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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 F. E. Brantley

Research was undertaken by the Bureau of Mines to assess the technical feasibility of smelting cement-copper precipitate in an electric furnace to produce commercial-grade copper. The blister-grade copper produced in smelting was refined by gaseous oxidation and reduction methods to rive a product equal in quality to fire-refined copper. The cement copper used in the study was typical of the material produced in commercial operations. The sample product was received in a partially oxidized state and analyzed 77.5 percent Cu, 3.4 percent Fe, 0.8 percent Pb, 0.05 percent Ni, 0.6 percent Sn, and 0.9 percent S. Smelting tests were made on the precipitate using laboratory-size induction and electric-arc furnaces. Three types of furnace linings were tested during, the investigation: Carbon, including graphite; clay-graphite; and silicon carbide. Although all proved satisfactory, either carbon or graphite was preferred because of their superior refractory properties and low permeability to molten copper. Copper recoveries in the induction and arc smelting tests averaged 92 percent in commercial-grade metal assaying 99.8 percent copper. Refining the molten copper by oxidation and gaseous reduction or by chlorine lancing increased the purity to plus 99.9 percent.

Jan 1, 1961

By R. Barany

This report contains the results of experimental work conducted by the Bureau of Mines to obtain the heats of formation at 298.15° K. of analcite, dehydrated analcite, lawsonite, anorthite, hexagonal anorthite, and leonhardite. Thermodynamic data for these minerals have applications in ceramics, extractive metallurgy, and particularly in geochemistry. Except for data on anorthite, no previous similar data existed. The present results will be a substantial aid in deriving the temperature-pressure-equilibrium relationships among these minerals. The heats of formation were determined by solution calorimetry, with hydrofluoric acid as the reaction medium. The results were expressed both in terms of the constituent oxides and in terms of the constituent elements. The heat of formation data were combined with related entropy values to obtain the free energies of formation at 298.15° K.

Jan 1, 1962

By K. K. Kelley

Thermodynamics data for silicates have applications in the fields of extractive metallurgy, ceramics, and geochemistry. To facilitate these applications, up-to-date tables of heats and free energies of formation are needed. It is the purpose of this report to supply such tables for anhydrous silicates. During the last 15 years the heats of formation of a substantial number of anhydrous silicates have been reliably determined at or near room temperature. This resulted from the development (first by the Bureau of Mines and later by the Geophysical Laboratory of the Carnegie Institution of Washington, by the Institute of Geology of the University of Helsinki, Finland, and by the Department of Geology of the University of Chicago) of accurate solution calorimeters, employing hydrofluoric acid as the reaction medium. Specific references to work of these laboratories will be made in the next section of this report. Also, entropy data at 298.150 K. and high-temperature heat-content values are available for many of these silicates, mainly owing to work of the Bureau of Mines. Most of these entropy and heat-content data have been compiled in Bureau of Mines Bulletins (13, 15).3

Jan 1, 1962

A spectrographic procedure applicable to the semiquantitative determination of 29 elements in tungsten is presented. The method is designed to give estimates of impurity concentrations up to 500 p.p.m. Limits of detectability range from 0.3 p.p.m. for the more sensitive elements to 100 p.p.m. for the less sensitive ones. Tungsten metal samples varying in particle size from minus 300-to 30-mesh are excited in the presence of 5 percent germanium with a direct current arc. Germanium acts to stabilize the arc, minimizes the volatilization of tungsten, and serves as an efficient carrier to sweep impurities from the tungsten into the excitation zone. Curves are presented that show the volatilization behavior of germanium, tungsten, and impurities in tungsten at different concentration levels. Data obtained were used as guides in establishing the method of analysis. In the absence of established reliable analytical procedures for determining many impurities in tungsten in the parts per million concentration range, the spectrographic method described here should prove to be helpful in evaluating high-purity tungsten.

Jan 1, 1961

By W. S. Landers

In contrast to the large fund of information available on the carbonizing properties of Eastern U.S. coals, the experimental data available for most Western U.S. and foreign coals are meager. To supply some self-consistent data, the Bureau of Mines conducted 220 low-temperature carbonization assay tests at 500° C. in a laboratory-scale carbonization apparatus. The results are included in this report. The U.S. coals tested are from Alaska, Arizona, Colorado, Illinois, Montana, New Mexico, North Dakota, Pennsylvania, Ohio, Texas, Utah, and Wyoming. Assays were also made on coals from Canada, Ecuador, France, Greece, India, Mexico, the Philippine Islands, Thailand, and Yugoslavia. In addition, one assay of pine sawdust and one assay of a peat from Ireland are reported. Prediction equations were developed relating the yield of products of carbonization obtained at 500° C. in the assay unit to the proximate and ultimate analyses of the coals. The equations for predicting the yields of tar plus light oil, char, and gas, and the heating value of the gas, are considered good, each equation having a multiple correlation coefficient of 0.90 or higher. The equation predicting volume of gas obtained upon carbonization is considered as fair, with a multiple correlation coefficient of 0.84. A reproducibility study of the assay made on 10 replicate samples of a subbituminous coal indicated that the standard deviation of the individual products was 0.31 percent or less.

Jan 1, 1961

By T. E. Gray

This report describes the preparation characteristics of the significant coalbeds in Boone County, W. Va., as determined by the Bureau of Mines. It is one of a series describing the coals suitable for producing metallurgical coke, either as mined or after beneficiation. Over 6.3 million tons of coal was produced in Boone County, W. Va., in 1959, of which almost 5.5 million tons was mechanically cleaned in eight preparation plants. On December 31, 1959, it was estimated that almost 8 billion tons of coal remained in the county in beds 24 inches or more in thickness. Thirteen samples were collected from nine coalbeds and washability tests were made on these samples.

Jan 1, 1961

By S. J. Gasior

Pilot plant studies showed the technical feasibility of fluidized-bed operation for producing hydrogen and synthesis gas by the steam-iron process. A mixture of iron and iron oxide from 20-to 100-mesh was partially reduced with a simulated producer gas and then oxidized with steam and/or carbon dioxide. Results of tests show the effects of pressure, temperature, bed height, gas-to-solids ratio, type of iron oxide, and composition of gas on the gas and solids conversions during reduction and oxidation. A baffled free-fall solids system was also found operable. The short residence time of about 5 seconds limited conversion of the solids.

Jan 1, 1961

By W. P. Haynes

The Bureau of Mines has been studying a modified steam-iron process using coal-derived producer gas for making either hydrogen plus carbon monoxide or methane. To provide a guide for this experimental study, compositions of equilibrium product gases for the reaction of steam plus carbon dioxide with iron were calculated and are discussed in this report. The calculations, which are described in this report, are based on thermodynamic data in the literature and cover temperatures from 800° to 1,300° K., pressures from 1 to 30 atmospheres, and hydrogen-to-carbon atomic ratios in the gas of 4 to 12. The equilibrium gas compositions are discussed in regard to making hydro-gen, carbon monoxide, and methane in the oxidation step of the modified steam-iron process. From the viewpoint of thermodynamics alone, assuming the reactions reach equilibrium, the discussion considers the effects of temperature, pressure, and composition of feed gas upon the composition of the product gas, the degree of oxidation of the iron, and the possible deposition of carbon. The results indicated the following: (1) Nearly all the carbon can be converted to methane at low temperatures (800° to 900° K.) and high pressures (over 20 atmospheres); (2) to obtain high yields of synthesis gas, high temperatures are required. For example, at 30 atmospheres, a temperature over 1,200° K. is required to convert 60 percent of the steam plus carbon dioxide to hydrogen plus carbon monoxide. Lower temperatures may be used at lower pressures) (3) oxidation of the iron increases with increasing pressure and decreases with increasing temperature; and (4) process conditions favoring carbon deposition were found within the range of variables studied, but it is thermodynamically possible to operate the oxidation process with steam and carbon dioxide outside this range of carbon deposition.

Jan 1, 1961

By Paul Meadows

This Bureau of Mines report presents operating practices and results of pressure maintenance and secondary recovery by water injection or by water injection supplemented by gas injection. Particular emphasis is placed on the results of water injection, which is the principal oil-recovery method employed in projects covered by this report. No attempt is made to study gas-injection projects or operations that are considered water-disposal projects. Also, this report does not include water-injection projects that have not been in operation long enough to evaluate results. Figure 1 is a map of north Louisiana showing the geographical locations of the projects included in this report. Most of the data used in this study were supplied by unit operators, operating companies, and the Louisiana Department of Conservation. Reservoir information and recovery data are generally those supplied by the operators, but include revisions where deemed necessary.

Jan 1, 1962

By J. J. Wallace

This report describes the initial phase of Bureau of Mines research in the hydraulic mining of bituminous coal. The mining site and equipment are described, and the test procedures and results obtained with a bar-mounted monitor are given. Tests showed that hard Pittsburgh-bed coal can be mined hydraulically from a solid face at water pressures of 4,000 pounds per square inch.4 Coal was penetrated to a depth of 4 feet in 20 seconds with 225 gallons of water per minute coming from a 3/8-inch nozzle at 4,000 pounds per square inch pressure. Some difficulty was encountered in cutting the binders occurring in the coal; it was not possible Lu penetrate directly the overlying draw slate.

Jan 1, 1961

By S. R. Borrowman

This investigation by the Bureau of Mines was undertaken to develop information on the extractive metallurgy of thorite ores because potential ore bodies of this mineral have been found recently in Colorado, Idaho, and Montana. Basic information on thorite ore treatment that would be useful in appraising the potential of these and other domestic thorium resources was developed. The work was done mainly on thorite ore containing 3.87 percent ThO2 from the Powderhorn district, Colo., and on a composite sample containing 0.52 percent ThO2 from the Wet Mountains district, Colo. Limited tests of d corroborative nature subsequently were made on a sample containing 2.30 percent ThO2 from the Lemhi Pass area on the Idaho-Montana border.

Jan 1, 1962

By S. R. Borrowman

Physical beneficiation, leaching, and solvent extraction investigations were made to recover a high-grade thorium oxide product from Bald Mountain, Wyo., conglomerate. The monazite in the Bald Mountain deposit contains 8.8 percent Th02 and, therefore, is higher in thorium content than the usual domestic or foreign monazite. A sample of composited drill cuttings for the study contained 4.3 pounds of monazite per ton of are. The work showed that the monazite, although unusually fine grained and friable, could be concentrated by tabling and magnetic treatment to yield a product assaying 5.65 percent Th02 with a recovery of 61 percent of the thorium. Subsequent decomposition of the concentrate by treatment with sulfuric acid and solvent extraction of the resultant solution with a primary aliphatic amine yielded a thorium oxide product of 99-percent grade.

Jan 1, 1962

By A. W. Henderson

The growing importance of halide metallurgy for preparing high-purity metals has stimulated research to extend halogenation reactions to the direct extraction of metals from low-grade sources. This Bureau of Mines investigation involves a pioneering study of chlorination reactions in the presence of a fluorine donor. Tin slags containing tantalum and columbium and a zircon concentrate containing a relatively high ratio of hafnium to zirconium were studied. Direct chlorination of these materials at 500° C. yields only a 5-percent conversion of tantalum and columbium or zirconium and hafnium to anhydrous chlorides. This investigation showed that small additions of calcium fluoride to the reaction increased the recovery of tantalum and columbium to 95 percent and the recovery of zirconium and hafnium to 27 percent. These results were achieved with ratios of calcium fluoride to mineral or slag of only 0.2. Silica, the major impurity in the materials studied, was found to be converted to silicon tetrafluoride during chlorination in direct proportion to the quantity calcium fluoride added to the charge. However, large additions of calcium fluoride decreased the volatility of the resulting halides of tantalum, zirconium, and hafnium. Smaller amounts of calcium fluoride also favored recovering minor metal constituents in the zircon concentrate (uranium, thorium, and rare earths).

Jan 1, 1962

By L. M. Burman

The phase-boundary pressure required to maintain a natural hydrocarbon fluid in a single phase must be considered in planning the recovery of reservoir liquids by miscible-phase processes. The change in the phase-boundary pressure at reservoir temperature that results when a light component or a mixture of light components is added to a reservoir fluid is an especially important consideration. The cricondenbar pressure (maximum phase-boundary pressure) and the critical pressure are unique correlated pressures that have been utilized to calculate the change in phase-boundary pressure that may result when the composition of a reservoir liquid is altered by an additive. In this study one reservoir oil and three gas-condensate fluids are used as examples. Correlations pertaining to the critical and cricondenbar states in chapters 4 and 5 of Bureau of Mines Monograph 10 (3)5 were used to demonstrate how butane and lighter components added to these reservoir fluids affect their phase-boundary pressures.

Jan 1, 1962

By Wesley Holmes

Concentrating, nodulizing, and smelting studies were conducted at the Albany Metallurgy Research Center of the Bureau of Mines to determine whether (1) western iron ores of the type found in the Carter Greek deposit near Dillon, Mont., could be utilized; (2) concentrates of acceptable grade with good iron recovery could be attained by wet-magnetic beneficiation; (3) nodulized concentrates could be smelted with reductants readily available in Montana; (4) iron concentrates could be smelted without prior agglomeration; and (5) high-purity iron could be produced directly from high-grade concentrates, Three small samples and two tonnage samples from the Carter Creek deposit were uniform in chemical composition, and their iron content averaged about 31 percent. They were found to be banded gneisses, and magnetite was the principal iron-bearing mineral.

Jan 1, 1962

By A. C. Rice

Investigation of a variety of mines to determine efficiency for rare- earth extraction has resulted in a solvent extraction technique wherein Primene 81-R,4 N-benzylheptadeeylamine (BHDA), and Primene JM-T give favorable extraction from sulfate solutions. Extraction from chloride, nitrate, and perchlorate solutions is negligible. Distribution coefficients for 10 rare-earth elements with Primene 81-R establish an extraction sequence beginning with lanthanum and proceeding through lutetium according to atomic number. Yttrium and ytterbium are exceptions in the extract ion sequence.

Jan 1, 1962

By M. I. Copeland

The investigation of the iron-gadolinium phase diagram is part of a project undertaken by the Bureau of Mines and sponsored by the Atomic Energy Commission to investigate rare-earth alloys. Data from the investigation of the iron-gadolinium phase diagram revealed a single eutectic system with very limited terminal solubility and three intermediate phases. The eutectic point occurs at about 85 percent gadolinium, and the eutectic isotherm, which occurs at 850° C., extends from the compound Fe2Gd to 99-plus percent gadolinium. Very little solubility of the solid phases in each other was observed. The three intermediate phases, FegGd, Fe3Gd, and FeaGd, melt incongruently at peritectic isotherms at 1,320°, 1,150°, and 1,080° C., respectively. The crystalline systems of the three phases were determined as follows: FegGd, hexagonal; Fe3Gd, hexagonal or rhombohedral; and FeaGd, face-centered cubic. No lowering or raising of the alpha-gamma iron transformation at 910° C., the gamma-delta iron transformation at 1,388° C., or the gadolinium transformation at 1,262° C. was observed. The principal methods used in determining the iron-gadolinium phase diagram were melting-point determinations, thermal analyses, metallographic examination, and X-ray diffraction analyses. Melting, heat treating, and thermal analyses were conducted in a vacuum or under a helium atmosphere because of the avidity with which oxygen combines with gadolinium at elevated temperatures. A few hardness values were determined, but they had no part in the derivation of the phase diagram. No other mechanical properties were determined.

Jan 1, 1962

By G. W. Birge

Carbonizing properties of the principal coal beds of Perry County, Ky., are described in this Bureau of Mines report. Seven samples, representing the Hindman, Flag, Haddix, and Fire Clay 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. Carbonizing properties of blends of Flag and Fire Clay coals, with 20 and 30 percent Pocahontas No. 3 low-volatile coal from McDowell County, W. Va., also were determined. Expanding properties of the Flag and Fire Clay coals and their blends were determined in the Bureau of Mines sole-heated oven. The Perry County coals tested are high-volatile A bituminous in rank and, with the exception of the Hindman-bed sample, which contained excessive sulfur, were chemically suitable for metallurgical use. The three coals tested in the sole-heated oven contracted less than normal for Appalachian coals of similar rank, Blending the Fire Clay and Flag coals with 20 or 30 percent low-volatile coal increased coke strength appreciably but increased the expansion beyond normal limits for industrial blends.

Jan 1, 1962