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By D. R. Douslin

This report describes an inclined-piston pressure gage that operates from a zero-pressure datum level. The gage is adaptable to accurate vapor-pressure measurements in the low and intermediate pressure range, 0.01 to 40 mm (mercury). Residual friction in the oil-lubricated piston-cylinder combination is eliminated by a unique oscillatory method that is free of end thrust on the piston and allows the full sensitivity of the gage to be realized. The axial component of the weight-to-area ratio of the piston is determined by measuring the angle of inclination with a goniometer that can be read to 1 sec. Accuracy of the gage proper is estimated to range from 0.001 to 0.012 mm from lower to upper pressure limits. Its highest practical sensitivity is about 0.0005 mm. As a test, the vapor pressures of ice and water were measured in the range -30° to +20° C.

Jan 1, 1963

By A. R. Taylor

Low-temperature heat capacities of cesium chloride (7° - 300° K) and cesium iodide (13° - 300°K) were measured with an adiabatic calorimeter. The heat-capacity measurements were analyzed graphically to determine smooth values of heat capacity, entropy, enthalpy function, and free-energy function at 10° K intervals and at 273.15° and 298.15° K.

Jan 1, 1963

By Charles Prasky

This report describes and appraises recent progress in the development of a differential sulfatizing process for recovering a ferrograde manganese oxide from low-grade manganiferous ferruginous materials in the Cuyuna range. Individual process steps were carried out successfully using a 20-inch-diameter shaft for continuous countercurrent sulfatization of the manganese, a multiple-compartment rotary drum for leaching the water-soluble manganese sulfate, a submerged-combustion evaporator for the recovery of monohydrate crystals of manganese sulfate, and a shaft furnace for the thermal decomposition of sulfate crystals for production of a ferrograde manganese oxide and a sulfur dioxide gas suitable for sulfatization of fresh are. Of the two general kinds of Cuyuna manganiferous materials--the carbonate slates and the oxidized ores--only the slates were studied at pilot scale.

Jan 1, 1963

By M. M. Wong

Electrolysis of titanium carbide and a material consisting of titanium, carbon, nitrogen, and oxygen as soluble anodes in Used electrolytes was investigated by the Bureau of Mines for the preparation of crude titanium metal. Tests made in all-chloride electrolytes showed only a low recovery of titanium as well as a substantial volatilization of titanium trichloride (TiC13) when present in the electrolyte. Electrolysis at 750° to 850° C in a mixture containing 85 percent NaC1-15 percent potassium floutitanate (K2TiF6) yielded as high as 91 percent recovery of titanium from titanium carbide and 62 percent recovery of titanium from the titanium-carbon-nitrogen-oxygen material. Problems associated with the preparation of crude metal by fused-salt electrolysis are discussed. The crude metals produced from both anode materials were electrorefined in a sodium chloride-titanium chloride (NaCl-TiC12) electrolyte, and ductile titanium metal was obtained.

Jan 1, 1963

By T. A. Henrie

A technique was devised for measuring the rate of chemical reactions between reactive metals and molten-salt mixtures at high temperatures. The rate of the heterogeneous reaction between high-purity titanium metal and titanium trichloride in molten sodium chloride was determined. The reaction is surface-controlled, and the heat of activation is 8.29 kilocalories per mole TiC13. An active site or reaction nuclei is created by adsorbing a TiC13 molecule at the metal surface. Reaction of the second TiC13 species forms an activated complex that decomposes into three TiC12 molecules.

Jan 1, 1963

By William C. Miller

This report describes investigations by the Bureau of Mines designed to establish the noise level and spectrum of various types of pneumatic rock drills and to furnish information that would be useful in conducting sound measurements in mining environments and in reducing the noise generated in pneumatic drilling. These investigations show that (1) the noise generated by the drills in the frequencies below 100 cps is caused by the impact of the piston and drill steel, in the frequency range between 100 and 2,000 cps by the exhausting of air from the ports, and in the frequencies above 2,000 cps by the resonant frequencies of steel drill parts and of drill steel; (2) satisfactory instruments and instrumentation systems are available for field and laboratory measurements; (3) reliable sound measurements can be made in mining environments; and (4) devices can be developed that will abate the noise.

Jan 1, 1963

By W. E. Robinson

Samples of raw oil shale and kerogen concentrates were oxidized by alkaline potassium permanganate, air, nitric acid, oxygen, and ozone to obtain information about the chemical structure of organic kerogen in oil shale. In one test, oil shale and oil-shale products were oxidized exhaustively with alkaline potassium permanganate, and the distribution of the organic carbon in the final oxidation products was determined. Comparing results of this oxidation with those obtained from other carbonaceous materials and known compounds gave information about the structure of kerogen. Alkaline potassium permanganate oxidation also was used partly to degrade kerogen into soluble products for characterization purposes. Structures present in these degradation products were indicative of type structures originally present in the kerogen. Nitric acid, oxygen, and ozone were used also for partly degrading kerogen to soluble oxidation products. Carbon-balance oxidation tests using alkaline potassium permanganate showed that Colorado oil-shale kerogen differs from many other carbonaceous materials such as coal and kerogens from other areas. Composition of the degradation products indicated that Colorado oil-shale kerogen is predominantly cycloparaffinic and saturated heterocyclic structures with some long-chain paraffinic and aromatic structures present. The ring systems may be connected through short carbon chains or bridges containing oxygen, nitrogen, and sulfur.

Jan 1, 1963

By David J. Kusler

A gravimetric method for the determination of carbon dioxide, carbon monoxide, hydrogen, methane, and oxygen in blast furnace top gas is described. Nitrogen may be determined directly by volume measurement or by difference. The method is direct, permits continuous as sampling, and provides an averaged analysis over a selected range of sampling intervals from 1/2 to 24 hr or more. Neither expensive equipment nor specialized personnel are required. The method is suitable for routine analysis, and the results compare favorably with those obtained by established methods.

Jan 1, 1963

By Albert J. Rambosek

The results obtained in a study of the stress conditions existing in a drill bit-point area and in the underlying rock, when the bit was in full but nonpenetrative contact with the rock, are presented. This investigation by the Bureau of Mines was the preliminary exploratory phase of a long-range program of research on rock drilling to establish criteria for the maximum economically feasible rate of rock penetration. The photoelastic technique of experimental stress analysis was the principal method used to obtain the data. Transparent models and transmitted light were employed to investigate patterns in drill-bit models and isotropic materials under the bit when subjected to a concentrated static load. Comparative stress data for anisotropic rock were obtained by the reflective photoelastic technique. Brittle lacquer and an extensometer were used obtain supplementary information wherever substantiating data were desired to check photoelastic results. The zone of maximum shear occurs along an arc near the contact face of the bit. The stress distribution pattern in an isotropic model rock near the area contacted by the bit was nearly a mirror image of that exhibited within a similar areal zone of the bit. The stress pattern in granodiorite specimens was similar, though not symmetric, to the pattern in the isotropic model rock. The asymmetry of the stress pattern in the granodiorite was attributed to the anisotropic characteristics of the constituent minerals of various sizes.

Jan 1, 1963

By Alla D. Mah

Combustion energies of barium and strontium were measured by means of the combustion bomb calorimeter. The heats of formation obtained for the oxides were ?H298.15 = -139,060 ± 700 cal/mole of barium oxide (BaO) and ?H298.15 = -144,440 ± 400 cal/mole of strontium oxide (SrO). Tables containing heats and free energies of formation from 298.15° to 2,000° K were prepared.

Jan 1, 1963

By Laird Crocker

This report describes a study of beryllium recovery from sulfate leach liquor by di-2-ethylhexyl phosphate (EHPA) solvent extraction in conjunction with caustic stripping. The work was one phase of Bureau of Mines research on process development for Spor Mountain, Utah, ores. Solution for the solvent extraction studies was prepared by sulfuric acid leaching of ore containing 0.6 pet BeO, Before solvent extraction of beryllium, the leach liquor was treated to prevent coextraetion of iron by either (1) removal of ferric iron by amine solvent extraction or (2) reduction of ferric iron to nonextractable ferrous iron by treatment with sulfur dioxide. Beryllim was extracted from the aqueous leach liquor by countercurrent multistage contacting with a kerosine solution of EHPA. The loaded organic solution was stripped with sodim hydroxide solution. Subsequently, beryllium hydroxide was precipitated by boiling the sodium beryllate strip solution and converted to beryllium oxide of 98 pct BeO-grade by calcining. Material of this grade can be directly processed into beryllium-copper alloy or be used as starting material for further refining to produce high-purity, nuclear-grade beryllium. Over 90 pct of the beryllium contained in the leach liquor was recovered as beryllia.

Jan 1, 1963

By Sara Jane Boles

The purpose of this Bureau of Mines investigation was primarily to isolate and examine the effect of liquid content upon the apparent porosity and bulk density of compacts pressed from high-purity, fused aluminum oxide, and, secondarily, to study the actual mechanism by which the liquid content affects the bulk density. No attempt was made to approach the theoretical maximum density of the oxide by introducing additives, particle packings, or similar variables; instead this study is an intercomparison of the bulk densities obtained as functions of the water contents of the compacting mixtures. Water content was varied from 7 percent to 25 percent, on a total-weight basis. The data gathered indicated a well-defined optimum water content for obtaining minimum apparent porosity and maximum bulk density, under the conditions of the experiment. During the course of this study, a number of additional variables in the forming process were discovered and are introduced in this report, although a thorough evaluation was found to be beyond the scope of this present investigation.

Jan 1, 1963

By Alla D. Mah

Energies of combustion of vanadium nitride (VN) and vanadium carbide (VC) were measured. Correcting to vanadium tetroxide (V204) as the final state, the heats of combustion were ?H298.15=-118,700±100 cal/mole of vanadium nitride and ?H298.15=-240,270±360 cal/mole of vanadium carbide. With vanadium pentoxide (V205) as the final state, the heats of combustion were ?H298.15= -133.440±100 cal/mole of vanadium nitride and ?H298.15=-255,020±360 cal/mole of vanadium carbide. Combining these results with vanadium oxide data, the heats of formation obtained were ?298.15=-51,880±200 cal/mole of vanadium nitride and ?H298.15=-24,350±400 cal/mole of vanadium carbide. Heats and free energies of formation of vanadium nitride and carbide were calculated to 2,000° K.

Jan 1, 1963

By Walter Kawa

The hydrogenation of phenyl ether, benzyl ether, and phenyl sulfide in the presence of iron catalysts was studied by the Bureau of Mines to gain a better understanding of the role of iron catalysts in the hydrogenation of coal. The carbon-oxygen and carbon-sulfur bonds in these compounds may be similar to some of the carbon-oxygen and carbon-sulfur bonds in coal which react during the early stages of liquefaction by hydrogenation. Experiments were made in batch autoclaves for 4 hours; hydrogen was at a pressure of about 540 atmospheres. In the hydrogenation of phenyl ether at 400° C, metallic iron catalyzed both hydrogenolysis (splitting-hydrogenation) and nuclear hydrogenation (addition of hydrogen to aromatic rings) reactions, Products were principally benzene and cyclohexane. The activity of metallic iron was decreased by adding carbon monoxide or a reactive sulfur-containing organic compound. Ferrous sulfide catalyzed the conversion of phenyl ether to benzene, phenol, and small amounts of cyclohexane. Hydrogenolysis of benzyl ether was catalyzed by metallic iron and to a lesser extent, by ferrous sulfide at 250° C. No nuclear hydrogenation was observed with either catalyst. Conversion of phenyl sulfide to benzene was nearly quantitative in experiments made at 250° C with equimolar quantities of phenyl sulfide and metallic iron or iron as ferric oxide. Conversions of metallic iron and ferric oxide to ferrous sulfide were nearly stoichiometric. No reaction of phenyl sulfide occurred in the presence of ferric oxide and water, and very little occurred in the presence of metallic iron and water. Ferrous sulfide also catalyzed the hydrogenolysis of phenyl sulfide to benzene, but conversion was lower than in experiments with metallic iron or ferric oxide. The activity of ferrous sulfide was increased by adding water and decreased by adding hydrogen sulfide. The results of this study suggest that ferrous sulfide is an active form of iron when iron is used as a catalyst for the hydrogenation of coal.

Jan 1, 1963

By Charles W. Huggins

Knoop hardness indentations were studied and measured with the electron microscope on TiB2, HfC, and A1B12 crystals. A detailed description of replicating the indentations using collodion and Faxfilm is made. A John Hopkins grating having 28,800 lines per inch was used to accurately determine the magnification used on the electron microscope. The primary objectives were to prepare carbon replicas of hardness indentations, to measure the indenations accurately, and to compare the results with those obtained with the light microscope. The resulting data showed excellent agreement between the measurements made on the replicas with the electron microscope and those made with the optical microscope. The replicas made from collodion showed slightly better agreement with the light optical values than did the replicas made from Faxfilm.

Jan 1, 1963

By H. W. Kilau

Thermodynamic calculations indicate that an electrochemical cell might serve as an analytical device for determining the composition of high-purity metals. An equation, readily derived, for the cell voltage, E, is as follows: [E I RT In F NFe unknown sample T of L NFe standard] The cell, however, must come to equilibrium, must be reversible, and must have no thermal effects or complicating side reactions whose magnitude is indeterminable. This Bureau of Mines investigation explores the feasibility of an electrochemical technique for the analysis of high-purity iron. Experiments were conducted using room-temperature aqueous cells and high-temperature molten salt cells. The room-temperature cells proved to be irreversible. The high-temperature cells utilizing FeCl2 and a eutectic mixture of KC1-LiCl were reversible, but did not attain a constant voltage necessary for analytical considerations.

Jan 1, 1963

By P. R. Tisot

Knowledge acquired from this research contributes to a better understanding of the physical structure of Green River oil shale and provides fundamental data and concepts that may serve to improve oil-shale technology. This study by the Bureau of Mines indicates that oil shale is a highly consolidated organic-inorganic system with no significant micropore structure, pore volume, or internal surface. This system is a form of physical structure that precludes rapid diffusion of either gases or liquids. The mineral matter consists essentially of nonspherical particles that tend to follow a log-normal size distribution. An excess of 99 weight-percent of these particles have equivalent spherical diameters of less than 44 microns--75 weight-percent are from 2 to 20 microns, and 15 weight-percent are less than 2 microns. The surface area (3 to 5 square meters per gram) of these mineral constituents is mainly external surface. The mineral constituents contain some micropore structure--pore radii ranging from 10 to 100 Angstrom--with the pore sizes randomly distributed. Distribution of the organic matter within the inorganic matrix is essentially interparticle and not intraparticle. The organic matter within the micropores of the mineral constituents is less than 4 percent of the total. Estimates made from surface area data suggest that perhaps only a small amount of the organic matter is bonded either physically or chemically to the mineral constituents.

Jan 1, 1963

By Arden D. Fugate

This work was conducted to determine a feasible process for converting siliceous fluoride offgases to a commercially usable product. The offgases were generated by pyrohydrolytic defluorination of low-grade fluorspar in a gas-fired rotary kiln, and fluorine was collected as a hydrofluoric-fluosilicic acid. A silicon-free fluoride solution for further processing was then produced by neutralizing the acidic scrubber solution with anhydrous ammonia, silicon being separated as orthosilicic acid. Ninety to ninety-nine percent of the fluorine originally present remained in solution as ammonium fluoride. Silicon was also separated from synthetic fluosilicic acids, having F-to-Si weight ratios ranging from 3.50 to 14.3. The solutions below a ratio of 4.06, the F-to-Si ratio of H2SiF6, containing dissolved silicon were desiliconized as completely as those containing less than the stoichiometric quantity of silicon. An electrolytic-grade cryolite was recovered from the ammonium fluoride solution by reacting with either sodium aluminate or alumina trihydrate and sodium hydroxide. A product containing 97 to 100 percent of the fluorine, represented by Na3A1F6, was recovered, and 94 to 99 percent of the theoretical yield was realized.

Jan 1, 1963

By W. W. Agey

Past investigations on waterborne impurities in the flotation process have been concerned primarily with the treatment of specific ores with particular local waters. Although some anions and cations present in water are known to react with flotation reagents, a definitive study has not been made on the effect of such common ions upon the flotation process. This report describes the fundamental research undertaken to define and measure the adverse and/or beneficial effects of different concentrations and combinations of several common anions and cations when oleic acid is used to froth-float limestone from a pulp of quartz and limestone. Research on the effect of waterborne impurities upon the flotation process was composed of two equally important phases. The first phase comprised development of a procedure for floating limestone from quartz that would give the same results in test after test. Some difficulty was encountered, but once such a procedure was developed, the second phase, comprising study and measurement of the effect of various ions c on to natural water upon the flotation of limestone, was quickly completed.

Jan 1, 1963

By Martin H. Stanczyk

Acid leaching of selected copper sulfide minerals, impure copper sulfide flotation concentrates, and a cement copper precipitate at elevated temperatures and pressures was investigated. Copper extractions of 97 to 99 pct were obtained by leaching chalcopyrite and the flotation concentrates with water under oxidizing conditions at 200° C for 30 to 60 min. In tests with bornite, chalcocite,and cement copper, addition of sulfuric acid or pyrite to the autoclave was required to obtain similar copper extractions. The chemistry of leaching copper minerals was studied. It was determined that different copper sulfides altered to covellite as one step in their dissolution.

Jan 1, 1963