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By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By Benjamin W. Haynes

This research was conducted as part of the U.S. Department of the Interior, Bureau of Mines program to recover metals, glass, and a combustible fraction from municipal solid waste (MSW). The objective of this analytical study was to determine the concentration of antimony, arsenic, and mercury in samples taken from various sampling areas in the Bureau of Mines raw refuse recycling plant and to compare these values with those for coals used in the generation of electricity. To provide the necessary analytical data, sensitive reproducible ashing-chemical digestion-atomic absorption procedures were adapted from published procedures. It was determined that antimony and mercury concentrations in the combustible fraction of MSW are approximately an order of magnitude higher than those found in coals presently used for power generation;' the arsenic concentration is similar in both fuels.

Jan 1, 1978

By N. A. Zeigler

Considerable work has been and is being done on the changes of physical properties that take place in alloys at elevated temperatures, and much information on this subject is published. Much less is known, as pointed out by Rickett and Woodll about reactions between the alloys and atmospheric gases and still less is known abut changes within the alloy itself under the influence of heat and given atmosphere. Moreover, most of the work published has been done on the alloys of "heat-resisting" type, in which chromium is an essential ingredient, the behavior of all other alloys being quite unknown, except perhaps of decarburization produced at the surface by oxidizing atmospheres. It has been shown2 that iron, with total amount of foreign ingredients not exceeding 0.01 per cent, if heated in an oxidizing atmosphere at above 900" C., may be saturated with oxygen to 0.1 per cent. It was suspected that something of a similar nature may take place in iron-silicon alloys (transformer material), the mechanism of such processes being either a direct diffusion of oxygen into the alloy, or oxygen combining with silicon to form SiO2 or more complicated (silicate) inclusions. Another possibility to be considered was that during annealing in oxidizing atmospheres, when scale is being formed, silicon may oxidize preferentially at the surface, thus impoverishing the alloy in silicon. In collaboration with Dr. T. D. YensenP3 the writer set out to investigate this problem about two years ago in order to settle these questions. Testing Procedure In the first part of the investigation, two pieces of 4 per cent silicon iron, prepared in hydrogen atmospheres and forged to 3/4-in. square bar,

Jan 1, 1934

By D. L. Leach

This report covers laboratory experiments simulating in situ copper recovery from primary sulfide ores in sulfuric acid systems pressurized with oxygen. Copper extraction and acid consumption data are correlated with temperature in the range 50-150°C and quenched pH in the range 0.25-2. Adverse changes in the chemical composition of the leach solution and the formation of gangue-mineral alteration products and secondary sulfides can severely limit the extraction of copper above 90°C. Keeping the pH below the self-buffered value of about 2 and the temperature below about 110°C produces the maximum extraction rates. Forcing the pH too low not only results in excessively high acid consumption but may also limit the extraction of copper at temperatures above 100°C.

Jan 1, 1975

By M. Kaufman, A. E. Palty

THE mechanical properties of an alloy under given test conditions are in the main determined by the grain size and the phases present, their distribution and temperature-time dependence. Alloys intended for use at elevated temperatures, especially multiphase alloys depending upon precipitation reactions for strengthening, are particularly susceptible to changes in the phases present. Unfortunately, for modern superalloys, very little published information exists which relates the mechanical properties to the basic structural variables. The present work is an effort to do this for an alloy widely used in aircraft gas turbines and related applications, Udimet 500.* The mechanical properties inves- two heats is within the normal specifications for the alloy. However, the elements which most strongly influence the phase reactions, C, Ti, Al, and Mo, are comparable in the two heats. There was no intentional addition of boron, but normal pickup is about 0.002 pct. The vacuum-melted material was received in the form of centerless ground wrought bar stock % in. diam. PHASE STUDIES A) Methods—Two methods were used to determine the phases present: X-ray diffraction measurements on electrolytically digested residues, and microscopic examination. No single commonly used electrolyte will reveal all the phases that may be present; therefore, two complementary acids were selected: HCl and H3PO4. The necessity for this will be shown below in the results. The acid concentrations used were 10 pct HC1 in alcohol and 10 pct H3 PO4 in water. The current density was maintained below 0.1 amp per sq in. Residues were rinsed and separated by centrifuga-tion. X-ray diffraction patterns were obtained in a 114 mm Debye-Scherrer type camera using cobalt radiation. A temperature of 2250°F was selected to obtain as complete solutioning of phases as possible without encountering incipient melting. Specimens were

Jan 1, 1961

By V. E. Erwin, W. W. Adams

"Production of explosives for industrial use in,the United States during 1934 continued the upward trend begun in 1933 from the low-level output of 1932, and the output in 1934 was only slightly less than in 1931.Reports to the United Stated Bureau of Mines from companies engaged in the manufacture of industrial explosives showed that the quantity of explosives manufactured in the United States and sold during 1934 for use within the various States was 314,767,922 pounds - 23 percent more than in 1931.Production during 1934 included 39,207,845 pounds of permissible explosives 5 206,625,027 pounds of high explosives other than permissibles, and,68,935,050 pounds of black blasting powder of which 37,192,700 pounds were in granular form and 31,742,350 pounds in pellet form. These figures represent an increase over 1933 of 15.6 percent for permissible explosives, 30.9 percent for other high explosive, and 7.4 percent for black powder.Coal-mining operations were the chief consumers of permissible explosives; 99 percent of the total output in 1934 was used, in coal mines. The proportion used by bituminous mines was 59 percent and by anthracite mines 40 percent. Coal mining was likewise the principal consumer of black blasting powder, taking 88 percent of the total sales during 1934; of this proportion, bituminous mines received 78 percent and anthracite mines between 9 and 10 percent. Consumers of high explosives other than permissibles were more varied; the reports showed that 11 percent of the total quantity sold was for coal mining, 22 percent for metal mining, 17 percent for quarrying and nonmetallic-mineral mining, 46 percent for railway and other construction work, and 4 percent for all other purposes."

Oct 1, 1935

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By D. R. Parrish, V. J. Berry

Reverse combustion is one thermal method of recovering hydrocarbons from porous undergrortnd formations containing oil or tar. In applying this method, air is introduced via an injection well and the mixture of air and hydrocarbons is ignited in the production well. A combustion zone then recedes toward the injection well, counter-current to the air flow. If the combustion-zorie temperature is sufficiently high, the oil or tar irz place is distilled arid cracked. The hydrocnrhon flows as a vapor to the production well and subsequently is condensed at the surface. Maximum temperature and velocity of morcment arc the two dependent variubles defining the progress of the combustion zone. A theoretical analysis has been made of heat flow in the reverse-comhustion process as.srtrning linear flow in a homogeneous system. The differentirll equatious, which include the oxygen-hydrocar-hon rctrction rate, have been solved numerically. Rescllts indicate that the maximum temperature reached and he cornbustion-zone relocity both increase with an incrense in air-injection rote. Heat loss to surroundings has little effect on the maximum comhustion-zone ten?perature achieved, but it is reflected in a reduced com-bustion-zorzc, velocity. It is also predicted that an increase in the oxygen-hydrocarbon reaction rate results in a reduction in the maximum temperature reached. The calculated results are in agreement with results from reverse-combustion experinments using samples of a tar sand. INTRODUCTION Reverse combustion is one thermal method of recovering hydrocarbons from porous underground forma-tions containing oil or tar.' In applying this method, air is introduced into the underground formation via an in-jection well. In one or more adjacent production wells, the mixture of air and hydrocarbons is ignited at the sand face. The combustion zone thus formed recedes toward the injection well, counter-current to the air flow (Fig. 1). Under certain conditions, the rate of recession of the combustion zone is sufficiently rapid that only a small fraction of the hydrocarbon at any point in the formation is consumed by combustion. If the combustion-zone temperature is sufficiently high, the uncon-sumed oil or tar in place may be partially distilled or cracked. This material then can flow as a vapor with the gaseous combustion products to the production well and subsequently be condensed at the surface. Under other conditions, the combustion-zone temperature may be so low that little, if any, of the hydrocarbon is vaporized. Nevertheless, the viscosity of the hydrocarbon may be reduced enough so that other recovery methods subsequently can be applied to produce oil at attractive rates. The maximum temperature achieved in the combustion zone and the velocity of movement are the two dependent variables defining the progress of the combustion zone. Presumably. knowledge of these factors will permit estimates to be made of oil recovery efficiency, oil and gas producticn rates and average amount of injection air required per barrel of oil recovered. The maximum temperature and combustion-zone vclocity are, in turn, expected to be dependent upon air flow rate, heat losses to surrounding formations, physical properties of the rock and the hydrocarbon. the extent to which the porous formation is saturated with the hydrocarbon, the rate of oxidation of the hydrocarbon and the amount of heat released. It is desirable that the relative importance of each of these factors be understood so that the results of laboratory tests of oil recovery by reverse combustion can be properly interpreted in terms of expected field performance. It is particularly desirable to assess the importance of heat lcsses because these are difficult to control or eliminate

By R. V. Ramani, C. J. Bise

INTRODUCTION Classification of coal seams as thin, medium, and thick is both subjective and relative and is more a reflection of the statistical mode of the thicknesses en- countered in a mining region. A geological factor more precisely understood as defined than thickness is the inclination of the seams to the horizontal, commonly referred to as the pitch or the dip of the seam. Thick and steeply pitching seams present far more challenges to the ingenuity of the mining men to devise methods for their extraction than the thick and less steeply inclined ones. In a marginal case, where a thick coal seam may be minable by surface or underground methods, the decision bears a close relationship to the technological developments in the mining scene. Near surface thick coal seams are a special gift of nature and are not as wide- spread as the ones that call for the application of under- ground methods. Recent advancements in surface mining equipment have made it possible to surface mine to great depths. Stripping ratios of 30: 1 (cu yd of over- burden removed per ton of coal) have been achieved. The extraction of thick seams which preclude the use of surface methods is the concern of this chapter. Specifically, the objective here is to outline the special technological factors in underground mining of thick coal seams and to illustrate through several case histories the methods that are practiced in the North American continent. For the purposes of this chapter, a thick seam is defined as one which is not readily minable with currently available equipment without modifications to the extraction method or the equipment. At the present time, a thickness of 4.8 m (16 ft) can be considered as the lower limit, although developments in equipment and methods can be expected to push this limit upwards. The data for the case histories were collected from two extended mine visits in 1975 and 1978, and from other published accounts of the mines visited. Reference is drawn particularly to reports by Bise, Ramani, and Stefanko (1976) and Rarnani and Kenzy (1979). THICK SEAM MINING METHODS The various methods of mining thick seams can generally be grouped into three major categories: full face methods, where the entire thickness of the seam is re- covered in a single pass; slicing methods, where the seam is extracted to its full thickness by horizontal or inclined slices either in an ascending or descending order; and caving methods, where the seam is undercut and the en- tire coal seam is recovered by caving the top coal into the excavated cut, or some variations of the basic sub- level caving method. As shown in Table 1, in each of these methods, the coal is removed by either room-and-pillar or longwall methods. Hydraulic mining and transport of the coal in open flumes or in pipelines are also practiced. Addition- ally, the void created by the removal of coal may be filled with a packing material (stowing) except in the caving methods. The pitch (dip) of the seam, particularly when it is greater than 0.26 rad (150), imposes severe operational limitations on mobile equipment. A more detailed general discussion of the methods can be found in Bise et al. (1976) and Vorobjev and Deshmukh (1964). Specific discussion on the many variations of the three basic methods can be found in the papers presented at the international symposia that were held in

Jan 1, 1982

By John M. Dealy, Robert D. Pehlke

This note presents a summary of the available literature on activity coefficients at infinite dilution in binary metallic solutions, Table I. These data should prove useful in not only examining the therm-odynamic properties of binary metallic solutions, but also in predicting the activity of a component in a complex alloy. The relationship proposed by wagner1 for expressing the activity coefficient in dilute solution is of the form:

Jan 1, 1963

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.' In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.' However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By T. S. Lundy, R. E. Pawel, F. R. Winslow, C. J. McHargue

The volume-diffusion coefficients of Nb-95 and Ta-182 in niobium have been measured over the temperature range 878° to 2400°C. High-temperature specimens (T 21500°C) were sectioned by conventional lathe and grinding techniques while low-temperature specimens were sectioned by an anodizing and stripping technique previously described. Over a range of more than ten orders of magnitude in diffusivity, the self-diffusion data is well-represented by the equation: D = (1.1+ 0.2) exp [- (96,000 * 900)/RT ] cm2/sec Upward deviations from this line are explained by short-circuit diffusion in combination with the loss of resolution of the sectioning techniques. Oxygen contamination within the range 100 to 450 ppm was found to have little or no effect on the self-diffusivitj 01 niobium. In a limited number of measurements, the diffusivity of Ta-182 in niobium was found to be about half that of Nb-95 in niobium. These data may be described by D = (I.0+0.90.5)exp [- (99,300 * 2400) /RT ] PREVIOUSLY reported studies of self-diffusion in niobium were by Resnick and Castleman1 and Peart, Graham, and Tomlin.2 The data of Resnick and Castleman over a temperature range 1585" to 2120°C show considerable scatter but. can be represented by D = (12.4 *0.8) exp [-(105,000+3OOO)/RT] cm2/sec The limited data of Peart, Graham, and Tomlin follow the equation D = 1.3 exp (-95,00O/RT) cm2/sec In view of recent diffusion data for ß zirconium3 and 0 titanium4 in which Arrhenius-type plots do not yield straight lines and of the potential high- temperature uses of niobium and its alloys, we thought it important to investigate the diffusion behavior of this bcc refractory metal over a large temperature range. This has recently been done for molybdenum,5 chromium,6 vanadium,"" and tantalum.9 Niobium was a particularly suitable material for this study largely because of the development of an anodizing and stripping sectioning technique which enables diffusivities as small as l0-19' sq cm per sec to be determined accurately.10 In addition to self-diffusion data, data were obtained for the diffusion of Ta-182 in niobium and for the effect of varying oxygen content on self-diffusion. I) EXPERIMENTAL PROCEDURE Materials. The niobium was obtained from three sources: 1) melting stock from Shieldalloy Corp., 2) electron-beam melted single crystals, 1/2 in. diameter, from Semi-Elements, Inc., and 3) oxygen-doped, electron-beam melted single crystals from Materials Research Corp. The melting stock was electron-beam melted and specimens 5/8 in. diameter by 1/2 in. long were machined from the center of the bar. The analysis supplied by the vendor and an interstitial analysis of one of the specimens are given in Table I. The single crystals (type 2 above) were cut with a jeweler's saw to specimens about 3/8 in. long. The interstitial analysis of this material is given in Table 11. This material was used

Jan 1, 1965

A universal grinding circuit model suitable for an arbitrary structure of flowsheet has been suggested. In this model classifiers and mills are described in a most general form. What puts the model in a class by itself is the automatic mass balancing in all streams of the circuit. In order to provide this a special classifier model is adopted. A previously published continuous steady state process model is used as a grinding model. Non-linearity of classifier model leads to a resultant circuit model which is equivalent to a non-linear integral equation. It complicates somewhat calculation algorithm in comparison to that of linear model, but provides a physically meaningful solution.

Jan 1, 1993

By R. H. Grau

This Bureau of Mines report describes methane liberation trends from all U.S. coal mines liberating over 100 Mcfd (100,000 cfd) (2.8 Mm3/d). Detailed are results from the latest Bureau survey performed in 1985 and shown are mine and company name, location, coalbed and methane liberation quantity. The report shows that in 1985, there were 180 mines producing more than 100 Mcfd (2.8 Mm3/d) and the total quantity of methane liberated by these mines was 303,900 Mcfd (8,605 Mm3/d). This data is compared with previous studies performed in 1971 , 1973, 1975, and 1980. From 1971 to 1985, there was a 10% decrease in the number of mines liberating at least 100 Mcfd (2.8 Mm3/d) but there was a dramatic 34% increase of liberations from these mines. The increase seems to be caused by new mines being developed in deeper, gassier coalbeds, particularly in Alabama. Likewise, in comparing the ten highest liberating mines in 1975, 1980, and 1985, an increase in methane liberations each year was experienced. The report classifies mines by three levels of liberations: greater than 100 Mcfd but less than 500 Mcfd (2.8 to 14 Mm3/d); 500 Mcfd to 1 ,000 Mcfd (1 4 to 28 Mm3/d); and greater than 1,000 Mcfd (>28 Mm3/d). It was found that 87% of liberations were from mines producing over 1,000 Mcfd but these accounted for only 38% of all the mines in the study.

Jan 1, 1987

By Georgy Cherkashov, Svetlana Babaeva, Tamara Stepanova, Firstova. Anna

Seafloor massive sulfides (SMS) study in the Russian Exploration Area at the northern equatorial Mid Atlantic Ridge began after signing the contract with International Seabed Authority in 2012. In order to evaluate the SMS resources in the course of exploration the major and rare metals with economic value should be determined. The evaluation is based on geochemistry and mineralogy and particularly on the type of rare metals occurrence in the SMS. As a case study research of the Semyenov cluster of SMS deposits have been conducted.

Sep 1, 2014

By N. S. Aouad

"Gaseous explosions are one of the most hazardous incidents in process and mining industries. Experimental research in this area is shown to be high risk and expensive. Computational Fluid Dynamics (CFD) techniques are reasonable alternatives to experiments; specifically when testing large scale gaseous explosions such as methane explosion in underground mines. The dimensions of a confined space where explosions could occur vary significantly. Thus, the scaling effect on explosion parameters is worth to be investigated using CFD tools. In this research paper, the impact of scaling on the explosion overpressures is investigated by employing two scaling factors. These two factors are the Gas-fill Length scaling factor (FLSF) and the Hydraulic Diameter scaling factor (HDSF). The combinations of eight HDSFs (1, 2, 4, 8, 16, 32, 64, and 100) and five HDSFs (0.5, 1, 2, 4, and 8) will cover a wide range of space dimensions where flammable gas could accumulate. Experiments were conducted to evaluate the selected premixed combustion and turbulence models. Large Eddy Simulation (LES) turbulence model was used because it shows accuracy compared to the widely used Reynolds’ averaged models for the scenarios investigated in the experiments. Researchers also simulated methane explosions in both deflagration and detonation regimes using different numerical schemes. Three major conclusions can be drawn from the simulation results. (1) The overpressure increases with both FLSF and HDSF within the deflagration regime; (2) in an explosion duct with length to diameter ratio greater than 54, detonation is more likely to be triggered for stoichiometric methane/air mixture; (3) overpressure increases as an increment hydraulic diameter of a geometry within deflagration regime. INTRODUCTION The most typical category of gaseous explosion accidents is methane explosion accidents in the mining industry. It normally leads to significant economic loss and massive amount of casualties (McPherson, 1993). It could occur in unconfined spaces, such as combustion due to flammable gas leakage, as well as confined spaces, such as inner-combustion in process equipment and methane explosions in airways of underground mines. Gaseous explosions in confined spaces are more intensive compared to unconfined spaces provided that the total energy of explosives is the same. In addition, explosion characteristics are also affected by the geometry of a selected confined space. The size of confined spaces commonly encountered in process and mining industries could differ as much as an order of four (Catlin & Johnson, 1992). A better understanding of the scaling effect on gaseous explosions could contribute to explosion mitigation and prevent operation activities within high risk regions. This research paper has investigated this scaling effect and its impact on explosion propagation. The approach to investigate explosions is either experimental or numerical. Large scale explosion experiments are often costly and dangerous (Catlin, 1991; Zhang, Pang, & Zhang, 2011). Lab scale experiments and numerical methods are common alternatives. However, it is not yet clear if the findings in lab scale experiments can be used to represent the explosion characteristics or not. On the other hand, CFD modeling has been used to simulate chemical combustions and, thus, can be used to evaluate the scaling effects in methane explosions."

Jan 1, 2015

By A. R. Troiano, W. J. Barnett

IN recent years the demands of space limitations and increased loads, particularly in the aircraft industry, have accelerated the trend toward utilization of ultra-high strength steels. The increased application of such steels has focused attention on the phenomenon of delayed failure or static fatigue. Parts subjected to a static load, after successfully sustaining the load for an extended period of time, may fail in a brittle manner. Subsequent examination of such failed parts by conventional laboratory tests in many cases reveals no apparent signs of embrittle-ment. That is, the material exhibits good ductility and impact resistance. Furthermore, consideration of the service conditions (environment and temperature) under which this brittle failure occurred eliminates its classification as a stress-corrosion or creep type of failure. Recently this unique time dependent fracture process has been the subject of numerous investigations. The most significant result of these studies was the recognition of hydrogen as the source of embrittlement. While the effect of numerous variables on the occurrence of static fatigue failure has been defined, an adequate explanation of these behaviors is lacking. The occurrence of this phenomenon in steels generally has been limited to strength levels in excess of 180,000 lb per sq in. Although steels at high hardness levels have exhibited delayed failure in the absence of hydrogen introduction after heat treat-ment,'.' this behavior was most prevalent when the material in processing had been subjected to an environment conducive to the absorption of hydrogen. Delayed failures have been produced in high strength steels by the introduction of hydrogen

Jan 1, 1958

By L. H. Shang

The 319 Al-Si alloy is one of the most prominently used aluminium-based alloys in motor vehicle and engine applications, Microporosity present in 319 alloy castings reduces the load bearing capacity of the castings, The quantitative prediction of microporosity levels in Al-Si castings has been a subject of much interest for several years. In this research a new criteria function, tf 1,98 R13° (tf: local solidification time, R: cooling rate) was developed by multiple regression analyses, correlating thermal data from simulation studies to experimentally obtained microporosity values. This new criteria function gives a general prediction of microporosity in 319 Al-Si castings.

Jan 1, 2005

By Eric Pirard

"A mineralogical and trace element analysis was performed on the Küre historical slags in order to evaluate the possible recovery of copper and cobalt. Reflected light microscopy, electron microprobe and image analysis were combined to determine the Cu and Co distribution in the slag.The results indicate that 81% of the total cobalt is chemically combined in the fayalite whereas only 3.4% is in the mechanically entrapped sulphides. The remainder being in hercynite and wiistite. On the other hand, 95% of the total copper is in the sulphide phase.This kind of applied mineralogical investigation gives invaluable information when it is performed preliminary to metallurgical experiments.IntroductionThe recycling of metallurgical slags is a growing business. The operation is directed toward recovering base metals (Cu, Pb, Zn), and by-products (Floyd and Mackey, 1981).Two reasons are invoked to explain metallic losses in slags: (1) mechanical entrapment of matte globules in the silicate melt; and (2) chemically combined metals in the slag-forming phases. Obviously, a chemical analysis of the slag cannot distinguish between those two modes. Grinding and flotation of the liberated sulphides have often been used to evaluate the importance of mechanical entrapment (Mechev, 1970; Imris , 1982).Recent studies in applied mineralogy of pyrometallurgical products (Bérubé et al., 1987; Pignolet et al., 1986) have demonstrated the benefits of quantitative mineralogical analyses of slags. Optical microscopy together with electron microprobe and image analysis offers a powerful and easy way of quantifying the relative importance of mechanical and chemical losses."

Jan 1, 1991