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By D. Montagna

Large quantities of zinc-base die-cast scrap containing 3 to 4 percent aluminum are presently refined by mixing with other secondary zinc products such as galvanizer dross and distilling in a retort. The Bureau of Mines investigated alternate aluminum removal processes utilizing low-cost fluxes. Basing the investigation on the metallurgical principle that a reactive impurity can be removed from a less reactive matrix metal by melting under a flux consisting of a salt or oxide of a metal less reactive than the impurity, three separate flux mixtures were studied. In the first flux system, [FeCl3] + NaCI (the active component is underlined), part of the aluminum is' eliminated by the formation of volatile aluminum chloride and the rest by the creation of a high melting point iron-aluminum intermetallic compound that can be separated from the remaining molten zinc by filtration. Aluminum removal in the second system, [Fe203] + CaClz + NaCI, is effected by the formation of the iron-aluminum compound and possibly aluminum oxide. The third system, spent sal skimmings--essentially a mixture of [ZnCl2], NH4Cl, and ZnO, depends solely on aluminum chloride formation. Of the three flux systems investigated, the best results obtained were with system 3. Aluminum was reduced in the molten die-cast alloy from 4.10 percent to 0.01 percent when depleted sal skimmings were used.

Jan 1, 1969

By P. T. Brooks

This Bureau of Mines study describes a process for recovering nickel, cobalt, molybdenum, and chromium contained in complex waste superalloy grindings that, for lack of an economical domestic recovery process, are being largely marketed abroad. The process, devised by laboratory scale operations, includes scrap preparation, dissolution of metallics in hot chlorinated acidic liquor, carbon adsorption, three successive solvent extraction separations, and selective chemical precipitations. Nearly 90 percent of the nickel, cobalt, molybdenum, and chromium were separated and recovered as oxides, carbonates, and basic sulfate products.

Jan 1, 1969

By Jack L. Henry

The ternary system A14C3-AIN-Al203 has been examined to determine compositions which may display desirable high-temperature refractory properties. Powder methods were employed in the synthesis of all test compositions. Forming and sintering behavior was examined and hot-pressing parameters were measured. Several properties were studied for each composition of interest in the system. The properties included hydrolysis rate in moist air, elevated temperature oxidation rate, density, softening point, tensile strength, and rupture strength. In most cases equilibrium was not achieved, and the data are representative of a nonequilibrium system. Approximately 16 separate phases have been observed in the system. Forming behavior and selected properties of five compositions of interest were compared with those of aluminum oxide and aluminum nitride. None of the compositions compared favorably. Oxidation and vaporization appear to be serious drawbacks to the use of these compositions at elevated temperatures.

Jan 1, 1969

By R. S. Warfield

Several reconnaissance-type surface and drill core samples of Arctic Northwestern Alaska coals were taken during the summer field seasons of 1964 and 1966 for coking studies. Surface samples were taken from the Kokolik River and the Cape Beaufort areas; core samples were obtained from the Kukpowruk River and the Cape Beaufort areas. Only one Kokolik River surface sample possessed coking properties. This sample, representing an 11.6-ft coal seam, made coke approaching metallurgical quality when a 30-pct portion of selected blending coals was added. Four Kukpowruk River core samples, each representing the same 19-to 20-ft coal seam, were all of about the same coking quality. No differences of coke quality attributable to depth of permanently frozen overburden were found, but the data confirm previously reported information that the 19- to 20-ft coal bed is a potentially satisfactory base coking coal. In the Cape Beaufort area, a core sample with appreciable coking properties was taken at depth from a coalbed determined noncoking in a surface sample.

Jan 1, 1969

By F. S. Karn

Conditions necessary to obtain optimum yield of useful products when coal is rapidly heated to extreme temperatures by laser irradiation were determined by the Bureau of Mines. Product distribution and yield were investigated as functions of several variables. Low-rank coals with high-volatile matter gave highest total gas yields. Medium-rank coals gave the highest yields of H2 and CA and low-rank coals gave highest yields of CO and C02. Macerals gave gases of approximately the same composition, but the total gas yield increased in the order fusinite, micrinite, vitrinite, and exinite. Total gas and C2H2 yields varied inversely with particle size. The addition of nominally inert gases such as Ar, He, N2 increased yields of H2, C2H2, and total gas. Metals such as nickel and platinum had little influence on the rate of coal decomposition. Total gas yield increased with total energy of irradiation, and the ratio of C2H2-CH4 increased with concentration of energy. A study was also made of the irradiation temperature, and a material balance was calculated.

Jan 1, 1970

By S. E. Khalafalla

The extremely sluggish oxidation of steel scrap was appreciably accelerated when the charge was pretreated in aqueous solutions of sodium metavanadate or sodium molybdate. The degree of oxidation acceleration was inversely correlated with the melting point of the promoter oxide possessing the highest valency. The magnitude of oxidation enhancement exhibited a systematic inverse dependence on the duration of pickling processes; mere dipping of the oxidizable charge in the vanadate bath was most effective. In general, the rate of steel scrap oxidation increased with increasing concentration of the pickling reagent. The results are explained on the basis of the hydrolytic decomposition of the pickling agent with subsequent slow interaction with the metal surface, coupled with the tendency of vanadium to form polyanions in alkaline media. The data not only served to elucidate the mechanism by which catastrophic oxidation takes place, but also showed that the accelerating species need not be alloyed with the oxidizable metal; surface impregnation by minute amounts of the accelerating species can still produce catastrophic effects.

Jan 1, 1970

By M. M. Fine

Chalcocite flotation concentrates (26-34 percent Cu and 6-7 percent S) were roasted in air to determine sulfur elimination as a function of temperature, airflow rate, and residence time. Fluosolids roasting was evaluated batchwise and continuously in a 4-inch fluid-bed reactor. Kiln roasting tests were carried out in a 4-inch ID by 6-inch-long rotary drum. Pelletizing the very fine concentrates prior to roasting was essential to minimize dust losses and accretions. Concentrate pellets, sized minus 10 plus 20 mesh and bonded with 2 percent bentonite, were excellent feed for fluosol¬ids roasting and limited dust losses to 10 percent or less. One-fourth-inch pellets were best suited to kiln roasting. Both techniques were capable of producing copper calcines analyzing well under 1 percent residual sulfur when operated at 900° C with average retention times of 3 to 4 hours. Calcined pellets were strong, porous, and readily reducible.

Jan 1, 1970

By L. C. Headley

A series of exploratory tests was conducted to determine the effects of steady electric fields on fluid flow and streaming potential in narrow passages and porous media, the effects of steady electric fields on fluid interfaces, and the influence of internal voltages on fluid flow in a porous porcelain sample. Voltages greater than about 5 kilovolts were found to influence liquid droplets emanating from a capillary tube. Solutions of polyethylene oxide and polyacrylamide in water exhibited widely different behavior than that of other liquids tested. Liquid-liquid displacement tests in porous samples to determine the influence of high voltage applied to the displacing liquid on flow rates and recovery gave no significant differences. No consistently measurable effects were noted, either on flow rate or streaming potential, when an electric field was applied transverse to the direction of flow in porous media and in narrow rectangular or cylindrical channels. Experimental values of formation factor and streaming potential for a porous porcelain sample agreed qualitatively with those calculated from electrokinetic theory for ultrafine capillaries. However, the agreement for the electroviscous effect was not good.

Jan 1, 1970

By John M. Gomes

Two methods for electrowinning tungsten from wolframite [(Fe,Mn)W04] were investigated. The first method, direct electrowinning from wolframite concentrate dissolved in molten salt mixtures composed essentially of various combinations of sodium phosphates, sodium borates, and sodium halides, yielded impure products. The second method was electrowinning from a halide-tungstate melt that was obtained from a high-temperature, two-phase extraction of tungstic oxide (W03) from wolframite. Electrolysis in electrolytes prepared from addition of sodium metaphosphate (NaPO3) and boric oxide (B2O3) to the halide-tungstate melt produced tungsten metal of 99.9 percent purity. Tungsten carbide (WC) was electrodeposited from the halide-tungstate melt when the melt was adjusted to contain 82 mole-percent NaCI and 6.0 mole-percent each of W03, sodium metaborate (Na2B204), and caustic soda (NaOH).

Jan 1, 1970

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove, grindability index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions 2 issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor; if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous sampling of coal as delivered is a check on the practical results obtained in burning the coal.

Jan 1, 1970

By D. A. Keefe, O&apos

The electrowinning of beryllium from beryllium oxide (BeO) using a molten-salt electrolyte composed of 56 LiF-37 BeF2-7 BeO (mole-percent) was investigated. Anodes made of porous carbon were found to be superior in current-carrying capacity and gave a lower cell voltage than other types of anode material tested. When porous carbon anodes were used) the resultant increase in anode area prevented anode passivation. The cell voltage was 3.3 volts) and electrode current efficiencies of 50 to 70 percent were obtained. The electrodeposited beryllium was recovered as beryllium powder or was coalesced to metal beads by heating to 1,300° C.

Jan 1, 1970

By L. A. Neumeier

The Bureau of Mines evaluated the properties and anisotropy in properties of rolled Zn-Cu and Zn-0.12 pct Ti-Cu alloys with various copper additions to 1.25 pct. The alloys were rolled cold and at various hot-rolling temperatures to reductions as high as 92 pct after breakdown rolling. The properties are extremely sensitive to various combinations of composition, rolling temperature, and rolling reduction, Zn-Cu alloys can develop good creep resistance, but they are inferior in that respect to Zn-Ti-Cu alloys. For alloys either with or without the titanium addition, cold-rolling results in recrystallization of the matrix and rejection of copper from solution, causing poor hardness, tensile, and creep properties, but high ductility. Peak tensile strengths develop when the alloys are rolled in the range 320° to 400° F, Best creep resistance for Zn-Cu alloys requires higher rolling temperatures when copper content is increased. Creep resistance is best for Zn-Ti-Cu alloys with about 0.75 to 1.0 pct CU rolled near 480° F. Some copper is soluble in the TiZn15 phase, which forms into "stringers" during rolling. The possible contributions to creep behavior of factors such as distribution of second-phase particles, grain size, and preferred orientation are discussed.

Jan 1, 1970

By R. B. Tippin

To study continuous operation of the heavy liquid separation (HLS) of minerals, the Bureau of Mines concentrated spodumene from a typical ore. The studies included heavy liquid concentration, removal of the heavy liquid from the mineral products, and recovery of the heavy liquid for reuse. The research program examined the influence of feed moisture, steam consumption, stripping time, and condition of steam. Operation of multiple cyclones in series resulted in spodumene concentrates assaying 92 to 95 percent spodumene and indicated mineral recoveries of 86 to 89 percent. Continuous filtration and steam stripping produced mineral products containing less than I pound of heavy liquid tetrabromoethane (TBE) per ton of material. Problems unique to this process are discussed, including heavy liquid properties and viscosity, toxicity, material handling hazards, and safety precautions.

Jan 1, 1970

By Larman J. Heath

Wellbore enlargement was tested using hydrazine hydrate in a gas-storage well in Ohio to increase the well productivity. The wellbore was to be enlarged by chemical disaggregation of the sandstone adjacent to the wellbore. Productivity immediately declined 49.1 percent and gradually declined to zero in 7 months. A down-hole camera survey showed a white-to-gray precipitate covering the entire wellbore surface. The precipitate was chemically analyzed and identified as mostly carbazic acid, a hydrazine derivative of carbonic acid. Formation of this precipitate was not anticipated; this viscous sub-stance caused the gradual loss in productivity of the well. The wellbore was not enlarged. Laboratory tests were run to determine what clay stabilization measures could be taken in sandstone cores to prevent clay swelling and particle migration caused by hydrazine hydrate. Normal clay stabilization methods did not prevent the virtually complete loss in permeability to hydrazine hydrate. Other laboratory tests using natural gas diluted with small amounts of carbon dioxide confirmed the ease with which carbazic acid could be formed in a hydrazine hydrate-saturated environment within and adjacent to the wellbore.

Jan 1, 1970

By R. L. Blake

The crystal structure of hematite, a-Fe203, has been refined as part of a continuing study of the behavior of phases in the Fe-O system during reduction and oxidation. Three-dimensional diffraction intensities were collected on two spherical single crystals of hematite with a semiautomated Buerger single-crystal diffractometer. The first crystal refined was a natural Elba hematite with minor impurities. The other, a synthetic crystal, was refined at the request of Mossbauer spectroscopy investigators concerned with impurities in the natural crystal. The structure has been refined with a least-squares program and the final structure for the natural crystal irradiated with CuKa-radiation gave a discrepancy factor (R) of 3.65 percent using 49 unrejected reflections of the 51 measured. For the synthetic crystal, using MoKa-radiation, the discrepancy factor converged to 2.8 percent using 95 unrejected reflections and was 3.3 percent for all 109 reflections. The structure model of Pauling and Hendricks has been confirmed with essentially no change in the iron coordinates and approximately a 5-percent change in the oxygen coordinates. Selected interatomic distances and angles were calculated as were anisotropic temperature factors.

Jan 1, 1970

By Daniel C. Boteler

Five lignites from the northern Great Plains province were carbonized at temperatures from 500° to 1,000° C in a bench-scale unit. A replicated Greco-Latin square experimental design was employed to allow testing of four independent variables at five levels. Independent variables investigated were temperature, source of lignite (mine), weight of charge, and moisture content of charge. Dependent variables were char yield, tar yield, light-oil yield, tar plus light-oil yield, carbonization gas yield, and carbonization gas heat yield. An analysis of variance indicated that, at the 99-percent confidence level, the independent variables of carbonization temperature, source of lignite, and weight of charge were significant for yields of char, tar plus light oil, and carbonization gas, whereas moisture content was only significant for carbonization gas yields. At the 95-percent confidence level, moisture content significantly influenced the carbonization gas heat yield per pound of lignite charge and the yields of dry tar plus light oil. All dependent variables were determined on a moisture- and ash-free basis. Multiple regression equations for predicting seven different factors of carbonization yields as functions of carbonization temperature and initial composition were developed using computer techniques. Equations for yields of char, tar plus light oil, and carbonization gas were compared with equations previously developed by others at the 500° C level.

Jan 1, 1970

By B. H. Eccleston

The effect upon automobile emissions in changing from leaded to lead-free gasolines was studied in experiments by the Bureau of Mines in cooperation with the American Petroleum Institute. Typical U.S. leaded gasolines and prototype lead-free gasolines of comparable octane quality were used in eight vehicles operated to simulate city driving. The experiments were run at 70° and 95° F. Exhaust and evaporative emissions were measured and the photochemical effect of the emissions was experimentally observed in an artificial smog chamber. Results of the study reveal the manner and degree in which the changes in fuel composition alter the amount and characteristics of both exhaust and evaporative emissions. Briefly, it is shown that the compositional differences between leaded and prototype lead-free fuels resulted in higher photo-chemical pollution potential of the emissions from the lead-free fuels. The effect is attributed to the photochemical characteristics of high-octane fuel components that are used in greater quantity in the lead-free fuels.

Jan 1, 1970

By W. R. Hardwick

Nuclear explosive fracturing has been suggested as a method to make hard rock amenable to extraction by a modified block-caving method. To evaluate this possibility, conventional and nuclear blasting practices are discussed, underground mining methods for large deposits and their costs are described, and the cost of fracturing ore with a nuclear explosive and subsequent mining by a modified caving system is estimated and compared with both open-stope and block-caving mining costs. While the direct cost of fracturing the ore in hard rock with a nuclear explosive is less than with conventional explosives, additional costs imposed by the use of nuclear explosives may make their use unattractive for deep mining.

Jan 1, 1970

By K. Robert Dorman

Spray-applied polyurethane foam was used to insulate the walls of heated rooms excavated in permafrost. The experiment was designed to determine whether polyurethane foam can be sprayed successfully on frozen ground under freezing conditions and to measure the effectiveness of the insulation in maintaining--at elevated temperatures for an extended period--a room excavated in frozen ground. Two manufacturers' foams were investigated in the laboratory. Subsequently, one of the foams was employed to insulate two small rooms, one in frozen gravel and one in frozen silt, in an experimental tunnel belonging to the U.S. Army Cold Regions Research and Engineering Laboratory (USACRREL) near Fairbanks, Alaska. Following insulation, heat was introduced into the two rooms. Heat migration across the insulating barrier into the walls, in addition to wall closures, was monitored over an 8-month period. The results show that polyurethane foam can be successfully sprayed on frozen ground in below-freezing temperatures. Given this type of insulation, together with winter cold to supercool the surrounding ground, it should be possible to maintain a shaft or heated room in permafrost for several years.

Jan 1, 1970

By W. R. K. Wu

This Bureau of Mines report presents a statistical study of the repeat abilities of coal-plasticity parameters obtained in the tests with the Gieseler plastometer and the Audibert-Arnu and Hoffmann dilatometers. Repeatability is expressed in terms of one or two standard deviations for the differences between duplicates. The statistical method employed here is summarized. Results are tabulated for the temperature and nontemperature parameters of the three tests.

Jan 1, 1970