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By H. E. Peterson

Rhenium occurs in very small quantities (12).4 In order for the Federal Bureau of Mines to conduct an investigation of rhenium sources and methods of extraction, it was necessary to devise improved techniques for detecting and measuring minute quantities of the metal. A modification of the procedure of Malouf and White (46) was developed which can be used to detect rhenium in concentrations as small as 0.1 part per million and can be used to measure quantities of 1.0 part per million. It can be used for the analysis of siliceous and calcareous ores, of molybdenite concentrates, of fumes, of flue dusts, and of other metallurgical products. Development of the method involved devising an amine extraction procedure for separating rhenium from all interfering elements except tungsten and a selective distillation procedure for separating rhenium from tungsten. Adoption of these separation procedures permits use of large samples and precise determination of rhenium by colorimetric analysis of the thiocyanate complex of rhenium by means of a spectrophotometer.

Jan 1, 1961

By James Westfield

Following is a brief resume of the Division's activities that have had a favorable effect on health, safety, and the reduction of injuries at coal mines: 1. The Federal Mine Safety Code for Bituminous Coal and Lignite Mines of the United States was issued originally by the Director of the Bureau of Mines on July 24, 1946, after consulting with management and labor representatives of the coal-mining industry. The code has been used by Federal coal-mine inspectors while inspecting bituminous-coal and lignite mines as a basis for determining the existence of unhealthful and unsafe conditions and practices in these mines. A revised code was issued by the Secretary of the Interior on October 8, 1953, after further consultations with representatives of management and mine workers and was incorporated by reference in the 1952 and subsequent bituminous-coal wage agreements. The agreement of May 29, 1946, between the Secretary of the Interior, acting as Coal Mines Administrator under authority of Executive Order 9728, and the United Mine Workers of America, covering bituminous-coal and lignite mines in Government possession, charged Federal coal-mine inspectors with the responsibility of making periodic investigations of the mines and reporting to the Coal Mines Administrator any violations of the Federal Mine Safety Code. Federal coal-mine inspectors also had temporary authority to close mines found to be imminently dangerous, but such authority under Executive Order 9728 was removed on June 30, 1947, when Government control of the mines was terminated.

Jan 1, 1961

By R. W. Lewis

The Federal Bureau of Mines Boulder City Metallurgy Research Laboratory conducted experiments in order to develop a spectrochemical method for determining the concentrations of impurities In high-purity tungsten. This report presents a procedure, developed by these experiments, for determining 19 impurities in high-purity tungsten. Metal samples were thermally converted to the oxide, mixed with graphite, which was prepared and mixed with an internal-standard element, and excited in a d.c. arc. Sixteen of the impurity elements were determined with one set of conditions, using germanium as an internal standard. Lanthanum was used as an internal standard in the tests for boron and chromium. Molybdenum required the substitution of sodium chloride for the graphite and the use of copper electrodes. Data on the precision of the method are included in this report. The coefficients of variation vary considerably but average about 15 percent. Higher concentrations of impurities than those investigated may be determined with some modifications of the testing procedure, provided attention is given to the possibility of interelement interferences.

Jan 1, 1961

By W. M. Dressel

The objective of the research reported in this publication of the Federal Bureau of Mines was to devise a mineral dressing procedure that would concentrate zinc silicate minerals from certain deposits in southwestern Missouri. The best flotation results were obtained by batch laboratory flotation using sulfidizing agents and ethoxylated cocoamine. The flotation concentrate contained 70 percent of the zinc at a grade of 47.8 percent. Gravity concentration tests showed that 55 percent of the zinc could be recovered at a grade of 48.3 percent.

Jan 1, 1961

By Robert K. Koch

The reactions of alumina and alumina monohydrate with wet hydrogen fluoride gas were studied by the Federal Bureau of Mines to determine the feasibility of producing commercial-grade aluminum fluoride from offgases generated by pyrohydrolysis of siliceous fluorspars. The test results showed than an aluminum fluoride reactor operating at maximum efficiency could retain 96 percent of the fluorine contained in off-gases generated by pyrohydrolysis of siliceous fluorspar. The requirements are a reactor temperature of 200° C. and a reactor entrance gas containing 5 mole-percent hydrogen fluoride. Partial pressure equilibrium constants were determined for the reaction of alumina monohydrate and wet hydrogen fluoride gas from 200° to 350° C. and for the reaction of alumina and wet hydrogen fluoride gas from 350° to 700° C. Both reactions are reversible, and they proceed in directions that are dependent upon the temperature and the relative HF:H2O concentration. Logarithms of the equilibrium constants were used to plot the reaction isobars; these can be used to calculate the theoretical maximum efficiency of a reactor processing wet hydrogen fluoride gas between 200° and 700° C. The theoretical maximum efficiency decreases with increasing temperature.

Jan 1, 1961

By D. Bienstock

In connection with air-pollution studies, the Bureau of Mines is cooperating with the U.S. Public Health Service in investigating the use of solids for removing sulfur dioxide in concentrations of less than 0.5 percent from combustion and waste gases. Removal of sulfur dioxide at flue-gas tempera¬tures would no longer result in the cooling of scrubbed gas, which is inherent to liquid scrubbing processes used exclusively in industry today. Results are reported of extensive investigation, using metallic oxides as absorbents, adsorbents, and oxidation catalysts at 130° and 330° C. (temperatures at which flue gas may be treated in powerplant practice). The most active absorbents tested were the oxides of manganese, cobalt, copper, and alkalized alumina; 23 to 33 grams of sulfur dioxidn were removed by 100 grams of absorbent at 130° C., while scrubbing more than 90 percent of the sulfur dioxide from a simulated flue gas, and 19 to 61 grams of sulfur dioxide were removed at 330° C. A more detailed study is reported on absorption and regeneration, using manganese oxides and alkalized alumina. Adsorption of sulfur dioxide on activated carbons and molecular sieves at elevated temperatures is considerably less efficient than removal by absorption--a maximum of 7 to 8 grams of sulfur dioxide could be removed with 100 grams of adsorbent at 130° C. A potash-promoted vanadium pentoxide is effective in converting sulfur dioxide to trioxide; complete conversion in a simulated flue gas containing 0.35 percent sulfur dioxide was obtained at 365° C. Pilot-plant and cost studies are being made by the Bureau to determine the economic feasibility of removing on an industrial scale the sulfur dioxide present in gases in low concentrations.

Jan 1, 1961

By W. R. Huff

This report describes the development and operation by the Bureau of Mines of a pilot plant designed for using high-volatile A bituminous coal-in-water suspensions as a source of preheated coal and superheated steam in the pressure gasification of coal with oxygen. Figure 1 on page 2 is a block diagram of the integrated gasification process, in which a total of 70 tons of coal was fed from slurry and gasified. The present work included (1) development of equipment and methods both for mixing pulverized coal and water to produce slurry and for pumping and metering the slurry at gasification pressure; (2) development of equipment for heating the flowing slurry and, because slurry that can be pumped produces more steam than is necessary as a gasification reactant, developing equipment for removing and metering the excess steam; and (3) demonstration of the process under actual gasifier operating conditions, at a coal rate of about 800 pounds per hour and gasification pressures in the range 100 to 300 pounds per square inch gage. By using the forced-convection principle, a flow of slurry made from a caking, high-volatile A bituminous coal can be continuously heated to 600° F. in a coil-type heater. The flow rate and concentration of the slurry and the temperature gradient along the length of the heating coil must be closely controlled. In a radiant-type heater, involuntary reductions in flow rate, even momentary, can lead to coking and plugging of the heater coil.

Jan 1, 1961

By Arden D. Fugate

The Federal Bureau of Mines conducted extensive studies on solid-state defluorination (laboratory scale) and tests on molten defluorination (intermediate scale) of siliceous fluorspars. The studies were made to develop a pyrohydrolytic process for liberating fluorine from offgrade fluorspars. Test results showed that more than 90 percent of the fluorine can be evolved by solid-state defluorination at 1,300° C., and more than 97 percent can be liberated by molten-state defluorination at 1,420° C. Solid-state defluorination conditions were established by conducting tests on mixtures of ceramic-grade fluorspars and high-purity silica flour. Pelletized mixtures were defluorinated under varying conditions of time, temperature, and relative concentrations of silica, calcium fluoride, and water. The effects of adding various amounts and combinations of aluminum oxide and iron oxide on defluorination were also studied. Investigations of solid-state defluorination indicates that the following two reactions are involved: 2CaF2 + 3SiO2 = 2CaSiO3 + SiF4, and CaF2 + Sio2 + H20 = CaSiO3 + 2HF, The second reaction is dominant, although significant defluorination can be achieved by the first reaction.

Jan 1, 1961

By E. G. King

The work described in this Bureau of Mines report was undertaken to fill a need of industry for high-temperature heat-content data for uranium tetrafluoride. Without such data, heat balance evaluations of processes involving this substance are seriously hampered. Measurements of the heat content of uranium tetrafluoride were conducted at temperatures from 298° to 1,350° K. The melting point and heat of fusion were determined. The results are presented in suitable tabular form, and representative heat-content equations are included.

Jan 1, 1961

By F. E. Block

The metallic reduction of vanadium chlorides was investigated by the Federal Bureau of Mines as a possible new route for preparing vanadium metal in an effort to develop a production process that would be adaptable to large-scale plant production and would yield metal of uniformly high quality. Vanadium tetrachloride was usually prepared by chlorinating vanadium pentoxide in the presence of carbon. Although oxygen-?free tetrachloride was difficult to prepare this way, it could be prepared by the direct chlorination of vanadium carbide. Lower valent vanadium trichloride was prepared by the thermal decomposition of vanadium tetrachloride. Vanadium dichloride was also prepared by the thermal disproportionation of vanadium trichloride.

Jan 1, 1961

By C. P. Mabie

This report summarizes studies by the Bureau of Mines in developing a simple method for estimating the phosphorus pentoxide (P205) content of finely ground sedimentary phosphate ores and beneficiated products. The method used involved leaching, filtration, and precipitation. The Bureau found that measurement of the volume of ammonium phosphomolybdate precipitate obtained from samples containing 16.8 to 37.7 percent P205 and the use of an appropriate calibration curve permitted estimates of percentage of P205 content accurate within ± 1.1 to ± 2.6 percent, respectively, at the 95-percent confidence limits. Incidental to mineral dressing and petrographic investigations of western phosphate ores in 1959, the Bureau of Mines undertook development of a simple process-control method for rapid on-the-spot evaluation of phosphate-mineral recovery. Because of the fine-grained and obscure character of western phosphate ores, chemical, rather than microscopic or petrographic, techniques were investigated. The described method involves acid decomposition of the ore or product, filtration, addition of ammonium molybdate reagent to the filtrate, and centrifuging and measuring the volume of yellow ammonium phosphomolybdate precipitate produced.

Jan 1, 1961

By V. M. Benson

A simplified, routine method for determining lithium in lithium-bearing rock is presented. The sample is decomposed by repeated treatments with nitric, hydrofluoric, and perchloric acids. Since this procedure does not appreciably dissolve beryl, interference by beryllium (the principal interfering cation) is minimized for most samples. The salts are brought into solution with water and enough citric acid-ammonium citrate buffer is added to make the final volumetric dilution 0.20 M with respect to citrate. The addition of citrate greatly reduces anion interference in the hydrogen-oxygen flame, slightly increases the intensity of the lithium 671 millimicron emission line, and reduces the effect of most of the interfering cations to the extent that analytical separations are not necessary. The accuracy of results of single determinations of lithium in a pegmatite containing spodumene, lithium-bearing mica, and beryl are approximately equal to that obtained by other flame methods, INTRODUCTION This investigation was undertaken in Bureau of Mines laboratories to develop a reliable, rapid, routine analytical method for determining lithium in lithium-bearing minerals. The requirements of the procedure were that the method should be applicable to the analysis of a variety of lithium-bearing ores and test products, and the results would be reasonably accurate for materials containing 0.05 to 8 percent Li20.

Jan 1, 1961

By R. L. Montgomery

The heats of solution of erbium chloride in water and in hydrochloric acid and of erbium oxide in hydrochloric acid were determined. The results reveal a discrepancy of 10.5 kcal. per gram-atom between the heats of combustion and solution of erbium reported in the literature, the heat of combustion being more negative. The heat of combustion of erbium t4)4 and its heat of solution in hydrochloric acid (1, 18) have been reported in the literature. The heat of solution of erbium chloride was determined in two studies (2, 19). The present work was undertaken to check the reported heats of solution of erbium chloride and to determine the heat of solution of erbium oxide in hydrochloric acid. The latter quantity permits the heats of combustion and solution of erbium to be compared for mutual consistency. It was also desired to determine the degree of similarity between the thermochemistry of yttrium and erbium.

Jan 1, 1961

By M. F. Koehler

[THE LITERATURE contains relatively few thermodynamic values for interoxidic compounds, and these often are unreliable. This is especially true of data for ferrites and aluminates for which heat of formation determinations may involve extreme experimental difficulties. This report contains the results of new experimental work for obtaining the heats of formation of five ferrites (Ca2Fe2O5, CaFe2O4, MgFe2O4,, NaFeO2, and LiFeO2) and one aluminate (CaAl4O7), and a review and revision of previous similar work of this laboratory on five aluminates (Ca3A12O6,, 12/7 CaO-Al2O3, CaAl2O4, NaA1O2, and LiAlO2), The results for the 11 compounds are combined with entropy and high-temperature heat content data to derive tables of heats and free energies of formation (both from the oxides and from the elements) for the temperature range 298° 1,800° K, The relative stabilities of the compounds are discussed. The presented data all have application to ceramic reactions, and those for the calcium and sodium aluminates are applicable in considering soda-lime sintering processes for extracting alumina from silicate minerals such as day and labradorite.]

Jan 1, 1961

By T. T. Campbell

This report traces the development of techniques for the preparation of high-purity rare-earth metals. Rare-earth metals, excepting samarium, europium, and ytterbium, were prepared by converting their oxides to anhydrous chlorides or fluorides and reducing the rare-earth halides with active metals such as lithium or calcium. High-purity, anhydrous rare-earth chlorides were prepared by dissolving the rare-earth oxides in hydrochloric acid to form hydrated chlorides and by subsequently dehydrating the hydrated salts in the presence of ammonium chloride at temperatures ranging from 70° to 360° C. while under reduced pressure (50 microns to 1 inch Hg). The chlorides were also prepared by direct chlorination of rare-earth oxide-carbon mixtures. Reaction efficiencies in excess of 95 percent were obtained by either method; however, purer chlorides were prepared by the aqueous ammonium chloride conversion method. Purification of yttrium chloride by high-temperature vacuum distillation proved to be an effective method of separating, oxygen-bearing compounds from the chloride. Yttrium metal prepared from purified chloride contained significantly smaller amounts of oxygen (990 p.p.m. oxygen in yttrium metal prepared from raw chloride and 200 p.p.m. in that prepared from distilled chloride).

Jan 1, 1961

By Richard Havens

A flotation procedure was devised by the Federal Bureau of Mines for beneficiating Mount Wheeler, Nev., beryllium ores that contain the beryllium minerals bertrandite and phenacite in a complex association with calcite, fluorspar, mica, quartz, and other accessory minerals, The method also has proven to be effective in trials on ore from the Lake George, Colo., area. Samples used in most of the research ranged from 0.49 to 0.73 percent BeO. Beryllium mineralization varied from two-thirds bertrandite to all phenacite. An unusually high grade sample containing 5 percent BeO as phenacite was floated on a batch basis to prepare concentrate for utilization studies. The beryllium minerals were floated from undeslimed pulps at natural pH using sodium fluoride and sodium hexametaphosphate (HMP), as modifiers, and a fatty acid-fuel oil combination as the collector. Key factors were the use of a minimum of about 4 pounds of sodium fluoride and between 2 and 4 pounds of HMP per ton of ore. Efficacy of the HMP was related to the grind, mineralogical composition, corollary reagents, and type and time of conditioning. Addition of the fluoride, HMP, and collector in that order, followed by appropriate conditioning after each addition, was essential for satisfactory flotation.

Jan 1, 1961

By K. C. Dean

The combination of flotation and chemical processing methods presented in this report of the Bureau of Mines enabled treatment of typical low-grade ferberite ores from the Boulder County, Colo. area, to produce specification-grade synthetic scheelite. The overall recovery from ore to synthetic scheelite was 87 percent, based on a flotation recovery of 93 percent and a similar recovery in chemical processing. Preliminary mineral dressing studies revealed that the physical and mineralogical nature of typical ferberite ores precluded high recovery of tungsten in plus 60-percent-W03-grade products by these methods. Therefore, the flotation research was focused on attaining plus 90-percent recovery in a concentrate containing 10 percent W03. Detailed studies were made (1) to establish optimum grinding conditions for obtaining adequate mineral liberation, (2) to develop collecting and modifying reagent combinations that would enable controllable selective flotation, and (3) to define the influence of different pulp solids, temperature, pH, and time for conditioning and for the rougher and cleaner flotation stages.

Jan 1, 1961

By Ruth F. Brinkley

This circular summarizes the research and technologic activities and publications of the Federal Bureau of Mines Division of Explosives Technology4/ during fiscal year 1959 (July I) 1958-June 30, 1959). Part I briefly describes the programs that were active during the report period and presents a summary of some of the information not published elsewhere. In many instances the results are only preliminary and are subject to revision on the basis of continuing investigations. Detailed reports of all programs not security classified will be made later. Part II lists and describes briefly the publications of the Division during fiscal year 1959. If the published material has some bearing on activities still current during the report period, this is indicated by references in Part I.

Jan 1, 1961

By E. G. King

Sodium-aluminum and calcium-aluminum silicates are important rock-forming minerals. While many of them are of only theoretical interest, several are of practical importance--as ceramic raw materials and as potential future sources of aluminum. Heretofore, thermodynamic data for these minerals were incomplete; and in many instances missing data were difficult to estimate reliably. This has seriously hampered thermodynamic calculations pertaining both to the natural formations of these minerals and to their decomposition in sintering and fluxing reactions. This paper reports the results of the Federal Bureau of Mines measurements of low-temperature heat capacities of four crystalline silicate minerals--dehydrated analcite (NaAlSi2O6), hexagonal anorthite (CaA12 Si208), lawsonite (Ca2Al2Si2080?2H20), and leonhardite (Ca2Al4Si8C24?7H2O). It augments previous similar measurements of related minerals, which were summarized recently.4 The measured heat-capacity data were used to derive entropy values for the four minerals at 298.15° K. Some relations between these entropy values and those of other similar minerals were discussed. These relations illustrate the difficulty of estimating entropy values of tertiary (or higher) silicates.

Jan 1, 1961

By Edward J. Murphy

A comparative study has been made by the Bureau of Mines of several analytical methods for determining carbon monoxide and nitrogen oxides in toxic gases produced by the detonation of explosives. Laboratory and field methods and detector-tube devices are described. Analytical results are compared, and reliability of the various methods is discussed. INTRODUCTION In all underground mining there is ever-present danger to persons from possible overexposure to carbon monoxide and nitrogen oxides created by explosives or blasting agents. These health hazards, recognized for many years, led to the early establishment by the Bureau of Mines of specific requirements regarding fumes generated by explosives authorized for use in underground coal mines in the United States.3

Jan 1, 1961