Search Documents

By T. G. Chapman

The writer has carried on experimental work for several years with respect to the simultaneous dissolution of gold by cyanide and the adsorption of the dissolved gold on activated charcoal in ore pulps, followed by the recovery of the charcoal by flotation. The results of this experimental work have been sufficiently encouraging to suggest a new process based on the principle of simultaneous dissolution and adsorption of gold, applicable to certain ores and tailings that cannot be treated to advantage by countercurrent decantation or filtration. Applications for patents have been filed and The Dorr Company, Inc. has the exclusive right to license the use of the process. The purpose of this paper is to describe such a process, state its possible advantages and immediate field, and give some results obtained on a laboratory scale. Early Experimental Work In the early stages of the experimental work attempts were made to precipitate soluble gold from cyanide solutions with zinc and aluminum in ore pulps followed by flotation of the precipitated gold, but since the results were not promising enough to continue with these precipitants attention was directed to carbon. The first experiments with carbon comprised the addition of cyanide and alkali to the ore pulp, the addition of carbon at or near the end of the dissolving period, and the recovery of the carbon by flotation. With this method of procedure the assumption was made that carbon functioned as a precipitant of gold from cyanide solutions and as such should be added as are other precipitants, including zinc and aluminum; namely, at the end of the dissolution period. The assumption was then made that carbon functioned as an adsorbent, and that if such assumption proved to be correct, it could be added with success to the ore pulp at the time of adding the cyanide. The first experiment along this line was successful in that the feasibility of the dissolution of gold by cyanide and the simultaneous extraction of the dissolved gold by carbon in ore pulps was demonstrated, at least with respect to such treatment on a laboratory scale.

Jan 1, 1939

By C. M. Young

Wherever salt is extracted from the ground as an artificial brine produced by pumping down fresh water to dissolve the salt, subsidence of the overburden is a possibility, though apparently few cases of such subsidence have been noted and detailed records are wanting. This description is intended as a record of subsidence that may permit the forcasting of similar occurrences in other cases; the data were supplied largely by R. B. Lee, city engineer of Hutchinson, Kans. About eleven years ago, ground movement occurred at a neighboring salt plant, when the surface assumed the form of a shallow funnel. Movement was probably due to a flow of sand into a well through a poor seal or a broken casing. The salt deposit increases in thickness from the east until at Hutchinson, where the subsidence occurred, it is about 310 ft. thick. The interbedded layers of shale vary in thickness from mere traces to about 7 ft. While knowledge of the shale content of the beds is not exact, the log of a shaft 3 miles east of Hutchinson indicates that shale forms about 25 per cent. of the total thickness. This shaft does not reach the bottom of the salt by about 60 ft., but there is no reason to think that the lower part of the bed is different from the upper. Logs of wells sunk to the bottom are not sufficiently detailed to be of much value. Above the salt is the shale of the well-known Red Beds. The thickness of this is variable, principally because of its eroded surface, but at the mine it is 340 ft. This shale is variable in character and strength, but contains no strong members of limestone or sandstone. If the support is removed, very probably it will subside. The Arkansas River flows across the salt district and Hutchinson is situated on the flood plain. Between the top soil, which is about 8 ft. thick, and the shale is 60 to 100 ft. of water-bearing sand and gravel. The process of removing salt, at least in the case of the earlier wells with which we are concerned, is as follows: An 8-in. hole is put down through the sand and gravel by means of a drive pipe, which is bedded in the shale. Prom the top of the shale, a 6411. hole is drilled through the shale, to, or nearly to, the bottom of the salt. Casing is put in to a depth of about 140 ft. to shut off a water-bearing layer in the shale.

Jan 1, 1927

By Bruce Chalmers, D. C. Larson

Aluminum crystals with longitudinal-axis orientations of (111) . (110), and (100) were deforined in tension and annealed. The conditions of deformation were controlled so that the re crystallization nuclei originated in either the heavily deformed regions at saw cuts {artificial nucleation) or in the lightly deformed matrix (spontaneous nucleation). The artificial-nucleatioln experiments showed that in lightly deformed (110) and (100) crystals low-angle twist boundaries are most mobile, while in (111> crystals and heavily deformed (110) and (100) crystals high-angle tilt boundaries with near (111) rotations are favored. The spontaneous-nucleation experiments showed the existence of preferred orientations in the (111) crystals. The nonrandomness of the grain orientations is quantitatively determined through a comparison with the results which would he obtained from a randowl set of grain ovientations. PREVIOUS recrystallization studies have been performed on single crystals deformed in tension.1 7 The crystals used in these studies usually had random tensile-axis orientations and the extent of deformation was not a primary consideration. The present study concerns the recrystallization of single crystals with tensile-axis orientations of (Ill), (110), and (100). The emphasis of this work is on the influence of the tensile-axis orientation and the degree of deformation on both the nucleation and growth processes. The multiple-slip orientations were chosen because secondary slip or slip intersection promotes nucleation.1,5,8 These crystals recrystallize at lower strains than the crystals which are oriented for single slip. Also, the greatest variation in deformation behavior is exhibited by the multiple-slip orientations. The stress-strain curves for crystals with tensile-axis orientations of (111) are higher than the stress-strain curves for poly-crystals, and the stress-strain curves for crystals with tensile-axis orientations of (100) are lower (at large strains) than the stress-strain curves for the crystals which deform initially in single slip.g The recrystallization nuclei originated in either 1) the homogeneously* deformed matrix of the crys- tals or 2) the heavily and inhomogeneously deformed regions at saw cuts. The nuclei will be referred to hereafter as spontaneous and artificial nuclei, respectively. The two terms do not imply a difference in the nature of the nuclei; they imply simply a difference in the mode of introduction of the nuclei. During spontaneous nucleation very few (always less than ten) grains nucleate, while during artificial nucleation large numbers of grains nucleate. Only a fraction of the artificially nucleated grains penetrate very far into the deformed matrix during annealing. The grains that penetrate the farthest into the deformed matrix will be referred to as the dominant grains. EXPERIMENTAL PROCEDURE The thirty-five crystals used in this investigation were grown from the melt in milled graphite boats at a rate of 1.6 cm per hr. The crystals had dimensions of approximately 6 by 12 by 80 or 6 by 6 by 80 mm and the aluminum was of 99.992 pet purity. The as-grown crystals were annealed at 610°C for 24 hr and furnace-cooled. They were then heavily etched and electropolished in a solution of five parts methanol to one part perchloric acid. The crystal orientations were obtained by back-reflection Laue photographs and were accurate to ±2 deg. The tensile-axis orientations were (loo), (110), and (111). Two of the side faces of the (111) crystals were (110) lanes. The (110) crystals had both {100) and {110) side faces and the (100) crystals had (100) side faces. The crystals were deformed at a strain rate of 0.003 per min. Shear stress and shear strain were obtained by multiplying and dividing the tensile stress and strain, respectively, by the Schmid factor, m. For the (111) crystals m = 0.272 and for the (110) and the (100) crystals m = 0.408. The Schmid factor is effectively constant during deformation for all orientations. The deformed crystals were sawed into 1-in.-long specimens while the crystals were totally enclosed in a graphite boat. The sawing was performed very carefully in order to limit the plastic deformation to the sawed regions. The specimens were electropolished in the solution mentioned above to remove the sawed-end deformation as well as controlled amounts of surface material. A special stainless-steel grip was used to hold the specimens during the electropolishing treatment. The gripping faces were flat, with no teeth, to prevent the introduction of extraneous de-

Jan 1, 1964

By Vittal S. Bhandary, B. D. Cullity

Swaged iron wire has a cylindrical {001} <110> texture. The texture is also cylindrical after re-crystallization in the absence of a magnetic field, but <111> and <112> components are added to this texture when recrystallization occurs in a field. The mecizanical properties in tension and in torsion are not greatly altered by these changes in texture. AS shown in a previous paper,1 cold-worked wires of the two fcc metals copper and aluminum can be made relatively strong in torsion and weak in tension, or vice versa, by proper control of preferred orientation (texture). The deformation texture can be controlled by selection of the starting texture (texture before deformation), because certain initial orientations are stable during deformation. The present paper reports on similar work performed on bcc iron. In this case it was clear at the outset that there was no hope of controlling the deformation texture, which is one in which <110> directions are aligned parallel to the wire axis. (1t has usually been regarded as a fiber texture, but Leber2 has recently shown that it is a cylindrical texture of the type {001} <110>. In either case, <110> directions are parallel to the wire axis.) There is general agreement on this texture among a large number of investigators, which in itself suggests that the starting texture has no influence on the deformation texture. More direct evidence was produced by Barrett and Levenson,3 who reported that iron single crystals of widely varying initial orientations all had a single <110> texture when cold-worked into wire. Thus <110> is a truly stable end orientation for iron and probably for other bcc metals as well. Under these circumstances attention was directed to the possibility of controlling the recrystallization texture. This texture is normally <110> in iron,4 just like the deformation texture. However, it is conceivable that this texture could be modified by a proper choice of the time, the temperature, and what might loosely be called the "environment" of the recrystallization heat treatment. In the present work the environmental factor studied was a magnetic field. The effect of heating in a magnetic field ("magnetic annealing") on recrystallization texture has been investigated by Smoluchowski and Turner.5 They found that a magnetic field produced certain changes in the recrystallization texture of a cold-rolled Fe-Co alloy. The texture of this material is normally a mixture of three components, and the effect of the field was to increase the amount of one component at the expense of the other two. Smoluchowski and Turner concluded that the effect was due to magnetostriction. With the applied field parallel to the rolling direction, the observed effect was an increase in the amount of the texture component which had <110> parallel to the rolling direction. In the Fe-Co alloy they studied, the magnetostriction is low in the <110> direction and high in the <100> direction. Thus nuclei oriented with <110> parallel to the rolling direction will have less strain energy than those with <100> orientations and will therefore be more likely to grow. In a later paper on the same subject, Sawyer and Smoluchowski6 ascribed the effect to magneto-crystalline anisotropy and made no mention of magnetostriction. In the papers of Smoluchowski et al. the intensity of the magnetic field was not reported but it was presumably large, inasmuch as it was produced by an electromagnet. In the second paper6 it is specifically mentioned that the specimens were magnetically saturated. But if magnetostriction has a selective action on the genesis of stable nuclei during recrystallization, that selectivity must depend only on differences in magneto-strictive strains between different crystal orientations and not on the absolute values of those strains. Thus the saturated state does not necessarily produce the greatest selectivity, because the relative difference in magnetostrictive strains between different crystal directions may be larger for partially magnetized crystals than for fully saturated ones.7 In the present work the specimens were subjected to relatively weak fields (0 to 100 oe) produced by solenoids. MATERIALS AND METHODS Armco ingot iron rod (containing 0.02 pct C and 0.19 pct other impurities) was swaged from 0.25 in. in diam. to 0.05 in., a reduction in area of 96 pct. The mechanical properties in tension and torsion were measured as described previously.&apos; Textures were measured quantitatively with chromium or iron radiation and an X-ray diffractometer,8,1 and

Jan 1, 1962

By F. W. Jessen, H. Kazemi

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

Jan 1, 1965

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth&apos;s crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 million tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms. In 1951 an ambitious program aimed at the discovery of new orebodies and important extensions of abandoned deposits was launched by Attwood Copper Mines, Ltd. In this district so thoroughly searched by an earlier generation of prospectors, any orebody which had remained undiscovered must have little or no surface indication. Consequently, in addition to the basic detailed geological work, the program of exploration included magnetometer and self-potential surveys. Geological bets and geophysical anomalies were tested further, prior to diamond drilling, by a study of copper distribution in tree twigs and/or in the soil. The soil sampling and analytical methods used and some of the results seem of sufficient importance to warrant this paper. The authors had done some plant sampling in this and other districts, using the dithizone neutral-color-end-point method (Warren and Delavault, 1948, 1949; White, 1950),1-3 but they were unfamiliar with its soil application. Finally, after much experimenting in the field, they adopted the methods described here. These methods are not entirely original or defensible on theoretical grounds, but under field conditions of rapid sampling and analysis the results are reliable enough to be of use. Fig. 1, which shows the results of duplicate analyses of duplicate soil samples taken at 50-ft intervals across an anomalous zone, indicates the relative dependability both of the sampling and analytical methods. Sampling and Analytical Equipment A 2-ft piece of 1-in. solid drill steel, one end sharpened to a broad, conical point. The steel is marked at 1 ft from the point. A 2-ft piece of ½-in. black iron pipe, one end filed to a bevelled cutting edge. The pipe is marked at 1 ft 3 in. from the cutting end. A 3-lb hammer. A plastic or rubberized sheet about 18 in. square. Moisture-proof assay pulp envelopes. A 10-mesh seive made from window screen with the paint burnt off. A small assay spatula. A pan balance sensitive to 10 mg. Two ignition trays about 4 in. square, made of sheet iron turned up along the edges. A Coleman two-burner gasoline stove. An asbestos board about 5x8 in., used as a hot plate on the gasoline stove. A circular aluminum rack to hold 8 test tubes while refluxing (design of Almond and Morris). Pyrex Glassware Large refluxing test tubes, 25x200 mm, marked at 40 ml volume. Breakers, 20 ml. Pipettes, 1, 5, and 10-ml capacity. Graduate, 50 ml. Shaking cylinders, 100 ml, glass stoppers. Burette, 25 or 50-ml capacity, with holder. Chemical Supplies 1 N sulphuric acid. Hydroxylamine hydrochloride, solid crystals. Fisher Alkacid test paper. Copper standard solution. Dithizone standard solution 60 mg per liter. Water reasonably free of metals. Soil Sampling Method: The problem of how to take a soil sample is extremely crucial. The method outlined below, adopted after a number of tests, has the advantages of uniform pattern, uniform depth, and uniform size of sample. The area to be tested was marked off by chain and compass lines 100 ft apart, normal to the strike of possible ore deposits. Numbered stakes were set at 50-ft intervals along these lines and a soil sample was taken at each stake in the following manner. The drill steel was driven into the ground normal to the slope of the surface to the marked depth of 1 ft, moved slightly from side to side, then carefully withdrawn. The iron pipe was inserted to the bottom of this hole, tapped down to the marked depth of 1 ft 3 in. and withdrawn; the 3-in. soil plug in the

Jan 1, 1955

By J. J. Gilman

Zinc monocrystals, when compressed nearly parallel to their basal planes (within 20), deform in a new way; and certain deformation markings, called "-bands," are typical of this new mode. Characteristics of these bands are described. Mechanical behavior of low angle zinc monocrystals was investigated in some detail. Recrystallization did not occur upon annealing of banded specimens that were free of deformation twins. -Bands do not seem to be the result of nonbasal slip, but rather, a result of a microbuckling mechanism. u-Bands differ qualitatively and quantitatively from ortho kink bands. A dislocation model, consistent with some of the features of u-bands, is described. THE plastic deformation of zinc monocrystals with slip planes (0001) nearly parallel to the stress axis was studied in this investigation. In a previous investigation, it was shown that some low angle zinc crystals (those with slip planes making angles of more than about 2.5+1° with the compression axis), deform by ortho kinking while others (those with slip planes making angles of less than 2.5+1° with the compression axis) deform in a new way.&apos; This new mode of deformation will be described in some detail here. Some of its striking features are: 1—it operates only for compressive stresses, 2—its temperature dependence is anomalous, and 3—it exhibits a new type of "yield-point" behavior. The mode of deformation to be discussed is not new in the sense that no previous evidence of its existence had been reported. The markings that it creates on the cleavage surfaces of zinc crystals have been described by several investigators.&apos;" However, this is the first time that it has been made to operate under controlled conditions so that its response to mechanical variables, temperature, and aging treatments could be investigated and its geometry completely described. Apparently. Jillson&apos; as well as Holden3 and Pratt" believed that the small bands they observed were simply small versions of ortho kink bands. In fact, two of these authors3,6 "alled the markings "micro kink bands." In spite of the precedence, it is felt that this term is not entirely suitable because these bands do not have the same genesis as kink bands, and they are qualitatively different in structure. As will be indicated by later discussion, the bands seem to be related to the tensile deformation bands observed in aluminum. The present author has chosen to call the bands "micro deformation bands," or simply ",ubands," and the deformation process, &apos;&apos;p-banding." Experimental Methods Crystals were grown from 99.999+ pct Zn obtained from the New Jersey Zinc Co. The details of the technique are given elsewhere." It should suffice to say that the crystals were seeded for orientation control, and precision pyrex tubes were used for molding them. About 40 crystals were used, yielding some 130 specimens. Fig. 1 illustrates the typical form of the specimens and shows how the orientation angles are defined. The crystal specimens were usually 1 3/4 in. long and about 150 mil in diameter. The angle between the slip or cleavage plane (0001) and the specimen axis is designated by xo, while a is the angle between the maximum slope of the (0001) plane and the nearest close-packed direction [1210], vary ing from 0°to 30°. The crystals were cut into specimens with a jeweler&apos;s saw and the ends were squared by filing (specimens held in V-block). Crystals of this orientation are stiff toward bending, so this procedure introduced only deformation localized at the ends. Then the specimens were polished either chemically in 50 pct HNO³ or electrolytically in 20 pct chromic acid. The mechanical tests were made with an Instron testing machine. This machine weighs by means of electric strain gages on elastic bars and is quite stiff, since the full-load deflection of its load cells is at most 0.002 in. Most of the testing was done at a

Jan 1, 1956

By R. L. Boyer, F. Morgan, M. Muskat

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-&apos; In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.&apos; Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer&apos;s3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

By M. Muskat, R. L. Boyer, F. Morgan

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-&apos; In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By J. B. Stubbins, R. A. Blais

Extensive geological work was initiated — and continues — when operations of the Iron Ore Co. of Canada commenced in the Labrador-New Quebec area. Such geological operations include: mapping, test pitting, drilling, underground workings, volume factor and structure tests, and the calculation of ore grades and tonnages. Details of such work are given. Development is carried sufficiently ahead of mining to provide reliable tonnage and grade estimates and allow final mine planning. In order to make full use of geology in mining operations, the pit engineer combines the duties of geologist and mining engineer. The iron deposits of the Knob Lake range are located in the central part of the Labrador peninsula, a territory nearly twice the size of Texas, which is bounded by Hudson Bay on the west, Hudson Strait on the north, the Atlantic Ocean on the east and the Gulf of St. Lawrence on the south. The mining district proper is about 1000 miles northeast of Toronto. A 360-mile railroad links this mining area to the port of Sept-Iles on the Gulf of St. Lawrence. Schef-ferville, which is only a few miles from the open-pit mines, is the center of operations of the Iron Ore Co. of Canada. It has a population of nearly 5000. The nearest settlement is Labrador City, some 120 miles to the south, where this company is erecting a large plant for beneficiating its huge reserves of local low-grade iron ores. HISTORY The mineral possibilities of the area were recognized as early as the end of the last century, when A.P. LOW&apos; of the Geological Survey of Canada made his famous trek across the Labrador Peninsula. After mapping several belts of iron formation, Lovr recommended that the area be thoroughly prospected for iron. In 1929, two well known Canadian geologists, J.E. Gill and U&apos;.F. James, led a private expedition in central Labrador and discovered the first deposit of high-grade iron ore near what is now the Ruth Lake Mine. In 1936 the Labrador Mining and Exploration Co. was formed to 11ake over a prospecting concession of over 20,000 sq miles in central Labrador. An adjoining concession of 3900 sq miles in New Quebec was obtained in 1942 by Hollinger Consolidated Gold Mines, which had just Purchased the Labrador Co. The same year the M.A. Hanna Co. Purchased an interest in both exploration companies. From 1942 to 1950 extensive exploration was conducted by the Hollinger-Hanna technical staff to systematically appraise these vast concessions. More than 40 deposits of high grade ore were found and, by the end of 1950, the total ore reserves reached 418 million tons. In 1949 five American steel companies joined the Hollinger-Hanna interests and formed the Iron Ore Co. of Canada. Financing and full-scale construction were decided upon in 1950. This included the construction of a 360-mile railroad through very difficult terrain, the erection of two hydroelectric plants, the installation of terminal port facilities at Sept-IIes, the building of a modern town-site at Schefferville, the construction of crushing and screening plants, and the preparation of deposits for mining. Ore was first shipped in July 1954. Total open-pit mine production to date is 66 million long tons of direct-shipping ore. GEOLOGICAL ENGINEERING The above achievements would not have been possible without irtegrated teamwork of people of diverse skills and extensive use of geology. In their paper on the role of geologists in the development of this iron ore field, (Gustafson and Moss1 rightly emphasized the difficulties facing the early workers in the area. In an uninhabited land with no roads or railroads and no navigable rivers leading to the interior, everything had to be flown in. It was not until 1948 that aerial photographs and adequate base maps became available. In spite of these and other difficulties, an impressive amount of field work has been done since 1942. Nearly all this work has been directed by geological engineers and geologists. About 15,000 :sq miles have been geologically

Jan 1, 1962

By E. O. Wagner, V. F. Parry, W. S. Landers

Development work has shown that the yield of primary tar from coal is proportional to the heat in the volatile matter of the coal and that the yield of tar from noncoking coals may vary from 10 to 45 gal per ton on the ash-free and moisture-free basis. Pilot plant operations have proved that 100 to 135 pct of the bench-scale carbonization-assay yield of tar can be obtained. FOLLOWING investigations by the Denver Bureau of Mines on drying fine coal in the entrained state,&apos;. &apos; Texas Power & Light Co. employed the fluidized technique to upgrade Texas lignite for use in power plants. Because of the rapidly rising cost of natural gas in Texas the company agreed to cooperate with the Bureau of Mines in studying further the upgrading of lignite by low-temperature carbonization, since potential value of the tar would help offset the cost of fuel. Considerable interest was aroused, therefore, when Aluminum Co. of America decided to use dried lignite in its 240,000-kw power plant at Rockdale, Texas, operated by Texas Power & Light. Carbonization of coal before burning in a power plant is not new. Plants in Germany have been operated for many years on carbonized brown coal and lignite briquets produced in large integrated plants. Large-scale experiments in carbonizing pulverized coal with hot flue gases were made 30 years ago at Milwaukee," and many inventors have proposed other processes. In the U. S., technical and economic problems have prevented successful operation of large plants on carbonized coal. but new techniques of handling solids in fluidized beds may overcome these difficulties, particularly if the higher volatile noncoking coals are used. Any bituminous material will decompose when heated to about 900°F to yield primary tar, gas, and char. The quantity of tar obtained from various coals depends on their rank and volatile content and to some extent on rate and method of heating. The liquid products derived from thermal decomposition of peat, brown coal. lignites, oil shale, and noncoking bituminous coals can be easily liberated by rapidly heating these materials in a fluidized bed at about 500°C (932°F). Since it takes only a few minutes to heat small particles of fuel to carbonizing temperature in a fluidized bed, processing plants can be built to handle up to 50 tph at relatively low cost. The pioneering development work being conducted at Rockdale, Texas, by Alcoa and Texas Power & Light will solve many engineering problems of such operations. The Bureau of Mines at Denver has studied the carbonizing properties of several hundred coals by small scale assay at 500°C, deriving a simple correlation between the potential yield of tar and the proximate analysis. This correlation, shown in Fig. 1, compares the heat in the volatile matter of the coal with the potential yield of primary tar. The yield of primary tar varies from 12 to 50 gal per ton of pure coal." About the same amount of heat is needed to * MAF equals moisture-and-ash-free basis. distil any dry coal at 500°C, and the time required to carbonize a given particle size is about the same for any coal. It is therefore obvious that coals rich in volatile matter will show the greatest profits when processed. Texas lignites are rich in volatile matter, which contributes some 5700 Btu per lb of MAF coal, and the potential primary tar and oil yield from this lignite averages 12 pct by weight or 27 gal per ton from the pure lignite. Texas lignites are considerably richer in potential tar than lignites of North Dakota and Montana. During 1950 the Bureau of Mines conducted many experiments on carbonizing fine dry coal in the entrained state, publishing a report4 n major features of pilot and commercial-size units required to carry out the process. Additional experimental work has been done at Denver and the pilot plant has been improved, particularly the facilities for studying removal of fine dusts from tar vapors and gases at high temperatures by electrostatic precipitation. A number of materials have been carbonized, including sawdust, peat, brown coal, Brazilian oil shale, lignites, and the lower rank bituminous coals having noncoking properties. Straight coking coals cannot

Jan 1, 1957

By Andrew B. Crichton

THE oft repeated statements of the United States Geological Survey and the Bureau of Mines that the coal reserves in the United States are sufficient for 3000 yr have given us all a sense of security hard to disturb. If we discount that statement 66 pct, which to the uninformed seems drastic, we would still have 1000 yr supply, and why should mortal man worry about the difference between 1000 and 3000 yr supply of coal. That is exactly the attitude which many who should be better in- formed have taken toward the problem. A recent brochure "How Strong is America," by the New York Herald Tribune, states there is "no end to coal * * The truth is staggering * * U. S. has enough coal to last 4000 years." What the statement actually means is that the calculator got as high as 4000 yr and decided it was pointless to go on. The President&apos;s ERP Committee on Natural Resources and others in high places continue to assure the country of our superabundance of coal. In the past few days the “Wall Street Journal" carried an item from Director Boyd of the Bureau of Mines saying that within a hundred years we would need to triple our annual coal production of 6oo,ooo,ooo tons, making it 1,800,000,000 tons annually, and at that rate we had coal reserves sufficient for 1000 yr. In my humble opinion, we cannot now or ever produce 1,800,000,000 tons annually, be- cause we do not have the reserves in the producing districts to do it. Past reckoning in geology may be, as in the Psalms, a thousand years are as yesterday, but the future must be considered more realistically, and "a thousand years" is really a "heck" of a long time. In most developed areas, mining engineers can count the coal reserves in terms of a hundred years or less, and in some important areas now producing large annual tonnages in much under fifty years. They think when they hear of thousands of years coal reserves, reference is made to distant fields and "the fields are always green far away." The estimates of our coal reserves upon which we are relying were made in 1907 under the direction of Marius R. Campbell, Director of the United States Geological Survey. It is apparent this work was not well done. It was necessarily based on rather meager data because of the little development and prospecting as of that date. There were mistakes in the correlation of seams, and they assumed the continuity of thick seams throughout large coal bearing areas where coal often did not exist. The overstatement of coal bearing areas in the Campbell figures are common. The 1907 survey includes all coals over 14 in. in thickness to a depth of 3000 ft. The total coal reserves according to Campbell were 3157.2 billion tons. The production and mining losses that year would amount to -570 million tons and

Jan 1, 1948

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,&apos; however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.&apos; Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By S. Ramachandran, R. G. Woolery

INTRODUCTION Union Carbide is currently operating an in-situ leach project on the Palangana Dome area in Duval county. This deposit meets all the requirements for in-situ leach in that the ore (1) is below the water table, (2) is in a permeable horizon, (3) is amenable to chemical leaching, and (4) is confined by impervious layers. This project has been under commercial production since 1976, and its capacity has been expanded on three occasions since going on-stream. Recently, additional uranium reserves were discovered on the Rogers-Cardenas (R-C) property about 32 km north of the Palangana operation. The ore is located within the Oakville sands and its characteristics are quite similar to those of the ore at Palangana. Both are an unconsolidated Arkosic sand high in clay and calcium carbonate. The R-C ore, however, is somewhat coarser with a mean particle size of 0.15 mm as compared to a mean particle size of 0.07 mm for the Palangana ore. In all respects it would appear that this ore would be a candidate for in-situ leach as a satellite operation to Palangana. Unfortunately, R-C ore is above the water table and, therefore, not amenable to the Palangana practice. Because of the limited known reserves in this deposit, it is readily apparent that conventional mining and milling are out of the question. However, because of its proximity to our Palangana operation, it seemed worthwhile to consider other options. The most viable route based on our past experience was to heap leach the ore. Our recent success at our Gas Hills facility and our Maybell operation, in employing a heap leach practice to our marginal reserves seemed to be a logical approach for processing this ore. Our experiences at both locations are described in "Heap Leaching - A Case History" by R. G. Woolery et al., Mining Engineering, March 1978. In both instances the process is an acid leach circuit and acid consumption averages 20 kg/t H2SO4. A preliminary feasibility study showed that because of the high strip ratio required for the R-C project to be successful, additional ore reserves must be located and that a method of heap leaching with an alkaline circuit would have to be developed. As a result of this paper study, the decision was made to proceed with a program of additional exploration drilling to determine the total ore reserves that could be mined economically. The Mining Department will evaluate each ore zone for cutoff grade, strip ratio, and expected mining cost. At the same time, a laboratory program to evaluate the available core samples for amenability to heap leaching with respect to an estimate of uranium recovery and processing costs was developed. This program is currently in progress, and at this time, we are just completing our process amenability study. BENCH-SCALE EVALUATION OF THE R-C ORE The initial bench-scale slurry leach tests on the R-C ore showed an acid consumption in excess of 200 kg/t H2SO4. These data, of course, discouraged us from considering this process route. Not only would the acid cost be prohibitive, but the gypsum generated by the reaction of the sulfuric acid with the calcium carbonate of the ore would severely effect the percolation of the lixivant. For this reason, the laboratory program was directed toward an alkaline circuit compatible with heap leaching. Because of the proximity of the R-C property to our Palangana operation, it seemed advisable to integrate the processing of this ore into the production at Palangana. Doing so would enable us to bring the R-C property into production by merely enlarging our present facilities at Palangana; otherwise, construction of a grass roots plant would be necessary. Ideally, the simplest method would be to construct the heaps at Palangana and employ an ammonium carbonate/bicarbonate leachant compatible with the in-situ production liquor. The product liquors could then be co-mingled or processed separately as desired. To determine if this goal was practical, samples of the R-C ore were obtained, and a laboratory program initiated. Heap leach amenability testing consisted of preliminary bench-scale evaluation to determine optimum solution strength and ultimate uranium recovery, followed by small column tests to confirm the bench-scale metallurgy and to determine percolation characteristics. These bench-scale tests are being followed by pilot-scale testing approximating field conditions. As expected, the bench-scale tests showed that the dissolution rate is considerably slower for alkaline leach than has been our experience in acid leaching. Because of the slower reaction rates, product liquor grades will be lower than for acid, as greater volumes of solution are required for satisfactory uranium extractions. The greatest influence on reaction times found in the laboratory was the carbonate/bicarbonate strength and oxidant addition. However, the higher salt concentration reduced the efficiency of the IX resin circuit and about 25g/L salt proved to an upper limit compatible with subsequent IX treatment. The oxidant contributed significantly to the early extraction rate but seemed to have only minimal effect on the total practical U308 extracted or the time required to achieve it. This variable will require larger scale testing to determine if the added cost of the oxidant is actually justifiable. Thus, the small-scale laboratory slurry tests, based on the 0.088% U308 sample available, indicate that leaching at 25g/L ammonium carbonate/bicarbonate, with or without oxidant, we might expect an 80-85% U308 extraction on this ore.

Jan 1, 1979

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.&apos; 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 C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By Ross C. Anderson, William I. Weisman

THE manufacture of anhydrous sodium sulphate or salt cake from natural deposits in the United States has been in general somewhat of a marginal undertaking. Competition from foreign sources and from large quantities of byproduct sodium sulphate produced domestically in the manufacture of hydrochloric acid and other chemicals has existed and continues. For example, most of the sodium sulphate produced is a byproduct or co-product in the manufacture of hydrochloric acid through the reaction of sodium chloride with sulphuric acid. In recent years, many manufacturers of rayon have installed equipment to recover sodium sulphate from waste spin bath liquors; today this is an important source. Before World War II large quantities of sodium sulphate were imported from Germany. In 1949 imported material from Europe again appeared on the domestic market. Natural sodium sulphate from Canada in substantial quantities also enters the United States markets. Despite this kind of competition, numerous attempts have been made to exploit various natural deposits of sodium sulphate in this country, but only a very few of these have survived economically over a period of years. One of these few operations is the plant of the Ozark-Mahoning Co. located 13 miles south of Monahans in West Texas. Several factors contributing to the successful life of this plant may be summarized as follows: 1—Geographical location. Monahans is reasonably close, freightwise, to the Kraft paper mills in Texas, Arkansas, and Louisiana; the Kraft paper industry is the greatest consumer of sodium sulphate in the United States. 2—Availability of natural gas as low cost fuel. Proximity of the natural gas fields of West Texas has been a tremendous asset, as the availability of low-cost natural gas is to all industry throughout the Southwest. 3—The nature of the deposit. The occurrence of sodium sulphate brines in southeastern New Mexico and West Texas has been very well described by Lang,&apos; who writes that the brines are found in the Castile formation of the Delaware basin. Here weathering has altered the anhydrite so that a relatively porous gypsiferous zone overlies a dense impervious mass of anhydrite. This porous zone provides traps where percolating ground waters that have picked up soluble salts may lodge. These traps or pockets are the natural brine reservoirs exploited at Monahans. Although several hundred wells have been drilled, currently some 25 wells serve to supply brine to the plant. All are within 1 1/2 miles of the plant and are conveniently tied together by an electric power system serving electric motors driving the pumps. Having the raw material in the form of a brine which can be pumped from shallow wells makes possible much simpler and more efficient handling than if it were in form of solids. By contrast, other deposits of sodium sulphate, such as those in Arizona, Nevada, and North Dakota, are in the form of the solid minerals, thenardite and mirabilite, which present somewhat more of a mining and mineral dressing problem.&apos; The largest producer of sodium sulphate from natural sources in the United States is at Searles Lake, Cal., and there a brine also is utilized. 4—Water. Substantial quantities are needed for cooling towers and for operation of gas engines. An area underlain with brine is not a promising source of fresh water, but fortunately, after a long search, an adequate supply was found nearly two miles from the plant. It may be appropriate to discuss briefly the grades of sodium sulphate offered on the market. Salt cake is the name usually applied to the grade of sodium sulphate used by the Kraft paper industry. It may be a low analysis byproduct, 95 to 97 pct sodium sulphate, with as much as l 1/2 to 2 pct residual acid, or it may be a natural product. Usually salt cake is considered a low grade product, but a great deal of a higher grade of material is marketed under this name. The specifications for glassmakers&apos; salt cake are somewhat higher than those of the paper industry, usually requiring 98 pct sodium sulphate. Technical anhydrous sodium sulphate is a high grade material and usually exceeds 99 pct sodium sulphate. It finds the biggest market in the textile industry and is used as a builder in some synthetic detergents. Glauber&apos;s salt, Na2SO4. 10H20, is usually of high purity. Preferred for some uses, it normally has been recrystallized from an anhydrous salt. A unique manufacturing process has been developed at Monahans. This process results in the production of an exceptionally high grade of salt cake, and qualifies for nearly all uses, including many which specify the technical anhydrous grade. All of the finished product, which is very white, passes a 10-mesh U. S. Standard screen, and is retained on a 200-mesh U. S. Standard screen. It is over 99 pct Na2SO4 with main impurities being sodium chloride and magnesium sulphate. Iron content is less than 0.01 pct. As mentioned, the raw material at Monahans is a brine drawn from wells. Attention was first attracted to this location because a so-called alkali

Jan 1, 1954

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory investigatorsstate of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which andare useful for predicting machine performance and give acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary canexplain commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted.&apos;TheRittinger In its first form, as stated by P. R. Ritted.&apos;tinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include the concept of surface energy; in this form it was precisely stated by A. M. Gaudin&apos; as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended." According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported- hat support the theory in its first form by indicating that the new surface produced in different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work done on the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading, since it does not follow the regular breakage pattern of most materials but is regularrelativelybreakage harder to grind patternat the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory4 is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr /log 2." The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-l.V f a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The evaluation in terms of kw-hr per net ton of —200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of —200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1953