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By Ronald J. McGregor, Anton R. Hendriksz

INTRODUCTION The NIMCIX contactor was developed in the late sixties at the National Institute for Metallurgy in South Africa, for the main purpose of extracting uraniuy from relatively low-grade uranium solutions. ' The concept was sufficiently developed by 1974 to permit the operation of a 1500 litre per minute column to treat unclarified urgnium-bearing solution under industrial conditions. The plant operated so successfully that several large-scale units have subsequent18 teen constructed and are operating efficiently. ' Total resin consumption figures as210w as 3 per cent per annum have been reported, and the extraction efficiencies of the installations have been exceptionally good. All the solutions treated have been acidic in nature and in every case have been of such a nature as to significantly depress the maximum uranium loading on the resin beads. The chemical constituents of the leach solution fed to the loading column determines the ease with which the soluble uranium can be absorbed by an ion exchange resin. The concentration of competing ions and various resin foulants define the nature of the continuous ion exchange equipment required for efficient extraction performance. The basic NIMCIX concept is retained in these various alternate designs, but batch or continuous elution methods with fully automated or manual control systems may be selected for the different process solution conditions. BRIEF DESCRIPTION OF THE NIMCIX CONTACTOR The NIMCIX ion exchange column is a multi-stage fluidized bed contactor which is designed to permit a counter-current flow of solution and resin in order to maximize extraction efficiency. The flow o resin is periodic, based on the Cloete and Streat 5 principle of reverse flow. The basic operating cycle can be divided into five periods, as illustrated in Figure 1. For the purposes of describing the cycle, the loading column is considered; how- ever, a similar sequence may be applied to the operation of a NIMCIX continuous elution column. S'I'EP 1: During the forward flow period, Solution flows up through the column and fluidizes the resin contained in each stage. The uranium depleted solution overflows the upper flared-section of the column as the tail solution. Step 2: The flow of solution to the column is temporarily stopped and the resin is allowed to Settle onto the plates in the column. STEP 3: During the reverse flow period, a fixed volume of solution is drained from the column to the transfer vessel. This flow causes resin transfer to occur from stage to stage and also out of the bottom stage. At the end of this period, which expires when the low level switch (LS) is actuated, some of the resin is left in the conical section of the column and the pipe interconnecting the column and the vessel. STEP 4: The cone flush period ensures that all the resin left in the cone of the column and the pipe is transferred to the transfer vessel before forward flow commences. STEP 5: The loaded resin in the transfer vessel, which has been isolated from the column, can either be hydraulically transferred to the top of the elution column or eluted in the vessel before being transferred to the top of the loading column. The major advantages associated with the NIMCIX concept are: (i) Simple method of operation (ii) Contactor can readily be scaled up to large diameters. (iii) Because the resin does not pass through pumps or airlifts, and valves cannot be closed on resin beads at any time, the resin losses are exceptionally low. (iv) Operating costs are low. (v) Relatively few valves in the system. (vi) Stable operation is achieved over a wide range of feed rates and concentrations.

Jan 1, 1980

By D. M. Davidson, P. F. Kerr

The Permian Cutler Formation in Kane Creek, Utah bears uranium ore in fissure-type vertical veins. This fissure vein formation and its associated host rock bleaching, weak argillic alteration, and base-metal sulfide mineralization along with the development of hydrothermal minerals, a 60 m.y. isotopic Pb/U age, and well-crystallized uraninite's structural control, give evidence of ore deposition in a hydrothermal environment consistent with Laramide mineralization. Mica polymorph studies indicate first, that temperature during the hydrothermal alteration or subsequent ore deposition did not exceed 200°; hence Cutler deposits are classified telethermal; and secondly, that rock alteration and ore deposition are closely related both in time and space, as is seen in argillic alteration sequence. Ore deposition in an alkaline to slightly acid reducing environment is postulated. Ore textures and mineral associations and distributions also indicate that carbonate complexes may have been transported with the deposing ores. Bleached rock formations are not primary strati-graphic phenomena. Bleaching, or changes in ferric iron content, results from a chemical process involving reduction and conversion of hematite to a soluble aqueous ion. Nearby Chinle bedded deposits (Moss Rack sandstone), containing shale lenses, fossil wood, organic debris and minor fractures, overly the Cutler formation. Chinle ores have a single reported isotopic age of approximately 200 m.y. Their chemical environment is assumed similar to that of the Cutler ores, though slightly more acidic. Two genetic, paradoxically divergent interpretations of the bedded deposits are derived from available spectrographic, petrographic, X-ray and chemical analyses. Kane Springs canyon is located southwest of Moab, Utah, south of the Colorado River and northwest of the Lisbon Valley mining district (Fig. 1). Uranium deposits occur along the northeast flank of a Kane Creek salt anticline where two geologic formations bear ore, the Permian Cutler and the Triassic Chinle. The Cutler deposits' fissure vein formation is an unusual occurrence in the Colorado Plateau. The Chinle deposits appear to be of the normal sedimentary type. Associated with the vein deposits are a number of features, including argillic alteration of sedimentary strata. The minerals of these deposits and their associated features have been studied in detail in a two year program entailing both field and laboratory techniques. STRATIGRAPHY A stratigraphic section of the lithologic units in the Kane Creek area is given in Table I.

Jan 1, 1967

By L. H. DeWald

During the examination of various commercial brands of copper wire bars, which had exhibited different degrees of adaptability for being drawn into fine gages of wire by the present-day high speed machine, it was found that each brand had a more or less characteristic crystal macrostructure. The extremes of these macrostructures are similar FIG. 1.-EFFECT OF METAL TEMPERATURE IN CASTING ON CRYSTAL MACROSTRUCTURE OF BAR. Reading from left to right, metal temperatures were 1166" C., 1149" C., 1132" C.. 1121" C., 1093" C. to the maximum variation shown in the photomacrographs reproduced in Fig. 1. As the various brands did not differ materially in chemical composition, it was concluded that the differences in structure were the result of variations in casting technique.

Jan 1, 1931

By H. H. Wade, N. F. Schulz

The large quantities of iron-bearing materials, including taconite, semi-taconite,* and other low-grade ferruginous materials occurring in Minnesota and elsewhere, constitute an important potential source of iron. Satisfactory grade and recovery of iron ore concentrate cannot ordinarily be obtained from these ferruginous materials by simple methods of beneficiation. Iron is distinctive in that the free metal and two of its oxides [magnetite (Fe2O3) and maghemite (gamma-Fe2O3) ] are strongly ferromagnetic. The successful magnetic separation of natural magnetite from taconite has already been established on a commercial scale. The iron in semi-taconite, however, occurs largely as goethite (Fe2O3-H4O) and hematite (Fe2O3) which do not respond to ordinary magnetic separation methods. Magnetic roasting converts these iron oxides to magnetite, which can, after liberation, be magnetically concentrated. MAGNETIC ROASTING Hematite undergoes a stepwise reduction when exposed at moderately elevated temperatures to a reducing atmosphere containing hydrogen or carbon monoxide: Fe2O3? Fe3O4 ? FeO ? Fe Since the desirable product in magnetic roasting is Fe3O4, the conversion is halted after the first stage by controlling the reduction potential of the gas mixture with water vapor or carbon dioxide. The reducing gas mixture must be such that the oxygen partial pressure at the solid-gas reaction interface will be maintained intermediately between the oxygen partial pressures in equilibrium with Fe2O3 and Fe3O4 at the prevailing temperature. Because of the rapid increase in decomposition pressure of Fe3O4 with increase in temperature, the practical upper limit of useful reaction temperature is about 1400°F, above which over-reduction usually occurs in atmospheres containing hydrogen or carbon monoxide. On the other hand, useful reaction rates usually occur only above 800°F. Goethite reacts similarly except that the combined water probably has to be driven off thermally before the reduction to magnetite occurs. Iron carbonate must also be decomposed thermally to an oxide before conversion to magnetite. Iron silicates are apparently not amenable to magnetic roasting. The rate of penetration of the reaction toward the interior of a given ore fragment is dependent on the chemical composition and physical structure of the solid. Most ore fragments tested here reduced satisfactorily to 1/4-in. depth in less than 14 min at 1200°F. Some very dense fragments, however, were reduced to less than 1/32-in. depth under the same conditions. Determination of the optimum temperature, gas composition, ore fragment size, or time of exposure

Jan 1, 1961

By J. E. Lawver, B. J. Clingan, R. E. Snow

Response surface methodology is a well-known and powerful technique for determining optimum conditions in flotation systems. One disadvantage is the onerous task of the numerical calculations and curve plotting. This paper describes a system in which the investigator simply selects the range of several flotation variables after which the design of the experiment, data analysis, generation of response surface equations, and response surface plots are automatically carried out using a digital computer and a computer-driven curve plotter. Several typical response surfaces of important variables in phosphate flotation are presented as examples.

Jan 1, 1980

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 V. O. Struebing, K. A. Johnson, F. H. Ellinger, C. C. Land

The system Pu-Ce-(Pu,Ce)Co2 has been investigated by thermal, micrographic, and X-ray diffraction methods. The principal characteristics of this system were found to be: 1) a "eutectic" valley extending across the phase diagram from the 6 Pu/Pu3 Co eutectic at 408°C to the 7 Ce/Ce24Co11 eutectic at 42Z°C, the maximum temperature in the valley being 443°C; 2) three ternary inter mediate phases, each having an appreciable mutual solid solubility for plutonium and cerium; 3) eleven four-phase equilibria comprising one eutectic, four peritectics, and six Class II reactions; 4) a pseudobinary section between the ternary phase A and the y Ce solid solution, and another such section between the 6 Pu solid solution and the 77 phase (Pu3 CO) containing cerium in solid solution. ALLOYS of plutonium that are completely molten at temperatures in the vicinity of 500°C are of interest for use in the liquid state as fast reactor fuels. Since exploratory work1,2 on Pu-Ce-Co alloys had indicated that a "eutectic" valley extended across the ternary system between the Pu-co[6 Pu/n (Pu3co)] and the Ce-CO[? Ce/? (ce24co11)] binary eutectics, thus allowing alloys of any plutonium concentration to be selected within the temperature limitation, the present investigation was begun for the purpose of accurately defining the "eutectic" valley. However, when the existence of three ternary intermediate phases and the consequent complexity of the liquid-solid equilibria were discovered, the investigation was expanded to cover the complete system, except for the corner between the isomorphous series PuCo2-CeCo2 and pure cobalt. 1) EXPERIMENTAL The purities of the alloy components are given in Table I. Alloy buttons, each weighing about 5 g, were prepared by arc melting the accurately weighed components (±0.1 mg) under a purified He-Ar atmosphere. Weight loss as a result of melting was usually less than 1 part in 1000; therefore, the buttons were not chemically analyzed. One half of each button was re-melted by induction heating in vacuo in a magnesia crucible and furnace-cooled, so as to produce a somewhat coarser microstructure than that of the rapidly cooled arc-melted button. About 20 g of each alloy to be examined by thermal analysis were remelted in vacuo in a tantalum crucible of the inverted thermocouple well type. The thermal, X-ray diffraction, heat treating, and micrographic methods used in this investigation were essentially the same as have been described in earlier reports.3,4 Two etchants for these alloys were found to be satisfactory: A) 8 (parts by volume) orthophosphoric acid, 5 ethanol, and 5 glycol; B) 7 tetraphosphoric acid, 36 water, and 57 2-ethoxyethanol. Etchant A was used at 5 to 6 v for 15 to 20 sec, and etchant B was used at 10 v for 10 sec. 2) THE LIMITING BINARY SYSTEMS 2.1) Plutonium-Cerium. The phase relationships of this system have been investigated by Ellinger, Land, and Cramer,5 and by Selle and Etter.6 The over-all agreement of their phase diagrams is good, but there are some discrepancies in the positions of some phase

Jan 1, 1967

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.'-' The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By R. P. Carreker

ONE of a series, this report is concerned with the experimental documentation of the deformation behavior of pure metals over a wide range of temperature. Previous reports in the series describe the creep behavior of platinum1 and aluminum2 and the tensile behavior of copper,&apos; silver,& and molybdenum.5 Subsequent reports will describe the creep behavior of copper and silver and the tensile behavior of platinum, thus providing extensive creep and tensile data on four face-centered-cubic metals tested under comparable conditions. Material Two lots of high-purity aluminum were used in this investigation. One lot, designated AC, was obtained direct from the Aluminum Co. of America as high-purity aluminum in notch-bar form. A typical analysis of this type of aluminum is 0.006 pct Si, 0.015 pct Cu, 0.006 pct Fe, and 99.975 pct Al. Lot BS was obtained from J. I. Hoffman of the Bureau of Standards as a portion of the Aluminum A described in his report of the redetermination of the atomic weight of aluminum.6 Lot BS originated with the Aluminum Co. of America also, and was received in the standard notch-bar form. A detailed chemical and spectroscopic analysis of lot BS has been published.6 Principa1 impurities were 0.006 pct Si, 0.003 pct Fe, 0.002 pct Cu, and >99.987 pct Al. Samples were processed identically by room-temperature swaging and drawing to 0.030 in. diam wires from approximately ½ in. diam rods that were machined from the notch-bar pigs. Samples were cut from the cold-drawn wire, placed in a grooved graphite block in groups of thirteen, and annealed in air for 1 hr at each of several temperatures, with the results shown in Table I. The two lots of aluminum responded quite differently to annealing, the behavior of aluminum AC suggesting that its grain growth was controlled by impurities. The recrystallization texture of aluminum of similar purity comparably treated has been reported as predominantly <111> fiber with some <100> fiber present.7 Testing Procedure The testing procedure and method of analyzing the data have been described previously.2,3 Annealed specimens of 5 in. gage length were tested in an Instron tensile testing machine at a constant head motion corresponding to a strain rate of 0.04 min-&apos; at a number of temperatures. Instantaneous tenfold rate changes were employed in some tests to deter-

Jan 1, 1958

By K. P. Anderko

INVESTIGATIONS of the constitution of the system Mg-Ba were first made by Grube and Dietrich1 between 0 and 47 atomic pct Ba and then by Klemm and Dincke1acker" ver the whole composition range. Klemm and Dinckelacker corroborated intermediate phases of the approximate formulas Mg9Ba and Mg4Ba, and showed a third compound to have the formula Mg2Ba, rather than Mg5Ba, as suggested by Grube and Dietrich. Mg2Ba had been previously recognized by Hellner and Laves3 s a MgZn2 (C14) type structure. The main discrepancies between the results of Grube and Dietrich and those of Klemm and Dinckelacker exist, however, in the liquidus temperatures and solidification equilibria of alloys containing more than about 10 atomic pct Ba. The liquidus temperatures measured by Grube and Dietrich, and the outline of the liquidus of Klemm and Dinckelacker are plotted in Fig. 1 on an enlarged scale. Although there are strong reasons to prefer the results of Klemm and Dinckelacker, it was considered worthwhile to remeasure liquidus temperatures of some alloys in the controversial composition range. The alloys, made up from sublimed magnesium and 99.5 wt pct pure barium, were melted in an Armco-iron crucible in a dynamic argon atmosphere. Thermal analyses were taken using a Speedomax auto- matic recorder. Careful stirring during the solidification process was required in order to avoid segregation. After thermal analysis some of the cast alloys were chemically analyzed. The intended and analyzed compositions of the ten alloys prepared are listed in Table I. Since standard barium determinations cannot differentiate between barium present as element and as oxide, both the barium and magnesium contents of the alloys were analyzed. The fact that the sum of barium and magnesium was close to 100 pct in each case was taken as evidence that no excessive oxidation had occurred. The liquidus temperatures measured are listed in Table I and plotted in Fig. 1. As can be seen, they are in good agreement with the liquidus found by Klemm and Dinckelacker. This leaves no doubt that the thermal results of Grube and Dietrich above 10 atomic pct Ba are incorrect. This work was performed under the sponsorship of the Pitman-Dunn Laboratories of Frankford Arsenal, Philadelphia, Contract No. DA-11-022-ORD-1975. Sponsorship and permission to publish by this organization are gratefully acknowledged.

Jan 1, 1958

By John T. Norton

N order to attempt to arrive at a better under-Jl standing of the whole basic problem of sintering, these remarks will serve as an introduction for discussion that is included and will, perhaps, help to isolate specific questions which need to be answered or to suggest some definite avenues of investigation which should be followed. To bring some sort of logical order into the presentation, I will consider the various types of interaction between the metal to be sintered and the atmosphere which surrounds it, depending upon whether the phenomena are essentially chemical or physical in nature. For example, when the only necessary criterion for the satisfactory sintering of a certain powder is the removal of an oxide skin, then the problem of choosing a suitable atmosphere is primarily chemical; however, if a special surface condition as a consequence of the oxide skin removal is necessary for particularly effective sintering, then the problem becomes a physical one. Of course, the two aspects overlap considerably, but it may be possible to make a distinction in principle if not in practice. The chemical characteristics of the phenomena will be emphasized, since these are the better known. Metal-gas reactions involved in sintering are controlled primarily by the thermodynamics of the processes involved. In which direction will a reaction go and how far before it stops? The answer is to be found in the magnitude of the free energy change associated with the reaction. If a constituent is to be removed from the specimen as completely as possible or if a constituent is to be formed in the specimen as completely as possible, then one chooses conditions which are far from equilibrium so that the reaction is driven toward completion. On the other hand, if the composition is to be maintained at a desired value, then conditions are adjusted as closely as possible to the equilibrium point. This aspect of the problem is susceptible to quite precise analysis, provided, of course, that the significant reactions can be recognized and the required thermodynamic data are available. Conversely, if one asks how fast the reaction goes or how far it proceeds in a given time, the answer is frequently much more difficult to answer in quantitative terms. Yet the rate-con trolling factors of the reactions may be of primary importance in the success of a particular operation, especially where competing processes are at work. Both equilibrium and rate factors must be understood if a clear picture is to be obtained. For instance, in a process for carburizing titanium dioxide, is the difficulty of obtaining a stoichiometric Tic due to a true limitation of the equilibrium or simply to a very slow rate of reaction? An example of this appears in the work of Kalish and Mazza.&apos; They showed that the oxygen content of sintered iron compacts was lower when sintered in pure hydrogen than in the case where the hydrogen was diluted with either argon or nitrogen. The equilibrium oxygen content of the iron would be the same in the two cases, since it is determined by the ratio of the partial pressures of water vapor and hydrogen and this pressure ratio is unchanged by dilution. The rate of oxygen removal, however, under the conditions of a constantly replaced furnace atmosphere, depends upon diffusion and thus upon the concentration of hydrogen in the furnace atmosphere. Possibly the clearest way to illustrate the interplay of these two factors is to consider in more detail some of the typical metal-gas reactions. Adsorbed Gases It is common experience that fine metal powders with their very large surface areas often contain large quantities of gas. This gas, which results from exposure to air or perhaps from some step in the

Jan 1, 1957

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.&apos; Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.&apos; The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By Charles Wurms, Robert Steinitz

DURING an investigation to determine the compatibility of several metals with tungsten, the degree of reaction between tungsten and lead was determined. A literature survey showed considerable disagreement between the results of various earlier investigators. Information presented by M. Hansen1 states that, according to S. Inouye,2 tungsten has very poor resistance against attack by molten lead, even at the low temperature near the melting point of lead. A phase diagram in the same reference indicates a solubility of 30 wt pct W in molten lead at 1300°C. Contrary evidence was shown by Parkman and shepard3 in their investigation of materials for use in heat transfer systems containing liquid lead alloys; they performed experiments at 980°C for times up to 50 hr without noticing any appreciable attack on the tungsten. Tungsten sheet was immersed in molten lead contained in Vycor tubes evacuated to at least 10-4 mm Hg. R. Bernard4 and R. I. Jaffee5 also indicate that no reaction occurs between molten lead and tungsten. However, no experimental data were included in these reports. In order to settle the question of the solubility of tungsten in molten lead, tungsten powder with an average Fisher subsieve particle size of 6µ was pressed in a double-acting die at 6 tsi to small compacts. They were then sintered in an atmosphere of hydrogen for 2 hr at 1700°C, resulting in a sintered density of 64 pct of theoretical with final dimensions of 0.260 in. in height and 0.245 in. in diameter. For all tests, the tungsten pellets were immersed in molten lead. Table I is a summary of the experimental procedures showing atmospheres, temperatures, and times. The first experiments were performed at 650°C; at this temperature, the liquid lead should wet the porous tungsten better than at its melting point, and penetrate into the pores. The lead was heated in a graphite crucible with a graphite cover. No protective atmosphere was used, as it was expected that the formation of CO would be sufficient to prevent oxidation. This, however, proved to be wrong, and all tungsten samples showed a slight oxide film after treatment. The tungsten samples were immersed in the molten lead for times of 5 min, 10 min, 1/2 hr, 1 hr, and 2 hr. After this time, the melt was poured into a form and the

Jan 1, 1962

By H. F. Winham

THE history, development, subsurface geology, production, economics and estimated reserves are discussed in this paper. The Magnolia structure is an anticline with a known maximum structural relief at 372 ft., and the areal extent of the producing acreage is 4494 acres. Production is obtained from the Smackover oölitic lime and 116 successful wells have been drilled. The field, which was developed on 4o-acre spacing, has been under strict control. It is believed to be producing with a strong water drive. To date it has produced more than eighteen million barrels and the estimate of ultimate recovery is 220 million barrels. EARLY HISTORY The Magnolia field is in Columbia County, Arkansas, T. 17 S., R. 19 and 20 W. Various geologists had long been interested in this general area, and as early as 1921, John F. Magale was able to define a surface structure. The first wildcat, one of the first in Columbia County, was drilled in 1923 by Mid-States Oil Co., in sec. 10, T. 17 S., R. 20 W. This well was about 1 ½ miles northwest of the Kerlyn Oil Company&apos;s discovery well and was based on surface geological work done by jewel and Dobie. Subsequently, several shallow wells that were not carried below the Upper Cretaceous beds were drilled in the immediate area of the discovery well, but none of them contained any commercial showings of oil or gas. In the latter part of 1935, Elam and Magale (or Southwood) Garrett No. I was located in sec. 13, T. 17 S., R. 20 W., ¾ mile east of the discovery well. It was drilled to a total depth of 4018 ft. in the lowermost Glen Rose beds but failed to obtain any showings of oil or gas. Interest had been stimulated in this general area, however, by the discovery of several oil fields, mainly Glen Rose oil production in the Rodessa field in Louisiana in 1935, Smackover lime production in Snow Hill in May 1936, production from the Cotton Valley formation in Schuler in 1037, and Smackover lime production from the Buckner field in November 1937. With this background and subsequent seismic work, which was carried on partly because the old shallow wells drilled in the township had shown evidence of closure in the Upper Cretaceous beds, the discovery well, Kerlyn Oil Company&apos;s Barnett No. I, sec. 14, T. 17 S., R. 20 W., was originally projected to a total depth of 6300 ft., to test the equivalents of the Morgan sands of the Cotton Valley series, then producing at Schuler. The well was carried to a total depth of 6325 ft. and tested the objective beds without finding commercial production. In the meantime, however, one well had found production in the Jones sand and another in the Smackover lime at Schuler. Kerlyn immediately made arrangements to deepen the Barnett well to the Smackover lime. The top of the Smackover lime was encountered at 7618 ft. and the well was cored and drilled to a depth of 7740 ft.

Jan 1, 1942

By H. Kazemi, M. S. Seth

The effects of anisotropy and stratification on flow behavior and production performance of oil and gas wells have been studied by numerous authors.1-3 Lefkovits et al.l studied the performance of totally penetrated, stratified bounded reservoirs with no crossflow. Others have studied a similar problem, but with crossflow; Russell and Prats2 have summarized the findings of these papers. Muskat3 studied the steady-state behavior of liquid flow for a partially penetrating well in an anisotropic system and concluded that the productivity weakly depended on the directional permeability ratios (kz/kr>0.1). Nisle4 used the classical method of point source solution to the diffusivity equation to study the effect of partial penetration on pressure buildup of oil wells in an isotropic system. He found that the theoretical pressure buildup curves consisted of two straight lines, the one at early buildup times having a slope proportional to the flow capacity of the open interval (l-d)k, and the other having a slope proportional to the flow capacity of the entire formation hk,. Later Brons and Marting5 supplemented the findings of Nisle and concluded that partial penetration gave rise to a pseudo damage, which reflected itself as a skin factor in pressure buildup calculations. Using the pseudo skin, they calculated the impairment of productivity of the production wells, which agreed well with the results of Muskat.6 Pizzi et al.,? using an electrical analog of a stratified system, concluded that a high pseudo damage resulted if the reservoir was partially penetrated. Harriss studied the optimum spacing and arrangement of perforations in cased holes. Hantush9 derived an expression for pressure distribution in an unbounded reservoir with restricted flow entry. Seth10 extended Hantush&apos;s work to a bounded reservoir. Odehl1 has studied a similar problem for steady-state conditions. The purpose of this work was to investigate: (1) the combined effects of anisotropy, stratification with crossflow, and restricted flow entry on pressure transient analysis of flow and buildup tests, (2) the feasibility of calculating the horizontal permeabilities of intercommunicating stratified systems, and (3) the pressure interference tests in such systems. Theory The partial differential equation governing the isothermal flow of homogeneous fluids of constant compressibility is given by Eq. 1: The initial and the boundary conditions are: 1. The reservoir potential is initially constant, say 4v

Jan 1, 1970

University or College Society President Secretary Alabama, University of University. Ala Mining and Metallurgical Society Warren G. Payne Melbon J. Langley Alaska Agr. College and School of Mines, College, Alaska Alaska Mining Society Robert McCombe Robert Mize Arizona, University of, Tucson, Aria Miners&apos; Society Frank Bacon Charles V.&apos; Harris California University of, Berkeley, Cal...: Students Mining Association C. F. Bedford J. R. Hollcraft, Jr. Came is Inst. of Technology, Pittsburgh, Pa The Miners and Metallurgists Society Richard M. Barnhart Jack E. Morris Case School of Applied Science, Cleveland, Ohio Pick and Shovel Club R. H. Randolph W. B. Scott Colorado School of Mines, Golden, Colo Student Branch of A. I. M. E, Donald Peaker T. H. Evans Jones Harvard University, Cambridge, Mass Geological Club H. E. Quinn Lincoln Thiesmeyer Idaho, University of, Moscow, Idaho Associated Miners John T. Carpenter Robert D. Baily Illinois, University of Urbane, Ill Mining Society H. M. Adams R. M. Sherer&apos; Kansas University of, Lawrence, Kane : Student Branch of the A.I.M.E. Henry Gould Everett Stidham Kentucky, University of, Lexington, Ky : Norwood Mining and Metallurgical John D. Lancaster James A. Purnell

Jan 1, 1929

By G. B. Gibbs

Equations are developed which describe the growth of graphite nodules during a-phase graphi-tization under various limiting conditions. When carbon diffusion is rate controlling a modified Birchenall-Mead equation predicts an "apparent activation energy" of 31 keal mole-1 for the parabolic growth constant. If reaction at the graphite or cementite interface is the slowest process growth kinetics are linear and the activation energy must be >50 keal mole-1. A comparison with the experimental observations confirms that carbon diffusion determines the rate of reaction. Apart from minor approximations associated with Lou! carbon solubility in a iron the theory may also be applied to I-phase graphitization. It is well-known that cementite exists as a meta-stable phase in Fe-C alloys and that if a specimen is held at diffusion temperatures for a sufficiently long period the cementite decomposes and graphite is precipitated. Graphitization occurs by the nu-cleation and growth of carbon nodules and several impurity elements catalyze the reaction when present in minute amounts.1 The growth kinetics of nodules have been extensively investigated in the fee ? range2, 3 and recently in the bee a range.1, 4 Experimental growth curves (nodule radius vs time) have slopes which decrease with time, but the scatter of points is generally too great for the precise shape of the curves to be determined with certainty. Birchenall and Mead5 concluded that they are parabolic in ? iron, indicating diffusion control, and that the migration of carbon atoms determines the growth rate. Harris et al, 1 advanced similar ideas for a-phase graphitization. On the other hand, Burke3 chose to regard the initial growth region as a transient followed by a linear law indicating interface control (i.e., cementite decomposition or graphite crystallization as the slowest process). Jeminson and Higgins6 originally considered the initial steep portions of "parabolie" to represent a linear growth law also. In support of these ideas it has been noted that the apparent ac-

Jan 1, 1965

By A. V. Bradshaw, R. I. L. Guthrie

The behavior of large bubbles in the size range 4 to 25 cm3, rising through molten silver, has been studied. It was found that rising velocities were equivalent to those in aqueous systems of low viscosity. Mass transfer coefficients for oxygen bubbles dissolving in silver were found to be 0.036 ± 0.007 cm sec-1, being close to those predicted for transfer through the front surface of the spherical cap bubble only. It is suggested that the surface active nature of oxygen in silver could account for the relatively low coefficients obtained. MANY metallurgical processes involve interactions between gas bubbles and liquids. Examples include the removal of carbon monoxide in Open Hearth Steelmak-ing, the removal of sulfur by blowing air through copper matte during converting, and the removal of hydrogen from steel during vacuum degassing or inert gas flushing. The steps involved in such refining processes include; transport of the dissolved species to the bubble interface, adsorption and chemical reaction of the species at the interface, desorption of product molecules from the interface, and transport of product gas into the bulk gas phase of the bubble. It has been concluded1 that all the interfacial steps involved proceed so rapidly at steelmaking temperatures that transport of the solutes, present in the metal, become the important rate controlling factors provided nucleation phenomena are not restrictive. The O-Ag system was chosen for the investigation into gas bubble-molten metal interactions due to the relatively high solubility of oxygen that enables rates of oxygen transfer to be measured from changes in bubble volume. Other advantages of this system include the absence of a stable oxide phase at an oxygen pressure of 1 atm and the relatively low melting point of the metal which permits the use of a metallic container, providing that it is resistant to oxidation. In those metallurgical processes where bubbles have an important influence, bubble volumes are usually greater than 5 cm3. For this reason the present study relates specifically to single large bubbles of oxygen rising in silver. These bubbles adopt the characteristic spherical cap shape similar to that shown in Fig. 1 for a 30 cc bubble rising in water. After an initial investigation to determine the velocities of inert (nitrogen) bubbles rising in molten silver, experiments were carried out with oxygen and the rates of mass transfer between the oxygen bubbles and the silver were measured. EXPERIMENTAL Apparatus. The apparatus, Fig. 2, for containing molten silver, was constructed from "Nimonic 75" Alloy (75 pet Ni, 20 pet Cr, 5 pet Fe, Mn) and provided for the release of single bubbles from an hemispherical cup, situated at the bottom of the column. The cup was turned by translating the rotation of the drive shaft through 90 deg. This was accomplished by the use of a bevelled gear system, and a smooth drive was provided by the lubricating action of the silver on the gears. Since reliable high temperature seals at 1000°C were found to be impracticable, the filling and drive shaft tubes were extended outside the 3.5 kw resistance wire tube furnace, where connections were made using easily accessible O-ring seals. The apparatus remained gas tight to the atmosphere at pressure differentials far in excess of those used. The filling tube was connected via a small bore tube to the differential pressure transducer. Gas could be bubbled into the inverted cup from two i-in. tubes which passed down the inside of the column to preheat the gas. The temperature of the silver was maintained at 1020°C during all experiments. Measurement of Bubble Volume. In order to calculate mass transfer rates, it was necessary to obtain a continuous record of the bubble&apos;s volume during its passage through the column of molten silver. The method adopted for measuring the bubble volume involved closing off the top gas space to the atmosphere prior to each experiment, and recording the variation in gage pressure of this space during the formation and rise of the bubble. Since any change in bubble volume results in an equal change in top space volume, Boyles Gas Law may be applied (for isothermal con-

Jan 1, 1970

By Edward Keller

GOLD MOVEMENT ON SURFACE OF AURIFEROUS COPPER WHEN LATTER IS SUBJECTED TO OXIDATION SOME years ago the writer&apos;s attention was called to the fact that rolling-mill scales from auriferous copper do not have the gold content proportional to the gold contained in the copper from which they are derived. I So, later, he made a few simple experiments, which are described herewith. In: order to test the gold movement on the changing surface of a copper plate under the influence of oxidation, plates 6 in. by 8 in. by I in. (15.2 cm. by 20.3 cm. by 2.5 cm.) of converter copper, refined, of 99.29 per cent. purity, and leaded copper with a content of 95.65 per cent. copper, were obtained. Ten cuts were made through the thickness of the plates along the longitudinal center and the silver and gold content ascertained in each of the 10 samples in both plates, as shown in the accompanying illustration. The assay results, recorded in Tables 1 and 2, show that the gold distribution is relatively uniform in both plates, while silver has greater variations, especially in the leaded plate. The plates subjected to oxidation were placed in a red-hot muffle for about 2 hr., two small scorifiers being used as supports. Arranged alongside each other, they nearly filled the width of the muffle, and so were practically under equal conditions of heat and draft. The accurate observance of the time was not possible, however, because of other work, but the time of the exposure of each plate in a pair was identical. At the end of each period, each plate was plunged into water and completely freed of scale, which was carefully collected, dried, weighed, and analyzed. Samples of the plates had also been taken of the molten metal and duly analyzed. Table 3 contains the analytical data for the two plates and their several sheets, or layers, of oxide scales. These figures show that in the oxidations of the converter copper the silver is fairly uniform, while

Jan 1, 1919