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By R. E. Lindstrom

Separation efficiency of a 4 percent divinylbenzene (DVB) resin is not altered over a wide range in temperature. A 12 percent DVB resin, however, exhibits a marked sensitivity to temperature. When flow rates are high at ordinary temperatures, 4 percent DVB resin exhibits higher efficiency, but at 200° F. both resins are equal in performance. Effective separation of rare-earth mixtures may be obtained with hydrogen as a retaining ion by maintaining column temperatures above the solubility of ethylenediaminetetraacetic acid (EDTA) in the free acid form. Slightly lower separation characteristics were obtained with this method as compared with copper as a retaining ion, Recovery of 99 percent of the EDTA from spent eluting solutions that contain copper has been accomplished by a calcium-copper displacement reaction followed by EDTA precipitation. Impurities in the product are correspondingly low. Recoveries of EDTA from holmium solutions with sulfuric acid are substantial; however, those from yttrium solutions are quite modest. Radiotracer experiments show the presence of approximately 0.1 percent yttrium contamina¬tion in the recovered material. The study presented is one phase of a broad research program designed to assist the technology of separating and purifying rare-earth elements.

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 Robert H. Merrill

Measurement of the deformation of a borehole in rock subjected to a change in applied stress can be used to calculate the magnitude and direction of the applied stress, provided a satisfactory deformation-applied stress relationship exists , In this investigation by the Bureau of Mines the deformation of a bore- hole in a rock model subjected to a known applied stress was compared with the theoretical deformation of a hole in an elastic, isotropic plate and was found to be in good agreement. Hence, this relationship can be used to calculate the applied stress on a borehole from borehole deformation measurements.

Jan 1, 1961

By Leonard Obert

Subsidence to surface occurs in a large proportion of underground mines. Preliminary to any indication of subsidence on the surface, there is usually a breaking up and sloughing of the cover into the mine opening which, in a period of time ranging from minutes to many years, progresses to the surface, This process is referred to as subsurface subsidence. In many mining operations, information regarding the process of subsurface subsidence is important, For example, if there are buildings or other improvements on the surface, or if the direction of the subsurface subsidence might threaten other underground workings--such as shafts--or if the subsidence might be progressing in a direction which would fall outside the anticipated subsidence limits, the problem could assume special significance.

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

By K. E. Tame

A resume of the history and state of the art of physical beneficiation of uranium ores is presented along with a detailed description of research on concentration of uranium ores by attrition grinding. The information on flotation, gravity concentration, electronic sorting, and selective grinding was gathered to complement the study of attrition grinding methods. Both dry and wet grinding procedures were investigated as potential methods of upgrading a variety of ore types, ranging in grade from 0.02 to 0.42 percent U308. A Mardun4 disintegrator that employs high-speed rotating paddles in a cylindrical shell lined with interrupter bars was used in most of the dry grinding studies. Attrition scrubbing devices, which impart a violent mixing or attritioning action to ore pulps, and cylindrical mills, employing rods or punchings as grinding media, were used in the wet grinding tests.

Jan 1, 1961

By J. T. McCartney

Thin sections of coal have been prepared for many years either by cutting on a microtome (1,2)5 or by grinding and polishing (2,1). Specimens of most coals had to be demineralized in hydrofluoric acid and softened in caustic solutions before they could be successfully cut with a conventional microtome. Some lignites could be cut without pretreatment. Jeffrey (1) obtained sections from coals of all ranks, although long and tedious pretreatment was required for anthracite. His sections were less than 1 cm.2 in area (probably much less for high rank coals) and about 5 microns thick. Thiessen (2) also cut sections of softened coals, mostly of low rank. His sections were a few square millimeters in area and about 3 microns thick. However, Thiessen preferred ground and polished sections for detailed studies because they were larger and had not been chemically attacked by softening media. He prepared ground sections as large as 4 cm.2 in area and usually 5 to 10 microns thick. Thousands of such sections, covering complete column samples of many coal beds, were studied for a number of years (4). With the development of the electron microscope and increased interest in quantitative optical studies of coals, a need for much thinner sections arose. However, no suitable technique for preparing such sections was known until Fernández-Morán developed a diamond knife for cutting ultrathin sections of hard materials (5). Workers at the Centre d'Etudes et Recherches de Charbonnages de France applied this new tool to the cutting of coal sections and have recently described their technique to the Burg, of Mines. Using their methods, with some modifications, researchers of the Bureau of Mines have succeeded in cutting ultrathin sections of coals ranging in rank from lignite to

Jan 1, 1961

By N. H. Coates

As part of a joint program of the U.S. Atomic Energy Commission and the Federal Bureau of Mines for using nuclear energy to supply process heat, the Bureau designed and constructed a pilot-scale simulated nuclear reactor system. Although workable components were developed,5 the simulated nuclear reactor could not be operated continuously at its design conditions of 2,500°F. and 250 p.s.i.g. because the refractory materials used for insulation deteriorated. Replacement of these materials with porous carbon permitted sustained operation at design conditions, and a 1,000-hour demonstration run was completed successfully. No serious operating difficulties developed during the test. Leakage of helium after 1,000 hours was only 3 to 4 std. c.f.h. Inspection after the run revealed no damage to any of the components. Including earlier runs during previous research5 the system has been operated about 4,000 hours, of which 1,120 hours have been at 2,500° F. or higher. The helium-recycle compressor performed satisfactorily with no main¬tenance whatever for 2,445 hours, with about 2,000 hours at 900° to 1,000° F.

Jan 1, 1961

By Charles Prasky

The objective of this investigation by the Bureau of Mines was to determine the response to sulfatization of diverse low-grade manganiferous materials in the iron formation of the Cuyuna district. In line with this objective a bench-scale sulfatizing procedure was developed that was less expensive and more rapid than pilot-plant methods. Samples from the central and south- western parts of the North range were tested. Results of evaluating a total of 46 pelletized samples, originating in areas with an estimated potential resource of 94 million long tons with a manganese content of 7 percent, indicates that approximately 87 percent of the manganese may be recovered as a synthetic manganese ore. This is equivalent to more than 12 million long tons of a metallurgical-grade ore, containing 46 percent manganese. It is anticipated that a premium product, containing over 50 percent manganese, may be obtained by sulfatizing procedures. This report is part of a continuing investigation5 6 of Cuyuna iron range manganese deposits in Crow Wing County, Minn. Lewis and coworkers describe the manganiferous iron formation in the bedrock of the Cuyuna district and include a description of a high-temperature differential sulfatizing process for recovering a ferrograde manganese product. The low-grade manganiferous

Jan 1, 1961

By Harry R. Nicholls

A simple economical method has been developed for determining the in situ longitudinal and shear velocities in rock from which its elastic constants can be calculated. By detonating small charges of high explosives in shallow drill holes near a free surface, both longitudinal and shear waves were generated simultaneously. Accelerometers and velocity gages mounted to the rock surface were used to record the arrival time for both waves over travel path lengths from 50 to 450 feet, Measurements were made in two rock types. From the arrival time measurements, the longitudinal and shear wave velocities were calculated. From these velocities and the density of the rock, the elastic constants were calculated. The dynamic elastic constants of drill core samples of the two rock types were determined in the laboratory by the resonant-frequency method, The lab- oratory and in situ elastic constants are compared and significant differences noted. In general, there is less spread in the in situ data than in the laboratory data, and Poisson's ratio does not fall outside the theoretical limits for the in situ data as is often the case for laboratory-determined elastic constants.

Jan 1, 1961

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 Charles B. Kenaban

The possibility of using ultrasonic energy as a tool to improve the electrolytic deposition of copper and zinc from several electrolytes was investigated by the Federal Bureau of Mines. Sound with frequencies of 20, 26, 38, and 400 kilocycles per second and acoustical intensities of 0.25 to 1.5 watts per square centimeter was employed. Measurements of cell voltage, anode and cathode current efficiencies, and electrode potentials were made at various current densities. Effects of ultrasonics on the quality of the deposit and on anode corrosion also was noted. In the electrolytic recovery of copper from an acid copper sulfate solution at 50° C., adherent, well-consolidated deposits are normally obtained up to a current density of 30 amperes per square foot. As the current density is increased above this value, the deposits normally become progressively more spongy and less adherent. Ultrasonic irradiation resulted in adherent and well-consolidated deposits at current densities up to 300 amperes per square foot. Radiation also produced smaller grain size and preferred orientation of the copper crystals. In addition, radiation caused as much as 3-volt decreases in cell voltages at the higher current densities. These decreases were caused chiefly by depolarization of the anode, although small depolarization effects were also noted at the cathode. Radiation apparently did not greatly affect cathode-current efficiencies, but prevented excessive anode corrosion at the higher current densities and resulted in more uniform corrosion. Ultrasonic radiation at a frequency of 400 kilocycles per second was not as effective as radiation at the lower frequencies. Circulation of the electrolyte at rates up to 5 percent of the cell capacity per minute did not produce results comparable to those effected by ultrasonic radiation. Rapid rotation of the cathode up to 1,800 revolutions per minute gave results approaching those obtained with ultrasonics.

Jan 1, 1961

By A. G. Starliper

Research was conducted by the Bureau of Mines to determine feasible roasting methods for the removal and the recovery of germanium, cadmium, and lead as enriched fractions from sphalerite concentrates. The two types of roasting processes studied were: (1) Batch, with a stationary bed, and (2) continuous, with a suspended bed, Results indicated that either method gave satisfactory metallurgical recoveries} but the continuous process is recommended because of inherent advantages. Final products were enriched fractions that could be treated by conventional methods for production of metallic germanium, cadmium, and lead. In the batch process, the concentrates were placed in a large tube furnace and heated at 1,080° C, an average of 3 hours. During the heating period, inert, reducing} or sulfur-laden gases were passed over the stationary charge to convey the sublimed metal sulfides from the hot portion of the tube to a lower temperature condensing zone at the end of the tube, where the metal sulfides were collected on baffles and recovered. In the batch and fluidizing roasting processes alike, the gases passed over or through the charge and served only as carriers for the sublimates and as suspension media in fluidization roasting. Since both processes depended on the volatilization, at relatively high vapor pressures, of the sulfides of germanium, cadmium, and lead, it was imperative that very little oxygen come in contact with the charge to alter the sulfide minerals. Germanium has a high affinity for oxygen, but in this instance it was buffered by being in solid solution in zinc sulfide.

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 D. Z. Hobbs

Because an economic method for preparing pure boron has not been developed, a program was started by the Bureau of Mines to evaluate existing techniques or to develop new methods for preparing the pure element. This report describes investigations directed toward the development of techniques for the preparation of pure boron by fused-salt electrolysis. Only two of the several fused-salt baths tested were satisfactory for the preparation of boron. These baths contained (1) potassium fluoride, lithium fluoride, potassium fluoborate and boron trioxide; and (2) potassium fluoride, potassium chloride, and boron trioxide. Of these two mixtures, the latter was more satisfactory. Elemental boron of from 90- to 95-percent purity and, in isolated cases, as high as 98-percent purity, was prepared from these two types of fused-salt baths. There appeared to be no distinct differences either in the yields or the purity of boron prepared at current densities ranging from 795 to 1,000 amperes per square foot. Current efficiencies were as high as 85 percent.

Jan 1, 1961

By K. K. Kershner

This report describes an investigation by the Bureau of Mines designed to provide background data for extending and improving the applications of chlorine metallurgy in extracting metals from ores. Optimum conditions are given tor chloridizing galena, sphalerite, and chalcocite by contact with chlorine gas. Petrographic and chemical analyses of the sulfides used in the experiments are listed. Graphs are furnished showing the extent of chloridization of each metal sulfide over the temperature range of the observations. In each case, the first tests were made with the reaction chamber at room temperature. This temperature was increased by regular increments in succeeding tests until the temperature was reached at which quantitative conversion of the sulfide to chloride was observed. The data are also plotted for screen-size fractions of the sulfide minerals investigated. Data show that the extent of metal chloride formation was affected by chloridization time, particle size of the sample, and usually, the temperature of the reaction chamber. At 300° to 400° C. an anomaly was noted for both galena and sphalerite. The temperature at which this anomaly was observed varied according to the particle size of the mineral. Comparisons are made between the chloridizing characteristics of the mineral sulfides and their chemically prepared counterparts.

Jan 1, 1961

By R. J. Leary

Significant improvements in surface conditions or mechanical properties of steels have been attributed by several investigators to ladle additions of small quantities of rare-earth metals or their oxides. To investigate systematically these effects in wrought and in cast plain carbon and alloy mechanical steels containing approximately 0.35 percent carbon, heats of four representative compositions were melted by the Bureau of Mines in a 4-ton open-hearth furnace. Each heat was cast into three sets of ingots to exemplify respectively, treatments with (1) rare-earth metals, (2) rare-earth metal oxides, and (3) an untreated set as a control. The development of melting, casting and rolling practices is described and discussed. Lance injection of oxygen shortly after melt raised the temperature of the metal immediately as much as 500° F., principally because mechanical agitation exposed the high-carbon metal to the flame and furnace root. An exceptional degree of superheat in the metal at the termination of the refining period was attributed to oxygen injection during the refining period. Bath temperatures higher than industrial practice were permitted by the all-basic furnace lining. Rates of carbon elimination as high as 0.036 percent carbon per minute were achieved by oxygen injections.

Jan 1, 1961

By Joseph Grumer

An instrumented spherical vessel has been used for many years to study laminar combustion waves. Concurrent measurements of flame speed and pressure-rise rates have led to evaluations of burning velocities, the pressure dependence of the burning velocity, and the expansion ratios of the gases passing through the combustion wave. For the most part, these studies have involved flames initially at atmospheric or subatmospheric pressure. The old spherical vessel used by the Bureau of Mines was not designed for use at elevated pressures. Moreover, being made of wrought iron, it was susceptible enough to corrosion to prohibit its use with many combustible mixtures that figure in industrial research. In mid-1956, under sponsorship of the Office of Naval Research, the Bureau undertook the development of a stainless steel spherical vessel capable of withstanding explosions of gaseous mixtures at initial pressures as high as 20 atm. and initial temperatures as high as 250° C. The design called for a double array (cross) of closely spaced small windows for observation of the flame as it traversed the vessel and a piezoelectric transducer to measure concurrently pressure-rise rates. Because no commercial contractor was willing to bid on the construction of such a vessel, it was built at the Bureau's Bruceton machine shop.7

Jan 1, 1961

By Willard L. Hunter

The Bureau of Mines smelted samples of chromite ore and concentrate from the General Services Administration (GSA) purchasing depot at Grants Pass, Oreg., in a submerged-arc furnace to establish smelting conditions and the energy requirement to produce high-carbon ferrochromium. Raw material, in the form of ore, flux, and reductant, and electrical energy are available on the Pacific coast to smelt the chromite. The concentrate can be smelted without prior agglomeration by employing hogged wood (wood chips) as a major portion of the reductant. The energy requirement is relatively low, about 3,960 kw.-hr. per ton of alloy. The ferrochromium produced will contain about 60 percent chromium. In addition to the smelting data, a statistical summary of the grade and amount of chromite purchased during the stockpile program and estimated chromite reserves and production volume are given. It is estimated that 632,000 tons of Cr203 contained in chromite of all grades is available in the western coastal States. Of this total there appears to be sufficient metallurgical-grade and beneficiable ore to sustain a smelting operation for 25 years at a consuming rate of 25,000 tons a year, utilizing material comparable to that delivered to the Government stockpile.

Jan 1, 1961

By T. N. McVay

The Bureau of Mines has developed a field test for detecting the presence of columbium in a variety of minerals containing the clement. The test consists of fusing the mineral or rock powder with potassium pyrosulfate in a porcelain crucible, digesting the melt with hot dilute hydrochloric acid to release the columbium oxide (Cb205), and subsequently reducing the columbium oxide to a lower oxide by adding tin, which gives a blue color to the contents of the crucible. The method will detect 1 percent of contained columbium oxide (Cb205) in a mineral sample provided no tungsten is present. If a mineral containing appreciable titanium is test,-!d in the same manner, the solution in the crucible becomes violet. In the presence of columbium, titanium at first causes a violet coloration of the solution, which after a few minutes is masked by the stronger blue of the reduced columbium oxide. Although tantalum oxide (Ta205) does not interfere with the columbium test, tungsten gives a blue color that is indistinguishable from the color obtained with columbium. A simple method is available to detect the presence of columbium in the absence of tungsten, but when the presence of tungsten is suspected, the sample must be subjected to somewhat more elaborate chemical tests to determine the presence or absence of columbium. Although these latter tests can be made in the field, several steps are involved that arc best performed in the laboratory with simple equipment.

Jan 1, 1962