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By Charles H. Jacoby

The solution mining of evaporites has a history of approximately 5,000 years. The insitu leaching of metalliferous ore will have many of the same characteristic problems which have confronted industry for years in the production of evaporite minerals. Basically we will be converting the less soluble forms of valuable metals into their more soluble salts and producing these in much the same manner as, for example, sodium chloride. There are a number of problems which we are faced with that are more complex and complicated and, therefore, will require a higher degree of sophistication than previously employed. One of our most important undertakings will be the clearcut definition of the problems involved. While a great deal of expertise can be drawn from the solution mining of evaporites and the oil industry, problems peculiar to the hydrometallurgical field will need to be solved. One of these is the introduction of permeability into an impermeable rock so as to expose the sought after values of metals which by volume are infinitesimal when compared with sodium chloride, potash or other type water soluble mineralization. After establishing this permeability which will be miniscule when compared to a solution cavity, there will be the maintenance of this permeability. In general, salt deposits are of a somewhat uniform chemical composition and thus their chemistry was relatively simple. Each metalliferous ore body is somewhat unique in its chemistry and will need to be treated accordingly.

Jan 1, 1974

By W. T. Malone, J. R. Williams, R. L. Tiner, J. M. Tinsley

Hydraulic fracturing methods for production stimulation have become a common procedure in the oil and gas industry. Fracturing treatments are performed on wells of various potentials to help increase the production rate. In addition to the desire for increased production is the need to predict what increase might be expected. This knowledge is useful in economical treatment planning to accomplish the desired production goals for the well. Theoretical production increases due to horizontal radial fractures may be calculated using equations developed from mathematical analyses and electrical models.1,2,6 It also is possible to predict theoretical production increases due to vertical fractures using curves developed from electrical3 and mathematical models.8 However, these studies assumed that the vertical fracture height and the formation height were equal, which may not be true." In addition, the final fracture height through which fluid is produced may not be equal to the created height. The development of vertical fracture proppant transport relationships has made unrealistic the assumption that propped fracture height is equal to created fracture height. Through the use of published proppant transport equations,4'12 it is possible to calculate the height of a bed of propping agent deposited in a fracture of a given height. Assuming that the fluid flowing in the fracture moves through only the propped portion of that fracture (i.e., that the un-propped part of the fracture heals) it becomes essential to know how production increase varies with the ratio of propped fracture height to formation height. It should be recognized that future investigation may determine that the fracture does not heal completely and that a highly permeable channel exists over the deposited bed of proppant. The effect of this channel was not considered for the present study. The following analysis of experimental data allowed development of curves to determine theoretical production increases considering fracture height as a variable. Discussion In designing a fracturing stimulation treatment a number of variables must be considered. The size of the treatment, type of proppant used, proppant concentration, treatment fluid properties and well conditions are all factors affecting the dimensions and permeability of the fracture. Production increase due to a vertical fracture is affected by propped length, height, width and permeability of the fracture for a given set of formation conditions. Production increase may be defined as the ratio of production rate after fracturing to the production rate before fracturing at the same pressure differential, pe — pw. The producing rate in an

Jan 1, 1970

By Rodney L. Stone, David S. Cahn

As part of an over-all laboratory and plant test program to determine mixing ad other techniques for a more economic use of bentonite as an iron ore pellet binder, a settling test for measuring the bentonite content within a pellet or a batch of pellets has been developed. Through this test, it has been shown that dry fracture load is directly proportional to bentonite content in batches of pellets, but inversely propor tional to bentonite content in individual pellets of the same batch. This apparent paradox is explained by a negative correlation between a pellet's size and its bentonite content and the fact that large pellets can withstand a higher fracture load than small pellets. In past attempts to characterize green and dry iron ore pellets, the authors found large variations in the results of strength tests on closely sized pellets from the same batch.' Reasons advanced for such variations in the quality of pellets in which the binder is bentonite were the presence of internal flaws and the nonuniform distribution of the binder. Even when resulting pellet strength is good, there is still the question of whether the same strength could have been attained through a more effective use of a smaller amount of bentonite. The authors' own and other studies 2-3 have pointed out the strong dependence of pellet strength on the degree of "mixedness" of the iron ore concentrate and the bentonite binder. However, before such a relationship could serve as a guide for the development of better mixing techniques and the associated economy of

Jan 1, 1969

By R. W. Heins, N. Street

An investigation was made of the Rehbinder-Kuznetsov pendulum as an instrument to aid in the study of rock drillability and of the effect of surface active agents on rock drillability. The "critical weight", i.e., the pendulum weight at greatest sensitivity, was determined for several solids and it was shown that a change in surface environment changed the maximum value of the apparent hardness but not the critical weight, and the critical weight increased with increase of hardness of the solid used. Using silver halides as the solid material, and solutions of either silver nitrate or the appropriate alkali halide, it was shown that there is a hardness maximum at the zero point of charge of the particular silver halide. INTRODUCTION The development of relative hardness measurement by the method of damped oscillations, or what has been called the pendulum sclerometer, is due largely to the Russian workers P. A. Rehbinder and V. D. Kuznetsov and their co-workers.1,2 The apparent simplicity of the method has led to its use in a number of fields, particularly those where relative hardness has to be determined on a brittle solid. As will be shown, the simplicity of the method belies its complexities. THEORY OF THE PENDULUM SCLEROMETER The operation of the pendulum is quite simple. Make a sharp point such as a diamond, hardened steel or tungsten carbide, as the fulcrum of a pendulum, with the center of gravity of the system below the point of support. The attenuation of this pendulum is a function only of air friction, provided no fragmentation, breakage or other work is performed by the point. However, when the solid surface breaks or disintegrates under the point, and the latter penetrates the solid, part of the energy of oscillation is absorbed in the work of creating new surface, and the rate of attenuation increases. In the case of brittle solids, the point of the pendulum produces fragmentary particles, whereas the point produces plastic deformation in a plastic solid; but in both cases damping occurs. This pendulum damping is a function of the hardness or strength of the solid. Whereas a pendulum oscillating on a hard material attenuates primarily by air friction, in the case of a soft material, the points penetrate the surface of the solid, producing new surface, and the pendulum damps much faster. Thus the attenuation rate is a function of the hardness or strength of a material in both plastic and brittle substances. Russian workers initially used a single support for the pendulum, but this created many problems because of oscillation of the pendulum in more than one plane. A revised version used two points, or sometimes a prism as support, successfully confining oscillation to one plane. The version using two points was constructed and used throughout this investigation, making the recording of the attenuation as a function of time relatively easy. That both points should be in contact with the solid during the damping is implied. Rehbinder (c.f. Kuznetsov2) proposed that the hardness H as measured by this method could be expressed by a quantity which is inversely proportional to the relative initial rate of attenuation of amplitude. where H = hardness parameter (arbitrary units) a, = initial amplitude da/dt = rate of attenuation of amplitude with time. In the simplest case of damping with a constant logarithmic decrement, H can be regarded as a constant for the duration of the whole damped oscillation process. That is

Jan 1, 1966

By H. T. Kennedy, J. E. Little

An empirical equation for the prediction of the viscosity of several pure paraffin hydrocarbons and nitrogen is presented. It involves temperature, pressure and six constants of the material, and it applies reliably to both liquids and gases. The equation is similar in form to van der Waal's equation of state. For the paraffin hydrocarbons methane through r-hexane and nitrogen, an average absolute deviation of 1.9 percent was obtained on 1,006 data points described in the literature by 14 authors. When this equation is extended to complex, liquid hydrocarbon mixtures, a correlation was obtained with an average absolute deviation of 9.9 percent. INTRODUCTION Equations describing the flow of gas and liquid through porous media contain the viscosity coefficient of the fluid. If other pertinent variables remain constant, the volume rate of flow is inversely proportional to this coefficient. In dealing with condensate fluids and volatile oils, however, the compositional effects resulting from changing pressure materially affect the viscosity. The effect of compositional changes also may be significant in certain secondary recovery or pressure maintenance processes, notably miscible displacement or gas injection. Early attempts to describe the performance of reservoirs utilized a volumetric material balance method wherein gas and liquid in the reservoir were identified as produced gas and liquid at the surface. This method of analysis proved adequate for reservoirs at moderate temperature and pressure that contained gas with moderately low amounts of condensable materials. The volumetric material balance procedures for "black oil" reservoirs leave much to be desired when applied to condensate and volatile oil reservoirs because phase behavior and compositional changes are relatively more important in these cases. The alternative is a compositional material balance, which in turn, requires a correlation of properties of the reservoir fluid with composition. This paper supplies this correlation in regard to viscosity, for reservoir crude oils. REVIEW OF LITERATURE The literature contains many empirical equations describing the effects of composition, temperature and pressure on the viscosities of pure liquids and binary liquid mixtures. However, the applicability of a majority of these equations is limited to very low pressures and to a small number of systems. Most of them, when applied to complex hydrocarbon systems, are of little value. The lack of utility of the majority of equations results from the fact that they were developed to show the separate effect of temperature, pressure or composition on viscosity, but not to predict the viscosity as a function of all three variables. And with the few exceptions noted below, they were developed to apply to much simpler systems than hydrocarbon mixtures. Eakin1 developed an equation for the viscosity of pure light hydrocarbons applicable in the gas, liquid and dense fluid regions, and in its most general form is written as µ - µo =A(ebP - e-cpk) The pure component viscosity at atmospheric pressure and temperature T, µo, was calculated using the Sutherland equation: µo = BT3/2/T + S The constants in Eakin's equation permitted the term e-CPk to become quite small at high densities (above 0.215 gm/cc), and the general equation would simplify to

Jan 1, 1969

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By E. F. Koppe

The Upper Freeport coal in the Freeport and New Kensington quadrangles, Pennsylvania, varies from a bony streak to a thick coal deposit often exceeding ninety inches, the "Double" or "Thick Freeport". Distinctive basal partings, a central bone layer, and a canneloid top bench may be present. The appearance of a sandstone roof, sandstone rolls, and bony coal at the top of the main coal bench can be anticipated in thin Freeport areas when basal partings are absent. When the two basal partings are present, a shale roof is normal. These effects are correlated with the original topography upon which the coal was deposited. The original depositional high areas tend to coincide with present structural highs. Preliminary data indicate that coal quality, in part, is affected by the deposi-tional setting. In "high" areas, a tendency exists for the main coal bench to contain higher percentages of fusain and mineral matter. Within limits, some-what higher ash fusion temperatures appear to correlate with paleotopographic highs. As a result of these findings, critical examination of the paleotopography and related sediments is indicated in other areas and other coals. The Upper Freeport coal is quite variable both in thickness and composition in the Freeport and New Kensington quadrangles of Pennsylvania (Figure 1). The coal horizon in these quadrangles is marked either by a thin carbonaceous shale bed or by a single bed containing a variable number of partings (binders). The complex coal zone known locally as the "Double" or "Thick Freeport" contains the Upper Freeport Coal Bed at the base; but in addition, it has an overlying bone layer and an upper coal bed occasionally capped with a canneloid layer. The "Thick Freeport" often exceeds 90 inches in thickness, whereas the normal Upper Freeport coal usually varies between 34 and 50 inches.

Jan 1, 1961

By D. R. Cook

This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. The project was based on the idea of W. S. Burbank, U. S. Geological Survey, that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Here, an area of andesitic rocks, four square miles in extent, has been argillized, pyritized, chloritized and silicified. Geological, geophysical and geochemical studies were followed by the diamond drilling of three holes totalling 6,220 feet. Further alteration ang geochemical studies were made on the cores from these holes. A brief review of the alteration and geologic mapping, colored aerial photograph interpretation, geochemical soil and rock sampling, magnetic, gravity and radio-metric surveys are presented together with some conclusions regarding this work. This paper is a case history of an exploration venture for base metals, begun by the Rocky Mountain District of Bear Creek Mining Company in 1952 and completed in 1954. Important contributions were made to the project by personnel of the Rocky Mountain District and the Geophysics Division. Individual acknowledgements to these people are made at the end of the paper. BASIS FOR THE PROJECT The project was based on the idea of W. S. Burbank (1947, p. 444) that commercial deposits of base metals might occur in Paleozoic sediments beneath hydrothermally altered volcanic rocks in the Southern Bonanza mining district, Colorado. Paleozoic sedimentary rocks, including the favorable Leadville limestone, are exposed three miles south of the altered area, and reason exists to believe that they might underlie it within a reasonable depth. Alteration of pre-mineral volcanic rocks has been used successfully as a guide to concealed orebodies in the Main Tintic and East Tin tic mining districts, Utah (Bill-ingsley, 1933, p. 120-122; Lovering et al, 1949; Howd, 1957, p. 124-134; Cook, 1957, p. 73) and could be a useful guide here. GENERAL GEOLOGY AND STRUCTURE The Northern and Southern Bonanza mining districts are northwest of the San Luis Valley in southern Colorado, just within the northeastern edge of the San Juan volcanic province. The districts are1ocated on the southern extension of the Sawatch uplift, a prorninent northwest-trending structural high. The highly productive mining camp. of Leadville, Gilman and Aspen are on the northeastern and northwestern flanks of this uplift where Paleozoic limestones have

Jan 1, 1961

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,' and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-' e-:".'m'"'r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.' The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown' to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,' but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick's second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

By R. L. Fullman, J. W. Cahn

A method is derived for obtaining the distribution of sphere diameters and plate thicknesses (or pearlite spacings) from size distribution functions obtained along randomly oriented lines. The method described offers several advantages over existing methods. IT is often of interest to measure not only the average particle size but also the distribution in sizes of particles dispersed in an opaque material, such as an alloy. Particles of a single size will exhibit a range of apparent sizes on the plane of polish. If the sample contains a distribution of particle sizes, the distribution of observed sizes on the plane of polish is related to the distribution of actual particle sizes by an integral equation, For example, a distribution of sphere sizes, N(r),

Jan 1, 1957

By Paul H. Lu

Methods and results of measuring three basic parameters for ground stability control, ground pressure, strata movement, and geomechanical properties of mine rock are presented in this paper. It is found that these parameters can be measured in situ by simple and practical techniques with nonsophisticated and inexpensive instruments. Specifically, a drillhole dilation technique employing a cylindrical hydraulic borehole pressure cell (CPC) was used to determine the modulus of rigidity. Premining ground pressures were determined by pressure convergence tests with a combination of one CPC and two pre-encapsulated flat hydraulic borehole pressure cells (BPC) installed in a single drillhole. Abutment pressures and pillar loading were monitored with BPC's. Differential strata movements and bed separations were measured with self-recording 10-anchor-point extensometers. Roof-to-floor convergence was measured with self-recording convergence meters. Some applications of these in-situ-determined parameters to mine design and ground stability control are also discussed.

Jan 1, 1984

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Jan 1, 1938

By H. P. Stüwe

HE recent papers of Aust and Rutter112 have again brought to mind the importance of certain "special" orientation relationships between the lattices of two fcc crystals on the mobility of the grain boundary separating them. No theoretical treatment of this problem has been offered till now. The only principle published so far that has given an indication why certain orientation relationships should be "special" is the counting of "coincidence sites" according to the suggestions by Kronberg and Wilson.3 The "coincidence plots" published by these authors show, for instance, that two fcc lattices rotated by 38 deg around a common (111)-axis have 1/7 of their lattice sites in common. Such an orientation relationship is also characteristic for high boundary mobility. The accuracy of the orientation relationship needed for high mobility is not too rigid. Deviations up to 10 deg from the ideal orientation seem to be tolerable as can be gathered from the experimental data.'j4 The auestion arises, then. how the density of coincidence sites will be affected by a deviatioi from mathematical accuracy. This can be checked by a simple model. Two sieves are prepared, the arrangement of the holes corresponding to lattice sites on a (111)-plane in a fcc crystal. They are placed upon each other, Fig. 1. One is kept fixed, the other is rotated around an axis pushed through one hole in common to both. The light falling through holes of both sieves is then a measure for the density of coincidence sites. If the diameter of the holes is very small, light intensity is contributed only by holes the centers of which coincide "exactly." If the diameter of the holes is rather large, some intensity will be contributed by

Jan 1, 1962

By Earl L. H. Sackett

Barite, although not a glamour mineral and probably little known to many of those in the mining business, is produced in the US. in very respectable quantities and is an important factor in the mineral economy of this country. The scope of the various uses of this mineral is perhaps one of the most misunderstood things about it, for it is surprising how many of those with a casual knowledge of the subject speak of its primary utilization in terms of paint pigments and barium chemicals. The life blood of barite utilization, however, is the petroleum industry by virtue of its dependence on this high specific gravity, inert mineral as the weighting material in its drilling fluids. From 80 to 85% of barite usage in the U. S. is accounted for in this manner-in fact, its role in oil well drilling is the only excuse for some of the large-scale barite production facilities which have been developed. Other uses are important and widely varied, but comparatively they are of small scale. They include fine crushed barite of low iron content as a component in glass manufacture, barite as a source material for manufacture of barium chemicals, finely divided barite as a component of some rubbers and ground, bleached barite in pigments. The formerly substantial use of barite in lithopone, however, has declined markedly because of replacement of lithopone by titanium pigments

Jan 5, 1962

By Carroll Forbes

INTRODUCTION MANY different shapes of drill bits are in use with hammer drills, but little definite information is available whereby to judge which one of these shapes is the best. The following investigation was undertaken in order to determine what effect, if any, the shape of the cutting edge has on the cutting speed and wearing qualities of drill bits. The bits tested were those in common use, namely, the 4-point or cross bit, the 6-point bit, the Z bit and the "Carr" bit. The rock in which the tests were made was the red granite from southeast Missouri. It is a coarse crystalline granite containing an unusually large amount of quartz and is extremely hard, and on account of its uniform texture is admirably adapted to this work. While tests in other rocks might show somewhat different results, nevertheless it is the opinion of the authors that the relative cutting quality inherent in the shape of the bits would be the same in all rocks. Other qualities, such as mudding freely, freedom from fitchering, etc., might make one bit more desirable than another in softer rocks. DESCRIPTION OF BITS TESTED The 4-point bits were the usual shaped bits commonly made on the Leyner sharpener with 14° taper on the wings and a 90° angle between cutting edges. Some tests were run at 85 lb. pressure with a 4-point bit made with a 5° taper on the wings. This was made by using the Carr bit die. The 6-point bits were the usual shaped hits made on, the Leyner sharpener. The Carr bits were made with a 5° taper and an angle of 100° between cutting edges.

Jan 8, 1917

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By George Comstock

IT seems a common opinion among metallographists that all light-gray inclusions seen with the microscope in polished sections of steel are manganese sulphide. Examples of this belief are continually appearing, as for instance in the paper by Dr. Henry Fay on manganese sulphide as a source of danger in steel rails,1 and in Lieutenant-Commander Cook's paper on Metallography of Steel for U S. Naval Ordnance.2 Slate FIG. 1-TRANSVERSE VIEW OF THE EDGE OF A SMALL HOT-ROLLED STEEL ROD. ETCHED WITH PICRIC ACID. X 200. colored inclusions are considered to be silicates, and dove-gray inclusions, manganese sulphide. To show the danger in the latter unqualified assumption, it should be sufficient to examine the edge of any piece of steel that is covered with a fairly thick scale, and that has been polished in such a way as to prevent the scale from breaking away entirely below the polished surface. This can be done by protecting the scaled edge of

Jan 12, 1916

By R. Schuhmann

Jan 1, 1965

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957