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By K. K. Kershner, W. A. Calhoun, C. W. Funk

Future resources of aluminum may require the utilization of low grade ores to provide a more permanent protection for the nation. Aluminum minerals such as cloy, shale, and high iron laterites may become important sources. An evaluation of reserves is given. New laboratory results are reported on the Vereinigte desilication process. THIS report on future resources of aluminum metal emphasizes the necessity for investigating utilization of low grade potential ores to provide more permanent protection for the nation. Partial or complete interruption of the importation of high grade aluminum ores must be given consideration. Ultimately, aluminum minerals such as clay, shale, and high iron laterites may become the principal sources of aluminum. The development of extractive processes for treating these low grade materials is a step in long-range national preparedness that should receive more attention. In formulating such processes, the application of beneficiation methods for the purpose of classifying the several types of minerals before subjecting each type to the more expensive extractive procedures should be considered, and a careful survey of the basic factors of power sources, transportation facilities, and sources of raw material should be made. Domestic Bauxite Resources Of the domestic supply of current, treatable-grade bauxite, 95 pct comes from Arkansas. The present reserve of Arkansas bauxite suitable for metal production, including abrasive-grade, Bayer-grade, and modified Bayer-grade ores, is 34,000,000 tons. The total reserve of bauxite of all grades is approximately 75,000,000 tons. Reserves are estimated on a mined and dried basis. Data available to the Bureau of Mines in 1948 to 1949 were used in preparing Table I, which shows a breakdown by grades of bauxite for about a half of the reserves of the state. The modified Bayer ore, 10,555,500 long dry tons, is based on a cutoff of 8 to 15 pct silica. The sub- marginal 10,074,700 long dry tons is assumed to contain more than 40 pct gibbsite, more than 15 pct silica, and less than 32 pct available alumina. A considerable amount of this low grade material was consumed in 1949 and 1950. Additional tonnages of bauxitic and kaolinitic clays are indicated by the Bureau of Mines drilling project.' Applying a 50 pct factor to arrive at long tons mined and dried, the results of this project are approximately 31,500,000 tons kaolinitic clay at +35 pct Al²O3 and 11,800,000 tons kaolinitic clay at 20 to 35 pct A1,0,. Total reserves of kaolinitic clays are probably quite extensive—several times the reserves shown in the Bureau's work. Total reserves of bauxitic and high iron clays from the drilling program and previously established figures are 63,980,000 tons. The mineral dressing methods,' the lime-sinter process, he lime-sinter modification of the Pederson process," the lime-soda sinter process,"-' and the Alcoa combination processa. have been described in the literature and will not be elaborated upon here. The less familiar Vereinigte Aluminium-Werke process used by the Germans during World War 11 may require some amplification. It was used to bene-ficiate boehmite ores containing 12 to 18 pct silica for a feed to the European Bayer process. Ore was

Jan 1, 1952

By M. W. Clegg

The application of the Laplace transformation to problems in the flow of compressible fluids in porous media has provided a large number of exact solutions. For plane radial flow, however, these solutions are either complex integrals or infinite series and are of little value to the field engineer. In the case of production at constant well pressure, the available approximate solutions me valid for large times only. In this paper it is shown that an approximate inversion formula for the Laplace transform, developed for the solution of viscoelastic problems, is applicable to radial flow problems and provides simple analytical solutions to constant terminal pressure problems. The method may be used to obtain approximate solutions to many problems, including media with radial permeability discontinuities, multi-layer formations and pressure buildup in wells after shut-in. The results are compared with the few available computer solutions as well as the large time solutions, and it is shown that this approximate method greatly extends the time interval over which a simple analytical solution is acceptable. INTRODUCTION The study of transient problems in the flow of fluids through porous media has benefited greatly from the application of transform methods. The use of the Laplace transformation for solving parabolic equations has been widely discussed in the field of heat conduction and diffusion as well as in the petroleum literature. Removal of the time variable with the Laplace transformation generally reduces the problem to a boundary value problem which may be solved by standard techniques. A much more formidable problem then faces the engineer, however, for frequently the transform does not possess a simple inverse. The result is that the general inversion integral must be used and this leads to either an infinite integral or an infinite series, both of which are difficult to handle from a computational standpoint. Asymptotic approximations for the inverse have been known for some time and these yield approximate inverse functions that are valid for very large or very small times — but frequently the times of interest lie somewhere between these two extremes. Therefore, some acceptable approximation valid over a larger interval of time is desirable. During the past few years a number of methods for achieving this have been developed and some of these are discussed briefly in this paper. The relative merits of the various methods are not evaluated here, but some general conclusions reached by other authors are given. One of these methods has been applied to problems associated with the radial flow of compressible liquids to producing wells. In the case of production at constant well pressure, the method leads to simple analytical solutions for a number of standard problems; e.g., homogeneous formation, permeability discontinuities, pressure buildup. These solutions greatly extend the range of validity of the asymptotic ones (valid for large times only) and should be of value in studying the behavior of wells producing under constant pressure conditions. METHOD FOR THE APPROXIMATE INVERSION OF LAPLACE TRANSFORMS Much of the work that has been done on the approximate inversion of Laplace transforms has originated in viscoelastic problems. Apart from the asymptotic approximations,1 one of the first approximate methods was due to Alfrey.2 If (s) is the Laplace transform of f(t) defined by

By H. S. Price, D. A. T. Donohue

The system of equations describing displacement of a hydrocarbon liquid by a hydrocarbon vapor in a porous medium where mass transfer takes place between the phases is solved numerically for a variety of gas injection processes. Even though the method of solution is quite general, only systems with three hydrocarbon components are considered. Computer simulations of displacement processes wherein mass transfer between phases is both considered and neglected are compared, and it is shown that neglecting mass transfer can give pessimistic displacement efficiencies. INTRODUCTION The role of the gas displacement process in the recovery of petroleum has been subjected to a series of detailed analyses; as a result, a number of predictive models have been published in the literature. However, because of major simplifying assumptions, most of these models do not completely represent the physical system. As a result, the effect of making the simplifying assumptions is unknown. Therefore, a complete representation of this process — one without major simplifying assumptions —should lead to a fuller understanding of the process, and perhaps to methods of improving it. The general method of developing a model for two-phase fluid flow in a porous medium is to solve simultaneously the continuity equation, the energy equations and the equation-of-state for each phase under the prescribed initial and boundary conditions. For an isothermal system, the energy equations reduce to the momentum equation. Darcy's law. However, since natural gas is the vapor state of the reservoir liquid, interphase mass transfer may take place with concomitant changes in both the intensive and extensive thermodynamic properties of each phase. It is this phenomenon that has often been omitted in previous mathematical models. An additional relation, then, which accounts for mass transfer between the phases, must be included with the other equations to specify a complete model. Completely formulating the equations to be solved is not a difficult task1 but obtaining their solution has been intractable up to now. Availability of large-memory, high-speed digital computers now makes an attack on this formidable problem possible. This paper presents a preliminary study of the problem. Since this investigation is intended to be exploratory, it is restricted to the linear, horizontal, isothermal, two-phase viscous flow of oil and gas in an oil reservoir. In the early development of predictive models of this process, the reservoir system was considered as a unit and various forms of the material balance equation were proposed.2-4 Pressure and saturation gradients were then added in the Buckley-Leverett model.5 The Buckley-Leverett formulation considered the fluids to be incompressible; thus, the mathematical model reduces to a steady-state system. In the 1950's, studies incorporating numerical techniques were being published.6-9 These mathematical models differed in the efficiency of finite difference techniques, the inclusion or exclusion of capillarity or the number of space dimensions considered. To solve these nonlinear, partial differential equations, each phase was considered to be homogeneous with time; therefore, mass transfer between phases was neglected. The effect of mass transfer on the gas displacement process was first reported by Attra. 10 He simulated the one-dimension flow system by a series of cells in each of which the fluids were equilibrated during a time step. In addition, the pressure throughout the system during each time step was predetermined and constant-phase velocities were calculated according to the Buckley-Leverett incompressible fluid flow model. Welge et al.11 developed a model for the displacement of oil by an enriched gas where composition is considered to be a dependent variable. Fluid

By Edward B. Walker, Michel Grosmangin

The geological and economic conditions peculiar to the Greater Oficina area are presented to demonstrate the necessity of a low-cost, well-site method of distinguishing gas-bearing formations. The method of gas detection with the neutron log is briefly discussed and its limitations are explained. A new method is described which consists in running a second neutron log with a larger source-to-detector spacing. Field data indicate that under favorable conditions the larger spacing response is proportionately more influenced by the virgin gas zone than is the shorter spacing response. One important condition is that the gas sands be invaded, with a diameter of invasion equal to about two to three times the hole diameter. The calibration of the longer spacing log is made so that the two logs read the same deflection in shale and in a known water or oil sand. Under such conditions, gas is indicated by a positive separation, i.e., the curve for the longer device is displaced to the right of the curve for the shorter device. Because of the non-linearity of the long spacing response, low porosity formations also show positive separations. In sands with large porosity variations, the gas sands can no longer he located visually. They can be detected on a plot of shorter spacing vs longer spac-ing deflections. INTRODUCTION In the Greater Oficina area of Eastern Venezuela, the rapid and accurate detection of gas from well logs is of primary importance because of a combination of economic, geologic, and operational conditions. Briefly, these conditions are: economic—there is no market for gas at the present time; geologic—a single well may contain as many as 30 or more oil or gas sands for which intervals -to be tested must be selected; opera-tional—first, once opened to the casing through perforations, gas sands are extremely difficult and expensive to squeeze off, and second, gas detection must be rapid because the geologist must decide immediately, at the well, which sand to perforate. During the early period of exploitation in Greater Ofi-cina, when clay base muds were used, sidewall samples, together with electric logs, gave fairly good distinction between oil and gas sands. When exploitation became concentrated on deep fields of poorer sidewall sample recovery, and after the advent of oil emulsion muds, now the standard drilling fluid in Greater Oficina, the regular neutron log became the most reliable indicator of gas. In 1953, R. Norelius devised the dual-spacing neutron technique for gas detection. The dual-spacing neutron log has proved to be highly successful in detecting gas and has been adopted as a regular survey by all of the oil companies of the area. Several hundred dual-spacing neutron logs have been run in Eastern Venezuela and several tests per well are available for positive evaluation of the logs. The findings outlined below are based upon this extensive field experience. GEOLOGICAL CONDITIONS OF THE GREATER OFICINA AREA The Greater Oficina area lies on the south flank of the Eastern Venezuela Basin (Fig. 1). Nearly all accumulations of oil and gas in the area are trapped, in whole or in part, against normal faults. All known oil and gas reservoirs in Greater Oficina occur in the Ofi-cina formation (Miocene-Oligocene) or in the "U" sands. The U sands are the lithologic equivalent of the Merecure group (Otigocene-Eocene), which contains oil in many fields north of Greater Oficina. Most of the petroleum produced in Eastern Venezuela is from the Oficina formation.

Jan 1, 1958

By W. B. Hickman, J. J. Pickell, B. F. Swanson

Many physical properties of the porous media-immiscible liquid system are dependent upon the distribution of fluids within the pores; this in turn, is primarily a function of pore structure, liquid-liquiri interfacial tcnsion and liquid-solid wetting conditions. The cnpillary pressure hysteresis process provides a means of investigating the influence of pore structure upon fluid distribution for consistent sur/acc conditions. Invcstigntiot2s indicate that residual non-wetting-phase saturations /ollozuir,g the imbibition process (i.e.,wetting phase displacing nor2-wctting phase) are dependent upon both pore structure and initial non-raetting phase saturation and suggest that residual fluid is distributed as Discontinuous ,globules, one to a few pore sizes in dimension, thrnugh the entire range 01 pore sizes originally occupied. It clppears that air-mercury capillary pressure dala adequntely rellect the distribution of fluiris in a water-oil system when strong wetting condition preliczil. An oil-air counter-current imbibition technique has also been found to provide a rapid rneans of obtaining residual-initial saturation data. In a majority of cnses, rcsidual saturations detf-rniinecl from the oil-air or air-mercury process reasonably approximate residual oil saturation following water drive of a strongly water-wet medium. INTRODUCTION A reliable estimate of recoverable reserves depends not only on the amount of original oil-in-place but also on pore geometry and distribution of fluids within the pores. A critical parameter determining the recovery from a reservoir under waterflood, for example, is the amount and distribution of residual oil within the various rock types present. The purpose of this paper is to investigate the mechanism of capillary trapping and assess its importance in laboratory measureqents of residual oil saturation. The degree of wettability of a reservoir rock is recognized as an important factor in waterflood or imbibition experiments. In this paper, however, only the water-wet case has been considered. Considerable experimental evidence1 suggests that for water-wet rocks, capillary forces predominate in tile distribution of fluids and that viscous forces in the range normallv of interest in the reservoir have a minimum influence on residual oil saturation. It follows that if the ultimate recovery is controlled by pore geometry, a unique residual non-wetting phase saturation should exist for a given set of initial conditions. Two laboratory procedures.found to be extremely useful in the study of pore structure and degree of fluid interconnection at various saturations are decribed. Although air-nercury capillary injection curves have been used2 previously to characterize the drainage case, the withdrawal or imbibition case can provide valuable supplementary data. The air-mercury process, however, has several disadvantages; it is difficult to run in a sufficiently accurate manner, mercury does not always act as a strongly non-wetting liquid and in the air-mercury process the sample is rendered unsuitable for future analyses. An alternative process is described in which air is the non-wetting phase and naptha, hentane, octane or toluene is the wetting phase. INTERFACIAL TENSION AND CAPILLARY PRESSURE Interfacial tension between immiscible fluids is due to the difference in attraction of like molecules as compared with their attraction to molecules of the neighbouring fluid. This net attraction results in a tension at the interface. To extend the interface; thus, interfacial tension s can also be thought of as free surface energy. Interfacial tension is normally expressed as dynes/cm, and interfacial energy is measured in ergs/cm2 hence, both have dimensions ml A 2 and are numerically equal.

Jan 1, 1967

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,' Streicher,' and Mc Nutt' that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,' Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,' Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3'8'9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By H. W. Hockin, D. r. Brandt, R. H. Walsh, P. L. Dietz, P. R. Girardot

New Jersey, Florida, and Canadian ilmenites were reduced with hydrogen or coke under various experimental conditions and the phase changes occurring in the ilmenite upon reduction have been studied by microscopic examination of polished sections and by X-ray diffraction. The products formed were dependent upon the type of ilmenite, temperature, time and reducing agent. Of the reducing agents, hydrogen was the more effective at lower temperatures. 1 HE possible utilization of ilmenite as a source of both iron and titanium has resulted in the development of a number of methods for the separation of the iron and titanium content. Slagging processes as currently used in Canada are typical of such methods. Somewhat less attention has been given industrially to the reduction of the iron content at less than the slagging temperature. Although references maybe found to such work, in general only one type of ilmenite, either natural or synthetic, has been studied by each author. We have attempted to draw some relationship between the results of experimental reduction and the type of deposit from which the ilmenite was derived, as evidenced by phases occurring in the ores and in the reduction products. Ilmenite ores having from 27 to 61 pct titanium dioxide were included in this study and in each case reduction was carried out at such temperatures that only limited coalescence of the particulate iron product occurred within the ilmenite grains. The history of the individual ilmenite samples and the temperature of reduction were found to determine the occurrence of various phases and the mode of distribution of the iron. REVIEW OF EARLIER WORK ON REDUCTION One of the earliest references to the reduction of ilmenite at less than the slagging temperature was made in 1917.' The metallic iron produced was_____ leached out by the action of dilute sulfuric or hydrochloric acid, to leave a product high in titanium dioxide. Subsequent to this, numerous patents2-'? and other references13"21 have appeared concerning reduction of ilmenite by carbon, hydrogen, carbon monoxide, methane, coal gas, water gas, or the like in the absence of fluxing agents. Mineragraphic examinations were not reported, and in the main, the only examinations made were chemical analyses. However, in two cases3,13, titanium suboxides were reported in the products and in one case2' rutile was reported, in addition to metallic iron. Both were identified by X-ray diffraction. While reductions in the absence of fluxing agents were generally followed by either a wet or dry chemical process for removal of the metallic iron, a Canadian source17 reported removal of the metallic iron by magnetic separation. By the addition of fluxing agents during reduction, the metallic iron has been coalesced into "pearls." Each reference to such a process23-28 has shown that the coalesced iron could be removed by magnetic or gravity means after the product was crushed. In the absence of fluxes, the coalescence did not generally occur. The major part of the present study has been limited to reductions without fluxing agents in order to determine the primary reactions of naturally occurring ilmenites. Titaniferous iron ores have also been studied,29-33 17, l9 their reduction having been used as the basis of a commercial process for beneficiation of such ores in Norway29 and more recently considered in the United States34,35. The ease of reduction of titaniferous iron ores relative to that of hematite or magnetite has been referred to,33 with the conclusion that the more

Jan 1, 1961

By C. B. Sclar and

A graphical solution is presented for the equation v =v &-cU where vb is the volume of liquid b of density 6 that must be added to liquid a of volume va and density d, in order to obtain a heavy-liquid solution of preferred density dm for mineral fractionation. The equation is valid only for pairs of liquids whose volumes are additive, but empirical density-composi-tion data show that this condition is met over wide compositional ranges by all of the heavy solutions that are commonly used for mineralogical analysis. The chart is a nomograph which consists of two horizontal volume scales ad a vertical density scale arranged so that one volume scale occurs on each side of the density scale. All the scales are linear. For two liquids of density d, and &, respectively, each volume scale has an independent level on the density scale, ad the graphical solution for vb on the nomograph is obtained by construction of one straight line. The chart can be prepared easily to cover any density range with any desired accuracy by proper selection of the scales. Heavy-liquid separation of particulate samples is an indispensable analytical procedure in the mineralogical and mineral-process ing laboratory. Heavy liquids may be used 1) to isolate specific minerals in the form of high purity products or to fractionate samples into several products with density limits for petrographic, chemical, spectrographic, and X-ray diffraction analysis,'-' 2) to determine the density of minerals,'-l4 3) to facilitate the recognition and identification of optically similar associated minerals,15 and 4) to determine quantitatively the degree of liberation of ore minerals in ores and mill products at various limiting sizes." The preparation and recovery of heavy liquids suitable for mineralogical analysis are discussed fully in the literature and operational procedures and special equipment for heavy-liquid separation are described in numerous references.'747837' 13,18,25-42 Useful tabulations of heavy liquids for mineralogical analysis are given by Tickell, Mil-ner,' Twenhofel and Tyler,' and Lange and a very complete up-to-date list of minerals arranged according to increasing density is given by Mursky and Thompson. USEFULNESS OF THE DENSITY CHART For any particulate sample, the limiting densities selected for its fractionation by means of heavy- liquid separation depend on the respective densities of the constituent minerals and the specific objectives of the separation. In many instances, the densities of readily available and practicable heavy liquids do not coincide with those that are required, and suitable liquids of the proper density are obtained by dilution with miscible liquids. In the general case, one may wish to mix either a pure liquid (A) or a solution of two miscible liquids (AP,,) of known density with either a pure liquid (B) or a different solution of the two miscible liquids (A,B,) of higher or lower density in order to obtain a final liquid of the preferred density. In conventional practice, the latter is reached empirically by trial-and-error addition of increments of one liquid to the other. The density of the final solution may be determined either by accurately weighing a known volume of the final liquid,'' 532;4;40, or by means of I)a Westphal balance, 2)a hydrometer, a refractometer in the case of binary liquid systems for which density-refractive index data are available,15 4) natural or synthetic .indicators of known density, a pycno-meter. Like all trial-and-error methods, these procedures are time consuming and many require special equipment which may not be available, The purpose of this paper is to show that the volume of a liquid of known density which is to be added to another liquid of known volume and density in order to obtain a solution with an intermediate preferred density may be determined rapidly and accurately by a graphical method provided that the two liquids form ideal or quasi-ideal solutions whose volumes are additive. Empirical data47'8~'8~4B'49 show that solutions prepared from pairs of miscible

Jan 1, 1961

By M. D. Hassialis

[Surface Areas of Concentrates and Collector Coatings (T.P. 2002, by A. M. GAUDIN and G. S. PRELLER, Min. Tech., May. Discussion by M. D. HASSIALIS and the authors) . I Activation of Minerals and Adsorption of Collectors (T.P. 2082 by J. ROGERS and K. 1'. SUTHERLAND, Min. Tech., Nov. Discussion by A. F. TAGGART and the authors). . . . 3 Correlation between Mineral Behavior in Cataphoresis and in Flotation (T.P. 2005 by A. If. GAUDIN and S. C. SUN, Min. Tech., May. Discussion by M. D. HASSIALIS). . . . . . 8] Surface Areas of Concentrates and Collector Coatings M. D. HASSIALIS.*-In the current flotation theories there exists a common gap spanned by a common assumption pertaining to the arrangement and orientation of the collector ions at the solid surface. Also common is the belief that contact angle and flotation performance are dependent upon the arrangement and orientation of collector ions. This stimulating and informative paper sheds some light upon this general problem. One of the indices of arrangement is the area available per collector ion; in this connection, Gaudin and Preller have applied the B.E.T. method for surface determinations. In a surprising number of cases, their results show a greater specific surface for tailing than for concentrate. This cannot be accounted for by the differences in specific gravity and is attributed to the presence of clay minerals of "primary" sluices in the tailing. This is not a satisfactory explanation, for experience shows that when free slimed clay minerals are present in a flotation cell they will be carried mechanically into the concentrate. A part of the answer to the decreased specific surface of the concentrate would appear to be its usual flocculated condition, yet this should not entirely account for the large spreads reported. The possibility occurs that the nitrogen adsorption isotherms for clean mineral and collector-coated mineral are different. If that were true, and if the coated mineral surface exhibited decreased adsorptive powers, the discrepancy might vanish. In discussing the disposition of collector ions at mineral surfaces, the authors adopt the more consistent viewpoint that there exists some agreement between the ions of the substrate and those of the superstrate. In the case of xanthate ions on galena, a possible arrangement is shown in Fig. 2. This arrangement shows every xanthate ion being shared by two lead ions, whereas the chemical composition calls for two xanthate ions for each lead ion (p. g). This whole discussion is misleading. In the first place, it is known that xanthate ions are not abstracted by unoxidized galena, hence Fig. 2 should show as the substrate not Pbs but PbS„ Om. It would be equally erroneous to use the lattice arrangement of PGSO4, since the surface properties of xanthate-conditioned anglesite differ from those of xanthated galena. It is highly probable that the state of the galena surface exploited in its flotation is ephemeral, since weathered galena is only poorly, if at all, collected by xanthate. Just how a substrate of oxidized galena is to be pictured depends upon one's conception of the transformation from galena to anglesite. This writer is inclined to the following sequence of events. Surface sulphide ions undergo progressive oxidation. As more oxygen is taken up by the sulphide ions they become displaced from their equilibrium positions in the galena lattice, thus accommodating for the larger volume of the S„ Om ions. Concomittant with this change the forces acting on the lead ions

Jan 1, 1946

By Roshan B. Bhappu, Raul A. Deju

A method is proposed by which the chemical reactions between water and a silicate bed can be related to equations of flow. First the reaction mechanism is studied both theoretically and experimentally. Once the reaction mechanism is established, the equations of flow are solved, and a solution (under physically reasonable side conditions) is obtained. Experiments to substantiate the solution are also presented. The knowledge of surface reactions at the water-solid interface is of critical importance in extractive metallurgy. This is especially true in regard to the froth-flotation process of mineral concentration and all phases of hydro metallurgical recovery of metals. Similarly, the problem of ground-water contamination is one of growing concern, not only because of the increasing demands on our sources of supply but also because of the increasing necessity to find vehicles of waste disposal. The hydrochemistry of waste waters must be understood to exploit and develop such resources properly. To understand these problems, it is necessary to obtain a better insight into the reactions that take place between water and a solid packed bed. To do this, we will develop here in a theoretical model that predicts the fate of a chemical species in solution as it reacts with a silicate bed through which the liquid percolates. The treatment will be one-dimensional in nature and will not include dispersion. Experiments will also be presented to substantiate the theoretical model, using the silicate minerals listed in Table 1. This paper is preliminary in nature and is part of a larger study of the surface chemistry of the silicate-water interface. Mechanism of Surface Reactions In a previous paper,' the authors discussed the properties of various silicate minerals from a mineralogical standpoint. Now efforts will be made to study the reactions that occur when these minerals are put in contact with water. The reactions occur almost entirely in the surface layer of the mineralsa and are termed sorp-tion reactions. In this study sorption denotes the composite of all physical adsorption and chemical adsorption occurring between the silicate surface and the water in contact with it. A model of sorption as seen from a chemical-bond standpoint is presented below. On the basis of this model, the surface reactions between deionized water and a silicate mineral can be studied. Sorption Model: It is known that as the oxygen-silicon ratio increases from quartz to the olivines, a greater percentage of the oxygen bonding power is available for bonding to cations other than silicon. Hence, with an increasing oxygen-silicon ratio, the oxygen-to-metal bonding increases. Upon the fracturing of a silicate-mineral crystal, the oxygen-metal bond breaks more easily than the stronger oxygen-silicon bond, resulting in a negatively charged surface. Then, if the mineral is immersed in a liquid containing hydrogen ions, the negatively charged surface should tend to be neutralized by hydrogen ions from solution, resulting in a change of the solution pH. Thus, an increase in the degree of sorption of hydrogen ions must occur as the oxygen-silicon ratio in the crystal structure increases. Also in a previous paper,' the authors found that for a given silicate mineral the change of pH with time is given by

Jan 1, 1971

By D. C. Seidel, E. F. Fitzhugh

The cementation of nickel from acidic solutions by metallic iron is discussed. The cementation is carried out in pressure vessels at temperatures above 100°C. The results from bench scale studies on variables such as retention time, temperature, and solution pH are presented. A continuous processing flowsheet is proposed. Cementation is one of the oldest known hydrometal-lurgical reactions. The cementation of copper on iron was recorded by 'Paracelsus the Great' in about 1500,1 and by 1600 the technique was being used to recover copper at the Rio Tinto operations in Spain.2 At least one early author felt that cementation may have been one of the primary reasons for the alchemists' belief in the transmutation of metals.' The early writings state that when iron was placed in the clear waters from some mountain springs, the iron disappears and copper is found in its place. To the alchemists this may well have been one of the most convincing proofs that transmutation could and did occur. Since these early times the recovery of copper from acidic solutions by cementation has been practiced in plants throughout the world. Probably the cementation technique in some form has been common to more copper mining and milling operations than any other single recovery process. During current hydrometallurgical extraction studies, which were sponsored by the Republic Steel Corp. at the Colorado School of Mines Research Foundation, Inc., it was found that under the proper conditions, metallic nickel could be cemented from acidic solutions by powdered iron. The reactions are apparently similar to those that occur during the cementation of copper, but the nickel cementation had not been anticipated because iron and nickel are nearly adjacent in the electromotive series. The potential difference between iron and copper is approximately 0.78 v, while the potential difference between iron and nickel is less than 0.21 v. The cementation of nickel with iron at room temperature is almost negligible, but when the reaction is carried out in a closed vessel at temperatures in excess of 100°C, the nickel can be cemented almost quantitatively. The part played by this discovery in a practical method of nickel recovery is set forth in a separate paper.3 The following paragraphs are a discussion of experimental studies that were made to investigate this cementation reaction. The technique has been designated the HTC or High Temperature Cementation procedure. The cementation work was part of a study on hydrometallurgical techniques for the extraction of nickel from the garnierite or silicate type nickel ores. A hydrothermal extraction procedure had been developed, and this technique produced an acidic pulp or solution that contained both nickel and appreciable amounts of magnesium.3 Small quantities of ferric and ferrous iron were also present along with cobalt, manganese, and chromium. The potential for recovering the nickel from these acidic solutions by ion exchange or solvent extraction did not appear to be promising because of the relatively high magnesium content. The Ni ++ and Mg++ have nearly identical ionic dimensions and tend to be co-absorbed or extracted during ion exchange or solvent extraction treatments. Preliminary tests indicated that the nickel could be precipitated as a sulfide when using the high pressure H2S precipitation technique developed for the Moa Bay operations of the Freeport Nickel CO.4 This technique gave good recoveries, but the nickel sulfide product requires considerable additional processing before a marketable form of nickel is realized. The process also requires clarified feed solutions, and the solids-liquid separations on the garnierite residues are difficult. A program was initiated to investigate alternate procedures that might shorten the route to a marketable nickel product, and hopefully also permit bypassing the difficult solids-liquid separation steps required for the H2S precipitation technique. It was during these studies that the nickel cementation reaction with iron was encountered. EXPERIMENTAL EQUIPMENT AND PROCEDURES The bench scale precipitation tests which were conducted during this experimental program were made in 2-liter stirred autoclaves.* A photograph showing the form and arrangement of the autoclave

Jan 1, 1968

By B. J. Kochanowsky

TO improve blasting methods it is necessary to know how the explosive force acts and how rock resists this force. Because of the tremendous power developed within milliseconds and the great number of other factors directly affecting the technical and economic results, an analysis of the fundamentals of blasting theory is difficult. But since the rules used for layout design and for calculations of size of explosive charges are based on theoretical assumptions, complete knowledge of blasting theory has great practical importance in mining. Analysis of Blasting Theory: It is interesting to note the opinion of blasting experts with respect to contemporary blasting theories. F. Stussi; Professor of the University of Zurich, stated: "We do not have enough experience yet to change our army engineering regulations in blasting and base it on new fundamentals. It is our duty to collect more practical data and to do more research in blasting to close this gap." K. H. Fraenkel,2 editor of the Manual on Rock Blasting published in 1953 in Sweden and written by well-known Swedish, German, Swiss, and French blasting and explosive experts, said: "To the best of our knowledge no suitable formulas for civil blasting work are to be found in the American, French or German literature." Present blasting theory is based upon two assumptions. 1) The blasting force of explosive acts in concentrical and spherical form. 2) Rock resistance against the explosive force is directly proportional to the strength characteristics of the rock. The first classical formula based on theoretical fundamental in blasting theory for explosive charge calculation was introduced by Vauban, a military engineer who lived 300 years ago. It was Vauban who proposed the famous formula L = w3 q, where L is the explosive charge, w = line of least resistance, and q = specific explosive consumption proportional to the weight of rock. Later engineers used q as proportional to the strength of the rock. Since Vauban's time different suggestions concerning blasting theory have been proposed. However, the principles stated at that time so affected the thinking of later generations that his formula is still in use and practically unchanged. The first controversy concerned the form of crater. It was found that geological features of rock affected its form. The factor q was analyzed thoroughly by Lares3 and later by Ohnesorge," Weichelt,5 Bendel,6 and others, but the assumption remained that resistance against explosive force is directly proportional to the strength of the rock blasted. The greatest controversy, which has not yet been settled, concerned w. It was noted that w3 is more appropriate for long lines of resistance and w2 for lines of resistance less than 15 ft. Based on the assumption that the explosive force acts concentrically and spherically, spacings between charges were limited to distances not greater than the length of line of least resistance. Sometimes larger spacing is recommended, but this is due to the advantageous geological and physical properties of rock and not to the action of an explosive force as such. In addition to the classical formula, empirical formulas are used widely. These state that the explosive charge is directly proportional to the volume of blasted rock in cubic yards, and the amounts of explosive required are usually expressed in pounds of explosive per cubic yard of rock. Empirical and classical formulas are contradictory. In the empirical formula, but not in the classical formula, explosive charge is taken proportional to all three space axes: line of least resistance, spacing, and bench height. In spite of this contradiction, both formulas give good results. This is possible because as now practiced the explosive charge calculation for heavy burdens need not be highly accurate. Each, open pit or quarry, usually works with a certain relation between bench height and line of least resistance and between charge spacing and line of least resistance. When these relations are changed, however, the specific explosive consumption q changes greatly. This is one of the reasons why the principles on which the formulas are based appear to be incorrect. In addition to the formulas discussed, others exist and are based more or less on the same theoretical

Jan 1, 1956

By Norman Weiss, H. W. Kaanta

CUSTOM ores reach across the New Mexican mesa to American Smelting & Refining Co.'s new lead-zinc mill at Deming. The influx of ores justified increasing mill capacity from 12,000 tons per month to 20,000 tons per month with the installation of a second milling section. Deming mill has met a complex material handling problem with the successful instrumentation of modern machinery and knowledge. A tight, compact plant does a big job with the aid of the latest ore moving equipment. Location and Layout The mill is located three miles northwest of Deming in the tumbleweed covered valley of the Mimbres River, 30 miles north of the Mexican border. Deming has a population of 4000 and is about halfway between Lordsburg and Las Cruces and 54 miles southeast of Silver City. The AT&SF and the SP railroads and U.S. Highways 70, 80, and 260, cut across the mesa to the town. Asarco mill station is east of the AT&SF single track, and north of Deming. The nearly level terrain is covered with fine sand supporting only yucca and tumbleweed. Compacted gravel at depth affords excellent foundation bearing. The climate is semi-arid, but the district is underlain by water-bearing strata. Tailing disposal space is plentiful. The Deming site appeared favorable because of easy rail and highway access, central location in a mining district, excellent climate, plentiful water supply, space for all present and future requirements, and proximity to a town. The milling plant is a 250-ft square. The rail spur forms the west side; sampling plant, fine-ore conveyor and bins are on the east; track hopper, primary conveyor, and crushing plant lie on the south; and the mill building completes the north side of the square. Construction The mill site was chosen and the land purchased in 1,946 and 1947. Design began in 1948, and Stearns-Roger Mfg. Co. of Denver started construction in June 1949 completing work in April 1950. Construction is steel and concrete throughout, with main concrete floors supported on cellular steel beams. The building is covered by galvanized corrugated iron, attached to the frame by welded Nelson studs, and made dust tight at the joints with roofing paper and asphalt sealing compound. Crushing and Sampling Custom ores, delivered to the mill by railroad cars or trucks, are weighed on arrival. A Robbins car shaker dumps the ore into a 100-ton capacity steel hopper. Adjacent is a 40-ton truck hopper. Three 36-in. Pioneer apron feeders supply ore from the receiving hoppers to a 36-in. conveyor which runs to the crushing plant. A tramp-iron detector protects the primary crusher except when handling magnetite containing ores. A 2 ½ -in. spaced grizzly precedes the primary Traylor 24x36 in. jaw crusher set at 4 in. A Symons 4-ft cone crusher in closed circuit with 48x78 in. Robbins Gyrex screen completes crushing to 5/8 in. The discharges of both crushers drop upon a common conveyor, which, after gaining sufficient elevation, transfers ore to a return conveyor. This return conveyor passes under a suspended magnet and over a magnetic head pulley to the Gyrex screen. Screen undersize is conveyed by a 20-in. belt to the sampling plant. Crushing rate varies from 60 to 90 tons per hour. Ores containing magnetite and pyrrhotite nullify the magnetic detector and overload the magnets

Jan 1, 1952

By J. C. Scully

In June, 1965, Sanderson and scully5 reported at the Conference on Environment Sensitive Mechanical Properties of Materials at the Research Institute for Advanced Studies at Baltimore that thin foils of titanium could be prepared by chemical polishing in a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. The technique is simpler than that since reported by Rice and Orava. As-received annealed titanium (containing 0.8 pct Fe and 30 ppm H) in the form of sheet 0.05 cm thick is placed in the solution and moved up and down. The reaction is violent but suitable foils are obtained very easily and consistently. A typical micrograph is shown in Fig. 3. The small precipitates were not identified. Yamane and ueda6 observed many spotlike features which they referred to as small dislocation loops. While their spots may be due to the reaction of the warm foil with the air as suggested by Rice and Orava, the precipitates in Fig. 3 are also found when foils of titanium are prepared by electro-polishing at low temperatures and subsequently examined in the electron microscope without any inter- mediate warming. Furthermore, they are not a surface effect. It is necessary to add that alloys of titanium cannot be so easily thinned by the chemical polishing solution described above since it contaminates the a, phase with hydrogen and produces y hydride. These matters are described at length in a paper7 and their relevance to stress corrosion is considered elsewhere.'-* Author's Reply The authors are grateful to Dr. Scully for bringing to our attention his hitherto unpublished technique for thinning unalloyed titanium, and deeply regret the unintended apparent duplication. The chemical thinning solution (7 parts HNO3 and 3 parts HF, by volume) reported by us is the same as that with which, for some period in the past, we had experienced success in the preparation of foils from single and polycrystalline niobium. Its subsequent effective application to titanium was a logical step, which, clearly independently of Scully, was conceived by Mr. Rice, to whom full credit is due. A few comments are warranted concerning some of the details of the preceding Discussion. It is evident to the discerning reader that the two thinning techniques under consideration are chemically almost identical, and in that sense are equally "simple". The chemical aspect is, of course, the one of primary importance in both communications. Thereafter, the relative simplicity is dictated by the mechanics of the actual thinning operation selected by the individual investigator. Our standard dimpling, or dishing, procedure was chosen with a view toward providing, for the electron transparent areas of the sample, the maximum protection from extraneous deformation during handling. That the long, straight dislocations visible in Scully's electron micrograph of a seemingly recovered structure closely resemble handling dislocations would tend to indicate the merit of our adopted technique. Features similar to those which Scully has attributed to precipitates, without any apparent diffraction contrast confirmation, were not observed in any of our clean foils taken from annealed or deformed specimens. This was admittedly somewhat surprising since the 3700 ppm (nominal) Fe in the A-70 commercial-grade titanium examined should have given rise to TiFe precipitates. Presumably these existed but were un-resolvable. Curiously, Scully's "precipitate1' density is fairly high although the iron content quoted was less than one-fourth of that in our material. One is forced to conclude from the evidence that prior thermal and mechanical treatments are responsible for the two different types of structure observed.

Jan 1, 1968

By L. J. Ingvalson, Roy H. Miller

IN 1948, as part of a program to expand the copper tube mill facilities of the American Brass Co. plant at Kenosha, Wisconsin, plans were formulated to convert the 100 ton capacity anode casting furnace at the Great Falls, Montana plant of the Anaconda Co. to the production of 3 in. phosphor -ized billets. The furnace was rebuilt completely and construction was started on an addition to the building. Members of the Great Falls staff visited various billet casting plants to draw upon the experience of other producers of this type of casting. Many features of other plants were incorporated into the Great Falls plant but, in addition, many new designs were made and perfected to make the plant the most advanced of its type. Construction was begun in 1949, with the intention of having the plant in production in the early part of 1951. In January 1951, as the plant was being rushed to completion, the government placed restrictions on the production of copper tubing. As a result, work was halted and the plant lay idle for two years. Interest was reactivated in May 1953 with the lifting of restrictions on copper. Plans were laid to go into production in July and the first charge was taken out July 1, 1953. Basically the plant is designed to produce from cathode copper a 3 in. diam billet, 50 in. long. weighing 110 lb, and containing 0.013 to 0.036 pct P, at a rate of 150,000 Ib per operating day. These billets are to be pierced and drawn into tubing. Furnace The furnace is a 100 ton capacity reverberatory type, gas fired furnace; 21 ft long and 9 ft wide. Gas is introduced to the furnace through two 38 hole Mettler gas burners. These burners are of chrome nickel alloy with four jets per hole. The furnace is charged with cathodes from the Electrolytic Copper Refinery plus return scrap from the casting operation by means of a Wellman Seaver Morgan Co. 7,000 lb capacity charging machine. The charge crane has a 20 ft boom and fork peel provided with an air ram to push material off the peel. The machine travels on overhead tracks and can be moved in any direction. The boom can be raised and lowered and swung through an arc of 180". With well stacked units of 6,000 lb, an experienced operator can put the first charge into the furnace in 40 min. After charging, the steel framed silica brick charge door is put in place and sealed with clay. After melting and skimming off the slag, the copper is blown until an oxygen content of 0.40 pct is reached. The metal is then heated to 2180°F, covered with coke, and poled. Poling is continued until a 3 in. diam test billet, 8 in. long, shows a flat set. The oxygen content is usually 0.030 pct at this time. At the end of poling, a temperature of 2160" to 2180°F is desired. In the side of the furnace opposite the charging door is the taphole slot, extending 36 in. upward from the bottom of the furnace. It is 4½ in. wide at the outside face and widens to 9 in. at the inside face of the furnace. It is filled with a wet mixture of sand, fireclay, and crushed coal. Flow of metal

Jan 1, 1957

By J. Szekely, R. G. Carr

A method is presented which allows the extension of the Ergun equation for the description of gas flow through packed beds in a nonisothermal regime. The pressure profile in the packed bed is calculated by the establishment of a differential energy balance and the iterative integration of the integral equation thus obtained. The predicted values of the pressure distribution were found to be in excellent agreement with those measured experimentally, under carefully controlled conditions. MANY metallurgical processes are carried out in systems in which a gas stream and particular solids are contacted in a packed bed arrangement under strongly nonisothermal conditions. Ore sintering, the firing of pellets, the operation of regenerators, blast furnace technology may be quoted as examples. Although many aspects of these systems have been extensively studied, an important variable, the pressure distribution and the relationship between pressure head and flow rate, received only little attention to date. The purpose of the paper is to present a brief survey of relevant previous work, followed by a more rigorously formulated model, together with experimental results that afford ready comparison of theoretical prediction with measurement. PREVIOUS WORK A great deal of information is available in the chemical engineering literature on flow phenomena in porous media.' The experimental results pertaining to gas flow were generally interpreted in terms of models based on the analogy with the flow through a pipe of an incompressible, isothermal fluid. Of the numerous, semiempirical correlations that have been proposed to relate pressure drop to the volumetric flow rate, the Ergun equation2 is generally regarded as the most satisfactory: The strong nonisothermality of the metallurgical systems previously mentioned would render the direct applicability of Eq. [I] rather doubtful as both density and viscosity are temperature-dependent. Ergun has used Eq. [I] for estimating the pressure drop in the stack region in the blast furnace by neglecting the viscous term and evaluating the gas density at the integral mean temperature.3 His calculations showed a rather variable agreement with measurements and it was uncertain whether the discrepancy found was attributable to the model or to the inaccuracies often inherent in measurements on an industrial scale. Other work on nonisothermal systems includes studies of the pressure distribution in sinter beds, notably by Voice et a1.4 and Mitchell.5 Mitchell developed a method involving the subdivision of the bed into several zones and assigning average property values (temperature, gas density, and so forth) to each zone. The pressure drop was then calculated for each zone by using an expression analogous to Eq. [I]. This method was an improvement over that described by Voice et al., but even here prediction and measurement differed by as much as 30 pct in certain cases. It would appear that no really satisfactory methods are available for the prediction of pressure drop in packed beds with a strongly nonisothermal regime. The method involving subdivision of the bed into small enough sections, that may be regarded as isothermal, would show promise; however its validity has to be tested by both a rigorous formulation and comparison with experimental data obtained under controlled conditions. In the following a formulation is presented together with experimental data allowing ready practical evaluation of the theory. FORMULATION The mechanical energy balance over an infinitesimal section of a packed bed may be written as follows:

Jan 1, 1969

By C. R. Barrett, N. N. Singh Deo

The high-temperature steady-state creep behavior of a series of dilute copper-silicon alloys was studied to determine the effect of stacking fault energy on the creep-rate. The steady-state creep rate is, when taken at equivalent diffusivities decreases with decreasing stacking fault energy. The stress and temperature dependencies of is suggest that creep is a difusion controlled dislocation climb process. Electron microscopy studies of the creep substructure revealed: 1) the subgrain size is not a function of the stacking fault energy in these alloys, 2) the dislocation density not attributed to the subgrain walls seems to be higher during primary creep and decreases to a lower steady value during steady-state creep, and 3) the dislocation density during steady-state creep decreases with decreasing stacking fault energy. In the past few years numerous investigators have studied the influence of stacking fault energy on high-temperature creep strength. Most of these investigators have confined their attentions to studying the relationship between steady-state creep rate, is, and stacking fault energy, ?, when samples are tested under conditions of comparable stress and temperature. For the case of fcc metals, it was initially shown by Barrett and Sherbyl and since confirmed by many others2"4 that is decreases with decreasing ?, often following an empirical relation of the form i ?m where m is a constant about equal to 3. The application of theory to explain this observation has not been entirely successful. One of the main difficulties has been the almost complete lack of structural information (dislocation density, subgrain size, and so forth) for samples with different stacking fault energies, tested under high-temperature creep conditions. weertman5 has attempted to explain the stacking fault energy dependence of is on the basis of a dislocation climb mechanism. Assuming that both the rate of dislocation core diffusion and the ease of athermal jog formation decreases as ? decreases Weertman has argued that the rate of dislocation climb and hence the creep rate should also decrease as ? decreases. One questionable aspect of Weertman's analysis is the assumption that core diffusion down extended dislocations is slower than core diffusion down unextended dislocations. The only experimental work done in this area, by Birnbaum et al.6 on nickel and Ni-60 Co, has shown the core diffusivity to increase with decreasing ?. Theories of steady-state creep based on the diffusive motion of jogged screw dislocations often seem unable to predict even the qualitative nature of the es- relationship. Assuming that Weertman is correct in his assumption that the dislocation jog density decreases with decreasing ? then the jogged screw theories predict an increasing dislocation velocity with lower ?. It is usually assumed that the increase in dislocation velocity implies a corresponding increase in creep rate. However, two other factors must be considered before such a statement can be made. That is, we must know how both the mobile dislocation density and the effective stress (the difference between applied stress and internal stress) vary with ?. Significant changes in either one of these factors could outweigh any change in dislocation velocity accompanying a change in ?. And with the slower rates of recovery expected in low stacking fault energy materials it seems likely to expect both mobile dislocation density and effective stress to be dependent on ?. Sherby and Burke7 have suggested that stacking fault energy influences the creep rate in an indirect way. These authors cite evidence that the steady-state subgrain size generated during high-temperature creep is a function of ? decreasing with decreasing ?. Assuming the creep rate to be proportional to the area swept out by each expanding dislocation loop and that subgrain boundaries are good barriers to dislocations, then the creep rate should be proportional to subgrain area, hence increasing as ? increases. A critical evaluation of any of the above theories requires more quantitative information concerning the dislocation substructure generated during high-temperature creep. Accordingly this investigation was undertaken with an aim of studying the influence of stacking fault energy on tbe steady-state creep characteristics of a series of dilute copper-silicon alloys. Special emphasis was placed on studying the strain dependence of both the dislocation configuration and density. MATERIALS AND PROCEDURE Dilute copper-silicon alloys of the compositions shown in Table I were tested in tension at constant stress. The relative stacking fault energy of these alloys has been determined and is shown in Table 11. An Andrade-Chalmers lever arm was used to maintain constant stress and testing was carried out in a water

Jan 1, 1970

By N. C. J. Ros

The paper deals with pressure gradients occurring in flowing and gas-lift wells, a knowledge of which can be applied to the determination of optimum flow-string dimensions and to the design of gas-lift installations. The study is based on a pressure-balance equation for the pressure gradient. It appears that a pressure-gradient correlation of general validity must essentially consist of two parts-—one part being a correlation for liquid hold-up and the other part being one for wall friction. Dimensional analysis indicates that both liquid hold-up and wall friction are related to nine dimensionless groups. It is shown that in the field of interest only four groups are really important. On the basis of these four groups a restricted experimental program could be selected that nevertheless covered practically all conditions encountered in oil wells. This experimental program has been carried out in a laboratory installation. Three essentially different flow regimes were found. The pressure gradients in these regious are presented in the form of a set of correlations. Comparison of these correlations with a few available oilfield data showed excellent agreement. INTRODUCTION Prediction of the pressure drop in the flow string of a well is a widely known problem in oilfield practice. Accurate data on the pressure gradient of a simultaneous flow of gas and liquid in a vertical pipe are especially useful for the determination of optimum flow-string dimensions. It is well known that with moderate gas and liquid flows such a vertical string acts as a "negative restriction". The pressure drop decreases (1) when the throughput through a given pipe increases, and (2) when at a given throughput the cross-sectional area is decreased. The reason is that, with increasing velocities, the flow becomes more agitated so that the gas slips relatively more slowly through the liquid. With the resulting increase in gas content in the string, the static head decreases. When the area becomes very small, however, the high velocities entail great wall friction, which causes an increase in pressure drop. For a given flow, therefore, minimal pressure drop is obtained by using a certain cross section. This means that, in principle, each well can be provided with an optimum flow string for minimum pressure drop and, hence, maximum possible production rate. The procedure for the selection of the optimum string has been discussed by Gilbert.' A necessary tool in the procedure, however, is accurate knowledge of the pressure gradient to be expected for various values of the governing variables. Another application of pressure-gradient data lies in the field of gas-lift practice: they provide a means of determining the optimum gas-injection rate, optimum injection pressure and optimum injection depth. Much work has already been done in the study of the pressure gradient of vertical gas-liquid flow. Poett-mann and Carpenter2 presented a pressure-gradient correlation based on measurements in wells. This correlation has been found to provide accurate predictions in high-pressure wells and in high-production wells for flow through both tubing and annuli.2-5 However, when their method is checked on low pressure-low production wells or on wells with viscous crudes, serious discrepancies are found. As we shall see in the next section, this is due to the fact that their correlation factor, representing all irreversible energy losses, is given as a function of only one correlation group. Some important variables, such as gas-liquid ratio and liquid viscosity, are not incorporated in this group so that their specific effects are not accounted for. To study also the mechanism of vertical gas-liquid flow outside the ranges covered by the Poettmann-Carpenter publication and extensions, a laboratory investigation has been carried out. This study is founded on a pressure-gradient equation that is based on a pressure balance. To reduce the number of test runs required, a dimensional analysis has been carried out, followed by a selection of relevant dimensionless groups. These groups guided a subsequent experimental study, and with their aid the experimental program could be minimized while still covering the majority of the situations encountered in oilfield practice. In this paper the choice of a formula for the pressure gradient is discussed first. This is followed by a brief description of the experimental setup. Subsequently, the dimensional analysis is discussed and the relevant dimensionless groups are selected, resulting in the experimental program required. The general relationships of pressure gradient and liquid hold-up are then described; various flow patterns and a certain flow instability (so-called "heading") are discussed and a set of correlations is presented which shows a good agreement with the measurements and a few available field

By A. A. Venghiattis

A rational approach to the selection of the appropriate perforator to use in each specific zone of an oil well is presented. The criteria presently in use for this choice bear little resemblance with actual down-hole condilions. These environmental conditions affect the elastic properties of rocks. One of these elastic properties, acoustic velocity, is suggested as the leading parameter to adopt for the choice of a perforator because, being currently measured in the natural location of the formation, it takes into account all of the effects of compaction, saturation, temperature, etc., which are overlooked in the laboratory. Equations and curves in relation with this suggestion are given to allow the prediction of the depth of perforation of bullets and shaped charges when an acoustic log has been run in the zone to be perforated. INTRODUCTION When an oil company has to decide on the perforator to choose for a completion job, I wonder if it is really understood that, to date, there is no rational way of selecting the right perforator on the basis of what it will do down-hole. This situation stems from the fact that the many varieties of existing perforators, bullets or shaped charges, are promoted on the basis of their performance in the laboratory, but very little is said on how this performance will be affected by subsurface conditions such as the combination of high overburden pressure and high temperature, for example. The purpose of this paper is to show the limitations of the existing ways of evaluating the performance of perforators, to show that performances obtained in laboratories cannot be extended to down-hole conditions because the elastic properties of rocks are affected by these conditions and, finally, to suggest and justify the use of the acoustic velocity of rocks, as the parameter to utilize for the anticipation of the performance of a perforator in true down-hole environment. EVALUATING THE PERFORMANCE OF A PERFORATOR It is natural, of course, to judge the performance of a perforator from the size of the hole it makes in a predetermined target. Considering that the ultimate target for an oilwell perforator is the oil-bearing formation preceded in most cases by a layer of cement and by the wall of a steel casing, the difficulties begin with the choice of an adequate experimental target material. For obvious reasons of convenience, the first choice that came to the mind of perforator designers was mild steel. This is a reasonable choice for the comparison of two perforators in first approximation. Mild steel is commercially available in a rather consistent state and quality, and is comparatively inexpensive. The trouble with mild steel is that it represents a yardstick very much contracted; minute variations in depth of penetration or hole diameter and shape may be significant though difficult to measure. The penetration of projectiles in steel being a function of the Brinell hardness of the steel (Gabeaud, O'Neill, Grun-wood, Poboril, et al), it is often difficult to decide whether to attribute a small difference in penetration to a variation on the target hardness or to an actual variation on the efficiency of the projectile. Another target material which has been widely used for testing the efficiency of bullets or shaped charges in an effort to represent a formation—a mineral target as opposed to an all-steel target—is cement cast in steel containers. This type of target, although offering a larger scale for measuring penetrations, proved so unreliable because of its poor repeatability that it had to be abandoned by most designers. The drawbacks of these target materials, and particularly their complete lack of similarity with an oil-bearing formation, became so evident that a more realistic target arrangement was sought until a tacit agreement was reached between customers and designers of oilwell perforators on a testing target of the type shown on Fig. 1. This became almost a necessity about seven years ago because of the introduction of a new parameter in the evaluation of the efficiency of a perforator, the well flow index (WFI). The WFI is the ratio (under predetermined and constant conditions of ambiance, pressure and temperature) of the permeability to a ceitain grade of kerosene of the target core (usually Berea sandstone) after verforation. to its vermeabilitv before perforation. The value of this index ;or the present state if the perforation technique varies from 0 to 2.5, the good perforators presently available rating somewhere around 2.0 and the poor ones around 0.8, There is no doubt that, to date, the WFI type of test is by far the most significant one for comparing perforators. It is obvious that a demonstration of a perforator

By A. Grant Elliot, H. W. Lavendel

qualitative picture has been developed to describe the oxidation behavior of TaSi2-coated tantalum and CbSi2-coated columbium. These systems have a significantly lower inherent oxidation resistance than MoSi2-coated molybdenum does. This stems primarily from the fact that Ta2O5 and Cb2O5 are nearly as stable thermodynamically as SiO2, whereas MoO2 or Moos are not. Further, diffusion of silicon in the Ta- and Cb-Si system is considerably slower than in the Mo-Si system. These ,factors prohibit the mechanism of selective oxidation of- silicon which accounts for the oxidation resistance 01- MoSi2-coated molybdenum. The silicide can be stabilized by adding suitable Modifiers which increase the thermodynamic stability of the silicate formed during oxidation. Modifiers, such as aluminum, can be inroduced into solid solution in the coating. in controlled amounts through proper selection of the source in the pack cementation process of coating fov~rzatiorz. Addition of aluminum to TaSi2, coatings on tantalum was effective in moderately increasing the oxidation resistance. EXTENSIVE experimental work and analysis have established the nature of the oxidation behavior exhibited by MoSi2- and MoSi2 -coated molybdenum-base alloys, and defined the conditions for maximum protection against oxidation of the substrate.'-* The oxidation resistance of MoSi2 in the temperature-pressure range of 1100°C-PO2 > 10-5 atm to 1900°C— PO2 > 10-1 atm is due to the formation at the surface of a continuous film of SiO2 which results from selective oxidation of silicon. Under the prevailing kinetic conditions, this film is stable toward the molybdenum silicide with which it comes in contact. Initially molybdenum oxidizes also, but it forms volatile species. SiO2, however, nucleates and grows as a condensed phase. Once a continuous film of SiO2 has formed, the oxidation rate falls to that observed for the oxidation of pure silicon indicative of diffusion through the oxide film as the rate-controlling mechanism. This oxidation behavior is of course highly dependent upon temperature and oxygen pressure. Bartlett and Gage13 and Bartlett, McCamont, and Gagelb define precisely this dependence in terms of the oxygen partial pressures and silicon diffusivities required to support a stable SiO2 film. At low temperatures (near 500°C—the "pest" region) silicon diffuses too slowly to be selectively oxidized. Hence, molybdenum and silicon oxidize readily in proportion to their stoi- chiometry. At high temperatures and low pressure, SiOz dissociates to form volatile SiO(g), and a protective film cannot be maintained. Application of the MoSiz/Mo system is limited to temperatures below 1900oC, the eutectic between MoSi, and MO5Si3.5 The oxidation behavior of MoSi2-coated molybdenum is essentially the same as that outlined above with the exception that the MoSi2 is not in equilibrium with the molybdenum substrate. At the temperatures under consideration silicon will diffuse rapidly into the molybdenum eventually converting the coating to MosSi3.4 The rate constant for subsequent decomposition of Mo5Si3 into Mo3Si plus silicon, and/or the diffusivity of silicon through Mo3Si then becomes low enough to allow active oxidation of both molybdenum and silicon with subsequent degradation of the specimen. A stable silica film can be formed but at temperatures and/or oxygen partial pressures higher than those required with MoSi2 present as a source of si1icon.l, 4 Because of the similarity between the silicides of molybdenum and those of columbium and tantalum one would expect similar oxidation behavior for coatings in the respective systems. This is not entirely the case, however, as shown by the experimental results reported herein. Regarding tantalum and columbium disilicide coatings on tantalum and columbium substrates, respectively, the oxygen arriving at the surface of the coating partitions itself nearly equally between the metal and the silicon, and a two-phase oxide layer (Me2O5 plus SiO2) is always formed. The diffusion of silicon in the tantalum and columbium silicides is relatively slow, compared to that in the molybdenum silicides, which further enhances this equipartitioning of oxygen. Thickening of the coating during service by inward diffusion of silicon into the substrate is correspondingly slow, and the effective thickness of the coating at the roots of cracks and defects is only slightly changed providing high probability for premature coating failure. Furthermore, the SiO2 glass that is generated is not thermodynamically stable with respect to the coating. The metal silicide tends to reduce the SiO2 liberating either free silicon or SiO. The situation can be improved by suitably modifying the coating such that the stability of the protective glass which is generated during service is increased. Thus, selective oxidation of silicon and the modifying agent will occur, and the silicide coating will not tend to reduce the oxide layer. Modifying agents can be introduced into the coating by the pack cementation process. Using sources containing the modifier at controlled chemical potentials allows control of the coating composition. Partially substituting aluminum for silicon in TaSi2 coatings by forming a Ta(Si,Al)2 solid solution was effective in moderately increasing the oxidation protection.

Jan 1, 1968