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By Robert B. Paul

This paper describes the new lead smelter and refinery recently completed by the American Smelting and Refining company in Southeast Missouri.

Jan 1, 1970

By C. M. Young

The following paper has been prepared with the object of placing on record in the Transactions some facts concerning the present condition and future prospects of the coal industry of Illinois. In presenting it, the writer wishes to say that a considerable amount of the material contained is taken from the publications and records of the Illinois Coal Mining Investigations, the annual Coal Report of the State Mining Board, and the work of the State Geological Survey. Coal Beds and Mining Methods According to the latest maps of the State Geological Survey, there are only 19 of the 102 counties of the State some portion of whose territory is not within the borders of the coal measures. If outlying areas in Calhoun and Whiteside Counties are considered, the number is reduced to 17. This does not mean that all of the 85 counties that are partly or wholly underlain by coal measures will become producers, as there are some portions of the State in which the coal does not occur in beds of such thickness as to warrant the hope that it can be mined. The mining of coal is widespread, however, for in 1916 there was production from 61 of the 102 counties of the State, There seem to be no cases in which operations will be limited by depth, as none of the coal measures lie at depths much greater than those at which it has been proved that coal may be profitably mined in this field. In fact, the deepest shaft reaching a bed of bituminous coal in the United States is located in this State at Assumption, where coal only 3 ½ ft. (1.07 m.) thick is worked at a depth of 1004 ft. (306 m.). The coal beds occur in the form of a basin which is deepest along a line extending through the central part of the State and bearing a little west of north. The northern, western and southern borders of this basin lie within the boundaries of the State, but on the eastern side the Illinois field is continuous with the Indiana field. The glacial drift covers all except the extreme southern end of the State and the visible outcropping

Jan 1, 1918

By H. K. Birnbaum, H. B. Aaron

he authors suggest that a number of the types of yield phenomena which have been observed in high-purity fcc metals are due to dislocation interactions bccurring at the surface of the crystals rather than due to volume effects. Since rather different inter-pretationS2,7,12,14,15,21-23 of these effects have been suggested, it is of some importance to ascertain the role of the surface in these yield phenomena. It should be first noted that the high-purity fcc metals appear to exhibit several distinct types of yield phenomena. The "unloading yield point" which is observed on reloading the specimen after removing the applied load has been found to be independent of the time of holding in the unloaded condition. If however the specimen is aged while under load and re-tested without removing the load, a yield point is observed which does depend on the aging time and tem-perature. Feng and Kramer suggest that the removal of the unloading yield point on removing sufficient material from the surface of the specimen indicates that the effect is associated with dislocation interactions at the specimen surface. Their observations are counter to those of Haasen and Kelly5 and Birnbaum.12 Since the unloading yield points are extremely small (-2 pct of the flow stress) the results of the surface removal will depend on whether the material is removed uniformly over the gage length. The introduction of small etch pits or the removal of more material from one portion of the specimen than from another will result in preferential yielding and obliteration of the yield point. With the normal electropolishing techniques it would be difficult to avoid these effects. The data obtained by Aaron and Birnbaum, Fig. 10, on aluminum polycrystalline specimens indicate that, although the unloading yield point and the strain-aging yield point are not simply additive, a time- and temperature-dependent yield point is observed under conditions where no creep is observed. This does not agree with the results of Feng and Kramer but does agree with the results on copper15 and gold.7~23 The source of the discrepancy may be the procedure used by Feng and Kramer to correct their time-dependent yield points for the effect of creep. Since the strain-aging yield point is not independent of the pre-aging strain rate, Fig. 11, the effects of creep cannot

Jan 1, 1967

By W. H. Emmons

THE exploration of deposits of the metals will never become an exact science. There will always be an element of uncertainty in prospecting and developing mines. In countries where the surface has been closely scrutinized, most of the deposits whose outcrops contain valuable metals have probably been discovered. Many metalliferous deposits, however, are normally so much altered at the surface that the true significance of their outcrops is likely to be obscured. If a deposit is not exposed, its presence may become known by some one of its characteristics that is different in kind or in degree from a similar feature of the associated rock. Thus, a deposit that is not exposed may be discovered because of its magnetic property. So few minerals are strongly magnetic that the value of magnetic surveys is limited, but the dip needle has nevertheless proved of great aid in locating magnetic belts, and these in some regions are associated with workable iron ores. The Cuyuna Iron Range of Minnesota, which does not exhibit any outcrop of iron ore, was discovered by drilling "areas of attraction" that are due to belts of magnetic rocks associated with the iron ores. In some regions the use of the clip needle is justified, even if it does no more than reveal the strike of the rocks, since a knowledge of the latter enables the driller to locate and point his holes to advantage. The measures of gravity by the use of the pendulum are so accurate, or the limit of error is so small, that one might detect the presence of a concealed tabular deposit approximately at the surface, 34 ft. (10.36 m.) thick, having a density double that of the surrounding rocks. However, not many deposits have a density twice that of ordinary rocks and a thickness as great as 34 ft.; if they lie a short distance below the surface the density or the thickness must be even greater. Consequently, there is not much hope of sufficiently developing the gravity method of detecting deposits of heavy ores to make it of practical value. If the limit of error could be reduced to about one-tenth the present factor, and if the rather tedious and painstaking methods of determining gravity that are now in use could be simplified, the method would promise some degree

Jan 3, 1917

By J. M. Tobin, L. H. Cadoff, L. M. Adelsberg

The reaction between liquid zirconium and graphite at temperatures above 2000 °C has been investigated. The reaction products were found to be carbon-saturated zirconium metal and ZrC which formed between the graphite and the metal. Parabolic growth behavior was observed for the ZrC Phase at all temperatures of this investigation. The parabolic growth constant at temperatures between 2000° and 2860°C was measured to be 1.83 exp 84,300/RT) sq cm per sec. The reaclion mechanism was proposed to be the rapid carbon saturation of the liquid metal and the formation of ZrC at the metal-carbide interface with diffusion of carbon through the ZrC, the "rate - determining step" of the reaction. The concentration-independent diffusion coefficient of carbon in ZrC, (DZrC), was expressed as 0.95 exp? 78,700/RT) sq cm per sec. This value mas calculated using the temperature-invariant ZrC phase fields proposed in the literature. The [ZrQiq)] — [ZYQiq) + ZrC] phase boundary over the temperature range 2000° to 2800°C was determined and the ZrC + C eutectic temperature was found to be 2890° ± 50°C. ThE Group IV and VB transition-metal refractory carbides are of interest because of their high melting points, high temperature strength properties, and relative inertness in certain corrosive environments. The present-day understanding of these materials, however, is limited by the general unavailability of accurate and reliable physical and chemical property data. This is due primarily to the difficulties associated with the preparation of suitable, high-density, high-purity carbide samples, and the achievement and control of uniform high-temperature environments. Accurate measurement of temperature is also an important factor limiting the reliability of reported data. The Zr-C reaction was selected for investigation because of the high melting point (>34000C) and favorable nuclear properties of the reaction product, ZrC. The direct reaction method afforded an opportunity to obtain kinetic data on the fully dense carbide. In this paper, layer-growth techniques were used to estimate the diffusivity of carbon in ZrC and to investigate the phase equilibria in the Zr-C system at temperatures above 2000°C. EXPERIMENTAL PROCEDURES AND DATA Crystal bar zirconium (99.9 pct Zr), purchased from the Nuclear Materials and Engineering Corp., and ZTA graphite (99.9+ pct) were used in this study. The analyses of the materials are listed in Table I. A schematic of the high-temperature carburization apparatus is shown in Fig. 1. The sample was a zirconium metal charge in a 1/2 -in.-ID graphite crucible which was capped with a tightly fitting graphite stern. The crucible and stem were designed to closely approximate black-body conditions. The graphite crucible was packed in lampblack (outgassed 1 hr at 2100°C) which provided insulation and thermal stability to the system. The inert atmosphere was maintained by a constant flow of high-purity argon or helium gas. The nozzle-diffuser section on the top flange was sufficient to prevent back-diffusion of air into the system. Chemical analysis of the carburized samples revealed oxygen and nitrogen concentrations of less than 44 and 20 ppm, respectively. The sample was heated by induction with a Westing-house 5 kw-450 kc power source. Temperature was measured with a Milletron two-color pyrometer which was sighted into the crucible by reflection from an overhead front surface mirror. Optical losses due to glass absorption and light reflection at air-glass interfaces were minimized by the employment of the dynamic-gas seal. It was found that no correction was required for the front surface reflector. The pyrometer was calibrated periodically against a U.S. Bureau of Standards tungsten ribbon secondary standard. Temperatures inside the crucible were also calibrated against the Zr-ZrC eutectic (1850°C)1 and the Nb-Nb2C eutectic (2335°C)2,3 temperatures and agreed to within ±10°C of these values. The temperature was controlled by manually adjusting the power input; variations of

Jan 1, 1967

By R. V. Lukes, H. W. Scheeline

Knowledge of a large number of the physical properties of the hydrocarbons is needed in the calculations and studies of the production engineer. Since experimental data on these properties of the individual hydrocarbons and their mixtures are available in only a relatively few cases, the use of generalized correlations has developed rapidly in the last decade. The generalized correlations of pressure, volume and temperature,' enthalpy2 and vapor-liquid equilibria13 on the basis of reduced temperatures and pressures, are outstanding examples of this development. These correlations are of particular value to the production engineer interested in the flow of oil and gas, since they can be used to estimate the conditions under which segregation of phase occurs as well as the composition, density, and relative amounts of the phases. The technique of using the correlations for such estimations has been published by several authors4 and will not be considered in this paper. A considerable number of data have been obtained to check the generalized pressure-volume-temperature correlations, and these data indicate that such relations hold for the hydrocarbons from methane to heptane. The accuracy is in general sufficient for most engineering pressure-volume-temperature calculations. However, the generalized correlations of enthalpy and vapor-liquid equilibria have in general been developed from the pressure-volume-temperature correlations by thermodynamic calculations and only a relatively few experimental data are available to check these calculated values. The calculations from pressure, volume and temperature are likely to lead to large errors in the calculated enthalpy and vapor-liquid equilibria. Thus, in the calculations of enthalpies, slopes of the pressure-volume-temperature data are employed, and determining these slopes can greatly amplify small errors in the original data. In the vapor-liquid equilibria calculations it is necessary to have the pressure-volume-temperature relations of the mixture, and the latter propertics are much more questionable than those of pure components, particularly in the critical region. A considerable number of experimental data are

Jan 1, 1939

By R. V. Lukes, H. W. Scheeline

Knowledge of a large number of the physical properties of the hydrocarbons is needed in the calculations and studies of the production engineer. Since experimental data on these properties of the individual hydrocarbons and their mixtures are available in only a relatively few cases, the use of generalized correlations has developed rapidly in the last decade. The generalized correlations of pressure, volume and temperature,' enthalpy2 and vapor-liquid equilibria13 on the basis of reduced temperatures and pressures, are outstanding examples of this development. These correlations are of particular value to the production engineer interested in the flow of oil and gas, since they can be used to estimate the conditions under which segregation of phase occurs as well as the composition, density, and relative amounts of the phases. The technique of using the correlations for such estimations has been published by several authors4 and will not be considered in this paper. A considerable number of data have been obtained to check the generalized pressure-volume-temperature correlations, and these data indicate that such relations hold for the hydrocarbons from methane to heptane. The accuracy is in general sufficient for most engineering pressure-volume-temperature calculations. However, the generalized correlations of enthalpy and vapor-liquid equilibria have in general been developed from the pressure-volume-temperature correlations by thermodynamic calculations and only a relatively few experimental data are available to check these calculated values. The calculations from pressure, volume and temperature are likely to lead to large errors in the calculated enthalpy and vapor-liquid equilibria. Thus, in the calculations of enthalpies, slopes of the pressure-volume-temperature data are employed, and determining these slopes can greatly amplify small errors in the original data. In the vapor-liquid equilibria calculations it is necessary to have the pressure-volume-temperature relations of the mixture, and the latter propertics are much more questionable than those of pure components, particularly in the critical region. A considerable number of experimental data are

Jan 1, 1939

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B') where B and B' are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By R. R. Angel

Drilling rate is a parameter that should be considered in determining the volume requirements for air and gas drilling. The use of past methods which ignore the effects of the solids content upon the pressure and velocity of the annulus flow stream can result in undercalculation of the required volurne by as much as 50 per cent. A vertical-flow equation is presented for determining volume requirements. This equation includes the effect of the solids that are transported up the annulus in the flow stream by incorporating the drilling rate as one of the parameters. The effect of down-hole temperature on required circulation rates is also ana-lvzed. A simple approximate method of determining volume requirements is presented. This method is more accurate than the methods used in the past. Hole cleaning difficulties are analyzed for a recent air drilling job where past methods indicated that - excess air was being used. Sample curves of calculated boitom-hole pressures are presented for air and gas drilling in several hole sizes. INTRODUCTION In certain areas the use of air or natural gas as a circulating medium for drilling oil and gas wells is becoming a common practice. Large increases in penetration rate and bit life are achieved through the use of these media in preference to mud or water. Drilling rates as high as 90 ft/hr have been obtained in shales. The importance of maintaining adequate circulation rate is generally recognized; however, much disagreement exists among drilling operators as to what constitutes "adequate" circulation rate. In quarry drilling, where annular velocities can be accurately determined, an annular velocity of 3,000 ft/min of standard air is required for best results in rocks having approximately the same density as those commonly penetrated in drilling oil or gas wells'. Although this standard air velocity has proven satisfactory for quarry drilling, some oil and gas well drilling operators believe that an equivalent annular velocity of more than 4,000 ft/min is required; others believe that as little as 2,000 ft/min . is sufficient. Much of this disagreement results from determining the required circulation rates with methods which fail to incorporate the drilled solids in an equation which is applicable to vertical flow. Hughes Tool Co. Bulletins No. 23' and 23-A3 present data for determining circulation rates based on the Weymouth formula. These data do not include the drilling rate as a parameter and, therefore, neglect the effect of the solids being transported up the annulus. In spite of this apparent defect and the fact that the Weymouth formula is not applicable to vertical flow, the Hughes data have well served the drilling industry in many areas and are important and timely contributions to the science of air and gas drilling. The Hughes data purposely omit a correction for increasing down-hole temperature. At slow drilling rates this effectively compensates for the use of a formula which is not valid for vertical flow; however, volumes determined by the Hughes method are not sufficient to support rapid drilling rates at moderate and great depths. For example, Phillips Petroleum Co.'s Cauthorn "D" No. l in the Vinegarone field for Val Verde County, Tex., was air drilled from 1,500 to 9,300 ft using a compressor delivering 1,400 cu ft/min. The 8 3/4-in hole was drilled with 5-in. drill pipe, and drilling rates as high as 90 ft/hr were obtained between 7,000 and 9,300 ft. No water or caving hole was encountered. At 7,728 ft it was necessary to wash-out 60 ft of cuttings to reach bottom after a trip to change bits. At 8,130 ft a twist-off occurred and the drill col-lars were stuck in drill cuttings. These difficulties indicate that the 1,400 cu ft/min of air was not sufficient to keep the hole clean. Hughes data indicates that 1,180 cu ft/min is sufficient to produce an annular ve-

Jan 1, 1958

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By E. J. Duggan

It is a coincidence that the two plants in this country for treating copper ores by ammonia leaching came into existence at almost the same time, that of the Kennecott Copper Corporation at Kennecott, Alaska, in March, 1916, and that of the Calumet & Hecla Mining Co. in July of the same year. The success of both from their very beginning attests the merits of the process under widely different sets of conditions. As would be expected, in the time they have been operating these two pioneers in this field have greatly perfected their methods and improved their technic. The early difficulties inevitably encountered in undertakings of this nature have been largely surmounted and the process may now be considered to be well seasoned and matured. There have been no other commercial plants built in this country and but one elsewhere, the Bwana M'Kubwa in Northern Rhodesia, for the reason that this method of treatment may be employed on comparatively few ores. However, it has certain advantages, some of which are inherent to sand leaching processes generally and some to ammonia leaching in particular. Among these may be enumerated: (1) the avoidance of fine grinding; (2) the small amount of water required; (4) a high-grade product; (5) little likelihood of deleterious gangue constituents and fouling of solutions. It is true that great progress has been made in recent years in the flotation of the ores that come within the province of ammonia leaching. Nevertheless ammonia leaching has its possibilities and these may be overlooked in the present tendency toward the use of flotation for all ores. Probably the chief requisite to its further extension to suitable ores will be a cheap source of steam. Ammonia, the only reagent required, is unlimited in supply, readily transported and the price that is likely to obtain in the future should not make its cost at all onerous. Choice of Method for Kennecott Ores The Kennecott ores are typical limestone replacement deposits. The milling ores have a copper content of approximately 8 per cent in a limestone dolomite gangue. About half the copper occurs as sulfide, mostly chalcocite with some covellite, and the remainder in the form of the two carbonates, malachite and azurite. A comparatively coarse grind followed

Jan 1, 1934

A LARGE proportion of the steel that is melted and refined in the United States and poured into ingots is made in basic open- hearth furnaces. The capacity of these furnaces varies over a wide range with a large majority falling within limits of 50 to 200 tons (Fig. 1) The two general types of furnace design used are stationary [ ] and tilting furnaces, the former being much more common. The fuel burned in such furnaces is either one of several types of gas, or a liquid fuel such as oil or tar, or a combination of gas and liquid fuel. GENERAL FEATURES OF FURNACE CONSTRUCTION The design of a modern stationary furnace built to burn liquid fuel and with a capacity of 175 tons is shown in Figs. 2 to 4. The cross- section of the furnace at the tap hole is illustrated in Fig. 2, which shows the bottom construction, sloping back wall, and the rigid steel

Jan 1, 1944

By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant' on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,' aging took place during the creep tests. 'In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500' or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500' or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40' to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.' At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnxTe have been grown from nonstoichiometric, cation-rich melts with the objective of producing as-grown, bulk material containing carrier concentrations ranging from 1016 per cu cm to 1018 per cu cm. Three specific crystal composi-tions were investigated in detail; x = 0.00, 0.10, and 0.17. Pull rates of from I to 3 mm per hr were used. Single crystals were successfully pulled from melts containing as little as 30 at. pct Te. Hall coefficients, resistivities, and carrier mobilities of these materials were determined. The relationship between the composition of the melt and the carrier concentration in the as-grown crystal has been studied for the three crystal compositions of interest. BULK single crystals of Pb,-,Sn,Te have previously been grown from stoichiometric melts.1,2 Such crystals are p-type and have relatively high carrier concentrations ranging from -9 x 1018 per cu cm for PbTe to -8 x l020 per cu cm for SnTe at 77°K. These carrier concentrations result from deviations from stoichiometry (lead vacancies) in the as-grown crystals. Since lower carrier concentrations are desirable for electrooptic device applications, these crystals are usually subjected to long-term, isothermal anneals.' This paper reports on the growth of Pbl-xSnxTe single crystals from nonstoichiometric melts with the primary objective of producing as-grown material containing relatively low (1016 to 1018 per cu cm) carrier concentrations and also reports on the general characteristics of these crystals. The phase relationships in the Pbl-xSnxTe systems are such that materials solidifying from nonstoichiometric, cation-rich melts will have smaller deviations from stoichiometry than materials grown from stoichiometric melts. Fig. 1 is the T-x phase diagram for PbTe in the vicinity of the stoichiometric composition.3 A crystal grown from a stoichiometric melt will solidify at a melting point maximum at which the solid will contain -0.5002 atom fraction of tellurium. PbTe single crystals grown in our laboratories from stoichiometric melts have carrier concentrations of 9 x 10" per cu cm, indicating that the excess tellurium in the crystals is as expected from this phase diagram. However, growth of PbTe from a lead-rich melt will result in material having a more nearly stoichiometric composition. Although the addition of Sn to the melt shifts the solidus curve further toward the tellurium-rich side,4 the general discussion given for PbTe applies to the Pbl-xSnxTe systems as well. EXPERIMENTAL Single crystals of Pb1-xSnxTe have been grown in our laboratories from nonstoichiometric, cation-rich melts using the Czochralski technique and boric oxide liquid encapsulation. The details of the growth apparatus and growth technique have been reported in a previous paper on growth of these alloys from stoichiometric melts.2 In the present study, three specific crystal compositions were investigated in detail; x = 0.00, 0.10, and 0.17. Growth of alloy crystals from nonstoichiometric melts requires considerable care, and good quality single crystals were obtained in this study only by optimizing the mechanical and thermal stability of the growth system and by using pull rates of from 1 to 3 mm per hr (Pbl-xSnxTe crystals are easily pulled from stoichiometric melts at rates of from 5 to 10 mm per hr). The liquid encapsulation technique was found to yield near-ideal conditions, since the B2O3 layer increased the thermal stability at the growth interface, permitted easy attainment of near-ideal thermal gradients, and dampened vibrations at the melt surface. The hygroscopic character of the B2O3 was a slight problem and vacuum heat treating was necessary to completely remove the water from the boric oxide. During initial growth, the seed diameter was reduced and a narrow neck (1 to 2 mm diam) of several millimeters length was grown. The latter steps were found to be necessary for the growth of single crystals, i.e., if either of these two requirements were

Jan 1, 1970

By John Kafritsas

INTRODUCTION Deformations and failure of rock masses in elopes, foundations or tunnels can be caused by water pressures. On the other hand, deformations of a rock mass affect the flow of water (and hence water pressures) by changing joint apertures. Including the coupling between flow and deformation effects is therefore important both in assessing the stability and deformation of a rock mass and in determining the amount of seepage taking place through it. The model that will be presented hare treats the coupling of the flow and deformation behavior of a rock mass. Deformations are modeled using the Rigid Block Method (Distinct Element Method) (Cundall, 19741, that is by assuming that the rock mass is composed of rigid blocks with deformable contact points. Flow is modeled by recognizing its discontinuous features, as occuring in a system of interconnected conduits formed by the joints. The program can also deal with problems involving free-surface flow. Example problems involving representations of rock masses are presented. Coupled flow modeling of interconnected conduits should be contrasted to equivalent-continuum models on the one hand and to pipe network models on the other hand. Continuous models substitute an anisotropically permeable continuum for the discrete flow that occurs in rock joints. Pipe or parallel plates represent the other extreme of existing models; they account for the discontinuous character of the flow problem, but cannot model rock mass deformation and failure. The coupled rigid block-flow model can eliminate most of these restrictions. The coupling between water flow and deformation is most pronounced in rock masses which, because of the arrangement of their

Jan 1, 1984

By Worthen Bradley

A BETTER understanding of what is happening in the domestic quicksilver industry, and what is likely to happen, can be had after reviewing some of the highlights of the past four years. Hitting the high spots in chronological order, they are: February 1939-Army and Navy Munitions Board starts investigation on civilian and war needs of certain "strategic materials," including quicksilver, with a view to recommending stock piles. Every known producer is canvassed by the end of the year.

Jan 1, 1942

By Fritz F. Prugger, Peter R. Jones

This paper considers some of the main aspects of underground mining in the flat, rich, but deep lying deposits of Saskatchewan. It briefly describes the pertinent geological features as they relate to mining and the practical de-stressing techniques used to allow productive extraction in the high stress environment present in many of the province’s mines. Mining layouts, materials handling, and the evolution of some of the world's largest mining equipment are examined.

Jan 1, 1983

By P. Somasundaran, R. D. Kulkarni

Reagentizing at elevated temperature, reported in the past as beneficial for the flotation of hematite using oleate, is studied here as a function of collector concentration, solution pH and ionic strength at various levels of conditioning temperature. The study revealed strong interactions between variables; particularly, the effect of conditioning temperature was found to strongly depend on the ionic strength of the solution. Thus, while an increase of conditioning temperature at lower ionic strengths or that of ionic strength at lower temperatures resulted in an increase of both flotation and grade, an increase of the former at higher ionic strength or that of the latter at higher temperatures caused a significant decrease in both responses. These observations have been explained in terms of the increased chemisorption of oleate at elevated temperatures and the temperature effect of ionic-strength on the salting out of the oleate from the bulk solution. The above effects which were first observed during Hallimond cell flotation tests were subsequently tested with Denver cell using low-grade iron ore. The results obtained using the two test procedures were in agreement with each other. The implications of these effects and interactions for process control of optimum flotation performance must be noted since variation in the levels of the above parameters are likely under plant conditions.

Jan 1, 1978

By R. P. E. Hermsdorf

THE electrolytic refining of metals for the removal of undesirable impurities has become a recognized necessity in the nonferrous field. Copper, lead, zinc, nickel, silver and gold have been produced in this manner for years. The United States Metals Refining Co., realizing that considerable quantities of lead and tin could be made available to the trade if a satisfactory method of purification of these metals could be established, decided to investigate the possibilities of electrolytic solder. In cooperation with Dr. Edward F. Kern, of the School of Mines at Columbia University, the company developed a process of electrolytic refining of lead-tin alloys using a tin-lead fluosilicate electrolyte. A pilot plant was installed in November, 1927, and the commercial unit was put in October, 1929. Since that time thousands of tons of electrolytic solder have been produced in this plant and consumed by all branches of industry that use solder.

Jan 1, 1936