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By Seth C. Schaefer

The Bureau of Mines studied the standard free energies2 of formation of ferrous fluoride (FeF2) and ferric fluoride (FeF3) with high-temperature galvanic cells employing calcium fluoride doped with 1 mole-pet yttrium fluoride as the electrolyte. A free-energy change for the cell reaction Fe (s) + NiF2 (S) = FeF2 (S) + Ni (s) together with the standard free energy of formation of nickel fluoride yields a standard free energy of formation of ferrous fluoride from the elements of ?GF° = -168.74 + 30.63 x 10-3T ± 0.41 kcal/mole (897-1,098 K). (2) Combining the standard free energies of formation of magnesium fluoride, ferric oxide, and magnesium oxide with the free-energy change for the overall cell reaction 3MgO(s) + 2FeF3 (s) = 3MgF2 (S) + Fe2 03 (S) (3) gives a standard free energy of formation of ferric fluoride from the elements as ?Gf° = -281.45 + 90.46 X 10-3T ± 0,67 kcal/mole (880-935 K). (4) Free energies and equilibrium fluorine pressures for the two univariant equilibria of the Fe-F system are tabulated and illustrated.

Jan 1, 1975

By H. H. Fields, Joseph Cervik, G. N. Aul

Coal is a soft and brittle material. Drilling rates in the Pittsburgh coalbed using a drag bit exceed 3 ft/min at 2,500-pound thrust. However, maintaining the bit on a horizontal trajectory or parallel to bedding planes to attain lengths of 1,000 feet is difficult. This Bureau of Mines report presents a drill string configuration that can be guided through the coalbed. The angle of the borehole is measured periodically and by proper combinations of bit thrust and rotational speed (r/min), bit trajectory can be lifted or dropped to keep the bit in the coalbed. An example of a hole drilled to 2,126 feet is presented to show levels of thrust and rotational speed used to lift or drop the bit, the seemingly unexplainable events that occur, and the strategy used during drilling. Thrust levels during drilling range from 600 to 2,500 pounds. Hydraulic motors powered by a 30-hp, 440-volt motor provide ample power for drilling horizontal holes 2,000 feet long.

Jan 1, 1975

By Joseph Cervik

Coal is a soft and brittle material. Drilling rates in the Pittsburgh coalbed using a drag bit exceed 3 ft/min at 2,500-pound thrust. However, maintaining the bit on a horizontal trajectory or parallel to bedding planes to attain lengths of 1,000 feet is difficult. This Bureau of Mines report presents a drill string configuration that can be guided through the coalbed. The angle of the borehole is measured periodically and by proper combinations of bit thrust and rotational speed (r/min), bit trajectory can be lifted or dropped to keep the bit in the coalbed. An example of a hole drilled to 2,126 feet is presented to show levels of thrust and rotational speed used to lift or drop the bit, the seemingly unexplainable events that occur, and the strategy used during drilling. Thrust levels during drilling range from 600 to 2,500 pounds. Hydraulic motors powered by a 30-hp, 440-volt motor provide ample power for drilling horizontal holes 2,000 feet long.

Jan 1, 1975

By Walter W. Fisher

A kinetic investigation of copper cementation in a revolving drum was undertaken by the Bureau of Mines to explore the effects of a porous copper deposit attached to the iron surface and a fluidized slurry of copper particles surrounding the iron precipitant. The rate of cementation was found to be significantly enhanced by the increased cathodic areas provided by a porous copper deposit or the presence of a fluidized bed of copper particles contacting the iron precipitant. The cementation rate was found to be retarded by increased ionic strength, low pH, and the presence of oxygen. The cementation reaction was first order with respect to precipitant surface area. Copper cementation on iron is visualized to occur by two basic mechanisms. Precipitation may occur through a series of shorted electrochemical cells, whereby cupric ion precipitates on a growing cathodic copper deposit, or, deposition may occur via a fluidized cathode of copper particles contacting the ion precipitant.

Jan 1, 1976

By S. R. Borrowman

Mill tailings from conventional uranium extraction processes contain nearly all of the radium originally in the ore. Such tailings require controlled storage in perpetuity to safeguard the surrounding environment from radioactive contamination. Alternatives to controlled storage of the tailings are (1) removal of the radium from the tailings for separate storage or use or (2) removal of the radium when processing the uranium ore. In laboratory tests conducted by the Federal Bureau of Mines, radium was leached from tailings using either hydrochloric acid or ethylenediamine tetraacetic acid. A hydrochloric acid leaching method was used to extract both radium and uranium from the ore to yield tailings containing less radium than those produced by either conventional sulfuric acid or alkaline leaching processes. From 77 to 94 percent of the radium in mill tailings was concentrated by sedimentation in slime fractions representing nearly 25 weight-percent of the original sample.

Jan 1, 1975

By J. C. Franklin

A data-acquisition system was designed by the Bureau of Mines to monitor five detectors with radon continuously flowing through each. These detectors could be monitored up to 12 times an hour, but were only monitored according to a preset time, thus allowing radon to be monitored continuously in a uranium mine. The counter can be set to monitor each detector for any period of time up to 16.5 minutes. This allows very low concentrations to be monitored longer to reduce statistical error. There would be no upper limit in radon concentration that could be monitored, but there would be a lower limit of 50 picocuries per liter (pCi/l). Each detector was cylibrated in the laboratory by the Lucas flask method. Multiple samples were taken at two different concentrations, and the correction factor for each detector was determined by a least squares fit of the data. To verify the calibrations, a series of measurements at several concentrations were made against a constant source. Our agreement at low radon concentrations (300 pCi/i) with the two-filter method as within 3 percent; thus, the total error would be this difference plus the two-filter error. At high concentrations the coefficient of variation ranged between 2.1 and 9.8 percent for the five different detector units.

Jan 1, 1976

By B. T. Brady

Laboratory measurements by the Bureau of Mines indicate that failure in dry rock specimens measuring approximately 13 cm in length is preceded by tilt anomalies lasting a few milliseconds. The tilt behavior is qualitatively similar to that reported to precede earthquakes. Test results suggest that the time duration of this tilt anomaly for laboratory specimens of this length is independent of rock type, in agreement with theoretical predictions and other experimental data on rock failures including earthquakes.

Jan 1, 1975

By R. L. Stein

For the past several years, the Bureau of Mines has been actively engaged in developing two new oxygen self-rescuers through research contracts with private industry. These new oxygen self-rescuers are designed to be carried by a miner while he is at work and are used during emergency escape, supplying high-purity oxygen to the user and, at the same time, absorbing carbon dioxide (C02), The first of the two new self-rescue breathing devices is a 10-minute, self-contained apparatus developed by the Mine Safety Appliance Co, Size and weight of the unit are comparable to the currently used self-rescue devices. The second device, designed and developed by Lockheed Missiles and Space Corp., is 8. 4.5-lb package which supplies 1 hour of oxygen to the miner. Both devices have a canister which contains the oxygen-producing and CO2-absorbing potassium superoxide chemical, a breathing bag, a bite-type mouthpiece, noseclip, goggles, and hoses connecting the canister and mouthpiece. When needed in an emergency, the miner removes the outer protective cover and dons the unit. For both devices oxygen is immediately available once the mouthpiece is placed in the mouth. These two new units have received prototype approval from the National Institute for Occupation and Safety Health (NIOSH) and the Mining Enforcement and Safety Administration (MESA).

Jan 1, 1976

By R. A. Guidotti

The Federal Bureau of Mines studied the thermal decomposition of the nitrides of the Group V A metals (CbN, Ta3N5, and VN) with the goal of preparing high-purity metals. Solid-state purification and arc and electron-beam melting were examined. Electron-beam melting proved to be the most efficient means of nitrogen and oxygen removal. Columbium and tantalum of 99.9-pct purity were prepared by this technique; in the case of vanadium, however, nitrogen could not be reduced below the solid-solution level.

Jan 1, 1976

By K. J. Liles

Research was undertaken by the Bureau of Mines to determine the technical feasibility of producing lightweight aggregate from the waste glass fraction of municipal incinerator residues. Tests were conducted to determine the amount and optimum size of glass, the amount of sodium silicate, and the method used to form the material to be expanded. The most suitable mixture, 78 percent glass, 20 percent clay, and 2 percent sodium silicate, was pelletized and then expanded by exposure to a temperature of 1,550° F for 15 minutes The resulting lightweight material had a bulk density of 38 lb/cu ft and exhibited excellent pore structure. Concrete test cylinders made from the light weight aggregate had a unit weight of 104 lb/cu ft and a compressive strength of 2,550 lb/sq in after a 28-day steam cure.

Jan 1, 1976

By F. P. Haver

Primary lead is produced in the United States by the pyrometallurgical smelting of lead sulfide (galena, PbS) concentrates, which poses sulfur dioxide and lead air pollution control problems. The Federal Bureau of Mines has investigated an alternative hydrometallurgy procedure that does not generate gaseous sulfur oxides and diminishes the potential for the escape of lead into the atmosphere. The procedure involves leaching galena flotation concentrates with ferric chloride (FeC13) solution to obtain lead chloride (PbC12) and elemental sulfur as expressed by the following chemical reaction: PbS + 2FeC13 ? PbC12 + 2FeCl2 + S°. At 100° C, over 99 pct of the PbS in the concentrate is converted to PbCl2 in less than 15 min. The leach solution, composed of brine (NaCl) containing slightly more than the theoretical required amount of FeC13, dissolves the PbC12 as it is formed, leaving a residue of elemental sulfur plus gangue. High-purity PbC12 (>99.9 pct) crystallizes from the leach filtrate on cooling and is electrolyzed in a low-temperature, fused-salt cell to obtain corroding-grade metal (>99.94 pct Pb). Spent leach solution (FeC12) is regenerated for further use by reaction with the chlorine obtained in the electrolysis of lead chloride. Other values, such as Ag, Cu, Zn, and S°, are recovered by additional treatment of either the leach solution or leach residue.

Jan 1, 1976

By Carl F. Wingquist

Electrical resistance heating to effect thermal fragmentation of semiconductive rock was examined by the Bureau of Mines. Tests were carried out on copper-bearing ores of the Nonesuch Shale Formation in the laboratory and in the the field at White Pine, Mich. Fieldwork included primary and secondary breakage tests. Heating tests on in situ rock failed to produce thermal dam-age to an extent considered useful; however, boulders up to 30 ft3 were effectively broken by the method. Power input to the test rock was taken from a 50-kV, 5-amp dc power supply.

Jan 1, 1976

By Arthur M. Hartstein

The Federal Bureau of Mines, under a contract with Ultrasystems, Inc., investigated the thermal oxidative degradation characteristics of conveyor belts used in underground mines. This included the determination of smoke evolution, glow characteristics, char yields, and the identification and quantification of all volatile decomposition products in the form of gram of specific product formed per gram of belt sample tested. In addition to these investigations, degradation studies were conducted on some pure ingredients used in conveyor-belt formulations. Three basic classes of belts were investigated: neoprene, polyvinyl chloride, and styrene-butadiene rubber compositions. The studies indicate that styrene-butadiene-based belts exhibit good flame resistance and are the least hazardous in regard to overall formation of toxic decomposition products. Under this program, thermogravimetric analysis was definitely established as a method of material differentiation.

Jan 1, 1976

By E. E. Maust

The literature on the activation of sphalerite for flotation by short¬chain xanthates leaves unanswered the question of whether a compact surface film of activator sulfide is necessary or merely sufficient for high flotation recoveries. Studies by Guarnaschelli and Plaksin indicate that xanthate adsorption and flotation of sphalerite are increased with increasing hole/ electron ratio. These results, and the known acceptorlike behavior of many heavy-metal impurities in zinc sulfide, suggest that activation may result from a traditional semiconductor doping effect at the surface. Using the theory of chemisorption states on ionic crystals as developed by Levine and Mark, the Bureau of Mines has carried out A calculation to estimate the surface-state energies of various metals when they are substituted at zinc sites on (110) sphalerite surfaces. Based on a simple Madelung-Born treatment of ionic solids, the calculation indicates that many of the metals known to activate sphalerite for subsequent flotation have lower surface-state energies than nonactivators. The results of these calculations are discussed from the standpoint of consistency with the proposed activation mechanism and observed flotation results. The satisfactory agreement obtained is taken to be support for the proposed mechanism, and further elaboration of a surface-doping model is attempted.

Jan 1, 1976

By Joan T. May

The Bureau of Mines conducted laboratory tests to evaluate the production of high-purity H3P04 by HCl digestion and solvent extraction. Both batch and bench-scale continuous tests were made. Western phosphate rock concentrates were acidulated with HCI, and the digestion liquors were processed by solvent extraction. Phosphoric acid was extracted with isoamyl alcohol and recovered from the organic extract by contact with an NH4F solution. This solution was fractionally distilled to yield high-purity H3P04. The raffinate from solvent extraction was treated with lime to precipitate CaF2, which was subjected to steam pyrolysis to generate HF. This method was successful in recovering 95 pet of the phosphate and 80 pct of the fluoride contained in the concentrates.

Jan 1, 1976

By K. C. Dean

Time and motion studies were made by the Federal Bureau of Mines on the hand and machine dismantling of scrapped auto starter motors, generators, and alternators for recovery of copper, aluminum, and iron. The studies showed that an individual with power handtools and convenient access to a hydraulic press, power bandsaw, acetylene torch, and power lathe could, in an 8-hour day, disassemble about 100 starters, or 150 generators, or 30 alternators. The scrap copper yield would be 280, 390, and 45 pounds, respectively, and the iron yield would be about seven times the copper weight. About 100 pounds of aluminum would be obtained from the alternators.

Jan 1, 1976

By L. W. Higley

Electrowinning metals from solutions leached from low-grade ores is becoming an increasingly important extraction method as the metal industry turns to pollution-free recovery processes. Lead-alloy anodes are used industrially in the electrolytic recovery of zinc and copper. However, associated with the use of these anodes are the inherent problems of stability and lead contamination of the cathode. In an effort to eliminate these problems, the Bureau of Mines has developed a relatively inexpensive lead dioxide anode for electrowinning metals from strong acid solutions. The anode was prepared by depositing Pb02 directly on a titanium blank in a strong HN03-Pb(N03)2 solution at 2.15 to 6.45 A/dm2 and 60° C. This anode was tested in zinc and copper electrowinning cells containing 200 gpl H2S04 and 35 to 100 gpl metal ions at the current density of 3.23 to 6.45 A/dm2. Contamination of the cathode by lead was =0.005 pet. A 30-day test at 6.45 to 12.90 A/dm2 in an electrolyte containing 200 gpl H2S04 and no metal ions resulted in a slight change in surface morphology of the Pb02 anode but no measurable change in anode weight or dimensions.

Jan 1, 1976

By Noel N. Moebs

Valley Camp No. 3 mine was the scene of an experimental shortwall introduced in 1973 in an attempt to improve the recovery from the Pittsburgh coalbed in the Ohio Valley area where adverse ground conditions have imposed partial extraction methods with only 40 to 55 percent recovery of the valuable resource. The Bureau of Mines, under a cooperative agreement with Valley Camp Coal Co., monitored ground pressures and caving in the shortwall section in an effort to determine whether the roof strata, notably the limestone main roof, will cave to the extent that roof pressures at the face are relieved and whether the powered roof supports can sustain the roof load. The Bureau's efforts included mapping of clay veins, instrumentation of chain pillars and shortwall panels with encapsulated pressure cells, recording hydraulic pressures in the legs of the shortwall chocks, and core drilling underground and from the :surface. The experimental shortwall was a qualified success. Recovery increased 5.4 percent compared with partial extraction. Pressures in chain pillars and the abutment zone were not excessive. Hydraulic pressures in the chock legs did not approach the yielding pressure. Apparently, the limestone strata caved and the roof pressure at the face was relieved.

Jan 1, 1976

By P. T. Brooks

Electrochemical machining sludge, a troublesome fluid waste product, was dewatered on a bench-scale basis by three alternative methods tested by the Federal Bureau of Mines. These methods would enable recycling 89 percent or more of the liquid content of the sludge and allow the dewatered solids to be dumped as landfill or processed further to recover contained nickel. Dewatering by vacuum precoat filtration was estimated to be the least expensive. Based on treating 20,000 gallons per day of sludge, precoat filtration costs were estimated as totaling 1.96 cents per gallon of sludge. Two options of an alternative method, comprised of acidification, reprecipitation, thickening, and filtration, were estimated to cost either 3.41 or 3.60 cents per gallon of sludge.

Jan 1, 1976

By Philip E. Sanker

The Bureau of Mines conducted small-scale batch and semicontinuous tests on the reduction of zinc sulfide with iron according to the reaction ZnS + Fe ? FeS + Zn to determine reaction kinetics in the temperature range 1,000° to 1,400° C and to investigate the potential use of a scrap iron reductant. Batch tests indicated that a temperature of at least 1,300° C with a 1:1 mole ratio of Fe to ZnS is needed for good zinc recovery. Semicontinuous tests were conducted, using four zinc concentrate samples, containing various percentages of copper, cadmium, and lead, which were reacted with iron and iron contaminated with iron oxide and tin in an externally heated graphite furnace. Analysis of the zinc metal and FeS matte reaction products showed cadmium to be entirely in the zinc metal, copper to be in the FeS matte, and lead to be about 60 pct in the zinc metal and 40 pct in the matte. Tin reported to the matte, and none was detected above the O.OS-pct level in the zinc. Sulfur dioxide was not detected in the offgas when up to 20 pct of the iron was replaced by Fe203.

Jan 1, 1976