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By Edwards Wichers

The purpose of this paper is to set forth the matters of principal interest in connection with work done in the past few years on the purification of the metals of the platinum group, including the study and modification of methods already in the literature and the development of new procedures. For the most part, the results will be given in summary form, reserving the publication of detailed data and directions for a forthcorning paper to be issued by the Bureau of Standards. In recent years increasing interest has been shown in the preparation of the pure platinum metals, both by those concerned with the manufacture of the metals and their alloys for scientific and industrial purposes and those who are engaged in the study of the chemical or physical properties of the elements. The purification of the metals usually has been regarded as a matter so involved and difficult as to require the attention of specialists. It is hoped that this paper will show that any of the metals can be prepared in any desired degree of purity by relatively simple straightforward chemical methods. For the most part, it is thought that the methods given are suitable for small-scale refineries as well as for the laboratory; also, that they will bring the time required for the purification of any of the metals within reasonable limits. The new procedure suggested for purifying platinum should prove to be much shorter than any methods described in the literature. Treatment of Platinum Ore As is well known, the principal source of the platinum metals is a mixture of several native alloys of the metals, found chiefly in naturally concentrated deposits in stream beds or alluvial material. Without attempting to enumerate all of the minerals present, it may be said that the concentrated ore from such sources contains all of the six platinum

Jan 1, 1928

By J. A. Holmes

As the Appalachian mountains reach their maximum development in western North Carolina, we find also in that region indications of extensive dynamic disturbances and alterations undergone by the rocks in' connection with these mountain uplifts. Among the minor results of these changes have been the formation of numerous dikes or a veins " of exceedingly coarse granitic materials, which in some places are mined for the mica which they contain, and in other places are quarried for kaolin. These dikes are filled with quartz, feldspar, and mica, in varying proportions, very coarsely crystallized. Sometimes the mica (generally muscovite), sometimes the feldspar (generally albite or orthoclase) predominates. When the mica is present in considerable quantity, and in large crystals, the dike is usually spoken of as a mica-vein, and is often worked for mica. Sometimes these crystals of mica occur on one side or the other; sometimes on both sides; and sometimes they are largely concentrated toward the middle of the vein, or, it may be, distributed throughout the dike with a considerable degree of uniformity. In many cases the crystals of mica are too small and few to permit the working of the vein as a micamine ; in other cases, very little mica is present, and the feldspar constitutes the larger part of the material. This feldspar of the dikes undergoes, through the weathering action of the atmosphere, certain chemical changes, resulting in its alteration from feldspar into kaolinite—the kaolin of commerce. These dikes vary considerably in size, ranging from a few inches to several hundred feet in thickness, and up to many hundred yards in length. They are generally parallel to the schistosity of the crystalline rocks, which, however, in some cases, they cross at varying angles. The kaolin in those dikes which occur in the Unaka or

Jan 1, 1896

By F. F. Aplan

INTRODUCTION The production of coal is a major part of the mining industry. In recent years the production of clean coal has exceeded 600 million tons per year and is reported to have reached 660 million tons in 1977. Some data on the magnitude and utilization for the year 1975 is given in Table I. In that year 648 million tons of soft coal were produced and of this 267 million tons or 41% approximately was produced by mechanical cleaning. Of the 374 million tons of raw coal sent to the preparation plant, 28.6% or 107 million tons was discarded as refuse. In the same year approximately 6 million tons of anthracite were produced and nearly all of this was cleaned. Table I also gives coal utilization statistics for 1975. Excluding the approximately 20% that goes to the coke ovens or to export, the vast bulk of our production is used for steam power generation and a lesser amount for captive production of industrial power and process steam. While much of the nation's coal (e.g. strip mined western, sub-bituminous coal) may be removed from the ground in relatively pure form by modest selective mining techniques, other coal requires preparation in order to remove ash and sulfur constituents and produce an acceptable steam or coking coal. Preparation is often a valuable adjunct to mining in that rather non-selective, low cost, bulk mining techniques may be used underground while the preparation plant is used to reject refuse at low cost above ground. The principal reason for the use of coal preparation is to convert raw coal into an acceptable commercial product by removing the high ash and high sulfur refuse material.

Jan 1, 1979

By Roy W. Moore

The Tom Reed Extension and Big Jim mines of United Eastern Mining Co. are situated in the Oatman district, Mohave County, Ariz., about 28 miles southwest of Kingman, the nearest railway point. Articles descriptive of the mine surface plant, mill construction, and plant operations have been written by Otto Wartenweiler,' the designing engineer; Wheeler 0. North12 when he was assistant general manager for the company, and Earle M. Bagley, mill superintendent.3 The last article covers average costs for the full time the mill was operated. The geology of the mines is described by F. L. Ransome 4 of the United States Geological Survey. Production was started in January, 1917, and the known orebodies were exhausted in May, 1925, showing a life of seven years and five months. On account of the comparatively short life and the fact that stoping operations were confined to two orebodies, little experimenting was done with mining methods. The two orebodies were in what is generally called the Tom Reed-United Eastern vein, which occupies a fault fissure having a normal displacement of several hundred feet. Seven or eight very productive ore shoots were mined along this vein in a distance of 1 1/2 miles, the two worked by the United Eastern being 1 mile apart. The maximum dimensions of the Tom Reed Extension ore shoot were: height, 750 ft.; length, 950 ft.; thickness, 48 ft. The vein structure varied from a solid quartz-calcite filling to a series of parallel stringers separated by andesite. From this body, 511,976 tons of ore were mined. (Fig. 1.) The maximum dimensions of the Big Jim orebody were: height, 450 ft.; length, 850 ft., thickness, 35 ft. Its structure was similar to that of the Tom Reed Extension but larger sections of the vein were made up

Jan 1, 1928

By J. D. Miller, R. L. Atwood

The structure, properties, and composition of commercial chelating-type copper extractants are examined. Characterization of these extractants was accomplished using organic separation techniques and analytical tools such as NMR and infrared spectroscopy. Results indicate that only the trans isomer of the diphenylhydroxyoxime (LIX 64N) is capable of copper chelation. The effects of structural modification of the extractants on the extraction and stripping reactions are discussed.

Jan 1, 1974

By F. C. Blickensderfer

During 1914 and 1915, extensive experiments were conducted at the concentrator of The Detroit Copper Mining Co. of Arizona, at Morenci, Ariz., in order to test the relative grinding efficiencies of the Marathon, the Chilean and the Hardinge Mills. The Marathon mill used in the experiments was the first one ever built by the manufacturers; and since this was the first time that it was given a thorough tryout, with such remarkable results, the data have been assembled in the following paper and submitted in the interests of the milling profession. Description of the Flow Sheet The concentrator flow sheet, as it existed at the time of these tests, is shown in Fig. 1. The total mill feed, as delivered from the crushing plant, had as its maximum size 1-in. material. This material was screened dry on Cole Zig-Zag screens fitted with 4-mesh openings; the oversize going to one pair of coarse rolls, the undersize to five Wilfley tables fitted with Butchart National riffles. The coarse-roll product was elevated and screened wet on Zig-Zag screens fitted with 4-mesh openings, the undersize going to the five tables mentioned above and the oversize to one pair of fine rolls. The fine-roll product was elevated and screened together with the coarse-roll product; so that, before any concentrating operations took place, the total mill feed was reduced to pass a 4-mesh screen. After concentration on Butchart-riffled tables, the tailings from these tables passed to de-sliming hoppers, where two products were formed, viz., an overflow and a discharge. The discharge constituted the feed for the Chilean mills. It contained 16 per cent. slime (—200 mesh) and 3 parts of water to 1 of solids. The concentrator was equipped regularly with four Chilean mills (Monadnock type) to the unit; but, in order to

Jan 1, 1917

By W. M. McKewan

Magnetite pellets were reduced in flowing hydrogen at pressures up to 40 atm over a temperature range of 350° to 500°C. The rate of weight loss of oxygen per unit area of the reaction surface was found to be constant with time at each temperature and pressure. The reaction rate was found to be directly proportional to hydrogen pressure up to 1 atm and to approach a maximum rate at high pressures. The results can be explained by considering the reaction surface to be sparsely occupied by adsorbed hydrogen at low pressures and saturated at high pressures. PREVIOUS investigation1,2 have shown that the reduction of iron oxides in hydrogen is controlled at the reaction interface. Under fixed conditions of temperature, hydrogen pressure, and gas composition, the reduction rate is constant with time, per unit surface area of residual oxide, and is directly proportional to the hydrogen pressure up to one atmosphere. The reduction rate of a sphere of iron oxide can be described3 by the following equation which takes into account the changing reaction surface area: where ro and do are the initial radius and density of the sphere; t is time; R is the fractional reduction; and R, is the reduction rate constant with units mass per area per time. The quantityis actually the fractional thickness of the reduced layer in terms of fractional reduction R. It was found in a previous investigation2 of the reduction of magnetite pellets in H2-H,O-N, mixtures, that the reaction rate was directly proportional to the hydrogen partial pressure up to 1 atm at a constant ratio of water vapor to hydrogen. Water vapor poisoned the oxide surface by an oxidizing reaction and markedly slowed the reduction. The enthalpy of activation was found to be + 13,600 cal per mole. It was also found that the magnetite reduced to meta-stable wüstite before proceeding to iron metal. The following equation was derived from absolute reaction-rate theory4,8 to expfain the experimental data: where Ro is the reduction rate in mg cm-2 min-'; KO contains the conversion units; Ph2 and PH2O are the hydrogen and water vapor partial pressures in atmospheres; Ke is the equilibrium constant for the Fe,O,/FeO equilibrium; Kp is the equilibrium constant for the poisoning reaction of water vapor; L is the total number of active sites; k and h are Boltzmann's and Planck's constants; and AF is the free energy of activation. Tenenbaum zind Joseph5 studied the reduction of iron ore by hydrogen at pressures over 1 atm. They showed that increasing the hydrogen pressure materially increased the rate of reduction. This is in accordance with the work of Diepschlag,6 who found that the rate of reduction of iron ores by either carbon monoxide or hydrogen was much greater at higher pressures. He used pressures as high as 7 atm. In order to further understand the mechanism of the reduction of iron oxide by hydrogen it was decided to study the effect of increasing the hydrogen pressure on rebduction rates of magnetite pellets. EXPERIMENTAL PROCEDURE The dense magnetite pellets used in these experiments were made in the following manner. Reagent-grade ferric oxide was moistened with water and hand-rolled into spherical pellets. The pellets were heated slowly to 550°C in an atmosphere of 10 pct H2-90 pct CO, and held for 1 hr. They were then heated slowly to 1370°C in an atmosphere of 2 pct H2-98 pct CO, then cooled slowly in the same atmosphere. The sintered pellets were crystalline magnetite with an apparent density of about 4.9 gm per cm3. They were about 0.9 cm in diam. The porosity of the pellets, which was discontinuous in nature, was akrout 6 pct. The pellets were suspended from a quartz spring balance in a vertical tube furnace. The equipment is shown in Fig. 1. Essentially the furnace consists of a 12-in. OD stainless steel outer shell and a 3-in. ID inconel inner shell. The kanthal wound 22 in. long, 1 1/2, in. ID alumina reaction tube is inside the inconel inner shell. Prepurified hydrogen sweeps the reaction tube to remove the water vapor formed during the reaction. The hydrogen is static in the rest of the furnace. The sample is placed at the bottom of the furnace in a nickel wire mesh basket suspended by nickel wire from the quartz spring. The furnace is then sealed, evacuated, and refilled with argon several times to remove all traces of oxygen. It is then evacuated, filled with

Jan 1, 1962

By E. T. Turkdogan, M. L. Pearce

The rates of sulfurization and desulfurization of calcium aluminate, silicate, and ferrite melts by CO + CO2 + SO2 mixtures at 1550°C are reported. It is shown that for melts 10 to 15 mm deep transport of sulfide ions within the melt controls the rate of sulfur transfer. The rate data from shallow melts, i.e., 1 to 4 mm deep, have been analyzed on the basis of a diffusion or a reaction controlled process and indications are that the both processes may play a part in controlling the rate of sulfur reaction. The rates of desulfurization of silicate XVEACTION equilibria between metals, metal oxides, and gases have received considerable attention in recent years. However, the understanding of and aluminate melts increase with increasing PCO2/PCO ratio in the gas stream, the effect being most marked for aluminate melts. The sulfide equilibrium data obtained from the present work are shown to be in accord with the results of previous studies. It is shown that carbon dioxide has a measurable solubility in silicate, aluminate, and ferrite melts. Consideration is given to the partial equilibria which control the directions and the rates of reactions occurring simultaneously in complex heterogeneous systems. the kinetics of heterogeneous reactions, particularly those occurring at elevated temperatures has not been improved appreciably. Almost all the metallurgical reactions occur in heterogeneous systems involving two or more phases. Although in many authoritative text books and original Papers the basic principles concerning the kinetics of heterogeneous reactions are clearly underlined, they are seldom used to the best advantage in kinetic studies, particularly those involving the metallurgical reac-

Jan 1, 1963

By John Wellington Finch

In August, 1927, the writer examined certain copper deposits in New Mexico1 which occur in beds of sandstones and shale, and in connection therewith reviewed the literature upon deposits of this type. Such deposits are known and have been reported upon at various points in Texas, Oklahoma, Arizona, Colorado, Wyoming and Utah, but in New Mexico they have been given more development than elsewhere and apparently occur there more conspicuously than in the other states. Some 25 years ago the writer examined deposits of similar origin in northern Arizona and more recently other deposits in western and southwestern Colorado, and these examinations have led him to realize how widely scattered are the deposits and how generally noncommercial they are. On superficial development, to one without a comprehension of their geologic nature, they are alluring on account of occasional small amounts of high-grade ore and much misplaced capital has been expended upon them. This paper, therefore, aims to present briefly certain theories of genesis, some details of which may possibly be new, and to lead up to practical conclusions which may be useful to other geologists and engineers. A bibliography of the more important literature upon such deposits is given below.2 Coffin's Bulletin upon the Radium, Uranium and Vanadium Deposits of Colorado, published in 1921, is a particularly clear discussion. The most comprehensive recent statement is Butler's.

Jan 1, 1928

By B. A. Joyce, R. W. Bicknell, R. J. Bennett, P. J. Etter

Epitaxial layers of silicon have been grown on single-crystal quartz and alumina by two types of chemical reaction the hydrogen reduction of trichlorosilane and b) the pyrolysis of silane. These reaction systems are described. The cqsfallography of the two systems, as determined by electron and X-ray diffraction, is discussed, and epitaxial mechanisms suggested. The electrical behavior is briefly considered, and the design and properties of field-evert devices fabricated in the epilaxial material are also discussed. RECENT work carried out in these laboratories" has shown that it is possible to obtain epitaxial deposits of silicon on single-crystal quartz and alumina. The purpose of this paper is to describe the method of preparation of these layers using both the hydrogen reduction of trichlorosilane and the pyroly-sis of silane, to compare the crystallographic behavior of films on the two substrates, and to present some initial results of the electrical behavior of silicon layers on alumina. The structural study has been carried out using electron and X-ray diffraction and electron microscopy. The electrical assessment has been made in terms of conductivity and mobility determinations by the van der pauw3 technique, and by measurements on metal-oxide-semiconductor assemblies. 1) FILM PREPARATION Both quartz and alumina substrates, approximately 1 sq cm in area and 0.4 mm thick. were prepared from slices cut parallel to within a few degrees of (11.0), (10.0), and (00.1), and polished mechanically down to about 0.3 p diamond grade. Chemical polishing of alumina slices, using phosphoric acid at elevated temperatures, has also been used; epitaxial silicon layers have been grown on these substrates, but the process is not entirely reliable, possibly because the large strain present in the Verneuil-grown alumina crystal affects the chemically prepared surface. The two reaction systems are fairly conventional and are described briefly below. a) Trichlorosilane-Hydrogen System. The apparatus is shown schematically in Fig. 1. The substrate was heated by induction, with a fused-quartz encapsulated graphite hemicylinder as susceptor. The procedure for carrying out a deposition was to heat the substrate to reaction temperature in a stream of

Jan 1, 1965

By R. A. Davidson, L. Silverman

RESIDENTS of many urban centers are becoming increasingly aware of the obscuring effect of fume and smoke discharge from power, metallurgical, chemical, and other industries; and they, as well as the legislatures of these affected cities, are agitating for cleaner air. Management's most pressing problem is to find an economical way to reduce process effluents in response to the growing pressure from population and legislative demands. The removal must be done, if possible, without handicap to the current operation, since the costs of relocating are often excessive or prohibitive. In fume recovery or disposal, an important item to consider is whether or not the material being discharged has any value. If it has commercial value, the cost of its recovery may offset or aid amortization. For this reason, in making a study of the specific problem in hand, a major factor was the nature of the material emanating from the stack: in particular, its particle size, size range, and its chemical and physical composition, as well as its potential value and utility when recovered (in either a wet or dry state). Should the product have no commercial value, it must be disposed of at minimum cost in a way to prevent recontamination. Initial studies were therefore made to determine stack concentrations and volumes of material evolved from the operations. The next phase of the study concerned the physical and chemical nature of the collected fume. The third portion of this paper describes the wet and dry collector studies undertaken to recover the fume. Cleaning Requirements for Ferroalloy Furnace Operation The basic need for any effluent collection equipment is the highest possible efficiency and the lowest tolerable resistance when the power consumption involved is considered. Since the electric furnace effluent is largely composed of fume of small size (less than 0.5u), it has high light obscuring properties, and even low concentrations will cause some loss of visibility and be evident to nearby residents. The permissible limit for fly ash emission in many cities is based on a weight value (viz, approximately 0.4 grains per cu ft), but the smoke density values are dependent upon a shade of color. In the case of the Los Angeles County code, emission is restricted to pounds per pound of material processed per hour basis (but not exceeding 40 lb per hr for any one given plant operation). If an average particle size of the fume from ferro-silicon alloy electric furnaces is assumed to be 0.4u (as shown later, this is the approximate mean size) and an average loading of 1 grain per cu ft (stp), each cubic foot of stack gas will contain approximately 75x10 10 particles (based on assumed, and confirmed, spherical shape and a standard deviation of unity). When it is realized that the air in metropolitan areas, which are also general industrial areas, contains approximately 5x108 particles, the tremendous light scattering effect of this concentration becomes apparent. Consequently, nearly 100 pct collection would be necessary to equal the average concentration. Fortunately, however, discharge from a high point above ground (50 to 100 ft) will result in at least a thousandfold dilution, or the stack concentration reaching the ground in the foregoing case might result in a ground concentration of ' particles. If the concentration at the source could be reduced by a factor of 100 (99 pct efficiency of collection), then a concentration of 75x10" particles would be diluted to 7.5x10' which would be very satisfactory. An efficiency of 90 pct (factor of 10 decontamination) at the source would result in a discharge of 75x109 articles which upon dilution yields 75x10 which is still 15 times the general air value. Another approach to this consideration is to use the value of concentration of 0.005 grains per cu ft for the value of a visible effluent as cited by Kayse.1 To attain this value with an average loading of 1 grain per cu ft would require an efficiency of 99.5 pct. Since the foregoing value is not based on any reported size of fume particles, it is felt that the numbers' approach given previously is more reliable. These calculations serve to indicate the desirability of thorough cleaning, preferably at the source, and with efficiencies well above 90 pct, preferably above 95 pct (dilution 1:20). One of the most important items in any control program is to reduce the concentrations as close to their sources as possible. The use of better furnace design, deeper coverage over the electrodes, and the prevention of blows or breaks in the surface all help to reduce dissemination; consequently, all of these improvements should be made, if possible, to cut down the effluent load. In addition, in order to minimize the volume of contaminated air that has to be cleaned, the furnace should be enclosed as much as possible. Test Arrangements Before fundamental studies with collectors were made, a furnace stack selected for the test program was sampled to determine the gas temperatures and

Jan 1, 1956

By Jay Carpenter

THIS paper deals with only one step in the treatment of ore at the West End mill; not because the other steps are repetitions of practice in other mills, but because in this particular step there is in use the Trent agitator. This device, although it has apparently failed in many mills, is here giving excellent service and has proved to be well adapted for making a thorough replacement of pregnant solution with a minimum amount of barren solution. The strong and weak points of this agitator, its present simple construction, and its use as a thickener for agitator or battery pulp are features of interest; but perhaps the point of greatest interest to the metallurgist in this day of continuous decantation is its use in a series of tanks for slime treatment by the replacement method. The agitating department of the West End mill consists of six redwood tanks, 24 ft. in diameter, 18 ft. high, each equipped with aTrent agitator, a centrifugal pump, and a motor. The pulp is transferred by a pump from the top of a flat-bottomed tank to a set of arms and nozzles in the bottom of the tank, at just sufficient pressure to cause the arms to revolve. The streams from the many nozzles keep the bottom of the tank clean, and these streams, coupled with the effect of the revolving mechanism and the ascending current, keep the pulp in constant motion and of constant gravity. .These agitating tanks hold 90 tons of dry slime and 202 tons of solution with a 1.24 pulp, our ore having a specific gravity of 2.7. This capacity is about 10 per cent. in excess of the standard 15 by 45 ft. Pachuca tank. The tanks are connected in one series for continuous agitation, the pulp for each agitator being drawn by its pump through a branch suction from near the top of the preceding tank and. delivered to the bottom of the tank by the agitator arms along with the regular pulp of that agitator. This method works automatically, since the flow through the branch suction varies directly with the difference in head of the two tanks. The chance for new pulp to pass out quickly is, therefore, much less than in many other systems of continuous agitation, since the new

Jan 8, 1915

By Thomas M. Drown

In experimenting in connection with Mr. P. W. Shimer (now chemist of the Thomas Iron Company, Hokendauqua, Pa.) on methods for the determination of silicon in pig iron, in order to find one which should be accurate and yet give results in a few hours, I have adopted the following procedure, which, as far as my experience goes, leaves nothing to be desired. About one gram of pig iron or steel is treated in a platinum or porcelain dish with 25 cubic centimeters of nitric acid (sp. gr. 1, 2). When action has ceased, 25 to 30 cubic centimeters of dilute sulphuric acid (one of acid and three of water) are added, and heat applied until the nitric acid is nearly or quite driven off. The heat of a water-bath is sufficient, though the process may be hastened by heating higher on a sand-bath. Water is then cautiously added (as soon as the free sulphuric acid is sufficiently cool) and the contents of the dish heated until the crystals of ferric sulphate are completely dissolved. The solution is then filtered as hot as possible, the residue washed first with hot water, then with 25 to 30 cubic centimeters of hydrochloric acid (sp. gr. 1, 12), and finally with hot water. After drying and igniting, the silica will be found to be snow-white and granular. The following are some results obtained by this method compared

Jan 1, 1879

By Alan U. Seybolt

IN examination of some cold-rolled copper and cupronickel that contained a little columbium, it was discovered that these alloys were unusually resistant to annealing. This effect was sufficiently pronounced to warrant some investigation [ ] of the annealing characteristics of such compositions. EXPERIMENTAL PROCEDURE The alloys were made from cathode copper, electrolytic nickel, and a special copper-columbium hardener alloy furnished by the Electro Metallurgical Corporation. This hardener alloy contained 10 per cent columbium, with tantalum, aluminum and iron as major impurities. The melting was carried out in a clay-graphite crucible in a high-frequency induction furnace, under a charcoal or [ ] electrode carbon cover. No deoxidizing additions were made. The 7-lb. copper heats were poured into a steel mold, hot-rolled to ¼ -in. thickness, and annealed for ½ hr. at 760°C.; the cupronickels were annealed I hr. at 815°C. The material was then cold-rolled to a go per cent reduction in thickness and annealing tests were carried out on this 1/8-in. hard-rolled strip. A little silver was added to copper-columbium alloys 402 and 403 to find out

Jan 1, 1941

By K. H. Ribe

Water often enters an oil reservoir during completion or workover operations on a well and forms a partial "water block" to oil production. A mathematical study of radial two-phase flow, neglecting capillary effects, has been employed to study the formation of such a water block and subsequent re-moval by production from the well. The effects of reduced oil permeability about the well on the well productivity were studied. The fluid saturation distributions about the well during formation and removal of the water block have also been computed. Several relative permeability relations and viscosity ratios were employed. If water has invaded the formation, its influence through relative permeability effects alone can cause the following. 1. Oil productivity will be depressed for extended periods after production is resumed and will build up only gradually as the water is removed. 2. Oil injected for treatment of water blocking will delay rather than promote restoration of full well productivity by enlarging the region invaded by water. Thus, unless the specific action of chemicals contained in the oil is needed, oil injection appears undesirable. INTRODUCTION During oilwell workover operations, water may enter the oil-bearing formation from the wellbore. When production is resumed, oil must flow through the region invaded by this water. The presence of this region can cause both well productivity and oil production rate to be low and oil to be produced with high water-oil ratio for some time after production is initiated. This situation is sometimes described as a water block. The introduction of water into the formation may result in other actions which also lead to reduction in well productivity and which are also usually included in the connotation of the broad term, water block. Often considered, for example, are the possibilities of clay swelling by contact with fresh water and the formation of emulsions with the formation oil. If it is suspected that such specific actions have taken place, remedial treatments are undertaken which usually involve the injection of chemicals in oil. Since the introduction of water, even in the absence of specific interactions with the formation or oil, will cause a temporary water block (which might be misinterpreted as evidence of a more severe situation), it is of importance to evaluate the magnitude and duration of this blocking which results purely from the reduction in relative permeability to oil in the vicinity of the wellbore. It is also of interest to evaluate the effect of oil injection on the productivity of a well blocked by water in this manner. Inasmuch as this unfavorable condition may persist for some time, it may lead to premature condemnation of a workover or premature abandonment of a potentially productive pay zone. A quantitative evaluation of the influence of water entry on the oil productivity through changes in relative permeability was made by solving a radial form of the Buckley-Leverett equation. The distribution of water saturation around the wellbore during the entry of water was calculated and was followed by a similar calculation of the saturation distribution during the period of resuming production. At any stage in the removal of the invading water, knowledge of the distribution of its saturation permitted calculating the attendant loss in oil productivity. The influence of the shape of the relative permeability relationships was also evaluated by carrying out the calculations for two hypothetical cases. Further, the effect of the oil-water viscosity ratio was examined by repeating the calculations, for several ratios of unity and greater, with the same relative permeabilities. Fi-nally, results are presented to show how the length of time a well must be swabbed to resume production depends on the length of time it has been subjected to invasion by water. STATEMENT OF THEORY Differential Equations Water is assumed to enter a producing formation which is initially at the connate-water saturation and contains no gas. The water and oil are treated as in-

By W. O. Hotchkiss

IN CONSIDERING the question of mining methods the possible rate of production deserves much more attention than it often receives. Hoover's theorem that, in order to show the greatest profit, an orebody should be worked out in the shortest practicable time, should be better known. The author recently' obtained detailed statements of costs from iron-mine superintendents of the Lake Superior district. In discussing these, the effect of rate of mining on cost of production was considered and detailed estimates were made. The methods by which these estimates were made and the way in which they were presented are here described to illustrate the importance of this factor in mining operations. The saving due to lower costs is not the only factor that should be considered. The greater profit per ton is of much importance but of equal importance are the greater profit per ton that will be made on a greater number of tons per year, and the fact that the total profit will be received in a shorter; period. This last makes a great difference in the present value of a property, by shortening the period of discount on future profits. Another item of importance to those operating a number of mines is that the tonnage needed to supply the market can be obtained most profitably by operating the smallest number of mines that will supply the amount required when each is worked to maximum capacity. In the Lake Superior iron district there are many grades of ore, and the requirements for each are known. If the demand for a certain grade can be supplied from mines now operating, the development and mining of a new orebody of the same grade must result in lower rates of production and lower profits to all mines producing this grade. If a company is mining the same grade of ore from three mines when it can supply its needs by operating only two, by operating only two it can obtain the greatest profit. Royalty rates, lease terms, and other considerations modify this general statement, but if all three properties

Jan 5, 1922

By R. P. Agarwala, M. S. Anand, S. P. Murarka

Using the residual radioactivity technique, grain boundary diffusion of chromium in the a phase and lattice diffusion in the a and the ß phases of zirconiuttz have heen studied. The diffusivities (in units of square centiwzeters per second) have heen expressed as THE rate of diffusion of atoms along surfaces and grain boundaries is much greater than that through the bulk of metals. These processes dominate over volume diffusion at lower temperatures and can be isolated from it by virtue of the fact they yield high diffusion coefficients and low activation energies. In zirconium, however, it has been difficult to identify the volume-diffusion parameters separately. The values of diffusivities in a and ß phases yield activation energies which are much lower than those for volume diffusion calculated from semiempirical or empirical relations.1-3 Diffusion frequencies (Do) are also low, especially in the a phase, and they yield negative entropies of activation.4 Similar results have been obtained for the diffusion studies in titanium.5 It is yet to be investigated whether in these cases diffusion is controlled by some extraneous factor like high reactivity of these metals, or some different mechanism is operative as suggested by Pound et a1.6 However, Federer and Lundy,7 in a recent study of the diffusion of zir-conium-95 and columbium-95 in zirconium, and Gibbs et al.,8 in the study of impurity diffusion in titanium, found a temperature dependence of D, Do, and Q. Their study yielded low values of Do and Q at low temperatures, as has been found by other workers, and fairly high values at high tempera-

Jan 1, 1965

By L. P. Teas

Although 1927 in the Arkansas-Louisiana territory will probably pass into history as a year of small profits and little new production, nevcrtheless during this period two large gas fields were developed; two new oil fields were discovered, and two new oil horizons, hitherto of minor annual production Fig. 1.—Production of North louisiana and ARkansas by fields, for 1926 and 1927. (Upper blocks represent 1926 production; lower blocks, 1927 production ) importance, were developed. In spite of the "hard times" some of the leading supply houses did more business this year in this district than in any year since 1920.

Jan 1, 1928

THE CHAIRMAN (A. F. LUCAS, Washington, D. C.).-The activities of the Petroleum and Gas Committee for the half year have brought gratifying results, as exemplified by 14 technical papers, brim full of novel and attractive issues in which we are all keenly interested. I beg to extend my hearty thanks to all members and authors who have responded to my appeal, and to all those who have endeavored to meet the growing demand which has resulted in the augmented production of this commodity which is so essential for the Nation's welfare, comfort and safety. As you well know, within the last few years, petroleum and its products have been used for numerous and novel purposes, so that we have become accustomed to their use in thousands of activities, and pleasures as well, but we should also note that we have been wasting and misusing these wonderful products, apparently believing that their sources are inexhaustible.

Jan 1, 1918

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman' and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965