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By Robert B. Fulton

It is a pleasure to talk to you about the world economics of industrial minerals on this occasion of AIME's 100th anniversary. In order to fit this topic into the time and tenor of such a session as this where you are hearing subjects equally broad in scope one after the other, I will deal with the subject through the medium of eight minerals selected to illustrate import- ant economic factors. I must admit to some bias in the selection, since I picked personally familiar ones to elucidate facts of life in the industrial minerals business. It is a very interesting field, different in many respects from metals and certainly far different from petroleum. The minerals chosen are celestite, diamond, fluorspar, salt, sulfur, ilmenite, rutile and zircon. Celestite The market for celestite is mainly in the U. S. where it is consumed in the manufacture of strontium compounds for red-colored flares and other pyrotechnics, for the production of electrolytic zinc, for glass manufacture, and for the manufacture of ceramic ferrites. Smaller markets exist in Europe and Japan. Production comes from England, Mexico and Spain, and a new mining operation is being started in Nova Scotia. There is no significant production in the U. S. nor in the other principal consuming countries, except England; so it is mainly an international commodity. Celestite illustrates many of the factors important in the economics of industrial minerals. To have a marketable product, grade and freedom from deleterious elements are important for materials used by the chemical industry. In the celestite used to make strontium nitrate, calcium is the most objectionable of the commonly associated cations. Selling price is adversely affected because nitrate manufacturing costs are greatly increased if calcium is pre sent, hence less can be paid for the raw material. Meeting specifications can add significantly to the vendor's cost; hence a balance must be struck between the producer's capability and the consumer's requirements, permitting a reasonable profit for both. Sizing of industrial mineral products is often important to the consum-

Jan 1, 1971

Zinc is just now a very important metal. Its use in cartridges and shrapnel brass are in the public eye. But its uses after the war are no less important. Brass as an engineering material for electrical machin-ery, journal bearings, and plumbing fixtures takes fully 50 per cent. of the production, and its use in these lines would have been increased in the last few years but for the price. Its use for barbed wire is probably more in war time than in peace. In the composition of paints, it is becoming more and more necessary. One of the forms of pigment, litho- pone, is the base of nearly all interior wall paints; of all the sanitary enamels for bath-rooms and bath-tubs, and is now in great demand. Zinc oxide is also increasing in use for paint, and for manufacture of linoleum. When we realize that this district-Missouri, Oklahoma, Kansas and Arkansas-produces now over one-third of the zinc ore of the world, it is at once seen that a meeting where the geology, mining, concentration

Jan 6, 1917

By Fred C. Bond, Walter Maxson

Since the last publication of tabulated results of grindability tests by the authors1 the total number of ball-mill tests made has more than doubled, and rod-mill tests have become increasingly important. Nearly all of the standard closed-circuit ball-mill and rod-mill tests made to date are included in the present tabulation, together with additional information not previously published. Standard Ball-mill Grindability Tests The method of conducting these closed-circuit tests has not been altered. A sample of the ore or other material is stage-crushed in rolls set at 1/16-in. opening with a 6-mesh screen until all of it has passed the screen. The combined minus 6-mesh screen undersize is mixed, sampled and screen-analyzed, and its apparent specific gravity is determined by packing and shaking in a standard container, and weighing. The apparent specific gravity ordinarily is about 60 per cent of the true specific gravity. The unit volume present in the mill .in all tests is 700 C.C. of the packed minus 6-mesh roll product, and the number of grams occupying 700 C.C. is the unit test weight. This weight is placed in the mill dry, ground for the number of revolutions estimated to be necessary, discharged, and screened mechanically in three testing sieves of the mesh size at which the test is to be conducted. The oversize, or circulating load, is weighed, sufficient fresh minus 6-mesh feed is added to bring the total weight up to that of 700 c.c., and the charge is returned to the mill for a second grinding period. All standard ball-mill tests are conducted at 250 per cent circulating load, and the number of revolutions in the mill necessary to obtain this circulating load at any grinding period is estimated from the results of the previous period. The number of net grams of screen undersize produced per revolution of the mill approaches its final equilibrium value after several grinding periods, and this is recorded as the grindability, or relative ease of grinding, of the sample. A cylindrical ball mill, 12 by 12 in. inside, with a smooth lining and rounded corners, is used with a revolution counter Under standard grinding conditions it runs at 70 r.p.m., and contains a charge of 285 iron balls weighing 20,125 grams, ranging from I½ to ¾ in. in diameter. Tests are conducted at the mesh size to which the ore is to be ground in practice, and the capacity- to be expected from a given mill is calculated by comparing the grindability with that of a similar standard ore whose performance characteristics arc known. No satisfactory general formula for convertillg standard grindabilities into corn; rnercial power-consumption values has been

Jan 1, 1943

By Walter Maxson, Fred C. Bond

Since the last publication of tabulated results of grindability tests by the authors1 the total number of ball-mill tests made has more than doubled, and rod-mill tests have become increasingly important. Nearly all of the standard closed-circuit ball-mill and rod-mill tests made to date are included in the present tabulation, together with additional information not previously published. Standard Ball-mill Grindability Tests The method of conducting these closed-circuit tests has not been altered. A sample of the ore or other material is stage-crushed in rolls set at 1/16-in. opening with a 6-mesh screen until all of it has passed the screen. The combined minus 6-mesh screen undersize is mixed, sampled and screen-analyzed, and its apparent specific gravity is determined by packing and shaking in a standard container, and weighing. The apparent specific gravity ordinarily is about 60 per cent of the true specific gravity. The unit volume present in the mill .in all tests is 700 C.C. of the packed minus 6-mesh roll product, and the number of grams occupying 700 C.C. is the unit test weight. This weight is placed in the mill dry, ground for the number of revolutions estimated to be necessary, discharged, and screened mechanically in three testing sieves of the mesh size at which the test is to be conducted. The oversize, or circulating load, is weighed, sufficient fresh minus 6-mesh feed is added to bring the total weight up to that of 700 c.c., and the charge is returned to the mill for a second grinding period. All standard ball-mill tests are conducted at 250 per cent circulating load, and the number of revolutions in the mill necessary to obtain this circulating load at any grinding period is estimated from the results of the previous period. The number of net grams of screen undersize produced per revolution of the mill approaches its final equilibrium value after several grinding periods, and this is recorded as the grindability, or relative ease of grinding, of the sample. A cylindrical ball mill, 12 by 12 in. inside, with a smooth lining and rounded corners, is used with a revolution counter Under standard grinding conditions it runs at 70 r.p.m., and contains a charge of 285 iron balls weighing 20,125 grams, ranging from I½ to ¾ in. in diameter. Tests are conducted at the mesh size to which the ore is to be ground in practice, and the capacity- to be expected from a given mill is calculated by comparing the grindability with that of a similar standard ore whose performance characteristics arc known. No satisfactory general formula for convertillg standard grindabilities into corn; rnercial power-consumption values has been

Jan 1, 1943

By K. H. Coats

This paper presents the development and solution of a mathematical model for aquifer water movement about bottom-water-drive reservoirs. Pressure gradients in the vertical direction due to router flow are taken into account. A vertical permeability equal to a fraction of the horizontal permeability is also included in the model. The solution is given in the form of a dimensionless pressure-drop quantity tabulated as a function of dimensionless time. This quantity can be used in given equations to compute reservoir pressure from a known water-influx rate, to predict water-influx rate (or cumulative amount) from a reservoir-pressure schedule or to predict gas reservoir pressure and pore-volume performance from a given gas-in-place schedule. The model is applied in example problems to gas-storage reservoirs, and the difference between reservoir performances predicted by the thick sand model of this paper and the horizontal, radial-flow model is shown to be appreciable. INTRODUCTION The calculation of aquifer water movement into or out of oil and gas reservoirs situated on aquifers is important in pressure maintenance studies, material-balance and well-flooding calculations. In gas storage operations, a knowledge of the water movemenr is especially important in predicting pressure and pore-volume behavior. Throughout this paper the term "pore volume" denotes volume occupied by the reservoir fluid, while the term "flow model" refers to the idealized or mathematical representation of water flow in the reservoir-aquifer system. The prediction of water movement requires selection of a flow model for the reservoir-aquifer system. A physically reasonable flow model treated in detail to date is the radial-flow model considered by van Everdingen and Hurst.1 In many cases the reservoir is situated on top of the aquifer with a continuous horizontal interface between reservoir fluid and aquifer water and with a significant depth of aquifer underlying the reservoir. In these cases, bottom-water drive will occur, and a three-dimensional model accounting for the pressure gradient and water flow in the vertical direction should be employed. This paper treats such a model in detail — from the description of the model through formulation of the governing partial differential equation to solution of the equation and preparation of tables giving dimensionless pressure drop as a function of dimensionless time. The model rigorously accounts for the practical case of a vertical permeability equal to some fraction of the horizontal permeability. The pressure-drop values can be used in given equations to predict reservoir pressure from a known water-influx rate or to predict water-influx rate (or cumulative amount) when the reservoir pressure is known. The inclusion of gravity in this analysis is actually trivial since gravity has virtually no efFect on the flow of a homogeneous, slightly compressible fluid in a fixed-boundary system subject to the boundary conditions imposed in this study. Thus, if the acceleration of gravity is set equal to zero in the following equations, the final result is unchanged. The pressure distribution is altered by inclusion of gravity in the analysis, but only by the time-constant hydrostatic head. The equations developed are applied in an example case study to predict the pressure and pore-volume behavior of a gas storage reservoir. The prediction of reservoir performance based on the bottom-water-drive model is shown to differ significantly from that based on van Everdingen and Hurst's horizontal-flow model. DESCRIPTION OF FLOW MODEL The edge-water-drive flow model treated by van Everdingen and Hurst1 is shown in Fig. la. The aquifer thickness b is small in relation to reservoir radius rb. water invades or recedes from the field at the latter's edges, and only horizontal radial flow is considered as shown in Fig. 1b. The bottom-water-drive reservoir-aquifer system treated herein is sketched in Fig. 2a and 2b. Here the aquifer

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By D. Muraoka

Introduction Soda ash, anhydrous sodium carbonate, is produced from underground trona deposits occurring in the Green River Basin of southwestern Wyoming. Stauffer Chemical Co. of Wyoming, a jointly owned subsidiary of Stauffer Chemical Co. and Rocky Mountain Energy Co., mines the trona and processes it into high-purity soda ash. Stauffer Wyoming has been in operation since 1962 with a current production capacity of about 1.8 Mt (2 million st) per year of soda ash. The refinery has five parallel operating trains using the monohydrate process which is a series of chemical processing unit operations described below. Screening and Crushing The mined trona is brought to the surface in two counterbalancing ore skips. The ore is initially screened with refinery feed (less than peagravel size material) entering the process. Oversize is conveyed to an outdoor stockpile. Ore is recycled from under the stockpile via cone feeders as the refinery needs require. The ore is conveyed to hammer type crushers and screened. The refinery feed enters the process and the oversize is recycled to the crushers. Calcining The first step in refining trona to soda ash is calcining the trona ore. This is accomplished in concurrent flow, rotary kilns that are direct fired with natural gas. [2 (Na CO NaHCO 2H O) Heat 3Na CO + 5H20 + CO 2 3~3~ 2 ~~2 32] The trona ore is fed to the kiln at the burner end and is intimately mixed with the hot exhaust gases from the burner. Direct contact with the flame is avoided. The ore moves down the kiln by gravity and rotation aided by the kiln's internal lifters. The exhaust gases are cleaned to 99 + % particulate removal and discharged to the atmosphere. Dissolving the Calcined Trona The calcined trona is conveyed from the kiln discharge to a rotary drum dissolver where it is mixed with water and weak solution (unsaturated solution of calcined trona in water). The calcined trona is soluble whereas the impurities, primarily shale, are insoluble. The discharge from the dissolver is a slurry containing saturated solution (about 30% dissolved calcined trona in water), some undissolved calcined trona, insoluble impurities, and organic impurities. The dissolver discharge enters a rake classifier that makes the first solid/liquid separation in the process by removing the heavy undissolved material from the saturated solution. This undissolved material is conveyed to a second rotary drum dissolver and mixed with water to dissolve any remaining calcined trona. The secondary dissolver discharges to a second rake classifier that separates the solids from the liquid. The solids are now primarily insoluble impurities with very little unrecovered calcined trona. These wastes are conveyed to evaporation ponds for disposal. The liquid from the secondary rake is recycled to the primary dissolvers' weak solution system. Returning to the primary rake classifier, the saturated solution which contains suspended insoluble muds is pumped to a thickener. Flocculant is added to aid settling of the suspended muds. The flocculated muds are collected at the bottom of the thickener and pumped to vacuum cloth filters. The adhering saturated solution is separated from the muds that remain on the filter cloth. The recovered solution is returned to the dissolvers' weak solution system. The muds are reslurried and pumped to the evaporation ponds for disposal. Saturated solution, containing some suspended insoluble muds along with the organic impurities, overflows the thickener. Filtering the Saturated Solution The saturated solution overflowing the thickener enters a holding tank where it is pumped to a bank of pressure leaf filters. The suspended muds are captured on the filter leaves while the cleaned saturated solution is pumped to polishing filters. The polishing filters are also leaf pressure type, intended to remove any suspended solids that may pass the primary filters. Organic impurities are removed with activated carbon. The purified solution is now free of insoluble muds and has most of the organic impurities removed. Crystallizing and Drying the Monohydrate The purified saturated solution is pumped to evaporative crystallizers. The solution is circulated from the crystallizer vessel through a heat exchanger. Indirect contact with steam in the heat exchanger causes the saturated solution to boil, thus crystallizing the soda ash in its monohydrate form. Slurry crystal density is maintained in the crystallizer by simulta¬neous feed of fresh saturated solution and drawoff of the slurry.

Jan 1, 1986

By Iichiro Omori

THE Mabuki process, a Japanese hearth process for the treatment of matte, uses the same princi-ple as the Bessemer steel process. The only difference between the two is that in the Mabuki proc-ess a hearth furnace, not a converter, is used. Though the hearth is not as good as the converter, the first cost is very low and the capacity is compara-tively small; so the process is most suitable for smelters FIG. 1.-PLAN AND SECTION OF HEARTH. having a small production. To construct the hearth, an excavation, 6 ft. in each dimension, is made in the ground and a drainage channel is dug at the bottom. Then all side walls are faced with stone or slag brick and the cavity is filled with fireclay or brasque, except the hearth at the top.

Jan 9, 1922

SPEAKING generally, it may be said that leaching is the simplest method of recovering copper from its ores. Likewise it is perhaps the oldest method of treatment used by copper metallurgists of the modern era. Reliable records indicate that as early as 1752 cupriferous pyrite was leached in the famous Rio Tinto region in Spain. Though the manipulation was quite different from that in use today at Chuquicamata, New Cornelia, Inspiration, and Andes, it resembled that employed by Phelps Dodge at Bisbee, as described in Chapter XIV. Leaching consists of subjecting ore to the action of a liquid solvent or menstruum (usually an aqueous solution) which dissolves the major part of the soluble copper minerals. The resulting pregnant solution is drained off or otherwise separated from the residual ore; and the copper in the solution is then recovered by some appropriate means of precipitation. When sulphuric acid is the lixiviant, as is usual, the simplest procedure is to pass the copper-bearing solution through large troughs containing scrap iron. The iron displaces the copper in the solution, precipitating it as a slime coating the iron and varying in color -from bright copper to a dull black. This may be washed off at intervals, collected as a sludge, dried, and melted with a little fluxing material to produce reasonably pure copper. Usually, of course, the mud is sent to a smelter where most often its destination is the converter or reverberatory furnace. Modern practice uses precipitation on iron only as a complemental process to electrolytic precipitation or deposition, wherein the pregnant copper-bearing solution, acting as the electrolyte in a cell having insoluble anodes and copper cathodes, is depleted of the copper it contains. Cathode copper, 99.5 per cent pure, is produced ready for the market as refined copper, or for a simple process of melting, fire-refining, and casting in

Jan 1, 1933

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Thomas A. Read

THE internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of l00 when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose-that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals will be presented. EXPERIMENTAL PROCEDURE The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrement A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were .made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders ¼ in. in diameter and 1 ½ to 2 ½ in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is ¼ in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Wm. I. Weisman, Sid McIlveen

Sodium sulfate is an important industrial chemical, being one of perhaps a dozen or so chemical commodities produced and consumed in the United States in quantities exceeding 1 Mt/a. In recent years approximately half that production has come from natural sources, whereas 27 years ago only 25% was derived from these sources. Table 1 illustrates the history of production of natural sodium sulfate in the United States. Production of natural sodium sulfate from various types of deposits is the main source of this chemical in Canada and Mexico, and probably in Argentina, Chile, Spain, and the USSR. Mineralogy and Physical Properties Sodium sulfate is widespread in occurrence and is a common constituent of many mineral waters, as well as seawater. Atmospheric precipitation contains sulfate; it is one of the major dissolved constituents of rain and snow (Davis and DeWiest, 1966). Many of the saline lakes throughout the world contain varying amounts of sodium sulfate. Because sodium is usually the dominant cation, some workers make an anionic distinction, referring to lakes containing predominately sulfate as bitter lakes and those containing predominately carbonate as alkali, or soda lakes (Bateman, 1950). Sodium sulfate in its natural form is found as the hydrous salt mirabilite (commonly called Glauber's salt), and as thenardite, the anhydrous variety. The largest quantities occur in the form of mirabilite. Sodium sulfate is found in varying degrees of purity, from theoretically pure efflorescent crystals of mirabilite to combinations and admixtures of other salts and impurities. It is a common constituent of some brines; from this source much is extracted commercially. [ ]

Jan 1, 1983

By F. F. Skiba, J. E. Warren

An idealized miscible displacement process in a three-dimensional, heterogeneous porous medium has been studied via experimental computation based on a "Monte Carlo"' model. The macroscopic dispersion which results solely from variations in the permeability of the porous system is related to the scale of the heterogeneity as well as the distribution function for the permeabilities. The interpretation of laboratory data is often subjective and may bt? misleading since ambiguities are not always recognized. Furthermore, an experiment performed on a conventional oil-field core does not yield a valid measure of Macroscopic dispersion for reservoir engineering purposes since the scale of heterogeneity that is significant in the laboratory is not significant in the reservoir. The analysis of field-performance data is discussed and it is shown that a unique characterization of the reservoir can not be obtained from this information alone. A possible method based on a minimum of data, for estimating the spatial distribution of permeabilities in a reservoir is postulated INTRODUCTION Many studies concerned with diffusion and dispersion in porous media have been undertaken because of the potential importance of miscible displacement processes for increasing the recovery of oil. The results from a large number of these studies have been published; in a recent paper Perkins and Johnstonl presented a comprehensive survey of the pertinent literature and excellent appraisal of the "state of the art". In this investigation, dispersion resulting from macroscopic variations in the properties of the porous medium is of primary interest. Dispersion, in this sense, is caused by fluctuations in the velocities of the individual fluid elements as they move through the porous system. This phenomenon is the result of inhomogeneities in the permeability and/or porosity, but it can be amplified by differences in the characteristics of the fluids involved. The objectives of this study are the following: (1) to determine the qualitative manner in which macroscopic rock properties affect the observed dispersion coefficient; (2) to evaluate the possible influence of macroscopic dispersion on laboratory experiments; and (3) to appraise the significance of macroscopic dispersion with regard to reservoir performance. Investigations of this type are essential since many miscible displacement processes, while seemingly understood from a mechanistic point of view, do not behave in a predictable manner under field conditions. Although a plausible explanation is that the process is dominated by the environment, little serious effort has been devoted either to describing the reservoir itself or to determining the probable effect of the reservoir properties on the process. This study is intended to be exploratory in nature; however, it is hoped that it will provide additional insight into the physical problem and that it will suggest areas suitable for further investigation. EXPERIMENTAL COMPUTATION MODEL To limit the observed dispersion to that which results solely from variations in the properties of the porous medium, an idealized process in which one incompressible fluid displaces another identical fluid is simulated. This simulation is achieved by means of a modified Monte Carlo method — by tracking a number of mathematical particles (tracer) through the system according to the steady-state, single-phase velocity distribution. Then the system is characterized by the distribution of the residence times of the particles. Since any number of particles can be injected simultaneously (a true delta-function distribution) and only pressure conditions are imposed on the boundaries, the model is completely determinate. Furthermore molecular diffusion, microscopic dispersion, adsorption and/or reaction are automatically precluded from the model. The heterogeneous medium is represented by a rectangular, three-dimensional array of uniform, homogeneous porous blocks which are randomly arranged; it is assumed that any two opposing faces of the system are held at fixed potentials

Jan 1, 1965

By M. H. Gaskell, D. M. Kehn, G. T. Pyndus

A correlation of the bubble point pressure for black oil systems is developed using the standard physical-chemical equations of soiutions. The correlation is based on 158 experimentally measured bubble point pressures of 137 independent systems and is expressed in terins of the usually measured field pnrameters— flash separation gm-oil ratio, rank oil gravity, total gas gravity, and reservoir temperature. The data were obtained on systems produced in Canada, Western and Mid-Continent01 United States, and South America. The average error (algebraic) in the representation is 3.8 per cent, and the maximum error encountered is 14.7 per cent. INTRODUCTION In the absence of experimentally measured properties of reservoir fluids, it is often necessary for the field engineer to make estimates regarding the fluid properties based on the usually measured producing parameters. To aid in these estimations, various correlations have appeared in the literature in recent years. Among the pertinent properties of interest is the bubble point pressure. A correlation for this parameter has been reported by Standing'. However, this correlation was based essentially on California produced crudes and this limitation was pointed out with its presentation. The correlation presented in this paper utilized data on crude oil systems from Canada, Wes- tern and Mid-Continental United States, and South America. CORRELATION DEVELOPMENT The basic assumption used in this development is the same as employed by Standing', There is a wide variety of ways to combine these parameters; however, in this instance the combination was made on the basis of Henry's law2. Accordingly, the relationship proposed is Although Eq. 2 defines an individual system, it is of limited value since H' is a function of gas-phase composition and the system temperature. It was observed that for the systems where the bubble point was measured at several temperatures that the ratio of the bubble point pressures and the ratio of the corresponding absolute temperatures (R) were practically identical. Thus, for correlation purposes the bubble point pressure may be taken as a direct function of the absolute temperature. This relation is valid only for those systems that are not near the critical point. Accordingly, this correlation will be inadequate for systems in the region of the critical point. The solubility of the various hydrocarbons found in the gas phase increases with the molecular weight. Thus, the saturation pressure should be inversely related to the gas gravity. Applying these principles to Eq. 2 and rearranging terms gives: The variables 02 the left side of Eq. 3 were designated as the "hubble point pressure factor". The number of mols of tank oil per barrel is a function of the "mclecular weight" of the tank oil. Although the tank oil is a complex mixture, it was assumed for the purposes of this correlation that a unique molecular weight could be assigned to a given oil. This was designated as the "effective molecular weight", and was related to the oil gravity, This empirical relationship was developed simultaneously with the correlation by assuming values of M,. and working to obtain a smooth curve for both the correlation and the effective molecular weight. The relationship between the oil gravity and the effective molecular weight used in this correlation is shown in Fig. 1. The effective molecular weight is somewhat higher than the molecular weight of the C fraction. The difference between these values is largest for the low-gravity systems. It is noted that this effective molecular

By means of top-slicing methods, wide veins, masses, or thick beds of soft ore may be mined, where the caving of the overburden is of no consequence. The ore is mined in a series of horizontal floors or slices, taken in descending order, from the top of the deposit. Each floor is mined in small sections, the roof of each section being allowed or forced to cave before an adjacent section is attacked. The method as used in two mining districts—Marquette, iron, and Pachuca, silver-gold—is described in the two papers following:

Jan 1, 1925

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By W. I. Duvall, D. E. Stephenson

A theoretical solution is given for the energy that is radiated outward when either a cylindrical or spherical cavity located underground in a uniform stress field is suddenly created or enlarged. The method of derivation shows that the stress field in the solid rock surrounding the opening does work on the rock because of elastic displacements that result when the size of the cavity is increased. The amount of this work is sufficient to account for both the increase in the strain energy in the rock surrounding the opening and the seismic energy that radiates outward. Thus, the source of the radiant seismic energy is mainly the gravitational potential energy and not the strain energy stored in the rock. The amount of the radiant seismic energy is directly proportional to the volume of the rock removed from the opening or relieved of stress. Seismic energies from rockbursts are compared with earthquake energies. Also, the amount of gravitational potential energy released by underground explosions is calculated and found to be small compared to the seismic energy generated by the detonation of the explosive. A review of the early literature on rockbursts shows that a number of investigators calculated the amount of energy released by rockbursts. 1-5 However, none of these papers give the formula used to make these calculations or a reference to the derivation of any formulas. The general impression that one obtains from these early papers is that the main source of the seismic energy released by rock-burst is the strain energy stored in the rock before it is fractured. However, a few of the early papers appear to have considered the solid rock at a distance from the mine opening as a possible source of the seismic energy. Recently Black and starfield7 gave a theoretical solution for the strain energy in a stressed plate with and without a circular hole. Also, Press and Archambeau8 gave the theoretical solution for the seismic energy released when a spherical cavity is created in rock subjected to a three-dimensional stress field. Both of the above theoretical papers start with the condition of no opening and calculate the strain energy before and after the opening is suddenly formed. Neither of these papers appear to have calculated the work done by the applied stress field as the cavity is enlarged. The rockburst problem associated with deep mining is concerned with the failure of the solid rock surrounding an underground opening. Therefore, it seems appropriate to consider theoretically the problem of suddenly enlarging the size of an existing opening. The purpose of this paper is to present the theoretical solution for the energy that is available for release as seismic energy when an underground circular tunnel or spherical cavity is suddenly enlarged in diameter. To keep the mathematics as simple as possible, a uniform radial applied stress field is assumed and the rock is assumed to be isotropic, homogeneous and perfectly elastic.

Jan 1, 1965

By Charles Fulton

EXPERIMENTAL work on the process was begun on a laboratory scale at Cleveland, Ohio, in 1914, and transferred to East St. Louis, Ill. in 1916, where a commercial sized furnace was in technical operation until January, 1918. The essential steps of the process are as follows: Oxidized zinc ore or roasted zinc concentrate is mixed with crushed coke and coal-tar pitch and formed into briquets 9.25 in. (23.5 cm.) in diameter and 21 in. (53 cm.) long in a manner similar to that used in the manufacture of graphite or carbon electrodes, except that much less care and time are required. The composition varies with the nature of the ore; in one case, the composition was 100 parts ore, 70 parts coke, and 18 to 20 parts pitch. These briquets maintain their form and volume during and after the distillation of the zinc. This object is gained by using coke as the matrix and coal-tar pitch as the binder; this pitch becomes coke on heating and unites the ore particle and the original coke particle into a continuous mass. The briquet is an electrical conductor but only to such, a degree that it can be used as a resistor. The size of the ore, as in the present practice of zinc metallurgy, ranges from fine material, such as flotation concentrate, to coarse table and fine jig concentrate. The process is not restricted to any particular kind of ore, but is applicable to pure high-grade ores, ores high in iron, and complex zinc lead ores, since the residue from the distillation is held immovably in place within the briquet. In the case of complex zinc-lead ores, the distillation is conducted with a carefully regulated temperature so that a high percentage of lead is retained in the distilled briquet, which may then be smelted for its lead content. In present zinc smelting practice, the reduction fuel is from 40 to 50 per cent. of the weight of the ore. In the briquet, it is from 60 to 85 per cent. of the ore; but unless the ore is exceptionally high in residue, the distilled briquet

Jan 9, 1919

By B. C. Burgess

AFTER many years of close and friendly association with talc and soap-stone, this orthographically distinguished mineral steps forth in this edition, for the first time in a chapter of its own. Pyr, the Greek for fire, and phyllite, a rock or stone, form its name and at the same time refer to the first recorded use of pyrophyllite as firestones or hearthstones. Another derivation of "phyllite" is from the Greek phyllites, "of leaves," alluding to the beautiful white radial crystal aggregates that form when pyrophyllite is heated. Pyrophyllite used by the Chinese for carving is called agalmatolite, from the Greek agolma, meaning an image. COMPOSITION AND PROPERTIES Pyrophyllite has previously been grouped with talc because of the close similarity of the minerals in physical and optical properties. They have the same space group; and chemically they are closely related, pyrophyllite being the aluminum silicate A12Si4010(OH)2 and talc the magnesium silicate Mg3Si4010 (OH) 2. Another arrangement of the pyrophyllite formula is generally given as A12034Si02H20 because it expresses the chemical composition as usually determined (alumina 28.3 pct, silica 66.7 pct, water 5.0 pct). Vanderbilt gives pH values of pyrophyllite 5.6 to 8.4.29 Pyrophyllite usually is white, pale green, cream or pale yellow, buff or light gray. It is found in darker shades and other colors principally due to oxidation of contained iron minerals. It is translucent in thin sections. In hardness it is 1 to 2 in the Mohs scale. Its specific gravity is 2.8 to 2.9. In bulk specific gravity, the powdered mineral ranges from 0.4 to 0.7. Its luster is pearly to dull; it is infusible in the Bunsen burner flame, slightly affected by aqueous solutions of sodium carbonate and hydrochloric acid. It is decomposed by sulphuric acid, with separation of gelatinous silica. It is characterized chiefly by its micaceous structure and cleavage, its softness and greasy feel. Two other varieties occur

Jan 1, 1949