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By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts' method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s'- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts' apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts' method was used for this study and followed the procedures outlined previously.l' The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts' law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts' law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van't Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,' and Humbert and 1liott.l' The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i'- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967

By B. C. Mariacher

EXTRACTION of uranium from ores is being ac-complished by processes which. for the most part, subject the entire ore to acid or carbonate leaching. Ore deposits with a U 3 O 8 content below 0.10 pct U 3 O 8 are seldom considered suitable for treatment by leaching. A preliminary concentration that would enrich the uranium content of an ore by a simple, low cost process based on physical properties of the ore might result in some low grade deposits becoming commercial ores. In addition, the process might be employed in existing operations to reduce transportation and leaching costs and to increase capacity of existing leaching plants. A study to attempt the development of a preliminary concentration process for primary uranium ores was undertaken by the Colorado School of Mines Research Foundation under sponsorship of the U.S. Atomic Energy Commission. The objective of this work was to produce concentrates containing 0.25 pct U3O8 from the low grade ores tested. Ores Tested: The main effort was devoted to the low grade primary uranium ores from northwestern Saskatchewan. Samples were obtained from the Beaverlodge operation of the Eldorado Mining & Refining Ltd. Additional primary ores, obtained from deposits in Gilpin County, Colo., contained from 0.07 to 0.10 pct U3O8. Summary of Concentration Tests: The Beaverlodge ore was tested to determine amenability of the ore to concentration by magnetic, electrostatic, gravity, and scrubbing processes. None of these produced satisfactory results. Both gravity and magnetic processes produced fairly good concentrates when closely sized fractions of the ore were treated, but on the basis of treating the total ore, recovery was poor. Preparation of sized fractions and the low capacity of equipment for suitable concentration made these methods impractical. As flotation offered the advantage of treating the total ore without intermediate sizing, the main effort was in this direction. A flotation process was developed that fulfilled the concentration objectives as set by the AEC. Pilot plant testing was used to verify results obtained from laboratory batch testing. Mineralogy: A petrographic examination of the Beaverlodge ore included a study of polished sur- faces and identification of the radioactive mineral by autoradiograph and X-ray diffraction. Approximate quantitative mineral identification was as follows: quartz, 60 pct; orthoclase feldspar, 20 pct; chlorite, 10 pct; carbonates, 5 pct; and miscellaneous minerals, 5 pct. Included in this last group were plagioclase feldspar, pyrite, mica, chalcopyrite, pyroxene, sericite, magnetite, galena, and uraninite. The most general occurrence of uraninite was in the form of crusts and thin coatings on limonite-stained grains of pyrite, quartz, and pyrite-quartz intergrowth. At least 90 pct of the uraninite was still attached to other minerals in a 100 by 200-mesh size fraction. The uraninite crusts were as small as 10 to 20 µ diam, and 5 to 10 µ thick. The Flotation Process Petrographic examinations of the Beaverlodge ore had indicated the impracticability of attempting to concentrate the uranium by floating individual grains of uraninite. Liberation of the uraninite required grinding to sizes below those suitable for flotation. However, there was preferential association of the uraninite with some minerals while others were free of uraninite attachment. The approach to the development of a flotation process was, therefore, based upon an attempt to concentrate the uraninite by floating carrier minerals. The following paragraphs discuss the various stages of the process with regard to the factors tested and the conditions under which best results were obtained. Grinding: The most effective size range for flotation was —150 mesh + 13 µ. The —13 µ material in the final concentrate had a higher U3O8 content than the total ore, but not as high as the average concentrate; however, rejection of slimes before flotation was prohibitive because of the loss in uranium carried in the —13 µ fraction. Grinding techniques which contributed to a minimum production of fines, such as stage grinding, were then employed. Quartz and Silicate Depression: These minerals represented approximately 80 pct of the ore and were free to a large degree of uraninite attachment. Significant improvement in the grade of the concentrate was obtained by depression of these minerals with hydrofluoric acid or sodium fluoride. Promoter: Selective stage flotation of uraninite carrier minerals was simplified by development of a single promoter mixture. The mixture consisted of an emulsion of a fatty acid, fuel oil, and a petroleum sulfonate and was selected after a comprehensive series of tests. It contained three parts by weight of an oleic and linoleic acid such as Emersol 300,

Jan 1, 1957

By D. L. Katz

In the management of oil properties, it is always desirable to know the future behavior of oil wells and oil reservoirs. Some estimation of the quantity of oil and gas that will be produced must be made as a basis for decisions on possible returns on investments in lifting equipment, drilling of additional wells, and other operating expenditures. In new or wildcat areas, operating expenditures are considered highly speculative, but in the completion of partly drilled and the operation of producing fields it is good business to remove as much speculation as possible. An accurate knowledge of oil and gas reserves in such cases would solve many management problems. The term "oil reserves" usually signifies the future ultimate recovery without specifying the method of production. Thus with changing methods and innovations in the production industry, reserves of any definite reservoir may be increased by increasing the portion of oil recovered. The usual reserve estimates are made by comparisons of well and formation characteristics, by using a percentage recovery on the oil content of the formation volume using porosity data, by extending production curves on non-prorated wells, or by extending bottom-hole pressure-production curves. The most reliable method would appear to be one that would estimate the initial quantity of oil and gas present and then obtain percentage recovery values for various productive methods and formations from experience. It is the purpose of this paper to describe a method of estimating the initial quantity of oil and gas present in a reservoir. The method is based on field operating data and the properties of crude oil-gas mixtures. The principles involved, the data required, the assumptions necessary, and an example of the method will be given. The method is entirely independent of sand volumes and formation porosities. Principles of Method The method of estimating the initial quantity of oil and gas present is based upon the premise that the volume occupied by oil and gas in the reservoir is constant and that a mixture of crude oil and gas will behave in

Jan 1, 1936

By D. L. Katz

In the management of oil properties, it is always desirable to know the future behavior of oil wells and oil reservoirs. Some estimation of the quantity of oil and gas that will be produced must be made as a basis for decisions on possible returns on investments in lifting equipment, drilling of additional wells, and other operating expenditures. In new or wildcat areas, operating expenditures are considered highly speculative, but in the completion of partly drilled and the operation of producing fields it is good business to remove as much speculation as possible. An accurate knowledge of oil and gas reserves in such cases would solve many management problems. The term "oil reserves" usually signifies the future ultimate recovery without specifying the method of production. Thus with changing methods and innovations in the production industry, reserves of any definite reservoir may be increased by increasing the portion of oil recovered. The usual reserve estimates are made by comparisons of well and formation characteristics, by using a percentage recovery on the oil content of the formation volume using porosity data, by extending production curves on non-prorated wells, or by extending bottom-hole pressure-production curves. The most reliable method would appear to be one that would estimate the initial quantity of oil and gas present and then obtain percentage recovery values for various productive methods and formations from experience. It is the purpose of this paper to describe a method of estimating the initial quantity of oil and gas present in a reservoir. The method is based on field operating data and the properties of crude oil-gas mixtures. The principles involved, the data required, the assumptions necessary, and an example of the method will be given. The method is entirely independent of sand volumes and formation porosities. Principles of Method The method of estimating the initial quantity of oil and gas present is based upon the premise that the volume occupied by oil and gas in the reservoir is constant and that a mixture of crude oil and gas will behave in

Jan 1, 1936

By N. J. Gran, W. R. Opie

HYDROGEN in molten aluminum and aluminum alloys, which precipitates during cooling and solidification, is the principal cause of pin hole porosity in ingots and castings. Much attention has been given to determining the effect of temperature and pressure on the solubility of hydrogen in pure aluminum, but little data are available on hydrogen solubility in aluminum alloys. This investigation was undertaken to check results reported for pure aluminum and to show the effect of silicon and copper additions on the amount of hydrogen contained by molten alloys. Previous determinations of the solubility of hy-drogen in molten pure aluminum are plotted in fig. 1. The most reliable data appear to be those of Ransley and Neufeldl and of Baukloh and Oester-len.' The latter authors also report some results on the effect of copper and silicon additions. Up to 6 pct these elements decrease the solubility of hydrogen quite rapidly, with a definite minimum noted at 6 wt pct for both copper and for silicon, although no reason is apparent for these minima. Experimental Procedure The solubility of dry hydrogen in pure aluminum, aluminum-silicon, and aluminum-copper alloys was determined by the method of Sieverts.8 This consists of determining the volume of the gas system above the molten metal at a given temperature and pressure by using an insoluble gas. This volume is referred to as the "hot volume." The system is then evacuated and the soluble gas is introduced at the same temperature and until the same pressure is reached. It is necessary to introduce enough of the soluble gas to fill the space above the metal plus the soluble amount. The difference in the volume of soluble gas and the "hot volume" is the solubility. The accuracy of solubility measurements by the Sieverts' method is primarily depend-

Jan 1, 1951

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company's technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,' is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3' tests, however, this is not justified, and the D values

Jan 1, 1941

By A. Satter, J. M. Campbell

Reported herein are the results of a careful and detailed study of the non-ideal behavior of pure gases and their mixtures. Included are: (1) new data on five ternary systems composed of methane, ethane and H2 S; (2) a simple compressibility factor correlation that is inherently superior to present correlations, particularly for gases containing H2S and CO2; and(3) a detailed study of combination rules and the effect of system composition on the choice thereof. This study makes use of the rather large mass of data already available in the literature. A complete re-examination of the data and ideas presented in the last 25 years was considered desirable as a prelude to our basic concern — the effect of diluents on gas behavior. A consideration of both the macroscopic and microscopic properties of gases provides a better insight which, in turn, gives a firmer basis for improved correlation techniques. Such a study has shown that expressing the compressibility factor Z as a function of acentric factor w, as well as reduced temperature and pressure, yields a correlation that is broader in scope. The study of various combination rules has shown that better results are obtained by "tailoring" the rule used to the system composition. To do so improves the basic reality of results by overcoming some of the anomalies often found when using Kay's rule alone. Tentative recommendations are made regarding the most reliable combination rule for use with a given class of gas. The data presented are useful for estimating the direction and magnitude of the expected deviation when using a given rule. Although more work is needed, particularly around the critical region and with CO2 mixtures, the advantage of the classification scheme proposed is apparent. INTRODUCTION When one attempts to write a PVT equation to fit the data for actual gases, greater precision is obtained by the use of a multiple number of empirical constants. This has lead to multiple-constant equations such as Benedict-Webb-Rubin, Beattie-Bridgman, Keyes, etc., which are capable of yielding very precise results for pure gases in a range for which data to get the constants are available. As a matter of practicality, though, the use of such equations for gas mixtures is limited. Because of the infinite number of gas analyses available, any attempt to compile the constants needed requires a prohibitive amount of experimental data. This could be overcome by the use of a combination rule, but there is no real advantage in doing so because the end result offers no practical impovement over the Z factor correlation. The most widely used method of predicting the volumetric properties of pure gases is based upon the "theorem of corresponding states". According to this theorem, "all pure substances have corresponding molal volume at corresponding temperature and pressure if the reference point of correspondence is the critical point". Generalized compressibility charts for gases were prepared first by Cope and associates1 in 1931 and later by Brown and co-workers2 in 1932. However, the most commonly used charts are those of Dodge,3 Nelson and Obert,4 Hougen and atsson: and Standing and Katz.6 The work of Katz and co-workers has provided us with basic data for the hydrocarbons most widely used today. Their original chart6 was compared with a relatively large amount of multi-component data for gases consisting almost entirely of normal paraffin hydrocarbons. A deviation of only + 1.2 per cent was obtained.39 In the 20 years following publication of this work it has been found that the behavior of most mixtures of paraffin hydrocarbons could be predicted by this correlation within at least 5 per cent. Where difficulty has been encountered it has largely involved one or more of the following circumstances: pressures above 4,000 psig, mixtures containing large amounts of heavy ends and/or aromatics, systems in the critical region and mixtures containing polar compounds and/or CO2. The abnormal error sometimes found with such gases, not too unexpected for this method, is

By Charles Will Wright

The present struggle for economic and industrial supremacy by the Communist world is against the United States, its main target, and the other Free World nations. The basis of industrial power is minerals, so the Communist nations are building up mineral production within their borders, often regardless of costs, and are acquiring quantities of mineral products from Free World countries for future use. They are contracting for additional supplies and advancing funds for the development of these quantities. A number of the less developed mineral producing countries of the Free World are being infiltrated by Communists and Communistic influence. This situation is well known, but as yet little has been done to oppose these activities or to awaken the public to their seriousness. The Communist countries are still far behind the Free World Nations in production of many essential minerals. But, shortages are being made up from Free World nations in exchange for petroleum, manganese ore, chromite and other products. Restrictions on shipments of strategic materials to Communist countries have not been maintained.

Jan 1, 1964

BRADEN, the most southerly of the three big Porphyries in Chile and the first to start production (in 1910), is a remarkable mine. It would be interesting to know just how much it has contributed, and will contribute, to the earnings of the Kennecott Copper Corporation, which acquired 95 per cent of Braden stock in 1915 by an exchange of shares and which subsequently obtained the remainder. Because of this complete ownership no separate annual report is published (as is the case with Anaconda's South American subsidiaries, Chile and Andes). Income, taxes, operating costs, earnings, and other financial data, including the balance sheet, are consolidated with corresponding items applying to Kennecott's manifold operations in the United States and other foreign countries. If Braden were in the United States it would be possible to arrive at a pretty accurate estimate of revenue realized each year from the sale of copper simply by applying the average published market price to the production as reported by the company. However, because of the restrictions on sales imposed by the Chilean Government and the almost fantastic regulation of exchange rates in the past, no estimate of the sort would be reliable. This point is illustrated by the following comparison made by Charles R. Cox, president, in Kennecott's report for 1955: In each year, 1954 and 1955, Braden supplied about 30 per cent of Kennecott's total copper deliveries; but Braden's operations contributed 16.7 per cent of consolidated net income in 1955 against only 6.2 per cent in 1954. More will be said later about exchange rates, taxes, and restrictions, and the recent improvement in the situation. Of course another element of

Jan 1, 1957

By F. Windolph

There are no hard and fast rules for building tailing dams, and each case has to be analyzed individually because of special conditions encountered at each location. Certain criteria are used for building dams at Climax, Colo., where they must be placed in rather steep mountain valleys on foundations that are practically impermeable. The tailing is relatively coarse, and a coarse fraction stays near the berm where it is deposited, while most of the fines flow with the water to the pool. Thirty years experience has led to certain design for toe dams, decanter lines and towers and tailing dams. A new tailing disposal area, started at Climax in 1958, will ultimately have a height of 495 ft and impound about 300 million tons. The following applies to the construction of this new tailing area.

Jan 11, 1961

By T. S. Fuller

The tensile properties of steels at elevated temperatures have been studied by numerous investigatorsll primarily for the purpose of determining their suitability for structural uses. Tests with this objective have been confined largely to the temperature range of approximately 20" to 500' C., because of the rapidly decreasing tensile strength at the latter temperature. Tests have also been extended to higher temperatures2 for the purpose of determining the most suitable forging range. This temperature range is also of theoretical interest. The phenomenon if increased tensile strength and decreased ductility .in the so-called "blue-heat" range, approximately 200" to 300" C., is well known. It was suggested to the Bureau early in 1926 that a study of the properties of rail steels in this temperature range might prove of interest in relation to the studies of transverse-fissure failures in rails. There were available from another investigation3 several new rails from several different heats made to approximately the same specification requirements, the complete manufacturing histories of which were known. It was decided to determine, at least in the preliminary series of tests, only the ultimate tensile strength, elongation and reduction of area, because of the difficulty, time and cost involved in determining the proportional limit and yield point at elevated temperatures.

Jan 1, 1930

By R. A. Morse, W. O. Keller

The properties of limestone reservoir rocks such as the distribution and degree of continuity of the pore systems, and the relative volumes and permeabilities of the systems making up the complex cause large variations between performance of individual limestone reservoirs and their susceptibility to secondary recovery methods. The effects of these factors on the mechanism of fluid flow cannot be adequately evaluated with presently developed concepts, laboratory data, and geological information. The observance and interpretation of the performance of individual limestone reservoirs provides, at present, the most adequate approach for evaluating the integrated effects upon performance of the many. now immeasurable variations in the properties of limestone reservoirs. INTRODUCTION The development and application of techniques for increasing the efficiency of oil recovery from natural reservoirs is a problem of primary importance to the industry. During the past several years, a great deal of effort has been expended by the technical personnel of the industry toward the improvement of present known methods of oil recovery. and evaluating the factors which control the susceptibility of particular reservoir types to economic application of secondary recovery methods. Providing adequate and accurate laboratory data on the properties of the reservoir rock and its contained fluids. together with good production statistics, are available, methods have been evolved for estimating with reasonable accuracy the performance of an oil reservoir under either continued natural depletion or conditions imposed by introducing additional displacing fluid into the reservoir from an extraneous source through the injection of gas and/or water. The susceptibility of limestone reservoirs to secondary recovery by gas injection is very much dependent upon gas-oil relative permeability relationships for the reservoir in question. In a rock formation in which the porosity is of the intergranular type such as is found in sand stones and some non-fractured dolomites, a representative sample of the pore structure can be obtained in a small core plug. In this type of reservoir, it has been shown that relative permeability data obtained from laboratory experiments can be Properly applied to evaluate the flow relationships actually observed during the depletion of a reservoir. In addition, a good idea of the fraction of the reservoir which will be swept by the injected gas may be obtained from the spacing pattern used and the permeability profile of cored wells. From these data, it has been demonstrated that reliable estimates of performance and recoveries under gas injection operations can be made for reservoirs in which the Porosity is of the intergranular type. Limestone reservoirs on the other hand often present much more complex problems. One reason that the performance of limestone reservoirs is so variable is that there may be, in reality. two or more pore systems, the integrated performance of which will depend upon the physical properties of each system and their inter-relationship. For instance, in a limestone reservoir, the main pore structure, as far as void spaces for storage of hydrocarbons is concerned, may be represented by the intergranular openings of the rock. Usually in limes and dolomites, the intergranular pore openings are very small and the matrix permeabilities extremely low. Often, as in the case of Many dolomite and oolitic lime reservoirs, this is the only pore system, and performance is observed to be very similar to that of a sand stone of similar permeability. However, in the great majority of' the limestone reservoirs, there is present, in addition to the intergranular pore system, a complementary system of openings caused by fracturing or solution.',' The openings in the latter system are usually many times more permeable than the intergranular pore system due to their much larger size, and may contribute almost all the fluid carrying capacity of the formation, even though their volume may be a very small part of the total pore space in the reservoir. Obviously, the performance of such a complex under either primary or secondary control will deend upon the distribution and degree of continuity of both systems, the relative volumes and permeabilities of the

Jan 1, 1949

By R. A. Morse, W. O. Keller

The properties of limestone reservoir rocks such as the distribution and degree of continuity of the pore systems, and the relative volumes and permeabilities of the systems making up the complex cause large variations between performance of individual limestone reservoirs and their susceptibility to secondary recovery methods. The effects of these factors on the mechanism of fluid flow cannot be adequately evaluated with presently developed concepts, laboratory data, and geological information. The observance and interpretation of the performance of individual limestone reservoirs provides, at present, the most adequate approach for evaluating the integrated effects upon performance of the many. now immeasurable variations in the properties of limestone reservoirs. INTRODUCTION The development and application of techniques for increasing the efficiency of oil recovery from natural reservoirs is a problem of primary importance to the industry. During the past several years, a great deal of effort has been expended by the technical personnel of the industry toward the improvement of present known methods of oil recovery. and evaluating the factors which control the susceptibility of particular reservoir types to economic application of secondary recovery methods. Providing adequate and accurate laboratory data on the properties of the reservoir rock and its contained fluids. together with good production statistics, are available, methods have been evolved for estimating with reasonable accuracy the performance of an oil reservoir under either continued natural depletion or conditions imposed by introducing additional displacing fluid into the reservoir from an extraneous source through the injection of gas and/or water. The susceptibility of limestone reservoirs to secondary recovery by gas injection is very much dependent upon gas-oil relative permeability relationships for the reservoir in question. In a rock formation in which the porosity is of the intergranular type such as is found in sand stones and some non-fractured dolomites, a representative sample of the pore structure can be obtained in a small core plug. In this type of reservoir, it has been shown that relative permeability data obtained from laboratory experiments can be Properly applied to evaluate the flow relationships actually observed during the depletion of a reservoir. In addition, a good idea of the fraction of the reservoir which will be swept by the injected gas may be obtained from the spacing pattern used and the permeability profile of cored wells. From these data, it has been demonstrated that reliable estimates of performance and recoveries under gas injection operations can be made for reservoirs in which the Porosity is of the intergranular type. Limestone reservoirs on the other hand often present much more complex problems. One reason that the performance of limestone reservoirs is so variable is that there may be, in reality. two or more pore systems, the integrated performance of which will depend upon the physical properties of each system and their inter-relationship. For instance, in a limestone reservoir, the main pore structure, as far as void spaces for storage of hydrocarbons is concerned, may be represented by the intergranular openings of the rock. Usually in limes and dolomites, the intergranular pore openings are very small and the matrix permeabilities extremely low. Often, as in the case of Many dolomite and oolitic lime reservoirs, this is the only pore system, and performance is observed to be very similar to that of a sand stone of similar permeability. However, in the great majority of' the limestone reservoirs, there is present, in addition to the intergranular pore system, a complementary system of openings caused by fracturing or solution.',' The openings in the latter system are usually many times more permeable than the intergranular pore system due to their much larger size, and may contribute almost all the fluid carrying capacity of the formation, even though their volume may be a very small part of the total pore space in the reservoir. Obviously, the performance of such a complex under either primary or secondary control will deend upon the distribution and degree of continuity of both systems, the relative volumes and permeabilities of the

Jan 1, 1949

By John F. Allan

This paper does not pretend to advance any facts or improvements not known to many members of the Institute, but is intended merely to give a few practical hints on preliminary tests, and to call attention to a possible enlarged field for the cyanide process in the treatment of some silver-ores, which merits investigation. Broadly considered, the choice of a process for the treatment of silver-ores in Mexico is confined to the following alternatives: (1) Concentration for treatment by smelting; (2) milling and pan-amalgamation; (3) the patio and Ortega process; [4) chloridizing roast and lixiviation; (5) chloridizing roast and cyaniding; and (6) cyaniding of the crude ore. These methods of treatment may also be combined, and cyaniding or concentration, or both, may be introduced, at what-ever stage it is found to be most advantageous. The characteristics of the ore (especially its gold-content) and local conditions, such as distance from railway, cost of fuel, amount of water available, vary so much that it is impossible to make general comparisons between the different processes, either as to extraction or cost. Concentration and subsequent smelting may be made very expensive by long-distance transportation of concentrates; pan-amalgamation is undoubtedly expensive; and the patio process is barred when the ore contains appreciable amounts of gold, by reason of its poor extraction of that metal; yet there are many ores for which each of these processes is especially adapted, and the expense of treatment is compensated by the results obtained.

Jan 1, 1905

By David R. Maneval, W. E. Foreman, J. Richard Lucas

INTRODUCTION The objective of this chapter is to inform the industry, as well as the public, of the challenges in dealing with the problems associated with the contamination of air and water from coal preparation plants. The need for an informed industry is most important. It is hoped that some contribution may be given to a more efficient and economical approach to the problems of plant waste contaminants at individual plants. The problem has many facets, and consideration to specific area should begin early before any significant problems develop at a given plant. It is then possible to have a reasoned approach before the pressures of an emergency environment force hasty and incomplete solutions. It will be necessary to anticipate these problems in the design of new preparation plants and advance consideration should be given to all the problems concerned with contaminants. The first part of the chapter will concern itself mainly with the contamination aspects of fine-coal cleaning and "black-water" disposal. Also attention will be given to the nature and formation of water from coal-mine drainage systems and the treatment of these waters for industrial use. Some attention will be devoted to the cost of installing and operating the various beneficiation systems for the removal of suspended solids. The second part of the chapter will analyze the problems of air contaminants from coal preparation plants. The nature and the effects of these contaminants and their potential for air pollution will be examined. One of the most critical is the measurement and analysis of these contaminants. As a result of identifying and determining the extent of the problem, better control can be planned. One of the most serious contaminants in air involves the element sulfur, and its elimination as a source of air pollution is one of the most challenging areas in coal preparation today. The last part of the chapter will emphasize the long-range problem of refuse disposal and control. Minimum operating and maintenance costs are functions of the proper selection and geometry of refuse disposal areas. Disposal procedures are varied but must be rigidly pursued or difficulties will result. Maintenance of refuse areas, including monitoring of burning refuse, is critical. It should be recognized that fine-solid refuse disposal systems must be carefully designed to minimize contamination. WATER CONTAMINANTS FROM PREPARATION PLANTS Pollution Aspects of Fine-Coal Cleaning and "Black-Water" Disposal The effluents from coal washeries and waters draining from plant-site surfaces inevitably contain fine coal and coal refuse materials in suspen-

Jan 1, 1968

By A. Eilers

Although the process to which I refer in this paper has been in successful operation for nearly five years, during which time it has been introduced, superseding all other processes having in view the same end, in almost every lead refinery in the country, no description of it, giving economical data, has ever appeared in print, nor has the process been known in its details to any considerable number of engineers beside those conducting it at their works. A discussion of this subject at the present time becomes especially interesting in view of a late publication in the Prussian ministerial organ for Mining and Metallurgy, by Dr. Wedding, in which the method of treating the zinc-silver-lead alloy by distillation, as finally settled upon at Tarnowitz, is very minutely and fully described. It is the more interesting, because in that article reference is made to the American method in an unfavorable light, while, at the same time, it is clear from the article itself, that the most important details of the process, besides the one that it is conducted in black-lead retorts, mere not at all understood. In publishing herewith the details of our American method, one of my objects is to invite comparisons between our simple and direct process and the elaborate one at Tarnowitz. In extracting the silver from work-lead by means of zinc, it is always the intention, in this country, to obtain a zinc-crust so rich in silver that the rich lead resulting from subsequent distillation

By Charles M. Means

A thoroughly modern coal-handling system has been installed at the Pittsburgh Terminal H. H. &. Coal Co.'s new No. 8 shaft, or Cover-dale mine, about 11 mi. (17.7 km.) from Pittsburgh on a spur of the Montour R. R. The Pittsburgh scam, which is the one worked, is reached at a depth of 342 ft. (104 m.). Power is delivered to the mine at 22,000 volts over a transmission line of the bow-arrow type of construction. A private telephone line connecting the various mines and the main office in Pittsburgh is carried on the same poles. The high-tension line is brought to an outdoor, step-down, transformer substation, where three 833-kv.-a., single-phase, 60-cycle, oil-insulated, self-cooled transformers reduce the potential to 2300 volts. The transformers are protected by electrolytic, aluminum-cell lightning arresters, horn gaps, and choke coils. High and low-tension busses, together with fuses, choke coils and air-break horn-gap switches with thcir remote-control operating mechanism are mounted on a substantial structural-steel tower 25 ft. (7.6 m.) in height. Mine Substation The transformer substation is adjacent to a. pressed-brick building that houses direct-current substation equipment together with switchboards, etc., for the control and distribution of power. This building also contains the hoist for the men and supplies. Main Switchboard The 2300-volt circuit is carried underground in a conduit from the transformer substation to an oil switch in the substation and supply hoist building. This is the main switch controlling the 2300-volt busbars mounted back to a twelve-panel black-slate switchboard. From the switchboard, 2300-volt circuits are carried to transformers feeding the street and house lighting systems and to other transformers furnishing power for the elevator and lighting circuits in the store building. Other 2300-volt circuits run from this switchboard to the main hoist building, fan house and auxiliary or man-and-supply hoist. High-tension wiring,

Jan 1, 1922