder, only a few of which are used commercially. Several of the more important processes include: (I) atomization of the molten metal; (2) mechanical pulverization and other types of comminution; and (3) graining, in which molten aluminum is stirred during freezing. For pigment and certain pyrotechnic uses aluminum flake powder is desirable, because of its greater proportion of surface to volume; and large quantities of such material are made by a procedure that involves stamping or ball milling. In making flake intended for use as pigment,

Jan 1, 1943

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By M. Kaufman, A. E. Palty

THE mechanical properties of an alloy under given test conditions are in the main determined by the grain size and the phases present, their distribution and temperature-time dependence. Alloys intended for use at elevated temperatures, especially multiphase alloys depending upon precipitation reactions for strengthening, are particularly susceptible to changes in the phases present. Unfortunately, for modern superalloys, very little published information exists which relates the mechanical properties to the basic structural variables. The present work is an effort to do this for an alloy widely used in aircraft gas turbines and related applications, Udimet 500.* The mechanical properties inves- two heats is within the normal specifications for the alloy. However, the elements which most strongly influence the phase reactions, C, Ti, Al, and Mo, are comparable in the two heats. There was no intentional addition of boron, but normal pickup is about 0.002 pct. The vacuum-melted material was received in the form of centerless ground wrought bar stock % in. diam. PHASE STUDIES A) Methods—Two methods were used to determine the phases present: X-ray diffraction measurements on electrolytically digested residues, and microscopic examination. No single commonly used electrolyte will reveal all the phases that may be present; therefore, two complementary acids were selected: HCl and H3PO4. The necessity for this will be shown below in the results. The acid concentrations used were 10 pct HC1 in alcohol and 10 pct H3 PO4 in water. The current density was maintained below 0.1 amp per sq in. Residues were rinsed and separated by centrifuga-tion. X-ray diffraction patterns were obtained in a 114 mm Debye-Scherrer type camera using cobalt radiation. A temperature of 2250°F was selected to obtain as complete solutioning of phases as possible without encountering incipient melting. Specimens were

Jan 1, 1961

By Henry Rumfelt

8.1-1. History and Description of Shovels. The history of excavating machinery is not clearly defined but the machines seem to have been originally developed for dredging activities, principally involving rivers and harbors. The first, as far as can be determined, was a steam "spoon dredge" developed by Grimshaw of Boulton and Watt of Sunderland, England, in 1796. The land machine forerunner of the present-day power shovel was not developed until 1835. It was invented by William Smith Otis, a young partner of a Philadelphia contracting firm by the name of Carmichael and Fairbanks. The moving force behind this invention was the heavy activity in railroad construction. From this early start the power shovel has developed from steam powering to internal-combution-engine powering and to electric powering. In both directions it has developed to its present state of a finely engineered and precision-built tool. Through the interim the railroad-type shovel, about a half-swing arrangement designed especially for making railroad cuts and mounted on rails, was developed. The rail-mounted shovel gradually gave way to the full revolving shovel. It was high on the list in 1912 and was practically extinct by 1927. From the beginning, a few of the small revolving shovels designed primarily for the general contractors' market had found their way into quarry and mining operations. During this same period, the stripping shovel had been introduced-a 2 ½ cu. yd., 100-ton, full revolving stripping machine with a 41 ft boom. Although this shovel was designed especially for stripping, it was also used for heavy-duty, open pit mining service. In 1925 the heavy-duty, full revolving quarry and mine machine was developed. Strip mining shovels evolved through a somewhat separate path. Hand digging plows and mule-drawn slip scrapers were first reported used by Kirkland, Blakeney and Groves near Danville, Illinois for strip mining

Jan 1, 1968