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By Gerald W. Elger

This report describes development of the fusion-leach crystallization precipitation process for producing a hafnium content feed material for hafnium-zirconium separation plants. Mixtures of zircon, potassium silicofluoride, and potassium carbonate (or potassium chloride) were fused to prepare soluble potassium zirconium hexafluoride-potassium hafnium hexafluoride salts. High extraction of these salts was obtained by countercurrent leaching the fused material in dilute hydrofluoric acid. About one-half of the hafnium was recovered in hafnium-enriched mother liquor by cooling clarified lead: liquor to crystallize most of the zirconium salt. Additional hafnium was recovered from the primary crystals in a multiple dissolution-recrystallization step. Hafnium-enriched oxides having a hafnium-zirconium ratio of more than three times that of zircon were precipitated from the combined mother liquors. The hafnium and zirconium recoveries in the precipitate were 83 and 24 percent, respectively. About 71 percent of the zirconium and the remainder of the hafnium were recovered in potassium zirconium hexafluoride crystals of low-hafnium content.

Jan 1, 1966

By C. W. Schultz

The vapor pressure of manganese in equilibrium with a series of liquid iron-manganese alloys was determined by the carrier gas method over a broad range of alloy composition. From these data the activities of manganese in the iron-manganese system were calculated. The system appears to be ideal.

Jan 1, 1966

By Francis X. Cannaday

The Bureau of Mines developed equipment to measure the sonic velocity of pulses transmitted through rock samples varying in size from laboratory specimens to mine pillars in place. Pulses are produced by electronically excited piezoelectric ceramic transducers. Special equipment components were developed by Bureau facilities; other components are commercially available. The technique permits a nondestructive, repetitive, stable, shaped pulse to be used in place of explosive caps or hammer blows. Longitudinal wave travel time measurements were taken on an oscilloscope screen; transverse wave measurements were taken under special field conditions. Results were consistently repeatable within the accuracy of the oscilloscopes utilized.

Jan 1, 1966

By V. E. Homme

Low- and high-temperature reduction techniques were employed by the Bureau of Mines in study of conditions favorable to the formation of massive titanium crystals. '1,1,2 low-temperature method, feeding molten sodium to solidified titanium lower chloride-sodium chloride, produced higher quality and high quantity crystalline metal. The percentage of crystalline titanium was increased with increasing reactor diameter, melt depth, and titanium dichloride concentration. The high-temperature technique, feed molten sodium to melts above 8000 C, producing needle-type crystals of lower quality and with less consistent results than the low-temperature method. Layers of titanium foil, sponge, fine needles, wool, and crusts of sin-tered granules were formed during the earl, -art of the low-temperature reduction, and massive crystals were produced beneath this barrier in the latter part of the reduction. Crystalline titanium having an average hardness of Bhn 76 and representing 58 percent of the total titanium was obtained. Lamellar crystals up to 1 1/2 inches long with a hardness as low as Bhn 54 were also produced. A second-stage reduction for reclaiming titanium from offgrade sponge is described. Titanium produced by this method was comparable in quality to that from sodium reduction of titanium tetrachloride.

Jan 1, 1966

By M. M. Wong

Salt mixtures consisting of KC1, BaC12, and HfCl4 with RbCl or CsCl were investigated as electrolytes for refining hafnium. The presence of RbCI or CsCl in the electrolyte appeared to suppress the volatility of. Best electrorefining was obtained with an electrolyte containing 50.7 percent KCl, 27.l percent BaCl2, 15.7 percent CsCl, and 6.5 percent HfCl4. In this electrolyte, hafnium metal with an average oxygen content of 470 ppm was produced from an anode feed containing l,600 ppm oxygen. All metallic impurities were lowered, except titanium, manganese, and tin.

Jan 1, 1966

By T. S. Chen

A study was made by the Bureau of Mines of the temperature and thermal stress distributions in thin circular disks subjected to peripheral thermal shock at various rates of heat transfer. The theoretical analysis is based on one-dimensional radial heat flow by conduction in the disk, and on heat exchange by convection between the disk and its surroundings. Preliminary experimental data obtained from shock tests on thin circular disks of basalt, quartzite, and taconite show reasonably good agreement with theory. The case of constant properties and plane stress is treated. Solutions of the stress distribution are presented for both cooling and heating shocks. The elastic energy stored at fracture is examined, and on this basis an average stress theory is formulated. Physical properties vital to the studies include thermal conductivity, thermal diffusivity, tensile strength, Young's modulus, and linear coefficient of thermal expansion. This work is of importance in predicting the thermal shock responses of a rock body of finite size.

Jan 1, 1966

By J. P. Hansen

Reducibility tests were run by the Bureau of Mines on an open hearth lump ore and four groups of pellets whose smelting characteristics had been deter-mined previously in the Bureau's experimental blast furnace. When reduction data from various tests were plotted on specially prepared paper l-(l-percent reduction/100)1/3 against time, the plots were linear. The iron-wustite inter-face therefore advances at a constant rate. The rate of the interface advance in mm/min was used as a reducibility index. The reducibility index measured at 900° C, using 0.45 cu ft hydrogen per minute varied inversely with the surface area of the sample. Even with carefully controlled surface areas, how-ever, duplicate reducibility indices varied considerably. When enough tests were run to give a stable mean, the mean reducibility index did correlate with blast furnace production for the four pellet groups. Results indicated that if the interface speed itself were to be used for correlation with blast furnace production, a sample size of about 180 grams of minus 0.742-plus 0.525-inch particles should be used with a test temperature of 900° C and a flow of 0.45 cu ft hydrogen per minute.

Jan 1, 1966

By Henry C. Meeves

The nonpegmatitic sources of beryllium in Arizona, Colorado, New Mexico, Utah, and four adjacent states investigated by the Bureau of Mines are described. The investigations included 155 properties from which over 6,200 rock samples were collected; more than 5,500 samples were analyzed by the nuclear beryllium-detection technique. Twenty-four of the properties examined had rock containing more than 0.10 percent BeO. Many of the beryllium determinations were made in the field with portable detection instruments by direct scanning of outcrops and by testing samples of rock brought to the instrument. The large domestic resources of low-grade nonpegmatitic beryllium ore in Utah, which were discovered by private enterprise and which respond favorably to small-scale treatment processes, may come into commercial use and thus reduce the dependence of the United States on imported beryl.

Jan 1, 1966

By Jr. Koch

Statistical methods applied at the Bureau of Mines Denver Mining Research Center to data from metallic ore bodies were used to evaluate lignite reserves from core data and to predict the extent of lignite horizons in some Texas lignite beds. Six lignite seam units were studied using data from 361 drill holes. The data indicate a total of 214.2 million tons of lignite in the area examined, and probable reserves of 113 million tons in an area 2,000 feet beyond the limits established by the drill holes. It was demonstrated that lignite reserves present in lenticular beds could be reliably determined by statistical techniques, and that core drilling could be optimized to maximum information with minimum drill holes. The technique described is applicable to other coal beds.

Jan 1, 1966

By H. J. Heinen

The Bureau of Milts studied repetitive batch electrowinning of molybdenum from molybdic oxide ) to determine the effects upon the electrolyte life, purity of metal product , and overall cell performance. The electrolyte consisted of 54.0 weight-percent sodium tetraborate (Na2B407), 23.6 weight-percent sodium chloride (NaC1), 14.9 weight-percent sodium fluoride (NaF), and 7.5 weight-percent Mo03. The feed materials were pure and technical-grade Mo03. Electrolysis was conducted at l,000° C in a graphite cell in an atmosphere of air and carbon oxides. Electrolyte degradation did not occur during repetitive winning of molybdenum from pure Mo03 in an 8-day (5,400-ampere-hour) period of operation. Electrowon metal contained <0.1 percent total impurities. The electrode configuration is a key factor in the direct conversion of technical-grade Mo03 to metal by repetitive cyclic electrolysis. The best configuration found was a cathodic crucible and a central anode. Metal purity of 99.8 percent and a current efficiency of 91 percent were maintained until the combined impurity buildup the electrolyte reached 4.7 percent silicon, l.0 percent aluminum, and 0.6 percent iron. One pound of molybdenum was produced per 1.5 pounds of solvent salts employed. About 25 percent of the initial NaCl and NaF contents of the electrolyte were lost owing to volatilization and crucible penetration.

Jan 1, 1966

By J. E. Tress

The Bureau of Mines prepared submicron tungsten powder by reducing tungsten hexachloride with hydrogen. The particle diameters of the resulting tungsten powders ranged from 0.015 to 0.046 micron. Within the limits of the variables investigated, no clear-cut correlation was found between process conditions and final size of the powder. Oxygen was the major contaminant in the product; being present both as an adsorbed gas and as suboxides of tungsten. Studies showed that the powder yielded compacts of approximately 45 per-cent of theoretical density when compacted mechanically. Low-temperature sintering produced more rapid densification in these compacts than in compacts prepared from conventional powders. Adding up to 20 percent ultrafine powder to conventional tungsten powder caused an increase in density upon compaction with maximum densification occurring at approximately 12 percent ultrafine powder.

Jan 1, 1966

By Lars Osen

The Bureau of Mines investigated (1) the effect of torsion on yield and ultimate strengths of bolts when the torsion is applied first and tensile load is applied independently of torsion and (2) various methods of increasing the tension-torque ratio and/or narrowing the data spread of the tension-torque relationship. A special torsional attachment was fabricated to attach to a universal testing machine to independently subject rock bolts to combined tensile and torsional loads. It was found that initially installed torsion is nullified during tensile loading and the tensile yield and ultimate strengths are not significantly reduced. Lubricating various components of a bolt assembly or using hardened washers will improve the tension-torque relationship during conventional installation; however, the torsional load is not nullified during this type of loading. Hence, a bolt is subjected to a combined stress throughout the loading cycle; the yield point will thus be lowered compared with the pure tensile yield if care is not taken during installation to stay below the torsional yield.

Jan 1, 1966

By M. H. Stanczyk

The Bureau of Mines made bench-scale laboratory tests on a sample of typical Florida phosphate slime to determine alumina and phosphate extractions obtainable by agitation leaching, by baking and curing, and by a leach-electrolysis scheme. Recovery of mineral values from leached slime pulps by resin-in-pulp ion exchange contact and the reaction of the leached pulps to filtration, flocculation, and settling were also investigated. The best extractions of alumina and phosphate were obtained by (l) agitation leaching with sulfuric, hydrochloric, or nitric acid at an elevated temperature or (2) curing or baking the slime with sulfuric acid. Alumina extractions ranged from 80.8 to 90.0 percent and phosphate extractions ranged from 93.3 to 98.4 percent when the slime was leached at 90° C with sulfuric, hydrochloric, or nitric acids. Baking the slime with sulfuric acid at 200° C for 4 hours yielded an alumina extraction of 92.3 percent and a phosphate extraction of 97.0 percent, whereas curing with sulfuric acid at 100° C for 24 hours gave slightly higher alumina and phosphate extractions. Flocculation and settling properties of the slime were virtually unaffected in all cases. Filter area requirements, although somewhat improved as compared to untreated slime, remained relatively high. The lowest filter area requirement obtained was 44 square feet per ton of dry solids treated per day. Contacting leached slime pulps with ion exchange resins depleted the leach pulps of solubilized values; however, the filtration and settling properties of the barren pulps were unaffected. A leach-electrolysis scheme resulted in some concentration of solubilized phosphorus, but the method showed little promise of being commercially feasible.

Jan 1, 1966

By P. E. Churchward

The Bureau of Mines developed a process using amines for recovering tungsten as ammonium paratungstate from alkaline leach liquors without producing synthetic scheelite as an intermediate product. Over 90 pct of the tungsten in low-grade scheelite or ferberite concen-trate was recovered as ammonium paratungstate by (l) autoclave leaching the concentrate with Na2CO3, (2) solvent extraction of the acidified leach liquor with kerosine solutions of either a quaternary amine (Aliquat 336) or a primary amine (Primene JM-T), (3) stripping the tungsten values from the quaternary amine with ammoniacal NH4C1 or from the primary amine with NH4OH, and (4) crystallization of ammonium paratungstate from the strip liquor. Reagent consumption in pounds per pound of W03 recovered was, for the quater¬nary amine, 3 Na2CO3, 3.5 H2SO4 , 2.2 NH4Cl, 1 NH3, and 0.4 glacial acetic acid; for the primary amine, it was 3 Na2CO3, 3.5 H2SO4, .06 NH4Cl, and 0.9 NH3. Both reagents extract molybdenum along with tungsten. Silicate and phosphate are partly extracted and contaminate the product; leach liquors containing these impurities require preliminary purification.

Jan 1, 1966

By C. L. Klingman

The Bureau of Mines tested eight commercially available, activated charcoals experimentally to compare the following characteristics: capacity for adsorption of nitrogen at 77° K and 170 atmospheres&apos; pressure, surface area, carbon tetrachloride adsorption capacity, hardness, and density. The nitrogen adsorption test was devised to simulate plant conditions occurring in the final step of purification in Bureau helium faciliti.es. The remaining tests were patterned after empirical acceptance tests that are widely used throughout the adsorbent industry. Surface area and carbon tetrachloride adsorption correlated well with nitrogen adsorption. The samples with low density generally had better adsorption qualities than those of higher density. The carbon tetrachloride test appeared to be the most practical for selecting a charcoal to be purchased, but an attrition, or hardness test should also be run to be sure the charcoal will not crumble in use.

Jan 1, 1966

By Stephen D. Hill

The Bureau of Mines devised and constructed a modified Knudsen effusion apparatus, permitting a constant measure of the weight of effusing vapor, to determine the equilibrium vapor pressure of metal halides at temperatures up to 1,200° K and over the pressure range 10-5 to 10-2 torr. The reliability of the apparatus was established by determining the vapor pressure of potassium chloride. After correcting for partial dimerization of the vapor, data obtained on solid KCl between 750° and 950° K can be expressed by the following equation:

Jan 1, 1966

By Jr. Norman

The Bureau of Mines investigated the thermoelectric properties of yttrium selenides and tellurides from room temperature to 900° C. X-ray crystallographic data were determined for the yttrium-selenium and yttrium-tellurium compounds that were orthorhombic with a cubic substructure. The yttrium selenides and tellurides exhibited semimetallic to insulator conduction properties with figures of merit of 10-9 to 10-4 °C-1. The mono-selenide and monotelluride behavior was partially degenerate; unsatisfied bonds were the source of the large number of charge carriers. The higher stoichiometry selenide compounds were intrinsic semiconductors) but with high electrical resistivities. A critical defect or impurity ionization energy for carrier activation appeared to exist in the majority of telluride compounds. Mobility and energy band determinations are required to interpret completely the observed effects in most of the compounds studied.

Jan 1, 1966

By J. G. Donaldson

Binary alloys of molybdenum and tungsten were prepared by the Bureau of Mines in laboratory-scale experiments by hydrogen reduction of their vaporized hexafluorides. Near-optimum deposition parameters were determined, and the nature of the deposited alloys was investigated. Dense, homogeneous alloys were codeposited between 650° and 750° C with a reduction efficiency of more than 75 percent. The alloy composition was uniform when the hydrogen ratio in the gas feed mixture did not exceed 3 times the stoichiometric requirement. Regulating the proportions of the metal hexafluorides in the gas feed provided a large degree of control over the composition of the deposit. Hardness of the deposits varied directly with the proportion of excess hydro,,,, in the gas feed and with the weight-percent of tungsten in the alloy. Hardness was not affected by deposition temperature over the range 650° to 750° C for specimens of similar composition. Extreme brittleness and unsuitable physical shapes of the alloys prevented tensile strength measurements.

Jan 1, 1966

By N. H. Coates

The Bureau of Mines determined average film coefficients of heat transfer for helium flowing through smooth, water-cooled tubes at Reynolds numbers of 5,000 to 25,000, helium inlet temperatures of 1,600° to 2,600° F, average temperature difference across the helium film of 800° to 1,300° F, and heat flux to 215,000 Btu/(hr)(sq ft). Since helium was the only gas used, the ranges of values for physical properties of the fluid are limited--thermal conductivity from 0.15 to 0.20 Btu/(hr)(sq ft)(O F/ft), viscosity from 0.082 to 0.104 lb/(ft)(hr), and Prandtl number from 0.63 to 0.68. Four equations, three of them dimensionless, correlate these coefficients with other properties of the helium--bulk temperature, film temperature, dimensionless parameters based on temperature, and the ratio of wall temperature to bulk temperature.

Jan 1, 1966

By A. A. Cochran

Bureau of MinesThe Bureau of Mines studied the development of practical methods for recovering manganese from the extensive domestic resources of low-grade ores and open hearth slags. A one-step operation was developed on a laboratory scale in which manganese and iron compounds are treated with chlorine, volatilized, and separated by selective condensation. Manganese recoveries of 90 to nearly 100 percent were obtained from 9 of the most important domestic ores. Analyses of the manganese chloride product indicated that it was suit-able for aqueous electrolysis with little additional purification. A complete, integrated process that provides for the recovery and recycling of chlorine is proposed. This process appears to have distinct advantages over previously proposed manganese recovery processes, and, in sharp contrast to leaching procedures, it is applicable to practically any manganese-bearing material.

Jan 1, 1967