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By S. R. B. Cooke, H. S. Choi, I. Iwasaki

In a previous article1 the function of various fatty acids as collectors for iron ores was reported for the two alternate processes; (a) the flotation of iron-oxide minerals, and (b) the flotation of calcium-activated siliceous gangue. The selectivity of separation was shown to be markedly dependent not only on such common parameters as pH and the levels of collector and activator addition, but also on the structure and the degree of unsaturation of the acids used. The iron ores employed consisted primarily of hematite, goethite, and quartz and as the effectiveness of any one acid on the separation depends on the individual response of each constituent mineral toward the given collector, a comprehensive knowledge of the floatability of the individual minerals is desirable for the interpretation of the results obtained. The mechanism by which a collector ion becomes attached to a mineral-solution interface has been a subject of much investigation. From quantitative studies of the properties of the electrical double layer on mercury2 and on several solid surfaces3,4,5,6 , the adsorption of some flotation reagents at the mineral-solution interface is beginning to be understood. For example, it has been demonstrated from streaming potential measurements made on quartz5 and corundum6 that the interfacial electrical condition is strongly dependent on the pH. Thisoccurs presumably through the following electrolytic reaction at the interface, and in the presence of a flotation collector, controls the floatability of the solids. A concurrent investigation of the flotation behavior of goethite and of quartz carried out at the School of Mines and Metallurgy7 has shown a positive correlation with the electrokinetic behavior of these minerals. The purpose of the present investigation was to collect general information on the floatability of hematite, and to investigate the function of various 18-carbon aliphatic acids on the floatability of hematite, goethite, and of activated quartz. Electrophoretic mobility measurements, simplified flotation tests using a modified Hallimond tube, and contact angle and frothability measurements were employed. The results are of direct application in the interpretation of the batch flotation results on natural ores as

Jan 1, 1961

By Warren E. Wilson

THE transportation of solids in pipe lines is a matter of deep concern in many fields of engineering. Much experimental and theoretical work has been done in an effort to devise means of designing pipe lines that will satisfactorily transport given solid loads, but there remain many unanswered questions in this field. The present discussion will be confined to a rather narrow portion of this field and will endeavor to point out certain factors that may well be considered when comparing the relative economy of various installations. The data have been presented previously but a new interpretation was prompted by a suggestion in a paper by Professor O'Brien,1 of the University of California, that the friction work per pound of dry material should be considered in determining the relative efficiency of various installations. This method of considering relative economy in various pipe lines leads to some rather unexpected conclusions, especially with reference to the economy of large pipe sizes. A previous suggestion by the writer3 concerning the economy of a rather peculiar type of installation is strengthened. It is not believed that the considerations set forth herein apply directly in the case of dredge lines, where economy is largely a matter of a high rate of pumping in order to reduce the unit overhead charge. However, it is believed that some value may be gained from these considerations in cases involving the disposal of a fixed amount of solids per unit time with a minimum expenditure of energy and at a low cost for replacement of worn pipes. Such situations are not uncommon in the disposal of mill tailings and the disposal of solids deposited from irrigation waters. It was found that data leading to general conclusions for various pipe sizes were not available but certain definite trends are indicated and methods of analyzing available data are presented in the hope that they may be of assistance in preparing engineering estimates on designs of pipe lines of the type described above. ENERGY. REQUIREMENTS Carrying out the idea contained in Professor O'Brien's paper concerning the method of computing energy required to transport solids, the following analysis leads to some rather interesting conclusions. Let us represent: [Solids load in terms of mass per unit time by W Ratio of mass of suspended solids to total mass of mixture flowing by p Volume rate of flow of mixture by Q Length of pipe by L Slope of energy grade line by s Mass per unit volume of solids by m, Mass per unit volume of liquid by ml Mass per unit volume of mixture by m,,, We then have as an expression for the solids load: W = pQm¬] The work done per unit mass, P, on the mixture to move it along the pipe the

Jan 1, 1945

By L. M. Kaas

Production planning techniques, particularly a production scheduling model are proposed for use in taconite mining in Minnesota. Applications of the scheduling model, on a two-year mine plan, which evaluates the equipment involved, are detailed. Data and tables are included. INTRODUCTION Fifty years ago Walter Swart, a mining engineer investigating the Minnesota taconites for the Jackling interests, made this report: "There is no doubt in my mind that this taconite mining is a game worth playing and that it can be played to a successful finish. It seems now only a question of men, money, methods and details."' The prosperous industry envisioned by Swart and other taconite pioneers is today a reality. Its growth has been spurred by technological advances in mining and beneficiation, depletion of natural ore reserves, and improvement of the economic climate. However, the massive problems that were solved to make this development possible are only a foreshadowing of the questions of "men, money, methods and details" that will be encountered in the future. The increasing demands for higher quality taconite pellets have already forced producers to examine better methods of quality control for their operations. THE NEED FOR PRODUCTION SCHEDULING The maintenance of fairly constant crude ore characteristics is of major importance to mill quality control. Through careful mixing of ore from storage bins, the concentrator staff can partially reduce the deviations of the feed analysis from the analysis desired. However, the limited effectiveness of bin mixing systems has caused some mining companies to utilize large capacity blending piles to reduce grade variations. Although the analysis of material being reclaimed from such a pile is relatively uniform, raw materials still must be scheduled from the mine into the pile in such a manner that the average analysis of all material is close to the feed analysis prescribed by the mill. PRODUCTION SCHEDULING MODEL Minnesota taconite mining companies have used three analyses to estimate how a certain ore will react to concentration. These factors are the crude magnetic iron content of the ore, the iron content of the plant concentrate produced from the ore at a standard grind, and the grindability index of the ore. The actual laboratory tests used to determine these factors have been described by Apuli.2 These data are obtained from analysis of diamond drill cores, and are the established criteria used by mine planning engineers to formulate taconite production schedules. Variations in the grade of mine output should be controlled by any production scheduling system. However, to be truly practical, production scheduling methods must also consider many of the less tangible variables that affect mine operation. These include pit layout, available equipment, and ownership of ore leases. The number and scope of the variables inherent in this type of mine planning suggested that a computer simulation could be used to solve the problem. The preparation of information for use with a computer simulation program was the initial phase of this project. Meaningful data was developed from logs of diamond drill cores. Analyses were related to their respective areas of influence by means of mine maps, Fig. 1. The three assay variables and tonnages for each area were punched on cards. In addition to these values, a location code number was punched in the first eight columns of the cards. This code is explained as follows: Column 1 Bench number Column 2 Quadrant location as determined by mine reference lines Columns 3-5 East-west coordinate Columns 6-8 North-south coordinate The heart of any simulation techniques is a well engineered mathematical model. To develop a model for taconite production scheduling, the relationship between the three assay variables had to be established. Because changes in each analysis factor affect the mill circuits in different manners, a weighting system was used to determine the relative im-

Jan 1, 1967

By Robert B. Fulton

The use of industrial minerals by the chemical industry as raw materials for manufacturing and in processing spans a wide assortment of minerals. This chapter aims to supplement rather than duplicate the commodity chapters. Its objective, to describe the uses of industrial minerals in the manufacture of chemicals, is attained by considering minerals used by the chemical industry in terms of the chemical element required and by giving particular emphasis to market factors. The mineral aspect, which is covered in the commodity chapters, is subordinated and attention is focused on the chemical and market aspects. Condensing this broad subject into a few pages permits treating only the most important elements derived from industrial minerals. The elements derived from petroleum, hydrogen and carbon, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potash, and nitrogen for fertilizers and titanium dioxide for pigments. After eliminating on this basis, our definition leaves six elements of major importance: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Salt brines have particular importance as raw material sources for the chemical industry as shown in Table 1 "Salt Brine Derivatives" (Anon., 1967), which charts the chemical compounds derived from four types of brines: (1) Owens Lake type brines which are sources of boron and sodium compounds; (2) Midland type brines from which bromine, iodine, and chlorides of calcium, magnesium, potassium, and sodium are derived; (3) Searles Lake type yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak type produced mainly for lithium. Table 2 (Jones, 1973) affords an overview of the chief industrial minerals, the chemical products derived from them, and end uses of the products.

Jan 1, 1975

By Howard R. Pratt, Jimmie L. Bratton

The Air Force Weapons Laboratory (AFWL) has been carrying out a series of experiments whose principal purpose is to measure the dynamic response of rock media to large pressure pulses. Coupled with the field experiments have been theoretical calculations simulating this response. These two approaches allow an appraisal of the current ability to measure in-situ rock response under extreme conditions and also give a fair estimate of the current state-of-the-art in the area of computer calculation of the response of "real" geologic media to a large load. The area chosen for the test series is composed of a sequence of sedimentary units (shale, sandstone, and limestone) located in the Estancia Valley 45 miles east of Albuquerque, N.M. (Fig. 1). The units, which dip gently off the uplifted Manzano Mountains to the west, are essentially horizontal at the test site. An extensive geologic and geophysical investigation of the area was carried out in the form of surface mapping and seismic exploration. Numerous holes were cored and material properties were determined from tests of the cores. In-situ geophysical measure¬ments were also carried out. The experiment consisted of loading a 60X40 ft test area with a 4000-psi transient exponentially decaying pressure pulse. The pulse was initiated at one end and traveled the 60-ft length of the test bed. The test area was instrumented with acceleration, velocity, and strain measuring devices placed in drill holes to depths of 30 ft. Theoretical computer calculations of the response of the layered geologic media have been carried out on the AFWL CDC 6600 using one and

Jan 1, 1972

By M. N. Brodie, John Chapman

INTRODUCTION - DEFINITION & HISTORICAL PERSPECTIVE While this symposium is concerned with comminution which, by definition, relates to all stages of size reduction of an ore body to a form suitable for mineral separation, the electrical drive aspect of the grinding section will receive most attention in contrast to the crushing, screening and materials handling elements of the process. The reason for this is that today's large mills, thirty feet diameter and upwards, present mechanical and electrical problems which require a degree of sophistication in their solution not previously required. The ability to satisfy these demands, so far as electrical technology is concerned, largely results from the development of semi-conductor devices. These can now handle typical electrical distribution power levels within remarkably s m all volumes and with high efficiency when compared with the motor-generator sets, mercury arc rectifiers, rotating amplifiers, magnetic amplifiers and vacuum tubes which were commonly used to provide speed and torque controls as recently as the early nineteen-sixties. The hardware available to the electrical engineer has changed dramatically whereby even the simplest control system formerly using hard-wired relays is now superseded by the program m able logic controller with its computer-like memory containing the sequence of operation, in other words, the software. Reverting now to the mineral process itself, it is assumed that the ore body has been mined using explosives and is delivered to the concentrating plant in its 'run of mine' form. The problem becomes one of reducing the material to a size which will permit an acceptable recovery of the mineral with the most economical use of energy. The size of 'run of mine' material will range from about minus five feet for high tonnage open pit operations to minus two feet for the smaller underground mine. The final reduction in size may range from minus ten mesh to minus two hundred mesh (exceptionally as fine as minus six hundred mesh) depending upon the concentration method and dissemination of the mineral values within the ore. There is no single circuit that satisfies all applications, but the pattern of metallurgical equipment use shown in Table 1 appears discernable from current practice, in general terms.

Jan 1, 1982

By Frederic Benard

PRIOR to 1936, the Ontario Refining Co. received all incoming blister copper from The International Nickel Company's smelter in the usual form of 460-lb. cakes, or slabs. These were received in open cars in lots of 250 pieces. At the refinery the cakes were unloaded onto narrow-gauge cars, for convenient handling and pickup by charging cranes. In March 1936, an investigation was started on the feasibility of transferring converter copper in the molten state from the smelter to the refinery anode furnaces, a distance of 1 ¼ miles. Although common in steel practice, the transportation of blister copper in this form had not previously been attempted and a preliminary study of the various factors involved was therefore necessary. For this purpose, a series of experiments was made in which molten copper, removed at different stages during the furnace cycle, was held in a small portable holding furnace. This vessel was essentially a refractory-lined steel cylinder provided with ports for filling and emptying, heated by an oil burner. Dimensions of the steel shell were 3 ft. 10 in. diameter by 7 ft. 3 in. long, and thickness of refractories depended on the design and combination used for the particular experiment. The vessel was filled with approximately 2 ½ tons of copper at a predetermined temperature, the lining having been preheated to a definite point by means of an oil burner. All openings were well luted and temperature readings were made every 15 min. by means of an immersion-type thermocouple. In this manner the rate of heat loss resulting with different refractory design could be developed. The ratio of exterior surface to weight of metal was taken into consideration in comparing the experimental results with what might be expected for a full-sized unit, and observations were also made on type and degree of slag accretion. It was not possible to get as much information on this latter point as desirable, but all evidence showed that the problem would be control of slag build-up rather than attack on refractories. From the information derived, and in consultation with the engineering staff of the supplying company, an order was placed for the first

Jan 1, 1938

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By AIME AIME

The first session, held Tuesday evening, February 23, in North Sheffield Hall, was called to order by Louis V. Pirsson, Chairman of the Local Committee, who introduced Prof. Russell H. Chittenden, Dean of the Sheffield Scientific School of Yale University. Professor Chittenden, in behalf of the Governing Board, felicitated the Institute on its visit to New Haven, and cordially welcomed the members and guests to the University and the city. Dr. James Douglas, who presided at the meeting, responded in behalf of the Institute. The Secretary announced that, upon the proposal of many members, the unanimous report of the Committee on Membership, and .the unanimous recommendation of the Council, the following members had been unanimously elected by the Board of Directors Honorary Members in the American Institute of Mining Engineers Prof. Richard Beck, of Freiberg, Saxony, in recognition of his distinguished service to technical literature, and the cordial

Apr 1, 1909

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published ' and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By Robert S. Dewey

AS a result of drilling operations during 1943, West Texas again added sufficient new oil reserves to replace the oil produced during the year, but failed to maintain its position in currently available reserves because the deeper discoveries will require years for development. Drilling failed to provide the additional oil necessary to meet the increase in current and anticipated market demand. Although 13.3 per cent of the total footage drilled was in wildcat exploration, the ratio of oil discoveries to total wildcats was less in 1943 than in 1942, but comparable to that in 1941. Of the 732 field wells completed, 270 were at Slaughter, 55 at Wasson, 45 at Mascho and 31 at North Cowden. As of Dec. 31, 1943, there were 361 drilling wells including 71 wildcat and 290 field wells; 19.7 per cent were wildcats. It is anticipated that the percentage of wildcats of the total wells will be higher during 1944 than in either 1942 or 1943. Tables 3 and 4 present a three-year comparison of drilling activity and illustrate the downward trend of development that has been in effect during that time. Because of development lag in the deeper Ordovician fields, several years elapse before 2 sufficient number of wells is completed to give a substantial producing rate. As these new oil reserves cost more to find, and will cost more to produce on a barrel basis than the oil marketed during the year, their reserve replacement value to the industry is less in money. Costs While complete costs for deeper drilling are not yet available for analysis, it is evi- dent from the data on drilling rates to comparable depths, contract prices, and general increases in costs, that the cost of drilling has risen approximately 20 per cent during the year. One representative drilling contractor estimates that the average drilling time on a 5000-ft. field well has increased nearly one third and that out-of-pocket costs have increased a dollar per foot. Three major factors contribute to this increased cost: (I) less experienced labor, (2) deterioration in mechanical equipment and expendable material, and (3) increased contract prices. In the past, when there were more drilling rigs than wells to be drilled, some contractors would cut their drilling profit to keep their personnel and rigs working. As this practice is no longer necessary, the contract prices are adjusted upward to assure a profit. On deep and difficult drilling, contracts are let on a cost plus basis. A number of mechanical difficulties have become evident. Inferior quality of steel used in drill pipe and rock bits has added appreciably to drilling time and cost. Contractors are experiencing delay in obtaining repair work and repair parts for prime movers. As the length of drilling time required an shallow-field wells has not increased in proportion to that on deeper wells, it seems that the medium-sized drilling rig is better adapted mechanically than the heavy one to the work imposed. One of the main deficiencies in the heavy rig equipment is inadequate pump capacity. Drilling Mud The increasing amount of deep drilling has emphasized the importance and relationship of good mud to efficient and suc-

Jan 1, 1944

By Robert S. Dewey

AS a result of drilling operations during 1943, West Texas again added sufficient new oil reserves to replace the oil produced during the year, but failed to maintain its position in currently available reserves because the deeper discoveries will require years for development. Drilling failed to provide the additional oil necessary to meet the increase in current and anticipated market demand. Although 13.3 per cent of the total footage drilled was in wildcat exploration, the ratio of oil discoveries to total wildcats was less in 1943 than in 1942, but comparable to that in 1941. Of the 732 field wells completed, 270 were at Slaughter, 55 at Wasson, 45 at Mascho and 31 at North Cowden. As of Dec. 31, 1943, there were 361 drilling wells including 71 wildcat and 290 field wells; 19.7 per cent were wildcats. It is anticipated that the percentage of wildcats of the total wells will be higher during 1944 than in either 1942 or 1943. Tables 3 and 4 present a three-year comparison of drilling activity and illustrate the downward trend of development that has been in effect during that time. Because of development lag in the deeper Ordovician fields, several years elapse before 2 sufficient number of wells is completed to give a substantial producing rate. As these new oil reserves cost more to find, and will cost more to produce on a barrel basis than the oil marketed during the year, their reserve replacement value to the industry is less in money. Costs While complete costs for deeper drilling are not yet available for analysis, it is evi- dent from the data on drilling rates to comparable depths, contract prices, and general increases in costs, that the cost of drilling has risen approximately 20 per cent during the year. One representative drilling contractor estimates that the average drilling time on a 5000-ft. field well has increased nearly one third and that out-of-pocket costs have increased a dollar per foot. Three major factors contribute to this increased cost: (I) less experienced labor, (2) deterioration in mechanical equipment and expendable material, and (3) increased contract prices. In the past, when there were more drilling rigs than wells to be drilled, some contractors would cut their drilling profit to keep their personnel and rigs working. As this practice is no longer necessary, the contract prices are adjusted upward to assure a profit. On deep and difficult drilling, contracts are let on a cost plus basis. A number of mechanical difficulties have become evident. Inferior quality of steel used in drill pipe and rock bits has added appreciably to drilling time and cost. Contractors are experiencing delay in obtaining repair work and repair parts for prime movers. As the length of drilling time required an shallow-field wells has not increased in proportion to that on deeper wells, it seems that the medium-sized drilling rig is better adapted mechanically than the heavy one to the work imposed. One of the main deficiencies in the heavy rig equipment is inadequate pump capacity. Drilling Mud The increasing amount of deep drilling has emphasized the importance and relationship of good mud to efficient and suc-

Jan 1, 1944

By Enrique Touceda

FOR a number of years prior to the world war, the firm of Geo. H. Thacher & Co., of Albany, N. Y., was engaged in the manufacture of marine and other gray-iron castings. At -the outbreak of the war the firm decided to specialize in the manufacture f propeller wheels. It attacked the problem, therefore, from a foundry point of view, seeking to produce a casting that would be so accurate that no subsequent machining would be required on the blades, also from the point of view of the ship builder. There were two general methods f manufacture, the shortcomings of which have been freely acknowledged. In the sweep method, the nowel, or bottom half-mold, for each blade is swept up by a spindle beam and pitch race, while the top half-mold for each blade is built up individually. In the pattern method one individual blade, with the hub or hub portion, is mounted on a spindle and the individual -blade mold formed, the pattern is then rotated on the spindle to the position- for the next blade, etc. In rare cases wheels were made from a solid pattern. Owing to the cost of the pattern, its failure in many instances to be correctly made, and (when made of wood) its early and sure distortion the disadvantage of this practice is obvious, while metal patterns in most instances were prohibitive in cost. In these methods both green-sand and loam molding was practiced. The casting produced by either method can be considered only as a blank from which the propeller must be machined. The back surface f each blade must be chipped too the templet and through this procedure chipped to such accuracy, as will be required for a static balance. Inasmuch as the' work done by the machine tool is confined to the driving face of the blades, not only is perfection most difficult, but corrosion will be greater because of the removal of the dense skin f the casting and the local strains set up by the pneumatic tool in chipping. To produce a finished 9-ft. propeller for a Navy destroyer required from 8 to 21 days f foundry work and about the same length of, time for the machining. Through the use f the Thacher process, only as many hours are required, besides it is possible to produce a finished casting in perfect conformity, with any particular propeller-wheel design,

Jan 4, 1921

By Albert Zima

ACCORDING to recently published statistics, it is predicted that as much oil must be produced during the next 16 years as has been produced during the past 75, in order to satisfy the high rate of consumption of petroleum products. During 1934, over 17,000 oil wells were completed in the United States, and it is expected that over 20,000 additional wells will be drilled during the current year. Were it not for the remarkable progress made during recent years in the improvement of drilling technique and in the development of equipment used in the production phase of the oil industry, it is doubtful whether sufficient oil could be produced to meet present requirements. A few years ago, wells seldom were deeper than 3500 to 4000 ft., owing to the limitations of the drilling methods and equipment employed. Today, however, through the application of scientific drilling methods and the adaptation of modern equipment and improved materials, many wells range from 6000 to 8000 ft. in depth, and a few recent completions exceed 10,000 feet.

Jan 1, 1935

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By Ernst M. Cohn

The demonstrations of the "Silent Sentry" by Union Carbide Corp. in 1957 and of a special tractor-plow by Allis-Chalmers in 1959 ushered in the technology era of fuel cells. The idea for direct conversion of chemical to electrical energy, first published in 1801 by Davy in England and Ritter in Germany, has been kept alive by a few people through 150 years: Grove built the first hydrogen-oxygen fuel cell in 1839; Mond and Langer made electrolyte contributions around 1890 that are still used today; Baur worked on coal-based cells from 1900; Bacon started his work in the '30's, which resulted in the first multi-kilowatt unit in the '50's; Davtyan studied molten-salt electrolytes in the '40's, followed by Ketelaar in the '50's; and Justi developed highly active electrodes in the '50's, to name only some of the pioneers. Despite the tremendous increase in research and development of fuel cells, these direct energy converters are still in their infancy. They will find their functional application in space, where power density must be maximized and product water utilized. These early systems will provide valuable experience in system engineering and reliability.

Jan 9, 1964

By John Ward Smith

Dawsonite-bearing oil shale of Colorado's Green River formation offers a unique and vast (more than 5.9 Gt of A120 j) resource of easily extractable alumina. The processing methods required by the thermal reactions of dawsonite and its oil-shale carrier also require production of shale oil, soda ash, and nahcolite as marketable coproducts. These production methods are presented. The alumina production process is contrasted with the Bayer process to describe technical advantages of extraction of alumina from oil shale which may offset the problems associated with processing a relatively lean ore. While alumina production from oil shale requires development of new technology, the technical problems appear solvable. Only the political problems arising from the now onerous and completely unnecessary federal oil-shale withdrawal appear less solvable.

Jan 1, 1982

Jan 1, 1971

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By K. Takahashi, I. Iwasaki

it is well known1 that racemic mixtures of optical isomers can be separated by passing their solutions through a column packed with r- or 1-quartz powder so that one of the isomers becomes adsorbed selectively on the asymmetric quartz surfaces. Although the natural occurrence of r- and 1-quartz is more or less equally distributed, some localities show enough deviations toward a higher proportion of l-quartz2 to suggest that optical isomerism might influence quartz flotation. Beta-amines have an asymmetric carbon atom, and therefore optical activity may be expected. Beta-amines are reported to behave quite differently from alpha-amines in the flotation upgrading of certain oxidized iron ores.3 It is of interest, for both practical and theoretical reasons, to determine whether or not optical isomerism plays a role in the amine flotation of quartz. In this article the results of Hallimond tube flotation tests and of adsorption measurements using d-beta-phenylisopropylamine on both r- and 1-quartz are compared. D-beta-phenylisopropylamine was chosen for the tests because it is commercially available in optical isomers. MATERIALS AND METHODS Brazilian quartz crystals were hand-sorted according to the difference in trigonal trapezohedral faces, and each crystal was further checked by the Airy's spiral.4 The respective crystals were then crushed, and the -150 + 200-mesh fractions were screened out for the Hallimond tube tests. The samples were cleaned by brief leaching with warm, dilute hydrochloric acid, and then by repeated rinsing with distilled water. In preparation for the adsorption measurements, they were then dry-ground in a pebble mill for several hours, washed a few times with distilled water, and finally dried in a vacuum desiccator. By means of the Krypton gas adsorption method, the specific surfaces of r- and 1-quartz samples were determined to be 27,700 and 19,800 sq cm per gm respectively, the difference being due mainly to the decantation procedure rather than to the inherent difference in their grindability. D-beta-phenylisopropylamine was the only collector used in the study. It was solubilized by neutralizing with 110% of the stoichiometric requirement of 0.1 N hydrochloric acid. The specific rotation of the d-beta-phenylisopropylamine was determined with a polari-meter using sodium D line to be, Although the d-beta-phenylis~prop~lamine showed absorption maxima in the wave length region of 250 to 270 millimicrons, due presumably to the phenyl group, these peaks were too sensitive to be used for colorimetric determination of the residual concentration in the adsorption measurements. The amine-picrate method, used in the colorimetric analysis of dodecylammonium chloride,' was found to work satisfactorily for the d-beta-phenylisopropylamine. The adsorption densities were thus determined after equilibrating 40 gm of the ground quartz sample with 300 ml of solution by tumbling in separate glass-stoppered Erlenmeyer flasks for one hour. EXPERIMENTAL RESULTS Fig. 1 presents the adsorption densities of d-beta-phenylisopropylamine on the r- and 1-quarts in the pH range of 6 to 7.5. In agreement with data reported in the literature, the adsorption density of d-beta-phenylisopropylamine was slightly higher on the r-quartz than on the 1-quartz, although the difference was not as pronounced as one might expect from the capacity of r-quartz and 1-quartz to separate racemic

Jan 1, 1969