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By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By Ellis H. Gates

BENEFICIATION of the manganese oxide ores at Three Kids Mine near Henderson, Nev., has evolved over a period of years. Commercial application of the process is on a secure basis, and an effective working hypothesis has been formulated to help solve the problems encountered in flotation. An outstanding difference between the Manganese Inc. operation and other flotation processes is the necessity for high recovery of slime mineral values. Part of the manganese minerals in the Three Kids ore deposit occurs as primary slime or as minerals that are easily slimed by grinding. High recovery of this slime portion is essential to an economic overall manganese recovery. The aim of much of the research at Manganese Inc. was to recover these slimed and finely ground minerals by flotation. Early Agglomeration Processes: Tunbridge' in 1880, followed by Everson2 in 1886 and Cattermole" in 1904, discovered that under certain pulp conditions precious metals and sulfide minerals could be agglomerated if enough soap or oil were mixed into the pulp slurry. These agglomerated particles, Which under ideal conditions ranged from 1/16 to 1/4 in. diam, were recovered by screening, tabling, and hydraulic classification. Even flotation by air occluded in the agglomkrate particles by vigorous stirring was suggested. Cattermole nearly succeeded in getting his process into commercial operation, but it was finally abandoned, presumably because he could nat compete with the low reagent requirements of the new agitation froth process. Since Cattermole's time Christensen in 1921, Borcherdt4 in 1926, and Chapman and Littleford- in 1934 have attempted to apply the principles of agglomeration. In the light of current research at Manganese Inc. on conditioning of pulp at high energy input levels, it is interesting to note the variety of equipment such as tumbling mills, mixing drums, and shakers described by Borcherdt in his patent to produce the agglomerated particles. Ore Characteristics: Manganese in the Three Kids ore occurs as a 'complex mixture of manganese oxides commonly Known as wad. The manganese minerals have Been identified as psilorflelane, hollandite, coronadite, and pyrolusite with minor amdunts of rhodonite and rhodochrbsite. The ppincipal gangue miherals are quaktz, opal, kaolinite, montmoril-lonite, calcite, gypsum, fcelesitite, and barite. Most of the mangandse ore minerals are either porous and sponge-like in structure or soft clay-like masses composed of fine grained mineral particles approaching the size range of colloids. Consequently the ore minerals from the Three Kids mine have relatively large surface areas and high void content per unit weight. The specific area of various manganese ore samples measured at the California Research Corp. laboratories ranged from 32 to 58 sq m per g. The great surface area and high void content explains in part the unusually high reagent consumption required in the treatment of this ore. Current Milling Practice: At Henderson6 he ore is crushed to —1 in. and ground with rod mills in a closed circuit with spiral rake classifiers and cyclones. Sulfur dioxide solution is added to the pulp as it leaves the grinding circuit, immediately followed by addition of a reagent mixture of soap, oil, and wetting agent in the form of an emulsion. The reagents are initially well mixed into the pulp during their passage through centrifugal pumps to the conditioning equipment. All reagents are added prior to conditioning. The intense conditioning or mechanical stirring of the pulp, in which large amounts of power are consumed, is the principal difference between the flowsheet used at Manganese Inc. and a standard flotation circuit. As much as 38 kw-hr of energy per dry short ton of ore in a pulp containing 18 to 23 pct solids is used for conditioning. After conditioning, the pulp passes to a flotation circuit that consists of one roughing stage, a scav-

Jan 1, 1958

By J. A. Stachura

Continuous mining machinery provides the coal industry with one way to compete for a larger share of the total energy market. Various types of machines are discussed and some of the problems with continuous miners, encountered by operators, are reviewed. Equipment manufacturers are working with mine personnel to provide solutions for problems that arise. While coal production over the past 25 or 30 years has been on a horizontal plane, coal's share of the total energy market has declined. To participate more effectively in this total energy market, it is necessary to produce coal more efficiently. It is the obligation of all management, employes, and mining departments to gear the deep mining industry to the rapid progress and changing of today's modern industry. This can be accomplished in the near future with the selection of the proper type of continuous miner best suited to each operator's individual situation. In most mining operations there is tremendous incentive to undertake the continuous mining program. It can reduce the size of the mine greatly by permitting a minimum of working places; it makes pillar recovery work more efficient from the standpoint of overall cost, amount of coal recovered, and safety. The work force can be reduced materially permitting closer and more efficient supervision. It simplifies maintenance because equipment can be more readily standardized. The trend of the coal market favors the use of continuous mining machines. Although there appears to be a general feeling that continuous mining is still a relatively new program and will be slow in replacing conventional mechanical equipment, the fact is that tremendous strides have been made since the first machines were installed in 1948. This program is advancing at approximately the same rate that mobile loading machines replaced hand loading. From 1948 to 1955 there were approximately 450 continuous mining machines in service. In October 1959, a survey revealed that there were more than 700 continuous mining machines in service. Many operators have expressed a desire to undertake this program, but they feel that they could not do so at this time because of one or more of the following reasons: 1) the thickness of their coal seams, 2) seam characteristics, 3) soft bottoms, 4) bad roof conditions, 5) size consist, 6) insufficient flexibility in machines, 7) difficult ventilation problems, and 8) high maintenance costs. With the realization on coal about the same today as it was in 1948, or slightly less and since coal is still failing to participate to a greater degree in the total energy market, it is not surprising that the coal industry is desperately exploring more economical methods for deep mining. The manufacturers are aware that the coal industry is willing to invest in continuous miners if the equipment is built for maximum flexibility, will produce higher tons per man, and assure long life between overhaul programs. CONTINUOUS MINING MACHINES Before discussing details regarding the selection of a continuous miner, let us have a preview of some of the continuous mining machines which are available to the coal industry today. Jeffrey Manufacturing Co.: The machine shown is the Jeffrey 76 A.M. Colmol. This is their most widely used miner, and has been particularly successful in central Pennsylvania and in high-wall mining in western Kentucky. One of the outstanding features of this auger-type miner is its portability. The entire mining range can be changed from its lowest point to the maximum height without stopping the mining operation. Jeffrey 76 B.M. Colmol: This machine is similar to the 76 A.M. model; however, it is built bigger and stronger for a mining range of 50 1/2 to 72 in. This is the model that is now available (Fig. 2). Jeffrey has added two arms to the top row, omitted the odd arm in the bottom row, thus permitting a 50 pct larger throat opening. This eliminates one

Jan 1, 1961

By J. L. Giove, J. M. Hodge, R. G. Storm

The hardenability effect of molybdenum has been evaluated by a number of investigators, including one of the present authors.1,2,3,4,6 Considerable discreMncy exists, however, among the results of these various investigators, and two of them, Brophy3 and Kramer,4 have indicated that the apparent hardenability effect of molybdenun would vary, depending upon the other alloying elements in the steels being considered. The results of previous, unpublished work conducted at the Duquesne Works Laboratory of the Carnegie-Illinois Steel Corporation also have indicated significant differences in the hardenability effect of molybdenu~n in nickel and in chromium steels. The present investigation was undertaken in an effort to establish the mechanism governing this difference in the hardenability effect of molybdenum. This work involved both end-quench hardenability and isothermal transformation tests on two series of steels of varying molybdenum content. One steel contained 3 pct nickel and the other 1 pct chromium. It was hoped that such studies would shed further light on the mechanism of this behavior. Materials and Experimental Work MATERIALS The chemical compositions of the steels used in this investigation arc shown in Table 1. These steels were furnished by Battelle Memorial Institutc in the form of 100-lb induction furnace ingots. The top half of each ingot was forged to 1 3/8-in. square billets and then rolled to I-in. round bar stock for isothermal transforma- tion studies. The bottom half of each ingot was forged into approximately 1 1/4-in. rounds for end quench tests. All of the steels were normalized from 1650°F and tempered at 1100°F before nlachming to end quench or isothermal samples. END-QUENCH TESTS standard l-in. diam end-quench tests were made on each of the steels. The test bars were austenitized at 1600°F for 30 min,, quenched in a standard Jominy jig, and hardness surveys were made in all tests. The 95 pct martensite point was deterInined from hardness values5 and cheeked by metallographic examination. The jominy distance values for 95 pct martensite were converted to hardellability values in terms of ideal diameter (Dl), using a revised carve for the relationship between Jominy distance and ideal diameter. This curve was based on the cooling time from the A1 to the bainite nose temperatures rather than on the usual criterion of half-temperature time. The cooling rates as determined by Russell and Williamson9 were used as a basis for this relationship. The derivation of this curve is described in detail in the appendix. ISOTHERMAL TRANSFORMATION STUDIES Samples for the isothermal transformation studies were quarter sectors of 1/16.is-in. thick slices from the 1-in. round bars. All samples were austenitized for a total the of 15 min., transferred rapidly to a lead bath for isothermal transformation, and brine quenched from the lead bath. A time of 3 see was allowed for the sample to come to the temperature of the lead bath, and this time was not included in the isothermal transformation times. Each sample was examined metallo-graphically at a magnification of 100 diam. The per cent transformation was estimated by comparison with standard micrographs, and the values were plotted against the on log/log coordinate paper. At least 4 and as Inany as 10. points were plotted for each steel. A line was drawn through the points for each steel, and the times for 5 pct transformation were obtained from the plot for each steel. Isothermal transformation diagrams in terms of 5 pet total transformation, covering the temperature range of 800 to 1200°F, were determined in this manner for an austenitizing temperature of 1600°F. The times for 5 pct transformation at the bainite nose for austenitizing temperatures of 1800 and 2000°F were also determined in the same manner. These times for 5 pct total transfor-

Jan 1, 1950

By C. Chu

A theoretical investigation has been made of the forward combustion process using a one-dimensional linear mathematical model, taking into consideration the effect of the vaporization-condensation which occurs on the leading edge of the heat wave. This work involves the solution of five coupled partial differential equations. Besides the vaporization-condensation phenomenon, these equations account for conduction, convection, combustion, heat loss, diffusion and bulk fluid flow. For the one-dimensional linear model studied, the vaporization-condensation phenomenon does not induce appreciable change in the temperature at the combustion front; and its primary effect is to create a steam plateau and to increase the length of the heated zone ahead of the combustion front. This effect becomes more pronounced at lower pressures, higher porosities or reduced gas saturations. The peak temperature and the temperature profile on the leading edge of the heat wave stabilize after a certain period. The length of the steam bank remains practically constant, although the length of the water bank increases as the heat wave advances. INTRODUCTION The existence of the vaporization-condensation phenomenon in the heat-wave process and the important role played by the phenomenon have been recognized by several investigators. Kuhn and Kochl stated that steam plateaus were frequently observed on the temperature records of their experiments. The steam plateaus were attributed primarily to the vaporization and subsequent condensation of the interstitial water existing in the oil sand. Szasz2 suggested that both lighter hydrocarbons and water are vaporized on the leading edge of the heat wave, carried forward in the gas stream, and then condensed to create banks of oil and water. Martin et al suggested that the vaporization-condensation phenomenon is one of the main mechanisms of the heat-wave process, along with thermal expansion and viscosity reduction. Wilson et al. reported the existence of a steam plateau several inches in length in their small-scale tube-run experiments. However, this important phenomenon has never been taken into consideration in the numerous theoretical analyses by various authors. 5 The purpose of this work was to study the thermal aspects of a linear heat wave, taking into consideration the vaporization-condensation on the leading edge of the wave, to determine the effect of this phenomenon on the temperature profile of the reservoir, and to investigate how this effect varies when other process variables are changed. THEORY We consider a reservoir of porous medium of cross-sectional area A, extending from x = 0 to x = L. This reservoir contains, aside from the solid matrix itself, a gas phase and a "combined liquid phase" which is a combination of two immiscible liquid phases — namely, an oil phase and a water phase. The oil present in the reservoir is assumed to consist of three fractions, a noncondensable gas, a nondistillable residuum, and a vaporizable oil fraction which may be present in both the gas phase and liquid phase. Before the heat-wave process begins, preheating has taken place and has imparted an initial temperature distribution T,(x) to the reservoir. At the start of the process, a stream of oxygen-bearing gas is introduced through the face at x = 0. This gas supports the combustion of the residual fuel and supplies the heat throughout the process. In order to develop a tractable system of equations, the model properties are postulated as follows: (1) the system is isotropic and homogeneous; (2) there is a uniform fuel content throughout the reservoir; (3) combustion takes place in a moving vertical planar region of infinitesimal thickness; (4) the temperatures of the fluids and the solid matrix are identical; (5) radiation is negligible; (6) the gas and liquid saturations are uniform throughout the reservoir and remain unchanged

Jan 1, 1965

By B. B. Kunkle

The history of this refinery has been one of expansion. It now has the capacity to produce 240,000 tons of cathodes annually. A general flowsheet and descriptions of the plant layout, operations involved, and equipment used at one of the world's largest and most modern electrolytic copper refineries are presented. THE El Paso copper refinery of Phelps Dodge Refining Corp. was originally constructed by the Nichols Copper Co., in association with Phelps Dodge Corp. and the Calumet & Arizona Mining Co., in order to refine anode copper produced at the smelters of the two latter companies. Initial production was obtained from the plant in January 1930 and its annual refining capacity was 100,000 tons of anodes. In order to keep pace with Phelps Dodge Corp.'s increasing copper production in the Southwest, it became necessary in 1937 to increase the El Paso plant's refining capacity to 160,000 tons of cathodes annually. This was accomplished by adding two sections to the electrolytic tank house, increasing the number of anodes placed in each commercial electrolytic tank from 33 to 37, and making changes in the dc circuits which made it possible to put three generators on each of the two circuits instead of two, thus increasing the amperage on each circuit from 10,000 to 14,800 amp. The capacity of the two furnaces from which refined shapes were cast was increased by raising the sidedoor bays on the furnaces 6 in. An increase of 70 pct in the productive capacity of Phelps Dodge Corp.s Morenci Branch in 1942 again made it necessary to expand refining capacity. In order to accomplish this, Defense Plant Corp. set up a project to increase the capacity of the El Paso plant to 240,000 tons of cathodes annually. This project consisted of enlarging the tank house approximately 50 pct, the construction of another wire- bar furnace, and corresponding increases in other departments where necessary. The engineering work on this expansion was begun in March 1942. Actual construction was under way by August 1942, and the work was completed by March 1944. These additional facilities were purchased from Defense Plant Corp. by Phelps Dodge Refining Corp. in August 1949. The plant is in El Paso about eight miies east of the center of the city and near Highway 80 and the main lines of the Southern Pacific and Texas & New Orleans railroads. The plant site covers approximately 494 acres of company-owned land that is ideally adapted for its use, being well-drained sandy soil and having enough slope so that a minimum amount of excavation was required when the plant was constructed. There is still ample room on the plant site for any future plant expansion. The plant is constructed on four different ground levels and so arranged that the unrefined copper is unloaded on the highest level at the north side of the plant and the refined copper is shipped out from the lowest level on the south side of the plant. The receiving or unloading platform, weighing and sampling rooms, main floor of the tank house, acid and condensate storage tanks, and the slimes and copper sulphate plants are on the first or highest level. The tank house basement, yard scales, charging and furnace bays, balloon flue and stack, brick-storage building, substation and power house, boiler feedwater treating plant and pump house, water storage tanks, and change houses are on the second level. This second level also contains ample yard area for setting-up furnace charges, and for storage of custom scrap, cathodes, scrap anodes, blister, coke, and poles. The casting wheels, inspection conveyors, cathode shears, wire-bar scalping machine, slag

Jan 1, 1952

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By G. R. Countryman, G. H. Thomas, I. Fatt

Procedures are described for scaling up turbulent friction pressure drops of inelastic fluids and laminar friction pressure drops of inelastic/elastic fluids in circular ducts. The laminar scale-up calculation method does not require the use of arbitrarily defined flow models, and can be performed directly from laminar capillary viscometry data, or by means of a numerical solution of the integral equation for Poiseuille flow, inputing true shear rate-shearing stress data from other simple shearing experiments. e.g. Couette and plane Poiseuille flows. The turbulent scale up procedure, based on the Dodge-Metzner correlation for inelastic fluids, requires evaluating the characteristic rheological parameters at the existing wall stress under laminar flow conditions. Since the wall stress is the quantity sought in a pipe flow scale-up problem, a trial-and-err or solution is indicated, and therefore a calculation method has been developed and programmed for a medium-size magnetic-drum-memory digital computer. Laminar flow data from other somces may also be adapted to this turbulent scale-upmetbod for inelastic fluids. Comparisons between predicted and experimentally observed friction losses for generalized Reynolds numbers ranging from 3 — 32.000 indicate an error band width of less than 10 per cent in circular tubes ranging in size from 0.5 to 1.89 in. in diameter. INTRODUCTION Considerable effort has been devoted to the problem of establishing an accurate procedure for predicting the laminar and turbulent flow behavior of non-Newtonian materials in pipes from data obtained with small scale laboratory or pilot plant equipment, as evidenced by the variety of reviews on the subject.1-3 Although there does not appear to be a universally accepted scale-up method for laminar flow, the various methods currently employed can be divided into two principal categories depending upon whether a functional relationship between shear rate and shearing stress is assumed, or whether a generalized correlation is adopted. The methods of Hedstrom4 and of Weltmann are typical of the first category, while the generalized correlation of Metzner and Reed6 illustrates the second category. Under appropriate conditions either approach yields a reasonably satisfactory description of laminar flow behavior. In contrast, the prediction of non-Newtonian transitional and turbulent friction losses is much more complex. For example, certain types of materials have been observed to sustain laminar flow at much higher flow rates than Newtonian liquids. When turbulence does develop, the level of agitation is damped to such an extent that the friction factor is lower than that of the original low viscosity Newtonian medium. Extremely broad transition regions and "diameter effects" have also been noted in the turbulent flow of certain chemically complex materials.' Aside from the latter complications, which are attributed in part to viscoelasticity, the existence of a variety of scale-up procedures for predicting transitional and turbulent friction losses is due principally to the chioce of viscosity parameter used in the definition of the Reynolds number. In contrast, Dodge and Metzner have demonstrated that the friction factorReynolds number relationship for inelastic fluids can be satisfactorily generalized provided the fluid property parameters are evaluated at the existing wall shearing stress.* However, the quantity usually sought in a pipe flow scale-up problem is the wall stress, and hence a trial-and-error procedure is required when dealing with non-power law materials. In this report we discuss two calculation methods: (1) for determining the wall stress, and hence the friction pressure drop, for inelastic fluids under conditions of turbulent flow by means of an iterative procedure, and (2) for predicting laminar friction pressure drops without recourse to arbitrarily defined flow models.

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By D. L. Harris

Chemical upgrading testwork on Stillwater chomite concentrate shows that reduction roasting and leaching (sulfuric acid and/or ferric sulfate) can provide upgraded feed to ferrochromium furnaces for making upgraded ferrochromium. Two-stage reduction smelting in electric arc furnaces can make upgraded ferrochromium also. Sulfating roasts and leaching (acid and/or water) results using gaseous SO2—SO3 or solid ammonium sulfate were not satisfactory for upgrading chromite. Chemical upgrading of domestic Stillwater (Montana) chromite has been considered at various times1'2' to provide a material with higher chromium to iron ratio, more like foreign high grade ore, for the production of standard grade ferrochromium. Physical bene-ficiation of Stillwater chromite ore can provide a ratio, Cr/Fe, no higher than the ratio in the chromite mineral, which is approximately 1.7. For comparison the analyses of a foreign metallurgical grade chromite ore, a high grade electrostatic process Stillwater concentrate and a stockpile concentrate from the Stillwater ore are noted in Table I. Single stage smelting of the high grade foreign ore with a ratio, Cr/Fe, of 3.37 can provide a ferrochromium of over 65 pct chromium content. Similar smelting of the Stillwater concentrate with a ratio of 1.7 can provide a ferrochromium of 50 to 55 pct chromium content.' It has been demonstrated on a pilot plant scale that chemically upgraded Stillwater chromite having a ratio, Cr/Fe, of 3.0 also can be smelted to provide a ferrochromium containing over 65 pct chromium.5 Two major considerations for an upgrading process are the ratio, Cr/Fe, in the product and the chromium recovery. A minimum ratio, Cr/Fe, of 3.0 is required in the product but for economic reasons a higher ratio is desirable for blending purposes as long as the recovery is satisfactory. Data from different kinds of chemical upgrading testwork are presented in this report. Some of the testwork was conducted to make a product which was not intended to be feed for ferrochrome smelting, but the data are considered pertinent to chemical upgrading. Results reported by others are noted also for comparison. WORK REPORTED BY OTHERS The U. S. Bureau of Mines has contributed much to the literature on chemical upgrading of chromite and a summary is given in Table 11. Reduction roasting and acid leaching were reported by Boericke and Bangert,1 by Lloyd and Gorst, et a1,2 and by Boericke3 to demonstrate very good success on a laboratory scale and only fair success in pilot plant tests for Stillwater (Benbow) concentrates. This work included basic studies on thermodynamic properties to explain the reduction and leaching results. Canadian workers, Downes and Morgan,9 have reported experimental success in upgrading a low grade Bird River chromite, similar to Stillwater material by the same process. Russian workers1' have noted results on reduction tests of high grade chromite which may apply to low grade ores and which help in understanding the reduction process. The use of flux additives in the reduction process was an innovation of their work. The Canadian workers9 also reported other kinds of experiments, including autoclave leaching of the chromite in a limited amount of sulfuric acid. An insoluble basic chromium sulfate was formed and separated from soluble iron, magnesium, and aluminum sulfates to provide an upgraded material. U.S. Bureau of Mines workers, Lloyd, Rosenbzum, Home and Davis,' reported on autoclave leaching of Benbow concentrates as a means of obtaining chromium alum for electrolysis. This last work required selective crystallization of alum to separate iron from chromium. Chloridizing roasting of Benbow and Mouat concentrates has been reported by Hunter and Banning6 and others8 to show that the iron chloride could be volatilized from the chromite to provide upgraded residues.

Jan 1, 1964

By P. J. Root, J. E. Warren

An idealized model has been developed for the purpose of studying the characteristic behavior of a permeable medium which contains regions which contribute significantly to the pore volume of the system but contribute negligibly to the flow capacity; e.g., a naturally fractured or vugular reservoir. Unsteady-state flow in this model reservoir has been investigated analytically. The pressure build-up performance has been examined in some detail; and, a technique for analyzing the build-up data to evaluate the desired parameters has been suggested. The use of this approach in the interpretation of field data has been discussed. As a result of this study, the following general conclusions can be drawn: 1. Two parameters are sufficient to characterize the deviation of the behavior of a medium with "double porositym from that of a homogeneously porous medium. 2. These parameters can be evaluated by the proper analysis of pressure build-up data obtained from adequately designed tests. 3. Since the build-up curve associated with this type of porous system is similar to that obtained from a stratified reservoir, an unambiguous interpretation is not possible without additional information. 4. Differencing methods which utilize pressure data from the final stages of a build-up test should be used with extreme caution. INTRODUCTION In order to plan a sound exploitation program or a successful secondary-recovery project, sufficient reliable information concerning the nature of the reservoir-fluid system must be available. Since it is evident that an adequate description of the reservoir rock is necessary if this condition is to be fulfilled, the present investigation was undertaken for the purpose of improving the fluid-flow characterization, based on normally available data, of a particular porous medium. DISCUSSION OF THE PROBLEM For many years it was widely assumed that, for the purpose of making engineering studies, two param- eters were sufficient to describe the single-phase flow properties of a producing formation, i.e., the absolute permeability and the effective porosity. It later became evident that the concept of directional permeability was of more than academic interest; consequently, the degree of permeability anisotropy and the orientation of the principal axes of permeability were accepted as basic parameters governing reservoir performance. 1,2 More recently, 3-6 it was recognized that at least one additional parameter was required to depict the behavior of a porous system containing regions which contributed significantly to the pore volume but contributed negligibly to the flow capacity. Microscopically, these regions could be "dead-end" or "storage" pores or, macroscopi-cally, they could be discrete volumes of low-permeability matrix rock combined with natural fissures in a reservoir. It is obvious that some provision for the inclusion of all the indicated parameters, as well as their spatial variations, must be made if a truly useful, conceptual model of a reservoir is to be developed. A dichotomy of the internal voids of reservoir rocks has been suggested.7,8 These two classes of porosity can be described as follows: a. Primary porosity is intergranular and controlled by deposition and lithification. It is highly interconnected and usually can be correlated with permeability since it is largely dependent on the geometry, size distribution and spatial distribution of the grains. The void systems of sands, sandstones and oolitic limestones are typical of this type. b. Secondary porosity is foramenular and is controlled by fracturing, jointing and/or solution in circulating water although it may be modified by infilling as a result of precipitation. It is not highly interconnected and usually cannot be correlated with permeability. Solution channels or vugular voids developed during weathering or burial in sedimentary basins are indigenous to carbonate rocks such as limestones or dolomites. Joints or fissures which occur in massive, extensive formations composed of shale, siltstone, schist, limestone or dolomite are generally vertical, and they are ascribed to tensional failure during mechanical deformation (the permeability associated with this type of void system is often anisotropic). Shrinkage cracks are the result

By H. M. Strong

Nickel and carbon form a metastable nickel-nickel carbide eutectic system which was ohsen)able by freezing latent-heat arvests at pressures 210 khars. The eutectic freezing temperature Is pressure had a slope of -0.9°Cper kbar. At 50 khars, the nickel-nickel carbide eutectic was at 1297° * 5°C and 0.34 mole fraction Ni3C. The composition of the eutectic increased at an initial rate of 0.004 mol fraction per kbar. The carbon content of the a phase also increased with pressure. Seveval illustrations of nickel carbide microstruc-tures are given and data on the lattice expansion of nickel in terms of carbon content are included. IRON, cobalt, and nickel form a variety of carbides with compositions varying between MeC and MC. Of the three, the carbides of iron are most easily recovered. The nickel carbides are so unstable at temperatures above 900°C that their occurrence in Ni-C alloys is unusual. Under sufficient pressure, however, the temperature range for the stability of the ferrous metal carbides is likely to be increased, or their decomposition suppressed (e.g., see Hilliard' on FesC), providing an opportunity to study the unstable carbides more closely. This was found to be true for nickel carbide which, under pressure, formed a eutectic with nickel. This paper describes the conditions of formation of nickel-nickel carbide eutectic compositions and their subsequent recovery. Despite the comparative instability of the nickel carbides, something is already known about them through various chemical reactions at temperatures not exceeding a few hundred degrees, and from their recovery by the very rapid quenching of molten Ni-C alloys from temperatures of about 1450°C or above. At least four carbides of nickel have been reported: A discussion of the state of knowledge about Ni3C is given by ansen.' The studies of Morrogh and williams7 who obtained Widmanstatten nickel carbide structures and of sidorenko8 who first obtained nickel carbide eutectic structures are also of interest. Sidorenko used short heating times for molten nickel in a graphite crucible followed by very rapid quenching to obtain the eutectic structures. Long heating times produced only the nickel-graphite eutectic probably due to the presence of graphite crystals in the melt which nucleated graphite crystallization. According to the early work summarized by anssen,' nickel carbide may form at temperatures far above the melting point and may be recovered by very rapid quenching. More recently, Giardini and Tydings, working on diamond synthesis, found evidence for "free nickel carbide'' in high-pressure reactions carried to temperatures far in excess of the limit for diamond growth, followed by rapid thermal quench. They stated that nickel carbide was not found in association with diamond growth. In the present work, observations were made on the melting and solidification temperatures of Ni-C alloys as a function of composition, temperature, and pressure. The nickel-nickel carbide eutectic was found at pressures above 10 kbar and its variation with pressure followed up to 60 kbar. Nickel-nickel carbide microstructures were recovered by quenching under pressure from temperatures of about 1400°C and higher. The formation of nickel carbide structures under ordinary diamond-growing conditions was usually observed but the role of carbide formation as an intermediate step in diamond growth needs more study. EXPERIMENTAL METHODS The melting and solidification temperatures of various nickel-graphite compositions were observed by latent-heat arrests in the sample holder illustrated in Fig. 1. The samples were composed of mixtures of carbonyl nickel powder and National Carbon Co.'s SP-1 graphite packed to densities of about 6.4 g per cu cm. They were contained within

Jan 1, 1965

By L. A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region comprises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County. In this upper Gulf Coast region, which embraces the most heavily populated and industrialized parts of Texas, industrial and municipal water supply is obtained chiefly from wells. Largest center of ground-water withdrawal is the Houston-Baytown area, where about 200 million gallons per day was pumped in 1956 for municipal and industrial use. Other large centers of ground-water withdrawal include the Alta Loma sector and the heavily industrialized Texas City area in Galveston County, where about 23 mgd was pumped in 1956. In the Freeport area in Brazoria County about 6 mgd was pumped in 1956 for city and industrial supply. In addition to withdrawals in metropolitan districts, great quantities of ground water are supplied by irrigation wells to thousands of acres of rice. These wells are widely dispersed over many miles, principally in Harris, Waller, Fort Bend, Brazoria, and Liberty counties, and effects of pumping are not so readily noticed as in the industrial and metropolitan sectors. Subsidence: Starting with the 1905-1906 line from Smithville, Tex., to Galveston, the U. S. Coast and Geodetic Survey has extended a network of first and second-order level lines throughout the upper Gulf Coast region. In 1918, when a line was run from Sinton, Tex., to New Orleans, La., a tie was made to the 1905 leveling at Houston. In 1932-1933 a line was run from Palestine, Tex., to Houston, and a good deal of leveling was carried out in the vicinity of Houston. At this time the entire network was adjusted to the Sea Level Datum of 1929. In 1935-1936 and 1942-1943 several new lines were run and considerable releveling was performed. Supplementary adjustments were made after both the 1936 and 1943 levelings in order to reduce the elevations to the Sea Level Datum of 1929. These adjustments probably masked some of the subsidence that had occurred up to that time, although a certain amount of subsidence was noticed in the 1943 leveling. When several lines in the vicinity of Houston and Galveston were releveled in 1951, the regional nature of the subsidence became apparent.' Direct comparison with the 1943 leveling was possible because the datum was not changed. Comparisons with prior leveling were unreliable because of differences in the early and subsequent datums. In 1953-1954 many lines in the region were re-leveled and in 1957 the entire network, including the elevations previously determined, was readjusted to determine the changes in elevations as indicated by various levelings between 1905 and 1953-1954. In this instance the adjusted elevations were held fixed near the boundaries of the region where the bench marks seem to have remained stable. The only sea-level connection held fixed was the connection of the 1905 leveling to the 1903-1906 tidal series at Galveston. Almost the entire region has been at least slightly affected by the subsidence, some areas to a great extent. The profiles of subsidence (Fig. 2) and the map showing the contours (Fig. 3) illustrate both regional and local changes. A large area of subsidence is centered in the Houston-Baytown district, where the maximum recorded is about 2.7 ft between 1905 and 1954. This probably falls short of the actual maximum, since land surface subsided as much as 2.5 ft in the industrial section alone between 1943 and 1954. Sub-

Jan 1, 1960

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By F. W. Jessen, H. Kazemi

A washing technique has been developed to form a spherical cavity in massive salt. The technique is, basically, a process of controlling the fluid motion in the cavity, the concentration distribution of brine, the rate of dissolution at the walls of the cavity, and the particular settings of the wash pipe, or pipes (inlet and outlet pipe) employed. For a particular arrangement of tubing and casing, fresh water enters from the casing annulus at a position above the bottom of the tubing, and the dissolved material leaves the cavity through the tubing near the bottom of the projected hole. The initial configuration of the cavity is cylindrical, representing the drilled hole situated at the axis of the projected cavity. As washing progresses the original hole is enlarged radially (any direction perpendicular to the axis of the hole). An inert fluid (generally a hydrocarbon, natural gas, or air) which serves as a blanket is injected through the annular space between the original hole and the casing. The controlled downward motion of this blanket maintains the upper edge of the brine region that is expanding on the surface of the projected sphere. A large spherical glass container and a radial model were used to investigate the flow patterns and the concentration distribution of brine occurring during the progress of solution of the salt. Aluminum flakes and dye were injected and flow patterns were observed and recorded on motion picture film. Based on the results of these model studies and other work carried out in this laboratory, the controlled washing technique was formulated. INTRODUCTION Underground cavities leached in salt beds and salt domes have been used extensively for storing hydrocarbons. Little attention has been focused on the shape of the cavities as long as large volumes were obtained and the cavities were structurally stable. The general process involves circulating fresh water and removing brine. Two distinctly different circulating systems can be employed, each of which yields characteristically different shapes. By far the most generally accepted method of washing storage caverns in salt domes is the direct circulation system. Water is introduced through the innermost pipe of a concentric pipe system, and brine is withdrawn through the annulus. In the reverse-circulation method, water enters through the annulus and is discharged through the smallesc tubing string. The size of the operation, and hence the size of tubing and casing used, depends on such factors as cavity volume, length of hole, availability of water, disposal of brine and power requirements. Underground caverns are from 100 to 1,000 ft or more in length, and when completed vary from 40 to 100 ft in diameter, providing storage of 100,000 bbl or more. The volumes of water required per volume of salt removed vary from 6 to 7 for the reverse circulation method to 10 to 11 for the direct circulation method. Up to 80,000 BWPD are often circulated. In the direct circulation method, because water enters near the bottom of the projected cavity, solution of salt is greatest at this point, particularly in view of the fact that when the washing is begun turbulent flow undoubtedly exists in the immediate vicinity of the discharge of the inlet water. As the diameter of the hole increases, flow rates also are increased, so perhaps the condition of fluid turbulence is maintained for some time. During the later stages of leaching, when capacity of equipment may be the limiting factor in maintaining flow rates, there may still exist some turbulence adjacent to the point of influx; however, for the most part laminar flow conditions prevail. There appears, therefore, rather good evidence to indicate that the state of fluid motion is responsible for the typically shaped cavity which results from such washing — namely a cylindrical form, generally somewhat larger at the bottom than at the top. Depending on the number of so-called stages which might be employed, the walls or surfaces of the salt diminish rather uniformly from bottom to

Jan 1, 1965

By P. K. Weimer

Coinpletely integrated thin-film circuits inco?,porating more than 1000 active and passive elements have been fabricated reproducibly in the laboratory by evaporation of- all components. A 180-stage modified shift register comprising 540 CdSe TFT's, 360 resistovs, and 180 capacitors was deposited upon a glass substrate during one pump-down of the vacuum systeitl. Experimental units have been operated for more than 5000 hr at temperatures uP to 85°C without failure of any slages. The present pupper reviews the charvactevistics of evaporated thin-film transistors (TFT's) and discusses their application to integrnted circuils. INTEGRATED circuits most widely used today are based upon silicon technology, with the circuits formed on the surface of a block of single-crystal silicon1 or on a block of sapphire 2,3 upon which a thin layer of silicon has been deposited. Transistor patterns and interconnections are defined by photographic procedures using photoresist masking. Large groups of transistors are produced in batches which undergo many processing steps, some of which are carried out at elevated temperatures. Passive elements are formed by treatment of the semiconductor surface or are deposited by evaporation alongside the active elements. The size and complexity of the circuits are limited by defects in the devices and by the size of the available single-crystal chips. Capacitative coupling to the semiconducting substrate may also limit useful size and frequency response of the circuits. An alternative approach to integrated circuits is based upon the deposition by evaporation of all circuit components upon a noncrystalline, insulating substrate such as glass.4 Thin-film field-effect transistors,1'6 known as TFT's, can be deposited in large arrays on glass or plastic substrates at the same time the associated passive elements are being deposited. Although still in the research stage the all-evaporated approach is expected to offer certain advantages for many applications. In particular, the use of thin films upon a noncrystalline substrate offers the prospect of producing complex, large-area circuits not now feasible with single-crystal silicon. Important applications of this type include memory arrays for computers and imaging devices for television. The ease with which the evaporated TFT's can be deposited may permit continuous, automated production methods not possible with high-temperature batch processing. Recent advances7'8 in the fabrication of thin-film transistors have led to greatly improved reproduci-bility and life of the TFT's. Experimental circuits having over 1000 active and passive elements deposited upon a common glass substrate are currently being produced in the laboratory. The present paper reviews recent progress in the development of the TFT and in its application to integrated circuits. I) DESCRIPTION OF THE THIN-FILM FIELD-EFFECT TRANSISTOR The TFT is a field-effect transistor of the type having the control gate separated from the semiconductor by a thin insulating spacer. Although its operation resembles that of the silicon MOS transistorg its construction is based entirely on thin-film techniques. Fig. 1 shows a cross-sectional view of an evaporated TFT deposited upon a glass substrate compared with a silicon MOS transistor deposited upon single-crystal sapphire.3 The semiconductor in the TFT is a poly crystal line layer, of a material which can be readily evaporated, such as cadmium sulfide, cadmium selenide,l0 or tellurium." Silicon monoxide layers have usually served as the gate insulator, but other oxides, sulfides, and fluorides may be used. Film thicknesses range from a few hundred to a few thousand angstroms. The source, drain, and gate electrodes in the TFT are of metal. Qpical source-drain gap dimensions are 0.0003 x 0.030 in., with a gate strip whose width slightly overlaps the source and drain. The source and drain electrodes should make low impedance contacts to the semiconductor. With cadmium sulfide films, gold is a satisfactory material for underlying electrodes, while aluminum is preferable for overlying electrodes.12 Considerable variation in design of the TFT is permissible, with the electrodes being

Jan 1, 1967

By T. M. Geffen, J. L. Sanderlin, F. F. Craig, D. W. Moore

Scaled reservoir models have been used to study the effect of gravity on oil recovery performance in frontal-drive operations; namely, water, gas, or solvent flooding. The difference in density between the reservoir oil and the injected fluid causes their segregation, resulting in a non-uniform advance of the fluid front. In the laboratory flow tests, which simulated both five-spot and linear injection operations in flat reservoirs, the viscous, capillary, and gravity forces present in these operations were scaled. Dyed fluids were used so that the gross movement of the injected fluid could be observed. The studies covered a range of injection rates, formation thicknesses, and rock and fluid properties normally encountered in field operations. The results of the model tests indicate that the volume of the reservoir contacted by the injected fluid at its breakthrough into the producing well is less than that expected based on information which neglects gravity effects. This difference can often be as much as 80 per cent by gas or water injection in uniform sand bodies. Preliminary flow tests on a non-uniform sand body indicate that the uniformity of the flood fronts may in some situations be influenced to a much greater degree by permeability variations within the rock body than by gravity effects. The magnitude of fluid segregation due to gravity is controlled by the average injection rate, rather than day to day or week to week variations. INTRODUCTION One of the important factors controlling the oil recovery from a frontal-drive operation, such as water, gas, or solvent injection, is the volumetric sweep efficiency. This factor is a measure of the gross portion of the reservoir that is contacted by the displacing fluid. The volumetric sweep efficiency is influenced by gravity effects, well arrangements, and variations in rock permeability within the reservoir. The gravity effects are due to the displacing fluid being of different density than the reservoir oil. This causes the displacing fluid to move preferentially toward either the top or bottom of the formation. Non-uniform advance of the flood front can be caused by the relative positions of the injection and production wells. Variations in rock permeability also result in an uneven advance of the displacing fluid. Gas zones, representing paths of low resistance, may result in non-uniform movement of the injected fluid. The more uneven the advance of the displacing fluid, the lower is the volumetric sweep efficiency and thus the lower the oil recovery efficiency. The effects of well arrangement and permeability variations, upon the gross movement of the injected fluid have been the subjects of extensive investiga-ti0ns.1,2,3,4,5,6 Gravity effects have been recognized as being present in frontal-drive operations'.' but there has been little quantitative measure of their magnitude. Very likely the reason gravity effects have not been studied is that this problem does not lend itself to simple experimental or mathematical analysis. The development of reservoir modeling techniques has made possible a quantitative determination of the effect of gravity on fluid segregation and thus upon the oil recovery performance of frontal-drive operations. This paper presents a progress report on a laboratory investigation of gravity effects in fully liquid-saturated, horizontal, uniform as well as non-uniform systems. These results were obtained from scaled experiments on both linear and five-spot systems within the range of conditions normally encountered in secondary recovery operations. This study is concerned with the gross movement of the injected fluid to the time it first reaches the production wellbore. Therefore, it should be emphasized that the results of this paper can not be used to determine the effect of gravity segregation on oil recovery efficiency at abandonment conditions. MODEL SCALING The science of scaling models is relatively new as applied as petroleum production problems, Many of the scaling techniques have been adaptions of those used in basic studies of heat and fluid flow. There are

Jan 1, 1958

By J. C. Deppe

A method is presented for calculating approximate injection rates in secondary recovery operations. The method can be applied to cases of unequal fluid mobilities, irregular well patterns and boundary patterns. The steady-state pressure distributions for the four flood patterns reported by Muskat and for five additional patterns reveal that most of the difference in pressure between the injection and producing wells occurs in regions around the wells which can adequately be described as regions of radial flow. This leads to a method of calculating injectivity by approximating the flood pattern with radial flow elements (or a combination of radial- and linear-flow elements for some patterns such as the direct line drive). Irregular and boundary patterns can also be approximated by radial and linear elements. Each of these elements can be described by radial-and linear-flow equations and the results combined as series flow resistances to give an approximate equation for the initial injection rate. The mobility ratio does not affect the initial rate; therefore, if the well pattern is one of those regular patterns for which theoretical rate equations have been derived for unity mobility ratio, the approximate initial rate equation can be improved by adjusting it to match the theoretical equation. The available theoretical rate equations are listed, including five new cases. As the flood progresses, the injectivity changes because in general the flood front will divide the pattern into areas of different fluid mobilities. Simple shapes can be assumed for the flood front so that both areas can be divided into radial- and linear-flow elements. Radial- and linear-flow equations are applied to these elements to account for the change in flow resistance behind the front. To calculate injection rates after breakthrough, it is necessary to know the sweep efficiency at breakthrough. Areal sweep data are available in the literature for a number of patterns, and sufficiently accurate breakthrough sweep efficiency can be estimated from these data if it is not otherwise available. Again, simple shapes for the flood front can be assumed after breakthrough, and injection rates can be calculated for the remainder of the flood. When areal sweep data are available, these data can be used to cbeck. the calculated injection rates after breakthrough. Injection rates calculated by this approximate method compare favorably with available model data. INTRODUCTION When the fluid mobilities in the swept and un swept regions are equal, the injectivity will not change as the flood front advances; and for regular patterns it can be calculated by mathematical formu1as.l When the fluid mobilities in the swept and unswept regions are not equal, the injectivity will increase or decrease as the flood front advances. In this case, the injectivity has not been calculated by analytical means for any practical well pattern; and, furthermore, scale model and analog4,6 results have been published only for the five-spot pattern. The main object of this paper is to present an approximace method for calculating injectivity for the case of unequal mobilities. The method can be applied to regular, irregular and boundary patterns. Before the approximate method is discussed, the analytical formulas for equal mobilities will be summarized, and the analytical solution for radial flow with unequal mobilities will be used to show how the injectivity changes as the flood progresses. EQUAL MOBILITIES, REGULAR PATTERNS In a flooding operation the injectivity, the rate at which fluid can be injected per unit difference in pressure between injection and producing wells, depends on basic physical properties and, in addition, on three variables to be treated here—the area of the swept region, the fluid mobilities in the swept and unswept regions, and the well geometry (pattern,

By Robert E. Green, Kenneth Reifsnider

A microscopic X-ray diffraction technique was employed for the simultaneous study of the behavior of several families of lattice planes, whose local orientatiotz changes are manufestations of internal distortions resulting from specimen deformation. Photographs taken using aluminum were single crystals 1/64 in. In diam are presented which illustrate the appearance of various types of deformation- or growth- induced structural variations. Slip and lattice bending were detected in tensile tests for strains as small as 0.1 pct. Evidence of deformation bands, lineage structure, and void formation wns also shown. AmONG the most important methods of studying internal stresses in metals is the utilization of various X-ray techniques. The general subject of X-ray metallography has been treated in a most excellent manner by Taylor,1 and the use of X-rays for the direct observation of imperfections in crystals has recently been reviewed in an article by Newkirk2 and in the book edited by Newkirk and Wernick.3 Since the inception of metallographic X-ray analysis, there have been numerous technological developments and refinements, each with its particular advantages and disadvantages and, acrording to these, its particular applications. X-ray diffraction techniques can be divided into two general categories, that of X-ray diffraction microscopy and that of X-ray diffraction macroscopy. In the former are included such methods as those of Berg-Barrett, Lang, and Schultz2,3 which are concerned with microscopic imperfections such as dislocations. The second category includes all work concerned with the study of the condition of a crystal lattice structure as indicated by the marroscopic detail in its diffraction patterns. An example of this is the study of the diffraction manifestations of inhomogeneous plastic deformation as manifested by formation of deformation bands and inhomogeneous lattice rotations. The method used in the present investigation was an X-ray diffraction macroscopy technique. The geometry and analytical aspects of the method were similar to those of Julien and Cullity.4,5 The source was collimated with a single slit in a manner simi- lar to the "parallel beam'' method of Barth and Hosemann6 except that a continuous spectrum of radiation was employed. The apparatus produced large-beam transmission Laue patterns of thin cylindrical aluminum-wire crystals, which were deformed either in tension or torsion. Although the conventional X-ray target and interposed slit were not capable of the high resolution obtainable with a fine-focus X-ray source as employed in a microfocus apparatus, resolution was a secondary consideration in our technique, and was sacrificed to obtain sufficient intensity along a sizable length of the specimen. By using a grid indexing technique similar to that of Barth,7 we were able to study several diffraction lines from various planes simultaneously. The results of these tests give additional information with regard to the inhomogeneous deformation of single crystals, and the indexing procedure used provides a correlation between portions of the test specimen and portions of a diffracted beam. EXPERIMENTAL TECHNIQUE The experimental arrangement used is shown schematically in Fig. 1. A source of continuous X radiation from a vertically mounted Machlett X-ray tube possessing a copper target and operated at 20 kv and 10 ma was passed down a horizontal lead tube 80 cm long which terminated in an adjustable vertical brass slit. The slit opening was adjusted to correspond with the diameter of the test specimen. In front of the brass slit it was possible to place a screen wire mesh, one horizontal strand of which was a lead wire which served as a fiduciary mark, the screen itself serving as an indexing system as will be described later. Behind the screen was the test specimen which consisted of an aluminum single crystal wire 1/64 in. in diameter and 3 in. long. These 3-in.-long crystals were cut from

Jan 1, 1965