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By P. C. Good

To meet a growing need for thorium metal of high purity and amenability to fabrication, the Bureau of Mines devised a method for preparing thorium metal by the reduction of thorium tetrachloride. Thorium tetrachloride was prepared by chlorinating calcined thorium oxalate with carbon tetrachloride. The crude thorium tetrachloride, containing oxygen-bearing compounds, was purified by a double vacuum distillation at 800 to 900° C., and thorium metal was made in the form of a dense sponge by the reaction of metallic sodium or magnesium with thorium tetrachloride at 800° C. Vacuum arc melting was used to consolidate the sponge metal to ingot form for evaluation of its physical and chemical properties.

Jan 1, 1960

By H. S. Caldwell

This report describes work by the Bureau of Mines on the vacuum distilla¬tion of some of the more volatile metals such as cadmium, zinc, and magnesium from lead and tin. Evacuation within a distillation apparatus allows rapid diffusion of vapor away from the evaporation surface and prevents reaction of the vapor with residual gases. A reduction of pressure to several tenths of a millimeter makes possible practicable distillation rates, at temperatures for which the partial pressure of the metal vapor exceeds 10-3 atmosphere. The rate and selectivity of distillation depend primarily on the volatility and molal ratios of the alloy metals, and their chemical activity to each other. For very rapid evaporation or low concentration of the more volatile constituent, the rate is determined by the rate of diffusion of the evaporating metal, to the surface of the melt. Cadmium, zinc, magnesium, and tellurium were found to volatilize readily from both lead and tin. Tellurium appears to volatilize as an intermetallic compound rather than the pure metal. Antimony could not be removed from lead at 1,000° C.; the condensate was nearly all lead. Antimony, bismuth, and lead were removed from tin.

Jan 1, 1960

By J. L. Konchesky

The technical feasibility of gasifying powdered, noncoking, low-rank coal with steam in an externally heated tube has been demonstrated. The tube, 112 ft. of alloy-steel tubing shaped into a helix, served as an electrical conductor of electricity used for heating. The effects of the following variables were studied: Residence time of coal in reactor, average reaction temperature, steam concentration, and rank or geologic age of coal. Reaction pressure was maintained in the range 19-26 p.s.i.a. High carbon conversions and large yields of synthesis gas were obtained with low-rank coal. In one test, for example, about 88 pct. of the carbon in a subbituminous C coal was gasified at 1,910* F. with a residence time of 1 sec. The gas contained 58 pct. H2, 19 COD 15 CO, and 3 CH4; the yield was 30 cu. ft. (at 32' F. and 14.7 p.s.i.) of synthesis gas (CO + H2) per pound of dry coal.

Jan 1, 1960

By James M. Stuckey

In a search for improved methods of upgrading tar obtained by low-temperature carbonization of coal, monoethanolamine (MEA) was found to be effective in extracting tar acids from coal tar distillates derived from a subbitunwous and a lignite coal. Patch extractions showed that both yield and purity of the extracted acids improved with increasing volume ratios of monoethanolamine to tar acid, varied from 1:4 to 8:1. Yield improved, but purity decreased as the concentration of monoethanolamine was changed from 30 to 70 volume-percent, and as the concentration of tar acid in distillate was increased ad from 14 to 45 percent. In a continuous countercurrent extraction employing a double solvent (monoethanolamine and hexane) approximately 80 percent of the tar acids was extracted from 170° to 350° C. tar distillate when using 1.6:1 volume ratios of amine:tar acids. Tar acids isolated from his extract, although of improved purity, contained appreciable quantities of neutral oils and some tar bases. Aqueous monoethanolamine was not effective for extracting the last 10 to 15 percent of tar acids in 170° to 350° C. distillate oil from lignite coal. The highest yield of isolated tar acids and the best recovery of monoethanolamine were obtained by diluting the extract with water and saturating with C02. Some losses of solvent were encountered when aqueous monoethanolamine solutions were heated through decomposition of the amine with the liberation of ammonia.

Jan 1, 1960

By George L. Gates

This report presents is an evaluation by the Federal Bureau of Mines of the effect of clay-water, brine, and oil-base drilling fluids on the productivity of test wells drilled on the Umiat anticline in U.S. Naval Petroleum Reserve No. 4 in northern Alaska. Eleven, wells were drilled on the Umiat structure as part of the U.S. Navy's extensive exploration of the Reserve during 1944-53 to determine the possibilities for oil production. The Federal Geological Survey cooperated in the exploration program and has published a comprehensive report3/ on the geology of the area and case histories of the wells. The re¬port also includes the results of special studies by the Bureau in connection with the drilling and coring of well 9 with oil-base mud in hole and was the source of much of the information used in preparing this publication. Of the eleven wells, four were drilled with rotary tools and water-base mud (one of the water-base muds was an oil-in-water emulsion mud), five were drilled with cable tools with brine in the hole, one was drilled with cable tools with brine in the hole and later reamed with rotary tools and crude oil, and one was drilled with rotary tools and oil-base mud. Although all of the wells penetrated sandstones that contained oil and gas, some were productive and others were not. The latter two wells, one completed with crude oil in the hole (with some added brine) and the other with oil-base mud, had the greatest productive capacities. The wells drilled with cable tools and brine in the hole had lower productive capacities. In contrast, two of three wells completed with rotary methods and fresh-water drilling mud and the well com¬pleted with rotary and emulsion mud were unproductive.

Jan 1, 1960

By M. G. Zabetakis

The use of liquid hydrogen as a high-energy fuel introduces numerous hazards not ordinarily associated with the use of other more conventional fuels. These hazards are attributable to the unique properties of hydrogen in the liquid and gas states (table 1). Since little work has been conducted on explosion and related hazards of cryogenic fuels, a research program was undertaken to obtain basic data on such dangers for hydrogen and other combustibles under these conditions. These data were used to outline emergency procedures for protecting personnel and equipment when an accidental spillage of liquid hydrogen occurs and to establish a quantity-distance table for the storage of this fuel. The vaporization of liquid hydrogen from a surface is treated as a prob¬lem in heat transfer theory. Two extreme cases are briefly considered: (1) The transfer of heat occurs at constant temperature drop between, the boiling liquid and the hot surface, and (2) the transfer of heat is limited by the rate at which it can flow to the surface from a hot insulating medium. The available data indicate that the former case (1) is applicable when vaporizing from a conducting surface and, initially, when vaporizing from an insulating medium; the latter case (2) is applicable after initial flash vaporization has occurred from the insulating medium. The vaporization rate determines in part the rate at which flammable hydrogen vapor-air mixtures are formed above a spill area. However, the rates at which heat is transferred to the vapor, and air is brought in contact with it also are of importance. Accordingly, the distribution of flammable mixtures above a spill area was determined experimentally. In general, flammable mixtures were found to be both above and within the visible vapor cloud.

Jan 1, 1961

By Wilbur I. Duvall

Surface vibrations of ground, rock, and structures resulting from blasting or other sources are often measured with portable seismographs. These instruments are usually supported by a three-point mount or tripod which is simply placed on a horizontal surface on which vibration levels are to be measured. The rigid-body motion of a tripod-supported seismograph is considered from the point of view that there should be no slippage of the feet with respect to the surface and none of the feet should leave the surface as a result of imparted motion. From these studies the following design criteria are deduced which assure that the seismograph will respond accurately to vibration levels as large as 1/2 g.:3/ First, the coefficient of friction between the feet and the surface on which the instrument rests should be as large as possible, preferably approaching unity; second, the center of gravity of the instrument should be vertically above the centroid of the three-point mount; and third, the vertical distance between the center of gravity of the instrument and the centroid of the three points of contact with the surface should be less than the perpendicular distance between the centroid point and anyone of the three sides of the triangle formed by the three points of contact. Portable seismographs that do not satisfy these conditions should be clamped to the surface if vibration levels above 0.1 g. are to be recorded.

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 K. K. Kelley

This report contains heat-content values for hexagonal crystalline germanium dioxide between 298.15° and 1,350° K., and for germanium dioxide glass between 298.15° and 1,800° K. experimentally determined by the Federal Bureau of Mines. No similar data for these substances are to be found in the literature. The heat-content and corresponding entropy-increment data are presented both in tabular form and by equations. Free energy of formation values are estimated for germanium dioxide glass at 298.15° and 1,800° K.

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 A. D. Hahn

The Federal Bureau of Mines examined ilmenite-bearing sands in southern Texas as part of a program to discover sources of supply for the domestic titanium industry. Deposits were examined from May 1956 through January 1959 in the outcrops of sandstone beds in the Jackson group of Eocene formations in Lee, Burleson, Fayette, and Starr Counties on the Gulf Coastal Plain; in alluvial valley fill in Brewster County in southwest Texas; in the sand beaches of Matagorda Peninsula and the Galveston, Padre, and Brazos Islands--part of the offshore chain of barrier islands along the Texas coast; and in unconsolidated sediments in Willacy County on the Rio Grande delta in the southeast Texas.

Jan 1, 1961

By John P. Powell

A comprehensive study of the effects of hydraulically fracturing water-flood wells in Oklahoma has been made by the Federal Bureau of Mines. This report presents results of that study and an analysis of some of the factors governing the results of fracture treatment on waterflood properties. Originally, hydraulic fracturing was used to stimulate oil production from old wells producing by primary methods, and its application to water-flooding was regarded with skepticism by most producers. However, since 1953 the number of fracture treatments of both oil and input wells in waterfloods has increased steadily. Hydraulic-fracture treatments in waterfloods have generally been successful in stimulating production from oil wells and increasing the rate of injection into input wells. Hydraulic fracturing has enabled several producers to turn probable failures into economically successful projects.

Jan 1, 1961

By A. D. Hahn

This report describes reconnaissance by the Federal Bureau of Mines of titanium-bearing sandstone in Kemper County, Miss. The purpose was to determine the ilmenite, rutile, and associated heavy-mineral content of black-sand-bearing Eocene deltaic formations" The investigation was part of a survey of titanium resources of the United States. Ilmenite (FeTi03), an iron-titanium oxide, is the major titanium-bearing mineral consumed in the titanium pigment industry. Rutile (Ti02), titanium oxide, is used mainly in producing welding-rod coatings and titanium metal. The fieldwork was conducted during the first half of November 1959. Seven holes, totaling 304 feet of bore, from which 64 samples of cuttings were taken, were drilled in the north-central part of the county; and two holes, totaling 172 feet of bore, from which 34 samples of cuttings were taken, were drilled in the southeastern part.

Jan 1, 1961

By E. G. King

Difficulty has been encountered in making thermodynamic calculations of metallurgical reactions involving interoxidic compounds of the ferroalloy elements because of the serious lack of most thermodynamic data for these substances. This Bureau of Mines report (the first of a planned series dealing with entropies of vanadates, tungstates, and molybdates) presents low-temperature heat-capacity data and entropy values at 298.15° K. for three crystalline sodium vanadates--metavanadate (NaV03), orthovanadate (Na3VO4), and pyro-vanadate (Na4V2O7). The results are combined with data for the constituent oxides and elements to obtain entropies of formation of the vanadates. Previous to this report only one vanadate had been studied Similarly, ammonium metavanadate.4/

Jan 1, 1961

By Alla D. Mah

Relatively pure aluminum nitride (AIN) recently has been prepared in sufficiently large amounts to permit a variety of experimental studies.4/ Several mechanical and chemical properties have been investigated, which show that this substance has good potentialities as a container for liquid aluminum, gallium, and boric oxide. The present work by the Bureau of Mines was undertaken to obtain thermo-dynamic data pertinent to the calculations regarding thermal stability and reactivity of aluminum nitride. The following measurements were made: (1) determination of the heat of formation from the elements at 298.15° K.; (2) determinations of the heat capacity over the temperature range 51° to 298.15° K. and the evaluation of the entropy at 298.15° K. therefrom; and (3) determinations of the heat content over the temperature range 298.15° to 1,800° K. These data are combined to obtain free energies of formation from the elements between 298.15° and 2,000° K.

Jan 1, 1961

By Marvin L. Whisman

This report describes the preparation of tritium-labeled organic compounds to be used by the Federal Bureau of Mines in studying the role of certain gasoline constituents in gum-forming mechanisms. The gasoline constituents that have been investigated boil within a range of approximately 90 to 230° C. and can be classified as paraffins. naphthenes, olefins, diolefins, monocyclic aromatics, polycyclic aromatics, and organic sulfur, nitrogen,: and oxygen compounds. The technique of Wilzbach has been applied to more than 50 samples. Purification techniques have been developed that accomplish rapid and effective purification as well as removal of labile tritium in a one-step operation. Data are presented to show the rate of exchange between tritium and hydrogen that can be expected for a variety of compounds common to a full-boiling-range gasoline. These values should be useful to other investigators using tracer programs involving tritium labeled compounds.

Jan 1, 1961

By John D. Corrick

Three species of chemosynthetic iron- and sulfur-oxidizing autotrophic bacteria have been isolated from the leaching waters of copper mining areas. These species are: The sulfur-oxidizing Thiobacillus concretivorus, the iron-oxidizing Ferrobacillus ferrooxidans, and a sulfur- and iron-oxidizing bacterium closely resembling Thiobacillus ferrooxidans, INTRODUCTION Among several suggested new processes for treating marginal ores in the United States, none is more intriguing than the possibility of extracting metals from low-grade materials by the action of microorganisms One phase of a Federal Bureau of Mines investigation toward developing such a procedure was to isolate and identify specific chemosynthetic iron and sulfur. oxidizing autotrophic bacteria native to certain domestic copper deposits where leaching is practiced. The bacteria or microorganisms considered important to this investigation are those capable of producing solutions of ferric sulfate and sulfuric acid. Solutions of this type are excellent solvents for some copper minerals By establishing the presence of these bacteria at certain copper-leaching areas, strength would be given to a theory that microbial activity is partly responsible for the oxidation that takes place at these areas. Their presence also advances possibilities for controlled use of microbial action in metal extraction processes. Leathen4/ has demonstrated that one of the chemosynthetic iron-oxidizing bacteria, Ferrobacillus ferrooxidans, can oxidize 200 parts per million of ferrous iron to the ferric state in 3 days,

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 A. S. Prokopovitsh

A spectrophotometric method for the determination of small amounts of copper in tungsten metal powder using the principle of solvent extraction has been developed by the Federal Bureau of Mines. The metallic sample is dissolved in hydrogen peroxide, tartaric acid added, the pH adjusted, and the excess peroxide destroyed by boiling. Copper is reduced to the cuprous state, and the reagent neocuproine (2,9-dimethy1-1,10-phenanthroline) is added to form a colored complex with the copper. This colored complex is then extracted into chloroform and the absorbance of the separated chloroform layer measured on a spectrophotometer. Copper contents as low as 1 p.p.m. (parts per million) can be determined. The method is limited to finely divided tungsten powder. The interest of the Bureau of Mines in developing more sensitive methods for the determination of trace impurities in high-purity tungsten prompted an investigation of the possibility of using solvent extraction-colorimetric methods. The organic reagents now commercially available make possible many extremely sensitive colorimetric methods for the determination of metallic ions. Extraction of the colored complex into a small volume of organic phase can be used to further increase sensitivity (4) .4/ This general approach has the added advantage that no special equipment beyond that normally found in an analytical laboratory is required.

Jan 1, 1961

By T. E. Gray

This report describes the preparation characteristics of the signifi¬cant coalbeds in Preston County, W. Va. It is one in a series of reports planned to determine coals suitable for the production of metallurgical coke, either as mined or after beneficiation. Over 2 million tons of coal was produced in Preston County, W. Va. in 190, none of which was cleaned mechanically. Estimates as of January 1, 1959, indicate that more than 3 billion tons of coal remained in the county in beds 12 inches or more thick. The Bakerstown, Mahoning, Upper Freeport, and Upper Kittanning beds were selected by the Bureau of Mines for study based on current production and estimated minable reserves. Sample locations were selected after study of the literature, conferences with mining engineers and mining company offi¬cials in the field, and examination of available sites. Four samples were collected from the Bakerstown and Upper Freeport beds and one each from the Mahoning and Upper Kittanning beds.

Jan 1, 1961