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By D. J. Bauer

Solvent extraction techniques were used to determine the extraction sequence of yttrium and the rare-earth elements in an amine solvent extraction system. Single-stage extraction with Primene 81-R resulted in separation factors of 3.8 between yttrium and dysprosium and 25 between yttrium and cerium. Yttrium was concentrated in the aqueous phase. EDTA and DTPA, as aqueous phase counterextractants, enhance separation factors in mine-rare-earth sulfate systems. Yttrium separation from heavy rare-earth elements exhibits marked sensitivity to the position of yttrium in the selectivity scale of the rare-earth elements with the sequestrants. Yttrium-ytterbium separation is more effective with EDTA, whereas yttrium-dysprosium separation is more effectively increased with DTPA.

Jan 1, 1963

By L. J. E. Hofer

This Bureau of Mines study, part of a broad program of research in air pollution related to minerals, was conducted to determine the nature and extent of the poisoning of catalysts when used to remove certain air pollutants from exhaust gases. The poisoning examined in this investigation occurs when leaded gasoline is used as a fuel for automotive engines. This research was conducted in cooperation with the Public Health Service. The smog in the Los Angeles area is attributed to the effect of radiant energy on the mixture of hydrocarbons and nitrogen oxides found in the atmosphere there. A large portion of the hydrocarbons is believed to originate in the exhaust gases of automobiles. To prevent the escape of these hydrocarbons into the atmosphere catalytic mufflers have been proposed. In principle, these are simple and nonmechanical, consisting of a vessel charged with a catalyst capable of destroying the exhaust hydrocarbons by catalyzing their oxidation. However, these catalysts are severely affected by the particulate matter, mainly in the form of lead sulfate (PbS04), lead oxysulfate (PbS04.Pb0), and Lead chlorobromide (Pb(Cl,Br)2), contained in the exhaust gas. Deposition of lead on the catalyst as PbS04, PbS04, PbS0, and Pb(Cl,Br)2 restricts catalytic activity. As a result,after 20,000 miles of operation the temperature necessary to achieve 50-percent conversion of isopentane in a mixture of 0.2 percent isopentane, 2 percent carbon monoxide and 4 percent oxygen, and the balance nitrogen at 10,000 hourly space velocity has risen from 400° C. to 500° C. even with a catalyst taken from the exit portion of the catalyst bed. The rest of the catalyst was more severely affected. Therefore, it would appear that operation for 20,000 miles is near the limit for a catalyst.

Jan 1, 1963

By G. W. Birge

Twenty-eight samples, representing the Pittsburgh, Lower Kittanning, Stockton-Lewiston, Coalburg, Winifrede, Cedar Grove, Peerless, No. 2 Gas, Powellton, and Eagle beds, were carbonized by the Bureau of Mines--American Gas Association (BM-AGA) method, and yields of products and physical properties of cokes were determined. Expanding characteristics of 22 of the samples were determined in the Bureau of Mines sole-heated oven. The Kanawha County coals tested were high-volatile A bituminous in rank, with dry, mineral-matter- free fixed- carbon contents ranging from 53.9 to 66.3 percent. With few exceptions, they were chemically satisfactory for metallurgical use, and most of the coke-strength indexes were within the industrially accepted range for high-volatile blending coals.

Jan 1, 1963

By W. W. Weller

Low-temperature heat capacities of scandium sesquioxide (Sc203) and a mixture of cerium sesquioxide (Ce203) and cerium dioxide (CeO2) were measured over the temperature range from 50° to 298° K. The entropy of scandium sesquioxide at 298.15° K was evaluated directly as S°298.15 = 18.4 ± 0.1 cal/deg mole. That of cerium sesquioxide was extracted by combining the heat-capacity data for the mixture with those for pure cerium dioxide; the result was S298.15 36.0 ± 1.0 cal/deg mole.

Jan 1, 1963

By P. E. Churchward

Rhenium sources and recovery methods were investigated by the Bureau of Mines to delineate potential resources of the metal. The only significant rhenium resource appears to be about 28,000 lb of rhenium contained in the domestic annual output of approximately 20,000 tons of byproduct molybdenite concentrates from porphyry copper operations. An estimated 70 to 80 pct of this rhenium is potentially recoverable by processing the rhenium-bearing fumes and dusts obtained during conventional roasting of molybdenite concentrate. At 70 pct recovery this would amount to 19,600 lb of rhenium. A more conservative estimate by the Committee on Refractory Metals of the National Research Council (1513 is that 12,000 lb of rhenium metal could be produced annually from current production of molybdenite from porphyry copper operations in the United States. A procedure was developed in the laboratory for recovering rhenium in the form of electrolytic flake by electrowinning the metal from a solvent extraction strip solution. The procedure included (1) water leaching of molybdenite roaster flue dust, (2) selective extraction of rhenium from the leach liquor by contacting it with a kerosine solution of a quaternary amine, (3) stripping of rhenium from the loaded organic solution by a perchloric acid solution, and (4) electrodeposition of rhenium from the loaded strip liquor. Raw material for the studies was flue dust containing 0.48 pct Re, 35 pct Mo, and 23 pct S in sulfide and sulfate form, and small amounts of numerous metallic impurities. Water leaching dissolved 85 pct of the Re and yielded a solution that was 13 in sulfuric acid and contained, 1 g/l Re and 16 g/l Mo. The solvent extraction strip solution that was electrolyzed for rhenium deposition was 1 molar in perchloric acid and 1 molar in ammonium sulfate and contained 13 g/l Re and 0.01 g/l Mo.

Jan 1, 1963

By Walter C. Lorenz

Samples of materials containing pyrite from various coal mines and coalbeds were studied to compare their compositions and oxidizing characteristics. Pyrite was the only form of iron sulfide identified, but X-ray diffraction, emission spectrography, and microscopic analyses revealed similar suites of minerals and trace elements. The pyrite occurred usually in spherical clusters of very small crystals. The oxidation of pyrite in solutions of PeSO4 and Fe2(SO4)3 and in the presence of an iron oxidizing bacterium Ferrobacillus ferrooxidans, was studied through a manometric technique. FeS04 or Fe2(SO4)3 solutions had no appreciable influence on pyrite oxidation under the test conditions, The bacterium acted as a catalyst, greatly increasing the oxidation rates; however, in three samples that also contained calcites, bacterial oxidation was greatly reduced. The oxidation rates also increased approximately as the percentage of pyrite in the samples increased. For the series of samples studied, there was no definite correlation of the results with the location of the various mines nor with the acidity of alkalinity of the mine drainage.

Jan 1, 1963

By L. B. Pankratz

High-temperature heat-content values of pure lutetium sesquioxide and dysprosium sesquioxide were measured over the temperature range from 298° to 1,800° K. Similar data for cerium sesquioxide were calculated from measurements of a mixture of cerium sesquioxide and dioxide and known values for cerium dioxide. The results for lutetium sesquioxide are regular. Dysprosium sesquioxide has a minor thermal anomaly near 1,590° K, the extra heat absorption being 220 cal/mole, Hexagonal cerium sesquioxide undergoes a transformation around 1,050° K, which is only slowly reversible; consequently results were obtained for both the low- and high-temperature varieties. The original heat-content data are reported, and smooth values of heat content and the corresponding entropy increments are tabulated. Equations were derived to represent the heat-content values.

Jan 1, 1963

By C. L. Chaney

Investigations were conducted to develop spectrochemical methods capable of determining 0.01 to 100 micrograms of metals in 50 milliliters of solution. The use of gallium hydroxide (Ga(OH)3) as a carrier-precipitant to concentrate metallic ions is described. A porous-cup graphite electrode is used to collect the precipitate. A specially designed plunger permits the electrode assembly to serve as the sample-containing electrode in the subsequent spec-trographic analysis. Analytical curves are presented for antimony, arsenic, beryllium, and zinc. Sensitivities of detection are given for 13 elements. The techniques were applied to identify impurities separated from tungsten, to determine trace impurities in solutions containing high concentrations of magnesium, cobalt, or nickel, and to identify trace impurities in hydrofluoric acid. Laboratory glassware was a serious source of contamination when low levels of zinc were determined.

Jan 1, 1963

By Edward W. Parsons

Conventional rock-bolt anchors often fail when installed in weak formations. The purpose of this work was to develop an anchor that would utilize an explosive charge to secure anchorage in any type of rock. Laboratory work to develop a rock-bolt anchored by explosive forming was initiated using rock-bolt models which had a drilled explosive chamber and were composed of various metals. This was followed by the use of several types of seamless tubing which were expanded with a water-coupled explosive capsule. By attaching a length of solid bolt to the anchor tube, a prototype explosive-anchored rock bolt was made. More than 150 laboratory models were expanded during this phase of development, During two field tests in underground mines (A and B) and one in an open- cut mine (C), 87 explosive-anchored bolts, 9 slot-and-wedge bolts, 2 bolts anchored with expanding grout, and 28 expansion-shell bolts consisting of three types of shells were installed and subjected to pull tests. The field tests were run to determine the effects of variables such as the amount and placement of the explosive charge, design changes in the bolt, and the effect on anchorage of different pull-test techniques. The field tests revealed the following: Mine A. The explosive-anchored rock bolt was feasible, but changes were necessary in bolt materials and in some details of bolt design. Mine B. The design and materials of the bolt gave excellent results in hard fractured rock, but no information was obtained concerning variations in the dimensions of the anchor unit or in the explosive charge. Nine C. Varying the explosive charge to produce a beaded surface on the bolt tube and tightening of the anchored bolt before pull-testing were found to increase significantly the anchorage obtained in soft ground.

Jan 1, 1963

By R. Barany

The heats of formation of gehlenite and talc were determined by hydro-fluoric acid solution calorimetry. The results are reported in terms of the constituent oxides (?H298.15 = -31.1 ± 0.5 kcal/mole for gehlenite and ?H298.15 = -44.9 ± 0.3 kcal/mole for talc) and in terms of the constituent elements (?H298.15 = -952.8 ± 0.7 kcal/mole for gehlenite and ?H298.15 -1,415.5 ± 1.4 kcal/mole for talc).

Jan 1, 1963

By C. J. Thompson

Two sulfur compounds--the 2,2,5-trimethyl- and the 2,2,5,5-tetramethyl derivatives of thiacyclopentane--were identified in Wilmington, Calif., crude oil, using microdesulfurization and gas-liquid chromtography techniques.

Jan 1, 1963

By G. T. Krempasky

This report covers the installation and evaluation of lb reinforced concrete sets, 6 in each of 3 mines in the Goeur d'Alene mining district, Shoshone County, Idaho, and is the second of a series to determine the feasibility of a more permanent type of mine support. Closure measurements, where applicable, were made periodically of the concrete-set installations and were compared to the initial cross section of the sets. A different method of blocking was used at each test site; at one test site the type of blocking was changed several times during the test. Results from each test site are reported separately. No attempt was made to compare the cost of the concrete installations with the cost of other types of support used in the district. Such an evaluation of permanent types of support would require a longer period of time. At this time, tests are not complete enough to determine the applicability of underground concrete supports. However, results to date tend to confirm the general opinion that precast concrete mine supports could be used to advantage in openings that require support and must have long life, especially where decay of timber is an important factor.

Jan 1, 1963

By P. G. Clites

This study was undertaken to determine the effect of consumable-electrode vacuum arc melting on the properties of copper and to determine the applicability of the process to the production of cast shapes of copper. Ingots and castings were produced from electrolytic tough pitch copper (ASTM designation ETP), from electrolytic cathode copper (ASTM designation CATH), and from oxygen-free copper (ASTM designation OF). The products of this study were evaluated to determine the effect of the melting process on the removal of impurities from the copper and on the physical properties of the copper. The results indicate that consumable-electrode arc melting can be satisfactorily applied to the melting and casting of copper. Ingots prepared directly from electrolytic cathode copper contained slightly higher levels of impurities than are found in commercial oxygen-free copper, Excellent results were obtained with centrifugal castings of unalloyed copper, and reasonably successful static castings can be produced if proper mold and gating systems are employed.

Jan 1, 1963

By W. T. Abel

Laboratory tests were conducted with a closed, recycling system to evaluate the effectiveness of solid-in-gas suspensions as heat transport mediums. Micronized graphite in helium or nitrogen was circulated by a centrifugal compressor to determine the feasibility of the method and heat transfer capabilities of the mediums. Suspensions were circulated without plugging or eroding the compressor or piping. At low flowrates and light (0.1 to 0.2 volume-percent) graphite loadings, slightly less power was required to transport a given amount of heat with suspensions than with helium alone. Graphite deposition on the heat exchange surfaces of the cooler decreased the heat transfer effectiveness at higher solids concentration. Efforts to eliminate deposition are described.

Jan 1, 1963

By A. A. Cochran

The objective of the research was to determine the final distribution of cerium additions to steel, their effect on sulfide inclusions, and the usefulness of radiotracer methods in investigating steel problems. Fifty-gram heats of steel were prepared that contained either cerium 141 and nonradioactive sulfur, or sulfur 35 and nonradioactive cerium. These steels were studied by autoradiography, measurements of their surface radioactivities, optical microscopy, and chemical analysis. Samples of the crucibles were analyzed quantitatively for cerium or sulfur by radioactivity counting methods. The addition of cerium to steel melts reduced the size and number of iron sulfide inclusions in the resulting steel. A significant fraction of the sulfur and most of the cerium penetrated into the MgO crucible during the melting operation, The cerium inclusions in steel were identified as cerium sulfide. Radiotracer methods were found to be versatile and highly sensitive.

Jan 1, 1963

By M. J. Kovalik

The effect of oxidation by air at temperatures ranging from 200° to 390° C on the change of chemical and physical properties of Pittsburgh-bed coal was studied as a function of processing time and temperature. The goal was to prepare a nonagglomerating fuel from a strongly coking coal for use in continuous carbonizing processes and in fixed-bed gasifiers. The oxidized coal was carbonized in a bench-scale apparatus, and the coke strength was evaluated in a Roga tumbler. Strength of the coke was progressively reduced with time of oxidation until the coking power of the coal was apparently destroyed. Time requirements to obtain an essentially nonagglomerating product were inversely related to processing temperature. Gaseous products released from the coal during oxidation reduced the yield of the desired nonagglomerating product, which decreased with time of oxidation at constant temperature and with increase in processing temperature at equal time. Oxidation at a temperature slightly above the lower limit of the plastic temperature range of Pittsburgh-bed coal was most effective because of the short processing time required and moderate processing losses.

Jan 1, 1963

By Charles Prasky

This report describes fluidized bed techniques employed by the Bureau of Mines at Minneapolis to differentially sulfatize the manganese in two samples of low-grade manganiferous ferruginous carbonate slates from the Cuyuna Range district, Minn. Suitable mechanics of operation were established. A space rate of 1.25 to 1.5 fps, a retention time of 3 to 3.5 hours, a temperature of 700° C, and a 10 percent sulfur dioxide gas in air were adequate for sulfatizing the slates by fluidization. Under these conditions the overflow product removal rate from the 4-inch-diameter reactor was 4 to 5 pounds per hour. The sulfur dioxide was used more efficiently in the two-stage treatment than in the single-stage treatment. However, approximately 80 percent of the manganese was converted to sulfate by either treatment.

Jan 1, 1963

By R. E. Mussier

This investigation was made to study new methods to prepare high-purity yttrium metal, Various methods were used to prepare pure intermediate compounds, primarily chlorides, bromides, and iodides, which were subsequently reduced to metal. The process found most suitable for the preparation of pure anhydrous yttrium chloride involved thermal dehydration of a mixture of hydrated yttrium chloride and ammonium chloride while under vacuum. Yttrium bromide and iodide were prepared most effectively by the direct halogenation of yttrim carbide. Yttrim carbide was obtained by reacting and melting yttrium oxide-carbon mixtures in a carbon-arc furnace. Yttrium halides were purified by vacuum distillation and reduced by alkali or alkaline-earth metals. Lithium and sodium proved to be the best reductants from the standpoint of yield (>95 pct) and purity (>99.8 pct) of the yttrium. The product of the reduction step was sponge metal, which was consolidated readily by conventional cold-mold, arc-melting procedure. The purest yttrium obtained in laboratory scale work was prepared by sodium reduction of yttrium chloride and contained only 125 pp oxygen; other impurities did not exceed 1,000 ppm. In larger scale tests yttrium containing only 800 to 1,000 ppm total impurities was obtained by lithium reduction of yttrium chloride. The tensile properties of high-purity yttrium were determined. Mechanical tests showed that yttrium can be forged, extruded, rolled, spot welded, and deep drawn.

Jan 1, 1963

By L. H. Adami

This paper reports the results of solution calorimetry conducted to obtain the heats of formation of crystalline FeS04?6.952H20 and FeS04?1.008H20, from. which values were derived for the stoichiometric compounds FeS04?H20 and FeS04?H20. Also included are derived values of the free energies of formation and dehydration. This work was undertaken primarily to fill a need for data for pure, easily obtainable ferrous compounds that are suitable for use as calorimetric intermediates, The ferrous sulfate hydrates meet the essential requirements for this use.

Jan 1, 1963

By G. W. Birge

Carbonizing properties of the principal coalbeds of Elk, Clarion, Jefferson, Clearfield, and Centre Counties, Pa,, are described in this Bureau of Mines report, Twenty-six samples, representing the Upper Freeport, Lower Freeport, Upper Kittanning, Middle Kittanning, Lower Kittanning, and Brookville beds, were carbonized by the Bureau of Mines--American Gas Association (BM-AM) method, and yields of products and physical properties of cokes were determined. Expansion or contraction of the majority of the samples was measured in the Bureau of Mines sole-heated oven. Chemical analyses, agglutinating values, and free-swelling indexes are given for all samples. In this area the coals generally are characterized by high sulfur and moderately high ash content, and their suitability for metallurgical use would depend largely upon satisfactory cleaning. The samples from Elk, Clarion, and Jefferson Counties were high-volatile A bituminous In rank, whereas, most samples from Clearfield County and all those from Centre County were of medium-volatile rank. Coals from Clarion County had dry, mineral- matter-free fixed-carbon contents ranging from 56.5 to 60.3 percent and were weakly coking. With the exception of two samples which contained excessive ash, the medium-volatile coals of Clearfield and Centre Counties were strongly coking and, as indicated by sole-oven expansion results, would require blending with lower rank coal to avoid oven damage.

Jan 1, 1963