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By Kenneth G. Broadhead

Four applications of radiotracer techniques in metallurgical research are described: (1) In electrowinning tungsten from scheelite, molybdenum 99 was used to detemine the molybdenum concentration of the fused alkali-phosphate bath and the electrowon tungsten; (2) an attempt to detemine the solubility of tagged ceric oxide in molten CeF3-BaF2-LiF was unsuccessful, but a high rate of cerium ion exchange was observed; (3) iron 59 was added to cerium during casting and used to follow the migration of iron during solid state electrolysis; (4) radiotracers were used in developing special analytical techniques applicable to high-purity rare-earth metals produced by molten salt electrolysis.

Jan 1, 1963

By R. F. Zaffarano

Reservoir oil in the Greater Aneth area, Utah, part of the Paradox basin, was studied to detect variation in oil characteristics within the reservoir and to determine its relation to age of accumulation and fluid equilibrium. At least three subsurface oil samples were obtained from each of the four largest of five field divisions comprising a producing area of 45,000 acres. Height of the oil column in the Pennsylvanian Desert Creek zone is about 230 ft. In general, the oil characteristics were found to be uniform across the area, and averages were developed for use in engineering applications. Average saturation pressure was 1,780 psia; the oil was undersaturated at the initial reservoir pressure, 2,200 psia. Variation in saturation pressure shows a lack of complete fluid equilibrium and continuing diffusion of solution gas from the main body of the reservoir to two extensions linked by narrow arms. By assuming early accumulation, the time involved in this diffusion process was calculated to be about the same as the age of the reservoir formation. Cause of the concentration of gas in the main body is attributed to differential entrapment during accumulation of oil and gas from an exterior source.

Jan 1, 1963

By K. K. Kelley

The heats of formation of two lead vanadates (Pb2V207 and Pb3V208) and manganese vanadate (MnV206) were determined by hydrochloric acid solution calorimetry, supplementing previous Bureau of Mines measurements of the vanadates of calcium, magnesium} and sodium. Heat and free energy data for 11 vanadates were assembled on a common basis. The stability of comparable vanadates (with respect to the oxides) increases in the following order: Magnesium, manganese, lead, calcium, sodium.

Jan 1, 1963

By L. B. Pankratz

High-temperature heat-content values of gallium and scandium sesquioxides were measured over the temperature range from 298° to 1,800° K. The results fill gaps in the thermodynamic information for these compounds; no previous similar data existed. The heat-content values were combined with heats and entropies of formation to obtain free energies of formation of gallium and scandium sesquioxides to 2,000° K. The thermodynamic stabilities of the sesquioxides of aluminum, gallium, scandim, and yttrium were compared.

Jan 1, 1963

By P. A. Wasson

The investigation described in this publication was conducted by the Bureau of Mines to determine the effectiveness of the anionic silica flotation method on goethitic iron-bearing materials from the Cuyuna Range, Minn. Samples used in this investigation were a composite of drill core from 13 holes, and 3 samples from lean ore stockpiles. These samples are believed to be typical of the mineralization occurring in an area with a potential reserve of several million tans of submarginal iron ore. Results from batch tests showed that the iron-bearing minerals could be effectively concentrated by flotation removal of the siliceous gangue. The drill hole composite yielded laboratory flotation concentrates from locked tests containing 56.8 percent Fe and 6.1 percent silica, with an accompanying iron unit recovery of 94.2 percent. Concentrates containing 52.4 to 53.7 percent Fe also were produced from the lean ore stockpile materials; corresponging iron recoveries ranged from 71 to 79 percent in the batch tests, with the possibility remaining for additional recovery of iron from the middlings.

Jan 1, 1963

By W. L. Anderson

Standard tellurium analytical procedures were modified to obtain the greater sensitivity needed to support a survey of tellurium resources by the Bureau of Mines. Resulting volumetric and spectrophotometric methods for determining tellurium in all types of tellurium-containing materials are described. Sample decomposition and preliminary separations of interfering selenium, gold, and silver are the same in both procedures. The volumetric method is applicable to samples containing a minimum of 10 parts per million of tellurium, In this method the tellurium is reduced to elemental form, and the colloidal suspension is titrated with 0.01 normal iodine solution. The weight of sample for analysis, from 0.25 to 10 grams, should be selected so that the sample contains 0.1 to 5 milligrams of tellurium. To insure accuracy, duplicate samples should be run and the results averaged, particularly on samples of low tellurium content: The limit of determination is 0,001 percent tellurium, which is equivalent to 0.1 milligram of tellurium when using a 10-gram sample. The spectrophotometric method is particularly applicable to low-tenor materials containing from 0.5 to 50 parts per million of tellurium. Up to 10 gram samples are required for making accurate determinations in the low-concentration range. The sample used should contain between 5 and 100 micrograms of tellurium. The turbidity of a colloidal suspension of tellurium prepared from such a sample is determined in a spectrophotometer .t at a. wave-length of 440 millimicrons, and this value is compared with those of standard samples containing known amounts of tellurium.

Jan 1, 1963

By A. S. Peck

This report presents the results of a cooperative study between the Bureau of Mines and the University of Utah to define the mechanism involved in the adsorption of oleic acid and sodium oleate on fluorite, calcite, and barite, using an infrared spectrophotometer for identifying and measuring the adsorbed reagents and reaction products. Fluorite, calcite, and barite react with oleic acid and sodium oleate in a water system, forming chemisorbed and solution products. The chemisorbed species is a surface mineral cation-collector anion salt, Chemical analysis of solution resulting from the adsorption reaction indicates that the adsorption process causes displacement of mineral anions, namely, fluoride, carbon ate, and sulfate from the surface of these minerals.

Jan 1, 1963

By A. C. Rice

Aminopolyacetic acid chelating agents were added to separatory-funnel-scale solvent-extraction systems to determine the effect on separating rare-earth elements. Average values for separation factors between adjacent elements obtained with Primene JM-T2 increase 36 percent when EDTA is added to the aqueous phase. Adding HEDTA or DCTA also improves separation factors for certain rare-earth elements. Percentage of extraction and the separation factors exhibit marked sensitivity to concentrations of amine, chelating agent, and hydrogen ion. The chelating agents improved separation in Primene JM-T, BHDA, and Primene 81-R extraction systems.

Jan 1, 1963

By W. T. Benson

The nickel-bearing laterite deposits in the Pine Flat and Diamond Flat areas, Del Norte County, Calif., were investigated by the Bureau of Mines to determine the extent and nickel content of the two deposits and the amenability of the ores to metallurgical treatment. The work was based on drill-hole sampling and metallurgical tests in which attrition scrubbing and sizing, reduction roasting, and magnetic separation were used. Results of the sampling indicated that the deposits are comparatively small and are marginal or submarginal in grade. Metallurgical tests showed that no separation of cobalt from nickel and iron was made by sizing; however, a large portion of the chromium was separated. Reduction roasting and magnetic separation did result in upgrading the iron, nickel, and cobalt, and the simultaneous rejection of chromium.

Jan 1, 1963

By B. K. Shibler

A highly flexible laboratory-scale fluidized-bed reactor was designed, constructed, and successfully operated continuously at temperatures up to 1,300° C during an investigation of thermal methods for decomposing gypsum. This report discusses briefly the many problems encountered in developing the 10-inch-diameter reactor and describes its design and construction in sufficient detail to enable other research organizations to build a comparable unit. The reactor consists of a 10-inch-inside-diameter vertical tube which can be varied from 6 to 10 feet high; it is formed from 2-and 3-foot sections of silicon carbide pipe. The tube is surrounded by a 3-inch heating space formed by an outer 4.5-inch-thick circular wall of insulating firebrick. A cone-shaped fluidizing chamber is bolted to the bottom of the reactor. Fluidizing gas enters through the bottom of the cone, and ore is introduced by means of a screw feeder connected to an inlet located just above the gas port. A silicon carbide overflow tube of 1.25-inch inside diameter extends upward into the reactor. The depth of the bed is controlled by substituting different lengths of overflow tube. Twin dust-recovery systems, each composed of a cyclone and Fiberglas filter, are attached to two gas outlets at the top of the reactor tube. The reactor is designed for research on both exothermic and highly endothermic reactions. It can be fired externally by means of four natural gas burners that jet tangentially into the annular space at the base of the reactor. Alternatively, it can be fired internally, using a mixture of air or oxygen and natural gas as the fluidizing medium. A separate instrument panel contains flowmeters, manometers, an automatic program controller, and a multiple-point recorder for printing a record of the temperatures measured by thermocouples located at critical points in the reactor.

Jan 1, 1963

By Hal J. Kelly

A number of problems that developed in processing the halloysitic clays of eastern Washington and northern Idaho were investigated by the Bureau of Mines. The deflocculating effect of tetra sodium pyrophosphate is compared with several other compounds, and on the basis of current theory, the advantage of sodium pyrophosphate as a deflocculating agent is explained. The adsorption of the sodium ion by clay in a clay"-water system was established by a radioactive tracer technique, and the deflocculating action of sodium pyro- phosphate was postulated. The effective dispersion of the halloysitic clays was limited by the occurrence of tightly bound aggregates of small, individual crystals. Disaggregation of the agglomerates was investigated by liquid extrusion and ball milling of dilute slurries and by extrusion of the clay in a plastic state. The greatest increase in the production of small particles was by high? pressure liquid extrusion.

Jan 1, 1963

By F. D. Stevenson

A metal diaphragm pressure relay system was constructed to measure vapor pressures of the metal halides, oxyhalides, and other substances at temperatures up to 700° or 800° C. The vapor pressure of arsenic (III) oxide (As2O3) was determined to verify the reliability of the apparatus for such measurements. The data for the liquid AS2 Os (2820 to 4830 C) are represented by the equation, log Pmm = 6.875 - 2,929/T, from which the normal boiling point was calculated to be 461° C. The heat of vaporization calculated from this equation was 13.40 ±0.09 kcal/g mole As4OS and is essentially constant over the interval studied. The melting point of the octahedral arsenic (III) oxide was determined to be 278° C from the inter-section of the solid and liquid vapor pressure curves, A thermal analysis apparatus is also described by which melting and transition temperatures could be checked by a method independent of vapor pressure data. The melting points of the monoclinic and octahedral forms were determined to be 314.4 ±1.4° C and 278 ±5° C, respectively.

Jan 1, 1963

By P. A. Bloom

Bureau of Mines research was conducted to develop effective separation methods that might be used in exploiting substantial tonnages of complex barite-fluorspar ores in Arizona. The exploitable reserves now may be increased as recent batch and continuous flotation tests demonstrated that a complex barite?-fluorspar ore from the Red Chief deposit, Yuma County, Ariz., could be selectively treated to concurrently produce (1) fluorspar and (2) a barite byproduct of marketable grade. The sample contained 24.8 percent CaF2 and 24.3 percent BaS04. Processing comprised production of a fluorspar product containing 97 percent CaF2 with an 82 percent recovery, using a sodium fluoride-lignin sulfonate-fatty acid reagent combination. Concurrent retreatment of the fluorspar tailing, using sodium cetyl sulfate as a collector, yielded a barite product of 94 percent BaS04 grade with a 71-percent recovery. The products met specifications for acid-grade fluorspar and drilling mud-type barite.

Jan 1, 1963

By W. A. McKinney

Bureau of Mines Research has demonstrated that it is technically feasible to segregate oxidized copper ores by use of a direct-fired, refractory-lined rotary kiln. Previously, the segregation process had been effected only in much more complicated indirect-fired, stainless steel kilns, The method comprises heating crushed ore premixed with small quantities of salt and carbonaceous material, such as coke, to about 830° C to produce copper as fine flake and metallic films on the surface of the coke particles. After grinding of the cooled furnace calcines, the copper is recovered by conventional flotation. During direct-fired segregation it was necessary to closely control the air-gas mixture in the burner. Good copper recoveries were obtained only when adding air in the limited range of 1.15 to 1.2 times the theoretical amount required for combustion of the natural gas. Batch trials of the new technique on quartzite-, limestone-, sandstone-, and limonite-type oxidized copper ores containing from 1.4 to 6.2 percent copper yielded flotation concentrates containing from 3.7 to 45 percent copper, representing 84 to 95 percent recoveries. Analyses of the furnace gases showed that loss of copper by volatilization was negligible. The preliminary direct-firing segregation studies were complemented by continuous runs on the quartzite ore, containing 1.4 percent copper, in an integrated segregation-flotation pilot plant having a 60 pound-per-hour capacity. In a typical test, 84 percent of the copper was recovered in a cleaner flotation product containing 25 percent copper. The study will be continued to further delineate the conditions for good segregation as effective use of standard ceramic-lined kilns will render the process more attractive from a commercial standpoint.

Jan 1, 1963

By John J. Mulligan

The Bureau of Mines investigated coal deposits at Mount Gran (latitude 76°59' S, longitude 161°07' E), Victoria Land, Antarctica, during the austral summer of 1959-60 as part of the continuing U.S. Antarctic Research Program, which is under the auspices of the National Science Foundation. The coals and associated rocks were measured, sampled, and analyzed. Five coalbeds, ranging in thickness from over 10 feet to scattered fragments of coaly material in sandstone, occur in a sandstone-coal series overlying a series of crossbedded red-buff sandstones. Both series are part of the Beacon group of sediments, and both show some evidence of pressure metamorphism. The sandstones are poorly cemented and are composed dominantly of rounded and often frosted quartz grains. The sediments have been broken and uplifted by a series of massive diabase sills. The broken nature of the sediments precluded an estimate of the amount of coal present. The Mount Gran coals are highly attrital banded anthracites and semianthracites that have most commonly a moderately dull luster but do include bright bands. Coal in contact with or near diabase intrusives is partly graphitic but shows no evidence of coking. Apparently the coal was beyond coking rank before emplacement of the adjacent intrusives. Fragments of the plant Glossopteris indica found with the coal suggest Permian age but do not prove it. The coals appear to be derived from plant remains that collected in shallow basins; individual coalbeds would tend to be lenticular bodies that formed in different places as the dominantly sandy sediments were deposited. The wide distribution of coal indicates that coal-forming conditions prevailed over much of the continent; the great thickness of Beacon sediments indicates that similar conditions may have persisted through a long period of geologic time. Generally similar coal deposits may occupy widely separated stratigraphic positions.

Jan 1, 1963

By Albert W. Deurbrouck

This report describes the preparation characteristics of the significant, presently producing coalbeds in Mercer County, W. Va. Approximately 650,000 tons of coal was produced in Mercer County, W. Va., in 1960, of which over 630,000 tons was cleaned in four preparation plants. In 1960 the Pocahontas Nos. 3, 6, and 11 coalbeds supplied 99.5 percent of the total coal mined in the county. Because the number of working mines In this county was small, only six samples were collected; four of which were of metallurgical quality as mined. The remaining two samples could be upgraded by washing at suitable specific gravities. Many of the samples taken were of metallurgical quality as mined; however, the float-and-sink analysis on these coals has been included to point out their amenability to the production of premium quality, special purpose coals. In general the coals were low-volatile bituminous in rank with low ash and sulfur contents.

Jan 1, 1963

By Frank A. Peters

A series of evaluations is being made to determine the relative processing costs of producing metallurgical-grade alumina from low-grade aluminous materials. These evaluations include the estimated operating and capital costs as well as recommendations for additional research and development to improve the processes and to lower their costs. The design for each process is based on published work. The three processes considered in this evaluation are designed to leach alumina as aluminum sulfate from calcined clay with sulfuric acid and to remove the silica residue by filtration. The filtrate from leaching is then purified by one of the following methods: Removal of iron in electrolytic cells using mercury cathodes; removal of iron by chemical precipitation through the formation of an iron-manganese complex; or precipitation of the alumina from an aqueous-ethanol solution, leaving iron in solution. Both the operating and capital costs for these processes are higher than those for the Bayer process. For plants producing 1,000 tons of alumina a day, the estimated operating costs per ton of alumina are: Electrolytic iron-removal process........... $81.35 Chemical iron-.removal process............... 82.08 Ethanol purification process............... 86.17 The investment in mercury is not part of the operating cost since this cost is considered equivalent to catalyst cost which would not be shown. The estimated capital investments for 1,000- ton-per- day plants on a Marshall and Stevens chemical equipment index basis of 240.0 are: Electrolytic iron-removal process...... $116,775,500 Chemical iron-removal process............... 99,418,900 Ethanol purification process................ 94,210,200 These investments include the working capital but not the land for each of the processes. Included in the electrolytic iron-removal process is an investment of $4,859,400 for mercury. Investigation of other methods for removing iron, of the decomposition operation, and of the leaching operation could reduce these costs.

Jan 1, 1963

By L. W. Higley

Procedures were developed for reclaiming high-temperature alloy scrap in the form of standard cobalt-base alloy. A cobalt-base, multicomponent, high- temperature alloy, such as S-816, can be successfully melted from scrap, and its specified chemical composition can be retained. Induction furnace melting in a controlled atmosphere was used to obtain ingots that were subsequently fabricated by impact forging to provide specimens for heat treatment and testing. Of the numerous metal elements in S-816 alloy, only small quantities of molybdenum were lost in the melting operation as finally developed. Test results indicated that the scrap material, after melting, forging, and heat treatment, was equivalent in room-temperature tensile strength, in high-temperature creep and stress-rupture properties, and in chemical composition to commercially produced S-816 alloy made from virgin material.

Jan 1, 1963

By Robert M. Doerr

Isothermal oxidation kinetics were determined for three grades of Ni and for 99.99 percent Co in Ca and in air from 800° to 1,200° C. The oxidation reactions followed approximately the parabolic rate law. For 99.99 percent Ni in 02 at 1,200° C, the parabolic rate constant was 2 mg cm-2 hr-2. For 99.99 percent Co in dry air, the constant ranged from 1 mg cm-2 hr-2 at 800° C to 18 mg cm-2 hr-2 at 1,200° C; for 99.99 percent Co in 02 the constant was 2 mg cm -2 hr-2 at 800° C and 10 mg cm-2 hr-2 at 1,000° C. For 99 percent Ni in dry air, the constant ranged from 0.2 mg cm 2 hr-2 at 800° C to 3 mg cm 2 hr-2 at 1,200° C. By X-ray diffraction measurements, only divalent oxides were found in the scales. Volumetric and quartz-helix gravimetric methods were used. The volumetric apparatus was designed to permit less stringent restrictions on the corrosion specimens; it was also more convenient to use. The agreement between the weight gain determined gravimetrically and the 02 consumption determined volumetrically was not good enough for direct comparison of gravimetric and volumetric results.

Jan 1, 1963

By Robert C. Johnson

Water-swelling fluormicas and fluormontmorillonoids were synthesized and described. They were found predominantly in the system Mg0 - MgF2 - Si02, with varying amounts of Li+ or Na+, Some water-swelling synthetic minerals were prepared with only strontium or lead in the twelvefold position, Water- swelling compounds containing either K+ or Ba+ were not found. The synthesized water-swelling products were shown by electron microscopy, X-ray diffraction, and chemical analysis to be typically two-silica-layer, platy compounds, Except for the complete substitution of fluoride for hydroxyl, the compounds were similar to the natural micas or montmorillonites. The stability and properties of the compounds were further established by electrodialysis, by differential thermal analysis, and by anion and cation exchange methods. Fluoride in the interlayer positions was nonexchangeable except through decomposition of the product. Exchanging the sodium or the lithium of the synthetic fluormicas or fluormontmorillonoids with potassium ion, particularly those derived from KOH provided a product from which a completely inorganic paper of extraordinary flexibility was fabricated. This paper had excellent mechanical and electrical properties except for water adsorption and a high power factor. Neither of these problems was solved during this investigation. However, papers with dielectric strength from 1,500 to 5,000 volts per mil were readily fabricated, particularly from the lithium containing fluormicas or fluormontmorill onoids.

Jan 1, 1963