Search Documents

By D. B. Robinson, J. Lukacs

A knowledge of the equilibrium water content of hydrocarbon systems under pressure is important to the natural gas industry. The information available on the solubility of water in hydrocarbon, hydrogen sulfide, and carbon dioxide systems is reviewed in this paper and the influence of the more important variables such as temperature, pressure and molecular structure on solubility in liquids and gases is discussed. A suitable cbromatographic technique has been developed for determining low concentrations of water. Tailing of the water peaks has been elim inated by adding water to the carrier gas stream The method is applicable for both gas or liquid samples and is effective in the presence of hydrogen sulfide. The experimental study of water solubility in methane-hydrogen sulfide systems at a temperature of 16oF has shown that the presence of hydrogen sulfide causes only a modest increase in water content at pressures up to 1,400 psia. Theoretical considerations and data on pure hydrogen sulfide and carbon dioxide suggest that the effect of both these compounds will be greater at higher pressures and in the liquid phase. INTRODUCTION Before transporting or processing natural gases and gas condensates, it is usually necessary to dry them using suitable dehydration equipment. The design and operation of this equipment requires a knowledge of the amount of water present in the fluid at the reservoir and operating conditions. This is influenced by temperature, pressure and composition, particular1y when certain non-hydrocarbon components are present. Field experience indicates that hydrogen sulfide and carbon dioxide, for example, alter the usual water solubility relationships appreciably. However, an extensive search of the literature does not reveal any quantitative data on such systems. For sweet natural gases, generalized empirical correlations such as the one proposed by Katz, et al,6 can be used to predict water solubility with confidence at most temperatures and pressures of interest. However, existing theoretical relationships do not permit a calculation of the deviation from these curves when polar substances like hydrogen sulfide are present in the system. Thus one must resort to an experimental approach to obtain the necessary information. The fact that laboratory experimental methods frequently involve the use of mercury which reacts with hydrogen sulfide in the presence of water, and that hydrogen sulfide interferes with many chemical reactions specific for water has contributed to the difficulty of studying water solubility in systems containing hydrogen sulfide. In this investigation the water content of a limited member of methane-hydrogen sulfide mixtures was determined using a special technique with gas chromatography. REVIEW OF PUBLISHED DATA Experimentally determined water solubility data have been reported for methane, 14 ethane, 15 propane, 9 n-butane, 16 1-butene, 11 hydrogen sulfide 18 and carbon dioxide. 19 These studies report the effect of pressure, temperature and molecular structure on water solubility in single component gases and liquids. Fig. 1 compares experimentally determined water solubilities in several hydrocarbons, carbon dioxide and hydrogen sulfide at l00F as taken from this

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By R. W. Gurry

WHEN a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. EXPERIMENTAL PROCEDURE Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;1 it suffices to state here that the carburization lasted about 140 hr. at 760°C. (1760°F.) and 44 hr. at 1110°C. (2030°F.), these periods being long enough-on the basis of the calculations presented later-to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By W. D. Steele, S. D. Brady

The Pittsburgh coal seam in West Virginia contains the largest coal reserves of any coal seam in that State and is, therefore, one of the most important seams, and attains minable thickness and purity throughout that part of the seam extending from the Northern Panhandle to Monon-galia Co. thence south and southwest across the state to Wayne Co. near Hunt-ington. The Pittsburgh coal is also minable in the Upper Potomac region but is now practically exhausted there. The total minable areas of this coal amount to 2,165 sq miles and are estimated, by the West Virginia Geological Survey, to contain 13¼ billion net tons. The largest body of Pittsburgh coal outcrops on the western edge of West Virginia, along the Ohio River as far south as Moundsville, West Va., going under the river at that point and extending at various depths down the river as far as Wetzel Co. line where it thins out to such an extent that it has little practical value, and on the eastern edge this large body outcrops along the Monongahela River. The territory to be covered by this paper is the area known as the Northern West Virginia District comprising Wetzel, Mon-ongalia, Marion, Preston, Harrison, Dodd-ridge, Taylor, Barbour, Upshur, Lewis, Gilmer, Braxton and Calhoun Counties, and is also known as Dist. 3 under the Bituminous Coal Act. This region was originally opened for commercial mining along and adjacent to the Monongahela River around 1852 when the Baltimore and Ohio Railroad was constructed to Fairmont. It has been extensively developed, first, in 1880 (when the Monongahela River Railroad, now B. & 0. R. R., was constructed) between Fairmont and Clarksburg, and later, in 1916, between Morgan-town and Fairmont when the Monongahela Railway was constructed and placed in operation, this area furnishing the major portion of the production over the past years. With the mining out of a great deal of this territory adjacent to the Mononga-hela River considerable interest has been developed in the back acreage; and within the past few years a number of diamond core drill holes have been made in the back areas of Monongalia and Marion Counties. In this back area the oil and gas well drilling showed that the Pittsburgh coal seam was of minable thickness and ranged in depth from 350 to 1,000 ft below the surface of the stream valleys but this drilling did not furnish any definite data as to its thickness and quality. Economic Importance The Pittsburgh seam in Northern West Virginia is of primary importance as a coal resource not only because of its large reserves but because of its contributing a very large part of the coal used in this country for general steam uses. The Pittsburgh seam is a consistently thick seam, averaging 8 ft in thickness, with very easy grades underground, so it has always been

Jan 1, 1949

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.' Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942

By Ernest L. Ohle

The newly opened Hayden Creek lead mine represents a variation from the usual Southeast Missouri type. Galena mineralization occurs in sandy dolomite cementing a conglomerate of granite boulders and in cracks in the boulders. The conglomerate occurs at the base of the Bonneterre formation on the slopes of two buried pre-Cambrian knobs. IN 1943 diamond drilling from the surface in an area 2 miles southwest of Leadwood, Mo., discovered a lead deposit of a markedly different character from the usual southeast Missouri type. Subsequent drilling of about 500 holes indicated several million tons of ore, and in 1950 a 701-ft vertical shaft was sunk into the orebody. This paper describes the geology of this interesting occurrence insofar as it is known from the drilling and the small underground exposure at the bottom of the shaft. Geology The location of the Southeast Missouri Lead Belt and of the Hayden Creek property are shown in Fig. 1. As shown here, there are two separate producing areas, one from which the larger tonnage has come, located near Bonne Terre, Flat River, Desloge, and Leadwood, and the other to the south around Fred-ericktown and including famous old Mine LaMotte. The best published description of Lead Belt geology is by Tarr.* In pre-Cambrian time in this area, an assemblage of granites and rhyolitic flow rocks was eroded to a mature topography. Sedimentation, beginning in the Upper Cambrian, filled in the valleys and gradually covered even the highest hills. The first formation deposited was the La-motte sandstone; it is successively overlain by the Bonneterre dolomite, the principal lead-prodbcing formation, then the Davis shale. the Derby-Doerun limestone, and a succession of Cambro-Ordovician cherty dolomites. Several of these formations may be found in direct contact with the pre-Cambrian as their deposition progressively overlapped the older rocks on the flanks of the igneous knobs and ridges. Immediately overlying the pre-Cambrian there is, not uncommonly, a thin basal conglomerate of granite or porphyry boulders, which is incorporated into the overlying sediments. Deposition of the lower part of the rock section was fairly continuous, and the Lamotte sometimes grades almost imperceptibly into the lower sandy Bonneterre. Since the sediments were deposited on an uneven floor, they tend to reflect the irregularities in that floor. Most of the steep dips found in the district, that is, dips in excess of 10°, are original dips and not caused by deformation. Such domelike structures in the sedimentary rocks around the igneous knobs have localized a considerable number of the orebodies in the district and particularly those in the Frederick-town area. Many of the larger orebodies, however, have no close relation to the pre-Cambrian topography. Most of the lead production has come from the lower 150 ft of the Bonneterre formation, where disseminated ore spreads laterally parallel to the bedding for great distances. Average stoping height is about 20 ft, but in a few places there are stopes over 175 ft high.

Jan 1, 1953

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;' it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By R. W. Gurry

When a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. Experimental Procedure Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;' it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°C. (2030°F.), these periods being long enough-—on the basis of the calculations presented later—to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

Secretary Membership Committee Increase of Membership Papers and Publications Committee Library Committee Treasurer Report of the Secretary TO THE BOARDOF DIRECTORASN D THE MEMBEROS F THE AMERICANIN STITUTE OF MINING AND METALLURGICAENL GINEERS GENTLEME:N As will be shown by the special reports of the Finance, Membership, Library, Papers and Publications, Increase of Membership, and other standing Committees, together with that of the Treasurer, the year 1927 was one in which the Institute made very satisfactory progress in a number of directions. In total numbers the membership is no larger but in revenue from dues there has been a marked increase. This has been due to the promotion to full membership of Junior Associates of earlier years, to the larger proportion that come in originally as members rather than juniors, and to the keener interest in the work of the Institute reflected in prompter payment of dues. The latter is important, since experience shows that of those who fall behind a large number must ultimately be dropped for non-payment. Conditions in the mining industries have been healthy though not booming. It has been much easier for members to find employment and meet their financial obligations but there has not been that flow of young men into mining, and hence in part into the Institute, that characterized certain earlier years. Rather the tendency toward centralization and larger industrial units has restricted the number, though not the scope, of opportunities for technical men in the mineral industries. The Institute is constantly receiving resignations from members crowded out of mining into other lines of activity. On the other hand, those who remain in mining and metallurgy have a greatly increased necessity for i,dormation and contacts with technology. A few years ago many superintendents and most foremen were non-technical men. Today the reverse rule obtains and shift bosses and men who occupy even lower positions in industrial units are called upon to know and to apply such an amount of technical knowledge that graduate engineers are the rule rather than the exception. The curious situation has obtained that with a much smaller enrolment of students in the schools of mining and metallurgy there has been at times an actual shortage of young engineers for beginners' jobs. The young men retort that the conditions of employment and pay offered in mining are not equal to those in other lines and, while it is undoubtedly true that the young engineer beginning in mining is able to start under conditions markedly better as to pay, living, and responsibility than did the men who are now leaders, they are required to know much more and have usually spent more in time and money to qualify for their jobs. The whole matter is one which warrants much more attention than has been given to it. For the Institute it is important since the young men

Jan 1, 1928

By Ernest L. Ohle

The newly opened Hayden Creek lead mine represents a variation from the usual Southeast Missouri type. Galena mineralization occurs in sandy dolomite cementing a conglomerate of granite boulders and in cracks in the boulders. The conglomerate occurs at the base of the Bonneterre formation on the slopes of two buried pre-Cambrian knobs. IN 1943 diamond drilling from the surface in an area 2 miles southwest of Leadwood, Mo., discovered a lead deposit of a markedly different character from the usual southeast Missouri type. Subsequent drilling of about 500 holes indicated several million tons of ore, and in 1950 a 701-ft vertical shaft was sunk into the orebody. This paper describes the geology of this interesting occurrence insofar as it is known from the drilling and the small underground exposure at the bottom of the shaft. Geology The location of the Southeast Missouri Lead Belt and of the Hayden Creek property are shown in Fig. 1. As shown here, there are two separate producing areas, one from which the larger tonnage has come, located near Bonne Terre, Flat River, Desloge, and Leadwood, and the other to the south around Fred-ericktown and including famous old Mine LaMotte. The best published description of Lead Belt geology is by Tarr.* In pre-Cambrian time in this area, an assemblage of granites and rhyolitic flow rocks was eroded to a mature topography. Sedimentation, beginning in the Upper Cambrian, filled in the valleys and gradually covered even the highest hills. The first formation deposited was the La-motte sandstone; it is successively overlain by the Bonneterre dolomite, the principal lead-prodbcing formation, then the Davis shale. the Derby-Doerun limestone, and a succession of Cambro-Ordovician cherty dolomites. Several of these formations may be found in direct contact with the pre-Cambrian as their deposition progressively overlapped the older rocks on the flanks of the igneous knobs and ridges. Immediately overlying the pre-Cambrian there is, not uncommonly, a thin basal conglomerate of granite or porphyry boulders, which is incorporated into the overlying sediments. Deposition of the lower part of the rock section was fairly continuous, and the Lamotte sometimes grades almost imperceptibly into the lower sandy Bonneterre. Since the sediments were deposited on an uneven floor, they tend to reflect the irregularities in that floor. Most of the steep dips found in the district, that is, dips in excess of 10°, are original dips and not caused by deformation. Such domelike structures in the sedimentary rocks around the igneous knobs have localized a considerable number of the orebodies in the district and particularly those in the Frederick-town area. Many of the larger orebodies, however, have no close relation to the pre-Cambrian topography. Most of the lead production has come from the lower 150 ft of the Bonneterre formation, where disseminated ore spreads laterally parallel to the bedding for great distances. Average stoping height is about 20 ft, but in a few places there are stopes over 175 ft high.

Jan 1, 1953

By J. J. Lander, L. H. Germer

MOLYBDENUM and tungsten have desirable corrosion and temperature resistant properties, but the metals in bulk are expensive and their fabrication is difficult. Such considerations led to a search for a method of plating them upon base metals. This search was successful and led furthermore to a number of developments which could not have been foreseen. Neither pure tungsten nor pure molybdenum has been electroplated successfully, although the literature of electroplating is liberally sprinkled with the description of unsuccessful attempts. The process of plating these metals by thermal reduction of their halides has achieved only limited usefulness because of technical limitations and because of limited range of product quality. Plating by thermal decomposition of the carbonyls does not suffer from limitations of the same sort and the properties of the plate are readily controllable. This paper describes the plating of molybdenum and tungsten, and of compounds and alloys of these metals, by pyrolysis of their carbonyl vapors. Chromium also has been plated in this manner, but the experiments upon chromium have been less extensive and the results much less satisfactory. Probably the most important of the products which we have obtained are the alloys with carbon, and the carbides of the metals. Either molybdenum or tungsten can be deposited upon a base metal as a coherent and adherent coating. By adjusting the plating condition the carbon content of the coating can be made to have any value from substantially zero to about 35 atomic pct. The hardness is dependent primarily upon the amount of carbon in the plate and can be regulated over a very wide range, some coatings containing considerable carbon being harder than sapphire. In addition to products already known this method of plating has yielded new carbides of molybdenum and tungsten and alloys supersaturated with carbon. These new products are possible because, in the process of plating, carbonyl can be decomposed at temperatures as low as about 150'C, and thus in the presence of other substances reactions occur which could perhaps not be produced in any other way. In addition to carbides and alloys with carbon, sulphides and oxides of molybdenum and tungsten have been produced and studied. There are certain other advantages of the carbonyl method of plating. It is not required that the base have good electrical conductivity as in electrochemical processes, and the base need not have the temperature stability required in plating from a halide. Thus low melting glasses, as well as other ceramics, can be plated almost as readily as metals. In particular, the plating of glass with

Jan 1, 1947

By F. M. Lewis, J. E. Goodman

A larger, slow-speed, under-loaded ball mill and hydraulic classifier have almost doubled grinding efficiency at the lsabella mill. TENNESSEE Copper Co. operates two ore con-A centrators, the London and Isabella mills near Copperhill, Tenn. In 1948 and 1949 the small ball mills and rake classifiers in the London concentrator were replaced by one large ball mill and one hydraulic classifier. This new ball mill was designed oversize so that it could be operated at slower than normal speed. The proper operating conditions were established and the results published.' Later it was found that this mill operated more efficiently with a small ball charge." While this London grinding practice was being developed, the Isabella grinding circuit was not changed in any way. It remained a conventional two-stage rod mill—ball mill combination, the rod mill in open circuit and the ball mill in closed circuit with a rake classifier. Study of the data indicated that grinding cost could be lowered by converting to the London practice, but not enough would have been saved to warrant the expense of converting. No plan for improving this grinding operation could be developed. In 1953 this study was reopened when plans were made to increase the Isabella mill output from 1150 to 1500 tpd. At this time the grinding circuit consisted of a 6x12 rod mill followed by a 6x12 ball mill in closed circuit with a 6-ft rake classifier. Another 6x12 ball mill and 6-ft rake classifier would have been sufficient equipment and would have been the simplest and cheapest installation. However, this would have offered no improvement in grinding efficiency or operating cost. If, on the other hand, the grinding operation could be converted to the London practice, by installation of one large 101/2x9x9 tricone mill and a 10-ft hydroscillator,2 lower operating costs would justify the additional investment. Economics: Table I presents estimates for the two schemes for enlarging the Isabella mill. In the first scheme, column 1, one 6x12 ball mill and one 6-ft rake classifier were to be added. In the second scheme, column 2, the existing small ball mill and rake classifier were to be retired and one large mill and hydroscillator were to be installed. Estimated savings from the difference in operating costs made an attractive return on the additional investment for the large mill and hydroscillator. Actual costs of carrying out this plan are tabulated in column 3b. It will be seen that these costs follow the estimates in column 3a very Closely. The return on the additional investment is calculated from the difference in the operating cost in column 1 and the actual operating cost in column 3b. This too come very close to the estimate. Power and Steel: Power requirements and steel consumption for the rod mills and ball mills, both actual and estimated, are presented in Table 11.

Jan 1, 1958

By Robert Maes, Robert de Strycker

The solidifzcation reactions in the Cu-Sn-As system were determined by microscopic examination, thermal analysis, and X-ray diffraction. The system presents no ternary compound. There is a quasi-binary section, of a simple eutectic type, between the compounds Cu5As2 and SnAs; the system presents, in addition, one ternary eutectic reaction, one ternary peritectic reaction, and seven transitional reactions. The temp-peratures corresponding to each of these reactions were determined, most of them with an accuracy of *lLC. The isothermal lines of the liquidus surface were also established for almost the entire diagram. NO reference was found in the literature relative to the Cu-Sn-As phase diagram and this is believed to be the first study on this subject. The Cu-Sn diagram was taken from Hansen and Anderko;' it is represented by Fig. 1, with the phase designation which will be used in the remainder of this work. For the Cu-As diagram, the solution proposed by Hansen and ~nderko' must be modified to take account of recent data, principally from Heyding and Despault~ and from Hume-Rothery and Burns; this yields the diagram represented by Fig. 2. As for the Sn-As diagram, it is not established with certainty, particularly so far as concerns the solid solubility of tin in arsenic and the solidification reactions near the compound SnsAsz. For this last point, Hansen and Anderko propose two solutions: congruent melting of Sn3Asz with a eutectic SnsAsZ + SnAs or incongruent melting implying a peri-tectic reaction L + SnAs = Sn3As2. Microscopic examination of the few binary alloys prepared in this composition range made us prefer the second of these solutions, which gives the diagram shown by Fig. 3. EXPERIMENTAL METHODS The experimental techniques used in this work were microscopic observation and thermal analysis; a few X-ray diffraction patterns were taken to verify the

Jan 1, 1967

By R. J. Mellen

In a chloridizing roasting and cyanida-tion plant treating a manganese-silver ore, certain experiments pointed out the way to an improvement in roasting conditions by a change in the degree of crushing. The following short article is simply a description of the various changes that were necessary throughout the plant and of the results obtained. There is nothing unusual in these changes but they are of some interest in that they constitute a good many of the alterations usually resorted to in increasing production. In the beginning, the changes were brought about by an experiment that was not successful, but which clearly pointed to means of improving the operation, and is an example of the fact that often experimental work may result in failure and still be of value in arriving at correct fundamentals. This experiment also shows how far a metallurgist can get out of line in his deductions, particularly in a field with which he is not thoroughly familiar. The ore at the plant of Compania Minera Kildun y Anexas is crushed through a 13-in. gyratory, a 3-ft. standard Symons cone crusher and a set of 16 by 42-in. rolls, the latter in closed circuit with two Tyler type 400 screens. The crushed ore is then conveyed to two fine-ore bins. These provide storage and feed for two 6 by 90-ft. kiln roasters, which discharge directly to coolers. The coolers in turn discharge to a 6 by 12-ft. ball mill, where the ore is ground for cyanidation. Laboratory and pilot-plant tests previous to the mill construction had indicated that minus ¼-in. crushing was satisfactory for roasting, although results did not vary greatly with some coarser or considerably finer crushing. The plant was designed for a capacity of 300 tons per day on this basis. After a few months operation, the initial operating problems were overcome and the anticipated milling rate was reached but the results being obtained were not really good. The plant seemingly did not have much excess capacity in any department but the roasting operation was the most critically limiting factor both as to tonnage and the results obtained. If this could be improved there seemed some possibility of improving the total tonnage rate to some extent. Segregation of the calcine into various screen sizes showed that the coarser sizes were not giving the expected recoveries. In all of the laboratory and pilot-plant testing, any limiting conditions as to the percentage of salt used, temperatures, feed rates, etc., had affected the fine material more than it had the coarse, and even in making laboratory tests at this time the mill conditions could not be exactly duplicated. Further laboratory testing indicated that a segregation of the rushed Ore into a coarse and fine product for roasting might result in some improvement in roast-

Jan 1, 1947

By R. J. Mellen

In a chloridizing roasting and cyanida-tion plant treating a manganese-silver ore, certain experiments pointed out the way to an improvement in roasting conditions by a change in the degree of crushing. The following short article is simply a description of the various changes that were necessary throughout the plant and of the results obtained. There is nothing unusual in these changes but they are of some interest in that they constitute a good many of the alterations usually resorted to in increasing production. In the beginning, the changes were brought about by an experiment that was not successful, but which clearly pointed to means of improving the operation, and is an example of the fact that often experimental work may result in failure and still be of value in arriving at correct fundamentals. This experiment also shows how far a metallurgist can get out of line in his deductions, particularly in a field with which he is not thoroughly familiar. The ore at the plant of Compania Minera Kildun y Anexas is crushed through a 13-in. gyratory, a 3-ft. standard Symons cone crusher and a set of 16 by 42-in. rolls, the latter in closed circuit with two Tyler type 400 screens. The crushed ore is then conveyed to two fine-ore bins. These provide storage and feed for two 6 by 90-ft. kiln roasters, which discharge directly to coolers. The coolers in turn discharge to a 6 by 12-ft. ball mill, where the ore is ground for cyanidation. Laboratory and pilot-plant tests previous to the mill construction had indicated that minus ¼-in. crushing was satisfactory for roasting, although results did not vary greatly with some coarser or considerably finer crushing. The plant was designed for a capacity of 300 tons per day on this basis. After a few months operation, the initial operating problems were overcome and the anticipated milling rate was reached but the results being obtained were not really good. The plant seemingly did not have much excess capacity in any department but the roasting operation was the most critically limiting factor both as to tonnage and the results obtained. If this could be improved there seemed some possibility of improving the total tonnage rate to some extent. Segregation of the calcine into various screen sizes showed that the coarser sizes were not giving the expected recoveries. In all of the laboratory and pilot-plant testing, any limiting conditions as to the percentage of salt used, temperatures, feed rates, etc., had affected the fine material more than it had the coarse, and even in making laboratory tests at this time the mill conditions could not be exactly duplicated. Further laboratory testing indicated that a segregation of the rushed Ore into a coarse and fine product for roasting might result in some improvement in roast-

Jan 1, 1947

By A. B. Dyes

In the operation of a water-driven reservoir, a free gas saturation can he established by maintaining production rates fast enough to cause the reservoir pressure to decline below the bubble point. The benefit of such a procedure on the displacement efficiency of the oil by water is illustrated for two types of sandstone samples from one reservoir. Those rock samples showing the poorest recovery to water drive in the absence of a free gas saturation give the most improvement in the presence of a free gas saturation. Employing one type of reservoir fluid (low .shrinkage) the benefit of evolved gas on oil displacement is calculated at several reservoir pressures below the bubble point. This demonstrates the presence of air optimum pressure for water displace,rnent which is .several hundred pounds per .square inch below the bubble point. Displacement of oil at the optimum pressures results in the removal of 7 to I? per cent more oil than would be obtained by displacement at the bubble point pressure. In some instance. this magnitude of increase may be worthy of consideration in establishing the maximum efficient rate of production from many water-driven fields. INTRODUCTION For many years the belief that the use of gas could be combined with that of water to result in a better recovery operation than the use of either of these phases alone has been prevalent in the oil industry. This is evidenced by the several field trials which have employed the injection of gas and water in combination.1.2.v In most cases the small amount of any additional recovery, in combination with the limited knowledge available on the older reservoirs, has left uncertain the influence of gas on recovery in these earlier attempts to combine the use of gas with water. Research studies in recent years have demonstrated through laboratory. floods the magnitude of the benefit of the presence of gas on the displacement of oil from sandstones by water.5,6,7,8,9,10,11 In addition, studies of the distributions of the phases which are present during the displacement process have developed concepts concerning the mechanism by which this benefit is obtained."." It now remains for the engineer to incorporate these findings into the general technology of reservoir operations. It is the purpose of this paper to illustrate that the production of a water-driven reservoir at pressures below the bubble point is one such operation whereby improved oil displacement efficiency can be obtained as a result of gas evolution. The establishment of a gas saturation by evolution of dissolved gas was one of the techniques used by several investigators in the laboratory studies. The possibility of obtaining the benefit of gas evolution in water-driven reservoirs by producing at pressures less than the bubble point has 3150 been pointed out previously." The desirability of this operation has undoubtedly

Jan 1, 1955

By William T. Schneider, Taylor Cole

Drilling in West Texas during 1941 was more active than in any year since 1937, a total of 2325 wells having been drilled. Pre-Permian exploration was the greatest in the history of the area; 106 wells tested pre-Permian formations during the year. Wildcatting reached the peak since 1937, with 135 wildcats, of which 20 per cent were producers. The wells were drilled to a greater average depth than in any previous year. Slim-hole drilling was the common practice, using drilling equipment that is largely portable. Because of deeper drilling, more attention was paid to mud fluids, especially the use of materials to reduce water filtration. There has been slight improvement in the protection of the pay horizons while drilling by the use of reverse circulation, and drilling-in with oil as well as low water-filtration muds. The practice of setting and cementing the oil strings through the producing formation and perforating opposite the pay zones has increased in the fields producing from sands. It is doubtful whether this practice is of unusual value in dolomitic limestone fields. There have been few if any technological improvements in obtaining necessary information on the pay sections penetrated, by coring, core analyses, better sampling, and more detailed drilling time. However, more operators are beginning to realize the necessity of good samples. For a proper study of the reservoirs in West Texas, it is essential that better samples be obtained, that more core analyses be run, and that better methods of obtaining drilling time be initiated. It should be noted that increased drilling speeds and slim-hole drilling have tended to reduce coring and core recovery and have not aided in obtaining good subsurface samples. In fact, fast drilling speeds and slim-hole drilling have reduced the cost of drilling operations, but with the sacrifice of much needed subsurface information. Larger quantities of slower-reacting acid are being used per well. There has been improvement in shooting, in that a greater number of quarts per foot have been used and an attempt has been made to concentrate the shots opposite the pay zone. The use of mud logging to determine the characteristics of the pay section increased considerably over the year 1940. There has been a slight increase in obtaining reservoir information in the new fields, such as bottom-hole sampling, bottom-hole pressures, and records of gas, oil, and water withdrawals. However, there is great need for more data on these subjects, particularly accurate information regarding gas and water volumes. There are three repressuring projects and a fourth is nearly ready for operation in the Kermit field. There is one repressur-ing project in the Payton field and one in the North Ward field. So far, the gas-injection projects have not shown very impressive results. As yet, there are no water-flooding projects or water-disposal projects in West Texas. Not including gathering lines within the fields, 222 miles of feeder pipe lines were

Jan 1, 1942

By W. D. Lowry

As most of the industrial activity of Oregon is centered in the Portland area, the foundries there consume the bulk of the foundry sand produced in Oregon. Although a number of the larger towns scattered throughout the state have gray-iron foundries, the sand used by most of them is of local origin: The yearly consumption of foundry sand of all types for the past few war years in Oregon is estimated to have been approximately 40,000 tons valued at about $285,000, of which an estimated 18,000 tons was shipped in from the Ottawa, Ill., district for use largely by the steel foundries. Until 1945 much of the silica sand consumed by the steel foundries in the Pacific Northwest, approximately 50,000 tons in 1944, came from Ottawa, Ill. and surrounding regions. Although some silica sand was shipped in from Belgium in the past, none is known to have been imported in recent years. Early in 1945, a very promising high-grade silica sand being produced near Eugene, Oregon, was introduced, and all but two of the Portland steel foundries are using this new sand. Until a few years ago, the search for good local (Oregon) foundry sands was carried on largely by the foundry supply houses. Recently the Oregon Department of Geology and Mineral Industries has investigated a number of deposits and has carried on and fostered research on the most promising deposit near Eugene, about 120 miles south of Portland. High-grade silica foundry sand from this deposit is now being marketed in Oregon, Washington, and British Columbia. The Eugene sand is one of the very few outstanding western steel-foundry sands. Field investigations by the Oregon Department show that there are relatively few deposits of sand in Oregon suitable for foundry use. A knowledge of the geology of the state makes this readily understandable. The only major primary sources of the quartz present in sandstones in Oregon are the intrusive masses of granite, granodiorite, and quartz diorite of late Jurassic or early Cretaceous age found in the Siskiyou Mountains of southwestetn Oregon, a part of the old Klamath Mountain highland, and in the Blue Mountains of northeastern Oregon. Transportation militates against the development of any possible deposits of foundry sand found east of the Cascade Mountains in central and eastern Oregon because few railroads traverse that area. East of the Cascades, which separate western from eastern Oregon, many of the older sediments of Paleozoic and Mesozoic age have either been metamorphosed or contain much volcanic eruptive material, and even if some of the Mesozoic sediments are highly quartzose in places, they are in relatively inaccessible areas. All the Tertiary sediments there are of continental origin and contain much ash and other volcanic debris, for there was great volcanic activity during much of that period. In western Oregon much the same is true of the Paleozoic and Mesozoic rocks

Jan 1, 1947