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By Edward P. Chapman

In the Leadville district toward the close of the "intermediate mesothermal period" of mineralization, there occurred a stage of ore deposition marked by a rather complex mineral association. As bismuth minerals formed in many places during this period, it is here called the "bismuth stage" for convenience of description. The minerals so far identified with this stage, listed roughly in the order of prominence, are: chalco-pyrite; several varieties of galena, differing slightly from one another in their small contents of silver, bismuth and tellurium; altaite; hessite; galenobismutite; alaskaite; aikinite; gold; tennantite; argentite; and perhaps sphalerite and arsenopyrite. With the exception of gold, the age relations of these minerals are difficult to determine. As shown in their descriptions, they all appear contemporaneous and hypogene. Gold may be in part contemporaneous, but most of it is distinctly later. Where minerals of this stage occur so that they can be mined alone, as at the Tucson mine, they constitute high-grade ore. Elsewhere their presence in small amounts has served to increase greatly the value of what otherwise would be low-grade pyritic or zinc-lead sulphide ore. The distribution of the bismuth ores corresponds closely to the distribution of gold ores, though not so general. It seems probable that most of the old in the district was deposited during the "bismuth stage." These ores occur relatively near the supposed centers of mineralization in Breece and Printer Roy Hills or deep down along the Tucson-Maid fault, which is one of the well recognized channels of mineralization in the Iron Hill and Graham Park areas. Consideration of the high-grade nature of this mineralization and the fact that it appears to be found relatively close to the source of mineralization suggests that prospecting along some of the known channels, even deeper than they have yet been prospected, may offer hope of commercial success. Introduction The Leadville district has been studied sinee 1880, and numerous detailed geologic descriptions of it are available in print; so also are more or less complete summaries of the mineral paragenesis, representing what was known at various periods up to 1927, the year of publication of Professional Paper 148.V lie writer has been engaged as consulting geologist at Leadville since the year 1926, and has been able to examine various types of Leadville ores throughout this period. Inasmuch as

Jan 1, 1941

By Edward P. Chapman

In the Leadville district toward the close of the "intermediate mesothermal period" of mineralization, there occurred a stage of ore deposition marked by a rather complex mineral association. As bismuth minerals formed in many places during this period, it is here called the "bismuth stage" for convenience of description. The minerals so far identified with this stage, listed roughly in the order of prominence, are: chalco-pyrite; several varieties of galena, differing slightly from one another in their small contents of silver, bismuth and tellurium; altaite; hessite; galenobismutite; alaskaite; aikinite; gold; tennantite; argentite; and perhaps sphalerite and arsenopyrite. With the exception of gold, the age relations of these minerals are difficult to determine. As shown in their descriptions, they all appear contemporaneous and hypogene. Gold may be in part contemporaneous, but most of it is distinctly later. Where minerals of this stage occur so that they can be mined alone, as at the Tucson mine, they constitute high-grade ore. Elsewhere their presence in small amounts has served to increase greatly the value of what otherwise would be low-grade pyritic or zinc-lead sulphide ore. The distribution of the bismuth ores corresponds closely to the distribution of gold ores, though not so general. It seems probable that most of the old in the district was deposited during the "bismuth stage." These ores occur relatively near the supposed centers of mineralization in Breece and Printer Roy Hills or deep down along the Tucson-Maid fault, which is one of the well recognized channels of mineralization in the Iron Hill and Graham Park areas. Consideration of the high-grade nature of this mineralization and the fact that it appears to be found relatively close to the source of mineralization suggests that prospecting along some of the known channels, even deeper than they have yet been prospected, may offer hope of commercial success. Introduction The Leadville district has been studied sinee 1880, and numerous detailed geologic descriptions of it are available in print; so also are more or less complete summaries of the mineral paragenesis, representing what was known at various periods up to 1927, the year of publication of Professional Paper 148.V lie writer has been engaged as consulting geologist at Leadville since the year 1926, and has been able to examine various types of Leadville ores throughout this period. Inasmuch as

Jan 1, 1941

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By W. L. Phillips

Stress-strain curves were obtained for single crystals of 70 pct Ag-30 pct Zn tested in tension and shear. Samples tested in tension and shear had comparable resolved shear stresses and stress-strain curves. The {111} <110> slip system was observed. It zoas found that the9.e is a barrier to slip in both latent close -packed directions and that the magnitude of these barriers is proportional to prior strain during easy glide. It was observed that cross-slip in tension and shear was most frequent in crystals with an initial orientation near <100> "Oershoot" zoas observed in tension. The amount of this "overshoot" was independent of initial orientation. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of easy glide which is characterized by a linear stress-strain curve and a low coefficient, d/dy, of work hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In fcc metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close packed planes, is the existence of latent slip planes in the fcc crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.ls Several theories have been proposed to explain the linear hardening and parabolic stages of the stress -strain curve.6"10 The easy-glide region is the least understood of the three stages. The stress-strain characteristics of Cu-Zn, which shows a long easy-glide region, have been extensively investigated."-" In light of recent ideas on dislocations, cross-slip, effect of solute atoms, and stacking fault energy, it was felt that the certain features of this earlier work might be compared with another alloy, Ag-30 pct Zn, which also exhibits a long easy-glide region. Tension and shear stress at room temperatures were employed. The results obtained, together with some interpretation of the observations, are described below. EXPERIMENTAL PROCEDURE The silver and zinc used for mixing the alloys were 99.99 pct pure. The two components were weighed to within 0.1 pct of the weights required fo the alloy composition. They were then placed in a closed graphite mold and the mold and contents were heated in 100°C stages from 500&apos; to 900°C with sufficient time and vigorous agitation at each stage provided to dissolve the silver. The crucible was then heated to 1150°C and agitated violently before being quenched in oil. The resulting alloy rod was machined free of sur face defects and then placed in a graphite mold designed for growing single crystals. The graphite mold was closed with a graphite plug and was encased in a pyrex glass tube which was connected to a vacuum system. The tube and mold assembly were placed in a furnace; the tube was evacuated and the furnace was rapidly heated to a temperature sufficient for fusing and sealing the glass. The glass-encased evacuated mold and contents were then lowered through a vertical furnace. The top section of the furnace was held at 100 °C above the melting point of the alloy. The lowering rate was 1.5 in. per hr. The tension specimens were 1/4 in. diam; the shear specimens were 1/2 in. diam. These specimens were then removed from the mold, etched, and chemically polished with hot (60°C) Chase etch reagent (Crz03-4.0 g, NH4C1-7.5 g, NHOs-150 cc, HzS04-52 cc, and Hz0 to make 1 liter). In preparation for tensile testing, the specimens were carefully machined to a diameter of about 0.200 in. to permit a gage length of 6 in., annealed for 16 hr at 800&apos; to reduce coring, and then cleaned and polished. A modified Bausch-type shear apparatus which has been described previously18 were employed. The gage length was 1/8 in. This shear apparatus was placed in an Instron tensile testing machine. EXPERIMENTAL RESULTS A) Tension. Several specimens were extended at room temperature to determine the effect of initial orientation on the stress-strain curves of Ag-30 pct Zn. The initial orientation and the resolved shear stress supported by the active slip system at various total strains are plotted in Fig. 1. The critical resolved shear stress, t,, initial rate of work hardening, d/dy, and length of the easy-glide region are independent of orientation. The arrival at the symmetry line is shown by an arrow in Fig. 1. During the easy-glide region of the stress-strain

Jan 1, 1963

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By P.V. Roundy, G.R. Mansfield

Public lands in Florida were first withdrawn from entry by President Taft on July 2, 1910, as a conservation measure because of their possible phosphate content. The reserve thus established was subsequently modified by further withdrawals and by restorations, so that on Jan. 1, 1934, it contained 66,796 acres, of which only a small part had been definitely classified. The reserved land was in scattered parcels, ranging from less than 40 acres to 320 or more, distributed in many counties. For administrative purposes and for final disposal of any of the numerous parcels, mineral classification of the land is legally necessary. In 1934 and 1935 the United States Geological Survey, under two successive grants from the Public Works Administration, prospected some 83 tracts of these lands in Polk County, comprising in all about 3300 acres, and six tracts comprising 240 acres in Citrus and Marion Counties. The tracts in Polk County were all in the so-called land-pebble field and the others in the hard-rock field. The Survey field party was under the direction of P. V. Roundy, from whose unpublished report the material in this paper is largely taken. The foreman of the prospecting crew was J. H. Wingate of Zephyrhills, Fla. The individual tracts were identified through the cooperation of the General Land Office, by transitman Hugh B. Crawford. This prospecting work fitted well the classification adopted for Public Works projects in general: it could not be done on any considerable scale under the Survey&apos;s usual appropriations; it gave employment to unemployed labor; and it may be expected ultimately to repay the Government in royalties more than the cost of the exploration. Commercial, Prospecting Methods Commercial methods of prospeeting for phosphate in Florida have been briefly described by Mansfield.&apos; In the hard-rock field, where the floor of the phosphate deposit is extremely irregular, it is customary to drill a.:

Jan 1, 1938

By Herbert Clark Hoover, Lou Henry Hoover

QUALITIES which the perfect miner should possess and the arguments which are urged for and against the arts of mining and metallurgy, as well as the people occupied in the industry, I have sufficiently discussed in the first Book. Now I have determined to give more ample information concerning the miners. In the first place, it is indispensable that they should worship God with reverence, and that they understand the matters of which I am going to speak, and that they take good care that each individual performs his duties efficiently and diligently. It is decreed by Divine Providence that those who know what they ought to do and then take care to do it properly, for the most part meet with good fortune in all they undertake; on the other hand, misfortune overtakes the indolent and those who are careless in their work. No person indeed can, without peat and sustained effort and labour, store in his mind the knowledge of every portion of the metallic arts which are involved in operating mines. If. a man has the means of paying the necessary expense, he hires as many men as he needs, and sends them to the various works. Thus formerly Sosias, the Thracian, sent into the silver mines a thousand slaves whom he had hired from the Athenian Nicias, the son of Niceratus1. But if a man cannot afford the expenditure he chooses of the various kinds of mining that work which he himself can most easily and efficiently do. Of these kinds, the two most important are the making prospect trenches and the washing of the sands of rivers, for out of these sands are often collected gold dust, or certain black stones from which tin is smelted, or even gems are sometimes found in them ; the trenching occasionally lays bare at the grass-roots veins which are found rich in metals. If therefore by skill or by luck, such sands or veins shall fall into his hands, he will be able to establish his fortune without expenditure, and from poverty rise to wealth. If on the contrary, his hopes are not realised, then he can desist from washing or digging. When anyone, in an endeavour to increase his fortune, meets the expenditure of a mine alone, it is of great importance that he should attend to his works and personally superintend everything that he has ordered to be done. For this reason, he should either have his dwelling at the mine,

Jan 1, 1950

By P. V. Roundy, G. R. Mansfield

Public lands in Florida were first withdrawn from entry by President Taft on July 2, 1910, as a conservation measure because of their possible phosphate content. The reserve thus established was subsequently modified by further withdrawals and by restorations, so that on Jan. 1, 1934, it contained 66,796 acres, of which only a small part had been definitely classified. The reserved land was in scattered parcels, ranging from less than 40 acres to 320 or more, distributed in many counties. For administrative purposes and for final disposal of any of the numerous parcels, mineral classification of the land is legally necessary. In 1934 and 1935 the United States Geological Survey, under two successive grants from the Public Works Administration, prospected some 83 tracts of these lands in Polk County, comprising in all about 3300 acres, and six tracts comprising 240 acres in Citrus and Marion Counties. The tracts in Polk County were all in the so-called land-pebble field and the others in the hard-rock field. The Survey field party was under the direction of P. V. Roundy, from whose unpublished report the material in this paper is largely taken. The foreman of the prospecting crew was J. H. Wingate of Zephyrhills, Fla. The individual tracts were identified through the cooperation of the General Land Office, by transitman Hugh B. Crawford. This prospecting work fitted well the classification adopted for Public Works projects in general: it could not be done on any considerable scale under the Survey&apos;s usual appropriations; it gave employment to unemployed labor; and it may be expected ultimately to repay the Government in royalties more than the cost of the exploration. Commercial, Prospecting Methods Commercial methods of prospeeting for phosphate in Florida have been briefly described by Mansfield.&apos; In the hard-rock field, where the floor of the phosphate deposit is extremely irregular, it is customary to drill a.:

Jan 1, 1938

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By W. G. Woolf, A. Y. Bethune

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process&apos; for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt&apos;s earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.&apos;s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951

By A. J. Williams

THE province of Saskatchewan, situated in the center of the Great Plains region of Canada, has, like most prairie areas, an essentially agricultural economy. Most of its population of about 860,000 is located in the southern half of the province in the farming and ranching areas. To the north of the prairie is a broad forested belt supporting a considerable timbering industry, and the northern one third of the province is glaciated pre-Cambrian rock formation. This latter area is relatively barren of vegetation, but the presence within it of a considerable variety of radioactive, noble and base metals, and industrial minerals has been shown by prospecting in recent years.&apos; Glacial Geology The Keewatin ice sheet, considered to have accumulated in the country to the west of Hudson Bay in Pleistocene time, covered at its maximum advancement almost all of Saskatchewan and extended south of the international boundary. Only in the Cypress Hills in the southwest and around Wood Mountain in the south central portion of the province did the preglacial formations escape the action for this glacial period. The bedrock of the plains and forest areas therefore is overlain by moraines and modified glacial drift, which vary in thickness from a few feet to 400 or 500 ft.&apos; Glacial action in the pre-Cambrian area of the province was largely erosional, most of the more recent formations and some of the pre-Cambrian rock being transported out of the area to the south and west. It has been estimated that about 13 pct of this area is composed of lakes and rivers not too adaptable to rail or water transportation, so that until the use of aviation for exploration purposes became general, development of the area was slow. To the south, the heavy mantle of glacial drift has to some extent deterred the discovery of industrial minerals in the bedrock underlying the forest and prairie regions3 At the same time, this drift contains numerous deposits of those most elementary and necessary industrial minerals, sand and gravel. Sedimentary Basin The major feature of the sedimentary deposits underlying the plains regions is the basinal structure known as the Moose Jaw syncline, which runs from the southeast corner of the province in a northwesterly direction. To the west of this syncline the formations curve upward, then have been faulted and further upthrust to appear at the surface in the foothills of the Rockies in Alberta; to the east and north they curve upward into Manitoba and northern Saskatchewan, but the surface contacts are covered mostly with glacial drift.238 The axis of the syncline dips to the southeast, so that there is also an upward trend of the formations along the axis to the northwest. In illustration of the regional structure underlying the province, the pre-Cambrian basement has been logged in drillholes at the following depths in several locations: Ogema (south central), 9390 ft; Gronlid (northeast), 2599 ft; Vera (northwest), 4422 ft; Big River (north northwest), 2348 ft. Fig. 1 indicates the general surface geology of the province, ignoring such glacial overburden as may overlie many of the bedrock formations. Also indicated is the approximate location of the axis of the Moose Jaw syncline.&apos; Industrial Minerals Clays: The province is fortunate in possessing a widespread distribution of clays of ceramic value, ranging from those used for heavy structural products to the high grade pottery and china clays. Shales suitable for brick and tile production are found in the Upper Cretaceous and Tertiary formations across the south of the province where the glacial drift is thin or nonexistent. Many deposits of glacial lake clays suitable for such wares are found scattered over the rest of the province south of the pre-Cambrian area. The Whitemud formation of the Upper Cretaceous is a narrow sedimentary band of secondary clays found intermittently at points across the south of the province where glacial action did not disturb or remove them.&apos; In the southwest corner of the province, around Eastend in the Frenchman River valley, the refractory clays of this formation are contaminated somewhat with iron compounds or other alteration products of basaltic rocks. This eliminates the use of those clays in true whitewares, as they fire to creamy buff shades at the lower temperatures and to a blue-specked grey at cone 8 to 12, (2280°F to 2390°F), the range commonly used in firing whiteware. However, for use in the production of colored artware, caneware, stoneware or crockery, and sewerpipe, this type of clay makes an excellent body that requires little or no addition of flint, feldspar, or other fluxing materials such as are required in the higher class of ware.&apos; It is not a grade of clay that can be shipped great distances to the manufacturing centers, but a market for considerable tonnages has developed at nearby Medicine Hat, where cheap natural gas is available for the firing of the ware. Farther east in the south central portion of the province, the clays of the Whitemud formation are generally more refractory and white burning. The formation is divided into three zones, consisting of white clays, brown shale, and white sandy clays.

Jan 1, 1953

By George M. Schwartz, Ian L. Reid

THE Soudan mine in the Vermilion district of northeastern Minnesota is the oldest iron mine in the state. It has shipped ore every year since 1884 and still contributes a yearly quota of high grade lump ore. No comprehensive report on the Vermilion iron-bearing district has appeared since Clements&apos; monograph,&apos; but Gruner2 discussed the possible origin of the ores in 1926, 1930, and 1932, and recently Reid and Hustad have added data on mining and geology .3, 4 For many years geologists of the Oliver Iron Mining Div., U. S. Steel Corp., have kept up to date a series of plans and vertical sections of the Soudan mine. In connection with mine operation considerable diamond drilling has been done, and this, together with the mine openings, has permitted a reasonably accurate picture of the structure of the orebodies and wall rocks. It has long been evident to geologists familiar with the mine that the ores were not a result of weathering, a point emphasized by Gruner in 1926 and 1930. As the deeper orebodies were developed it also became clear that replacement had played an important part in their development. In recent years it has been recognized that other iron ores were formed by replacement, as Roberts and Bartly5 have argued strongly for the deposits at Steep Rock Lake. On the basis of these facts G. M. Schwartz suggested to members of the Oliver staff that it would be desirable to study the evidence of replacement, particularly the possible alteration of the wall rock which would be expected if the replacement was a result of hypogene solutions. Rock Formations: The formations directly involved in the iron orebodies of the Soudan mine are few though far from simple. The country rock is largely the Ely greenstone of Keewatin age consisting of a mass of metamorphosed lava flows, tuffs, and intrusives which have been more or less altered by hydrothermal solutions. The predominant rock is chlorite schist. Interbedded with the original flows and tuffs are a series of beds and lenses of jasper to which the name Soudan formation has been applied. In the Vermilion district the term jaspilite has been used for interbanded jasper and hematite. According to modern usage these jasper or jaspilite beds do not comprise a formation separate from the Ely greenstone, inasmuch as the beds of jasper are interbedded with the flows and tuffs of the upper part of the greenstone. It would more nearly accord with modern usage to consider the Soudan beds a member of the upper part of the Ely formation. Because of incomplete rock exposure and exploration the number of interbedded jaspilite beds is unknown. In the mine, however, as many as nine major beds of jasper are known on a cross-section of one limb of the syncline, with an equal number on the other limb. In addition diamond drill cores show beds of greenstone down to half an inch in thickness. The thin beds are probably always tuffs. Structure: Rock structure in the Soudan area is complex, and because there are no recognizable horizons within the greenstone it is extremely difficult to work out the details. Generally speaking, the major regional structure is an anticlinorium, the axis trending east-west, with a westerly pitch. The Soudan mine is related to a synclinal structure on the north limb of the anticline about a mile from the west nose of the folded iron formation. The general structure at the mine is that of a closely folded minor syncline on the major regional anticline. A cross fault has dropped the east side so that the bottom of the syncline has not been reached, whereas to the west it is well shown by the mine openings and diamond drill exploration. Throughout the mine the beds of jasper, and ore-bodies that have replaced the jasper, normally dip northward at angles of 80" or steeper. In detail the jasper beds are extremely folded, probably as a result of deformation while they were still relatively unconsolidated. Orebodies: Ore in the Soudan mine is mainly a hard, dense, bluish hematite. Locally ore has been brecciated and cemented by quartz. The vugs commonly occurring near the borders of orebodies are lined with quartz crystals. They seem to have formed as part of the ore-forming process and are evidence that no folding or compression of the ore has taken place. The orebodies are numerous, varying greatly in size. Many lenses of high grade hematite are too small to be mined. Some of the larger orebodies have been followed vertically for as much as 2500 ft and horizontally up to 1500 ft. The large ore-bodies are extremely irregular in outline in the plane of the beds of jaspilite. In width they are more regular, as they are strictly governed by the width of the jaspilite beds and the greenstone wall rock, which seems to have resisted replacement by hematite. At many places the orebodies replace the jaspilite completely and have a footwall and hanging wall of greenstone. At other places either one or both walls may be jaspilite. Geologists who have studied the orebodies in recent years agree that evidence for the replacement origin of the hematite bodies seems conclusive. AS noted above, many of the orebodies replace jaspilite beds from wall to wall with no evidence whatever of compaction. The replacement origin is also supported by details of the banding which is characteristic of the

Jan 1, 1956

By C. T. Wei, A. Kelly

USING a recently developed X-ray method, reported by Schulz,2 it is possible to make a rapid survey of the perfection of a single crystal at a particular surface. This technique has the advantage of allowing a large surface of a specimen to be examined by taking a single photograph and it compares well with other X-ray methods in regard to sensitivity of detection of small angle boundaries. During the course of a survey of the perfection of large crystals of aluminum produced by a number of methods, an examination has been made of a number of single crystals produced from the melt using a soft mold (levigated alumina)." Crystals grown by this method are known, from an X-ray study carried out by Noggle and Koehler,3 to contain regions where they are highly perfect. In the present work, it has been possible to obtain photographs showing directly the distribution of low angle boundaries at a particular surface of these crystals. single crystals were grown from the melt using the modified Bridgman method with a speed of furnace travel of -1 mm per min. These were about 1/10 in. thick, 1 in. wide, and several inches long. The metal was 99.99 pct pure aluminum supplied by the Aluminum co. of America. The crystals were examined by placing them at an angle of about 25° to the X-ray beam issuing from a fine focus X-ray tube of the type described by Ehrenberg and Spear4 and constructed by A. Kelly at the University of Illinois. A photographic film was placed SO as to record the X-ray reflection from the lattice planes most nearly parallel to the crystal surface. The size of the focal spot on the X-ray tube was between 25 and 40 u, and the distance from the X-ray tube focus to the specimen (approximately equal to the specimen to film distance) was -15 cm. White X-radiation was used from a tungsten target with not more than 35 kv in order to reduce the penetration of the X-rays into the specimen. Exposure times were approximately 1 hr with tube currents between 150 and 250 microamp. The type of photograph obtained from these crystals is illustrated in Fig. 1, which shows a number of overlapping reflections from the same crystal. The large uniform central reflection is traversed by sets of horizontal white and dark lines. These two sets run mainly parallel to one another. Lines of one color are wavy in nature and often branch and run together. Large areas of the crystal surface show no evidence of these lines whatsoever. The lines are interpreted as being due to low angle boundaries in the crystal, separating regions which are tilted with respect to one another. A white line is formed when the relative tilt forms a ridge at the interface and a black line is found when a valley is formed. In a number of cases, the lines stop and start within the area of the reflection and often run into the reflection from the edge, corresponding to a low angle boundary starting from the edge of the crystal. The prominent lines run roughly parallel to the direction of growth of the crystal although narrow bands can run in a direction perpendicular to this; see Fig. 2. Although they may change their appearance slightly, the lines tend to occur in the slightly,Same place in the X-ray image and to maintain their rough parallelism when the crystals are reduced in thickness by etching. Thus the low angle boundaries can occur at any depth within the crystal. The appearance of the lines is unaffected by subjecting the crystal to rapid temperature changes, such as plunging into liquid nitrogen or rapid quenching from 620°C. From the width of the lines on the x-ray reflection, values can be found for the angular misorienta-tion of the two parts of the crystal on either side of a boundary. The values found run from 1&apos; to 10&apos; of arc, but values of UP to 20&apos; have sometimes been found, e.g., the widest lines on Fig. 2. These mis-orientations are much less than those commonly found in crystals possessing a lineage structure. When a number of a and white lines occur, running in a roughly parallel direction across the image of a Crystal, the total misorientation corresponding to lines of one color is approximately equal to that corresponding to lines of the other color. The interpretation of the lines as due to low angle boundaries has been checked in a number of ways. Photographs taken with different specimen-to-film distances distinguish lines due to low angle boundaries from effects due to surface relief of the specimen. Normal Laue back-reflection photographs, taken with the beam irradiating an area of the surface showing a number of the lines, show white lines running through each Laue spot. Black lines are set to see by this method. X-ray photographs were also taken, using the set-up described by Lam-one et al.5 when the beam straddles regions giving rise to lines in the Schulz pattern, split reflections are observed within the Bragg spot. The misorienta-tions calculated from the separation of these reflections and that found from the widths of the lines on the schulz technique patterns show good agreement. An exposure was made with Lambot technique of an area of the crystal showing no evidence of low angle

Jan 1, 1956

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand there has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of -200 mesh material in the final product markedly increases costs of dewatering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins.

Jan 2, 1958

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By Leonard C. Grimshaw

Diffusion of carbon from gases into iron has been the object of much research, because of its long recognized importance in carburizing processes, but the direct diffusion of carbon from steel into iron has received relatively little attention. Because of the increasing use of clad metals in industry, direct diffusion from steel into iron is becoming of practical importance. Therefore, the object of this investigation was to study the diffusion of carbon from several different kinds of steel directly into relatively pure iron, realizing that elements in the steels other than carbon might influence the rate of carbon diffusion. The previous work on diffusion of carbon into iron has been considerable, and includes many reports in foreign languages. This work has recently been well reviewed by Mehll and Krynitsky12 and the reader is referred to their excellent bibliographies. Methods of Study There are two main methods by which the direct diffusion of carbon from steel into iron may be studied. In one method, steel is first decar-burized in part, and diffusion of carbon then allowed to take place from the steel into the decarburized steel. This method is open to two serious objections: (1) the decarburized steel is not iron, but contains elements such as manganese, silicon, chromium or tungsten, which may be an essential part of the steel under study, and which may seriously influence the diffusion of carbon into the decarburized area; (2) there is from the start of diffusion an unknown carbon-concentration gradient between the steel and the decarburized area. Another method, which possesses neither of these disadvantages, is to study diffusion from steel into a thick plating of electrolytic iron. Herc the chief difficulty is to secure an electrolytic deposit of iron upon steel without introducing an oxide film at the interface that will interfere with diffusion. The author is able to deposit iron upon any kind of steel without introducing an oxide film at the interface, so that diffusion of elements from the steel into the iron is free to proceed unhindered.

Jan 1, 1938

By R. J. Blackwell, A. L. Pozzi

Scaled laboratory-model studies provide a powerful method for evaluation of a proposed oil-recovery process. In recent years, models have been used extensively to evaluate processes in which solvents displace oil, both for general cases and for specific reservoir conditions. Since the performance of a miscible flood in a horizontal reservoir can be significantly affected by transverse mixing between solvent and oil, this displacement mechanism must be accurately simulated in the scaled model studies. Unfortunately, precise scaling of transverse dispersion coupled with the requirement of geometric similarity requires impractically large laboratory models and long times for experiments. If scaling requirements for miscible displacements could be relaxed while accurate simulation of essential displacement mechanisms is maintained, the utility of model studies would be greatly enhanced. The purpose of the work reported herein was to evaluate the relative importance of various mechanisms affecting miscible displacement and to ascer tain whether the essential features of the displacement process can be simulated even though some scaling groups are not satisfied. These studies were performed with completely miscible systems in linear, horizontal models packed with unconsolidated media. From the experimental results, a set of relaxed scaling criteria was formulated which allows the requirements of geometric similarity and equality of the ratio of viscous to gravity forces to be omitted for specified conditions. The relaxed criteria are valid whether transverse mixing is by molecular diffusion or by convective dispersion. Correlations which permit prediction of vertical sweep efficiencies in linear, horizontal reservoirs were developed from the experimental data when transverse mixing is by molecular diffusion. These same correlations may be used when transverse mixing is by convective dispersion if an empirically defined, effective, transverse dispersion coefficient is used in the description of the mixing process. The effective transverse dispersion coefficient correlation essentially duplicates the dispersion coefficient correlation for equal-viscosity, equal-density fluid systems. Experimental values for the effective transverse dispersion coefficient can be measured readily. INTRODUCTION One of the most effective methods for evaluation of miscible-displacement oil-recovery processes is that of displacements in laboratory models scaled to simulate reservoir conditions. For these laboratory studies to be meaningful, however, the essential displacement mechanisms affecting reservoir performance must be accurately simulated. Since the performance of a miscible flood in horizontal reservoirs, or in dipping reservoirs at high rates, can be significantly affected by transverse mixing of solvent and oil, this mechanism must be considered in the design of laboratory experiments. Unfortunately, precise scaling of transverse dispersion coupled with the requirement of geometric similarity requires impractically large laboratory models and long experiment times. This difficulty seriously limits the utility of laboratory model studies. Craig,et al,1 demonstrated that geometric similarity is not required when mixing is unimportant. Their experimental data indicate, for the cases studied, that the displacement is sufficiently characterized by scaling the ratio of viscous-to-gravitational forces. This work suggests that relaxation of the requirement of geometric similarity and, possibly, other criteria might also be permissible when mixing is important, provided suitable groups describing the mixing process are scaled. The purpose of the work reported here was to evaluate the relative importance of various mechanisms affecting miscible displacement and to ascertain whether the essential features of the displacement process can be simulated even though some scaling groups are not satisfied. Consequently, laboratory investigations were made of the dependence of recovery on dispersion and other variables,

By R. C. Buehl, J. P. Morris

F. D. Richardson—The authors are to be congratulated on this further contribution to our knowledge of the thermodynamics of the interaction between sulphur and carbon and silicon in liquid iron. As the authors state, the influence of carbon and silicon on the activity coefficient of sulphur in liquid iron is clearly of great importance in the blast furnace, since it must cause a three to fourfold improvement in the partition of sulphur between slag and metal. The influence of increasing temperature in further increasing the activity coefficient of the sulphur in the metal in the blast furnace by increasing the carbon content is also of interest. This effect, however, is probably only part of the reason for the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing temperature. Other contributing factors are the lowering of the oxygen potential in the presence of carbon by increasing temperature and the probable increase in the activity coefficient of the lime in the slag for the same reason. The former of these effects, which works via the (CaO) + [S] = (CaS) + [O] equilibrium, might possibly account for a 70 pct improvement in the sulphur partition and the latter might give a further 50 pct improvement. C. Sherman—I would like to compliment the authors on their very careful research. If I may, I would like to show results of calculations on the carbon-sulphur-iron system similar to the ones that were shown in our paper for the silicon-sulphur-iron system. For Fe-S-C ternary system k=PHgs/PH2 x 1/(f1°) (f2°) (%S) where fs = sulphur activity coefficient fs&apos; = fs for Fe-S system of equal pct S f3° = f2/f2 for Fe-S-C ternary system This same analysis has been used on other systems, but the results shown in fie.- 7 are for carbon and silicon. L. S. Darken—I would like to make two brief comments in addition to complimenting the authors on an apparently very precise and accurate investigation. The first is that the present work is in agreement with a calculation by Larsen and myself." Our calculation (much less precise than the present work) was based on: (1) Unpublished work on the sulphur content of molten iron (1.5 pct at 1500°C) in equilibrium with graphite and an iron sulphide slag; (2) the distribution coefficient of sulphur between slag and carbon-free liquid iron. We expressed the result in a form equivalent to log 7. = 0.18 [%C] which gives an activity coefficient (?s.) of sulphur only slightly higher than the authors find and certainly within the precision of the earlier work. My second comment concerns the correlation of the thermodynamic findings with atomistics. A rough pic- ture of the atomic arrangement in the liquid solution is rather easily conceived for this particular liquid solution containing iron, carbon, and sulphur. Carbon has a very much stronger affinity for iron than for sulphur. Hence we may conclude that a sulphur atom will but seldom be adjacent to a carbon atom—since this would be a position of high energy. From the metallic radii of iron and carbon we know that six iron atoms pack neatly around one carbon atom. Thus each carbon atom in retaining this shell of iron atoms (which latter may not be replaced by sulphur on account of the high energy requirement) decreases the available positions for each sulphur atom by six. Hence each atomic percent of carbon decreases the equilibrium sulphur content by 6 pct (of itself). Or, at low concentration each atomic percent of carbon increases the activity coefficient of sulphur by 6 pct. This is in good agreement with the observed increase (6 or 7 pct at low carbon content). It is indeed gratifying to find a case where, by such simple reasoning, quantitative agreement is found between precise data and the modern picture of the atomistics of the metallic state. J. P. Morris (authors&apos; reply)—We would like to point out that there is an error in the equation on p. 322 of the paper. The third equation should read: ½S2 (gas) + H2 (gas) = H2S (gas) The authors wish to thank everyone for the interest they have shown in the paper. In regard to the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing the temperature, Dr. Richardson is correct in stating that the cause can be attributed only in part to the increase in activity coefficient of sulphur resulting from the rise in carbon plus silicon content of the metal with rise in temperature. However, this factor is probably an important one. The results of one experiment, performed since this report was written, indicate that at a constant temperature the addition of silicon to a melt saturated with carbon causes an increase in the activity coefficient of sulphur even though the carbon solubility is lowered. In this test, 2.5 pct silicon was added to a melt saturated with carbon and maintained at 1400°C. Although the carbon content dropped from 4.85 to 4.1 pct, the activity coefficient of sulphur was increased by about 20 pct.

Jan 1, 1951

By Lo-Ching Chang, J. Chipman

The perennial and increasing interest in the chemical behavior of steelmaking slags has led to numerous attempts to formulate the thermodynamic properties of these solutions. The classical view is that of a solution of the component oxides in which certain acidic oxides are more or less completely held in combination with basic or metallic oxides, the nature of the interoxide compounds being derivable from the chemical behavior of the slag or from the mineralogy of a solidified specimen. The known electrical conductivity of slags has pointed to the existence of ions in the solution and a number of attempts have been made to account for the observed facts of slag behavior on the basis of a theory of complete ionization of the solution. It is the purpose of this paper to examine, in the light of ionic theory, a number of recently published series of data on slag-metal and slag-gas equilibria, with the purpose of obtaining a more complete or more satisfactory generalization than has been possible on either of the single bases of simple compound formation or complete ionization. The attempt to formulate the ionic constitution of a complex solution is fraught with many uncertainties. An ion is not something that can be plucked from the solution and examined in detail, nor can its true formula be determined with certainty by any single experimental method. In attempting to express the composition of a slag by various ionic formulas it can be expected that alternative hypotheses of essentially equal merit will present themselves. In the present state of early development of the ionic theory of slags, it may be necessary to make some rather arbitrary choices of ionic formulas in the absence of su- cient information to yield complete certainty. Acids and Bases The classification of slag-forming oxides as acidic or basic apparently dates back into the days of Berzelius. It is difficult to see how the concept could have originated in the early twentieth century when it was fashionable to define an acid or a base as an aqueous solution containing hydrogen or hy-droxyl ions. It is, however, entirely consistent with the modern and more general theory of acids and bases. In this theory, as originally formulated by G. N. Lewis,&apos; a basic molecule is one that has an electron pair which may enter the valence shell of another atom thus binding the two together by the electron-pair bond. An acid molecule is one which is capable of receiving such an electron pair into the shell of one of its atoms. The acid, the base, and the product of neutralization may be either ions or neutral molecules. The product of such a reaction may itself be a base or an acid if it is further capable of giving or accepting an electron pair. Thus a base is a donor of electrons, an acid, an acceptor. In oxide slags the typical and ever-present base is oxide ion, 0-—. In behavior and in importance it is analogous to hydroxyl ion, OH-, which is the typical base of aqueous solutions. There is nothing in the chemistry of slags which is quite analogous to the acid H30+ in aqueous solutions. This is not surprising for in slag systems there is nothing which can be designated as a solvent and no ubiquitous positive ion. The chemistry of slags is in fact more complex than the chemistry of aqueous solutions and the concepts which must be evoked in its study are correspondingly broader. In seeking a basis for a classification of slag-forming oxides as basic or acidic it must be remembered that these terms are not absolute but relative. A substance which acts as a base toward a second substance may act as an acid toward a third. This is less likely to happen among strong bases or acids than among the weak ones; there are numerous examples of weak acids which under the influence of a stronger acid behave as weak bases. Such substances are called amphoteric. A classification of the glass-forming oxides has been proposed by Sun and Silverman² and further developed by Sun3 in which the oxides are arranged in order of decreasing acidity or increasing basicity, each substance being potentially capable of acting as an acid toward substances below it in the list and as a base toward those above it. It is based upon the relative strengths of the metal-to-oxygen bond as determined by the energy required to dissociate the oxide into its component atoms.&apos; Data are available for computation of this energy, at least approximately, for the oxides of slags and glasses. In general those oxides from which it is most difficult to remove the positive atom are the strong acids while those in which it is most loosely held are the strong bases. It is in the latter, of course, that formation of oxide ion occurs most readily as, for example, in CaO which in solution ionizes to form the weak acid Ca++ and the strong base O—. The order of arrangement found by Sun is shown in the first column of Table 1, to which have been added the data for

Jan 1, 1950