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By V. F. Swanson

As part of the Bureau of Mines titanium resources examination program, samples of altered rock (saprolite) and unaltered rock from the Roseland anorthosite near Roseland, Nelson County, Va., were tested for amenability to beneficiation by flotation. A flotation technique was developed to produce bulk concentrates of ilmenite, rutile, sphene, and leucoxene. It was necessary to first float apatite using oleic acid as the collector, in an alkaline pulp with dextrine as a titanium mineral depressant. The titanium minerals could then be floated from the apatite tailing, using fluosilicic acid to depress the remaining apatite, morin to depress ferromagnesian minerals (when present), and oleic acid as the collector. A bulk titanium mineral concentrate, analyzing 66.0 percent Ti02 and 0.08 percent P205, was obtained from a sample of the unaltered rock which contained 5.45 percent TiO2 and 2.81 percent P205. Overall recovery in the concentrate was 47.1 percent of the total TiO2 in the ore. About 55 to 65 percent of the saprolite sample was clay and was removed by attrition scrubbing and decantation. The apatite prefloat procedure was applied to the saprolite sands; subsequent titanium mine: 1 flotation recovered 72.2 percent of the Ti02 in a bulk concentrate containing 65.1 percent TiO2 and 0.20 percent P205.

Jan 1, 1962

By E. G. King

An earlier Bureau of Mines report4 provided low-temperature heat-capacity and entropy data for three sodium vanadates. This report continues the study of vanadates by presenting analogous data for three crystalline calcium vanadates - calcium metavanadate (CaV206), calcium pyrovanadate (Ca2V2O7), and calcium orthovanadate (Ca3V208). No similar data for these compounds have been published previously. MATERIALS All three vanadate samples were prepared by the Bureau of Mines by heating stoichiometric mixtures of reagent-grade calcium carbonate and vanadium pentoxide.5 Calcium metavanadate was prepared at 610° to 660° C. A stoichiometric mixture was heated for 17 days with intervening grindings, mixings, and adjustments of composition, as shown necessary by chemical analysis. The final analysis gave calcium oxide, 23.48 pct. (theoretical, 23.57 pct.) and vanadium pentoxide, 76.32 pct. (theoretical, 76.43 pct.). The sample also contained 0.11 pct. acid-insoluble matter. The X-ray diffracton pattern showed no lines of free calcium or vanadium oxides. No X-ray diffraction patterns were found in the literature for any of these substances.

Jan 1, 1961

By L. M. Irwin

This Bureau of Mines investigation relates the physical properties of copper reverberatory furnace slags to changes in composition, The smelting of upper Michigan copper ore presents some problems that probably differ from those of other copper smelting areas. The study of these problems has, however, provided important data regarding slags in general and therefore will be of value to other operations as well. Conclusions reached from this study were: (1) Slag fluidity and refractive indices varied directly with the iron content and inversely with silica, lime, and alumina, and (2) there was no apparent correlation between slag fluidity and its copper content.

Jan 1, 1962

By J. H. Holden

Operations involving the processing of coal, oxygen, and steam into synthesis gas by means of two pressure-type gasifiers have demonstrated the effect of heat loss and operating variables on carbon gasified and oxygen and coal requirements. Carbon gasified is the fraction of carbon in the coal that is converted to gas. Oxygen and coal requirement is the quantity of each that is needed to produce a unit volume (M std. c.f.) of carbon monoxide and hydrogen. Operating pressure of the gasifiers ranged from 150 to 300 p.s.i.g. and coal was fed at 200 to 500 lb./hr./cu.ft. of reaction-zone space. Oxygen-to-coal ratios were 8.5 to 10.5 std. c.f./lb. Heat loss and residence time have opposite effects on carbon gasified; increasing the heat loss decreases the carbon gasified, but increasing the residence time (by raising the operating pressure or reducing the coal-feed rate) increases the carbon gasified. The effects of these two factors are difficult to separate because they usually change simultaneously. A comparison of the results obtained from the operation of two gasifiers with different levels of heat loss, however, permitted the effect of heat loss to be separated from that of pressure and coal-feed rate. When the results were deter- mined on the basis of constant heat loss, increase of the residence time increased the carbon gasified until the reaction virtually had come to completion. For example, at 150 p.s.i.g., decreasing the coal-feed ratio from 500 lb./hr./cu.ft. to 200 lb./hr./cu.ft. substantially increased the carbon gasified. At 300 p.s.i.g., however, changing the coal-feed rate had little effect on the carbon gasified because the reaction had almost reached completion and further increase in residence time resulted only in a negligible change.

Jan 1, 1962

By M. E. Tyrrell

To promote greater use of abundant domestic raw materials in the manufacture of synthetic mullite, the Bureau of Mines has undertaken a comprehensive investigation to determine the effects of the impurity oxides TiO2, Fe203, and alkali on physical properties of sintered mullite-forming mixtures. The first part of the report presents the results of work covering a major area within the mullite study; namely, the effect of impurity oxides on volume stability, one of the outstanding characteristics of mullite refractories. The volume stability of 20 compositions in each of 3 alumina- to-silica ratios, which blanket the range commonly found in purchase specifications, has been determined following procedures of Navy Specifications B-15606 A for Grade A high-alumina refractories. Results indicated that so long as 5 percent of impurities are combined approximtely in the proportions of 3 percent Ti02, 1 percent Fe203, and 1 percent alkali, sintered mullite-forming compositions in the almina to silica range tested will be volume stable. A permissible tolerance of one-half per- cent in each impurity oxide provides a range that includes values common in the natural minerals from which sintered mullite may be made. Within the total range of 5-percent impurity mixtures, a greater number of volume-stable compositions were obtained by increasing the alumina-silica ratio.

Jan 1, 1962

By J. P. McGee

The Bureau of Mines is doing research and development work on a coal-fired gas turbine plant initially developed by the Locomotive Development Committee, (LDC) of Bituminous Coal Research, Inc. The Bureau is redesigning the turbine blading and some of the auxiliary equipment, and is reerecting, the plant at the Morgantown (W. Va.) Coal Research Center. The present goal is a 1,500-hour run at virtually the same operating conditions used by the LDC in their final 1,100-hour test with the turbine. This will allow the Bureau to properly evaluate the new blade design. Erosion of the turbine blades (particularly the roots) by ash in the hot gases from the combustion of coal was the most serious problem in extended operation in earlier experimental work. New blades made of Stellite6 are being fabricated for the stator and rotor, and armored wear strips of titanium carbide will be inserted in the blades at the areas of probable maximum ash velocity and concentration. The trailing edges of the rotor and stator blades are being thickened and thinned, respectively, to induce the ash to travel to the casing and prevent it from returning to the base of the rotor blades. The first stage rotor and second stage stator blades are being removed to provide an annular space for maximum quantities of coal ash to centrifuge to the casing. Additional blades will be added to most of the rows in the stator to stop secondary flow of dust-laden gas toward the rotor. A contract has been awarded for fabrication of the new blades. The 1,500-hour run will be started as soon as the new blades are installed.

Jan 1, 1962

By M. M. Wong

Beryllium possesses attractive properties for use in the nuclear and space fields. Since fused-salt electrorefining can be employed to produce this metal in high-purity form from low-grade or scrap metals, the Bureau of Mines investigated electrorefining of beryllium in electrolytes composed of a LiC1-KC1 eutectic mixture plus varying amounts of BeC12. Results showed a 99- percent or better reduction of oxygen and magnesium and a substantial reduction of other minor metallic impurities. Extremely pure beryllium metal was produced. Operating variables, including BeCl2 concentration in the bath (3.5 to 16.5 mole-percent), temperature of operation (450° to 550° C.), and cathode current density (45 to 770 a,/sq, ft.), were studied; their effects on the deposition of metal, working condition of the bath, and purity of the refined metal are discussed. The safety precautions used in handling beryllium in the laboratory are also described.

Jan 1, 1962

By J. W. Town

This report summarizes the results of laboratory investigations made by the Bureau c! Mines on the recovery of mercury from caustic sulfide solutions by aluminum precipitation and by electrodeposition. Statistical methods were used to design the experiments and evaluate the resulting data. Precipitation studies demonstrated tint metallic mercury could be recovered from mercury sulfide-sodium sulfide solutions with aluminum. Other metals and their salts and aluminum, salts precipitated only black mercury sulfide. Over 95 percent of the mercury was precipitated from solutions prepared with reagent-grade chemicals and from cinnabar leach solutions. Two equivalents of aluminum were required to obtain 95 percent precipitation of the mercury. Under optimum conditions 1 gram of aluminum precipitated from 4 to 7 grams of mercury; the excess Aluminum was recovered for reuse. The effects of time and temperature on the precipitation of mercury were minor when compared with the effects of mercury concentration and aluminum equivalents. The particle size of aluminum had no significant effect over the ranges studied. When aluminum was used as a precipitant, the mercury concentration in solution was reduced to below 1.0 grams per liter. Adding arsenic and antimony sulfides to the mercury solution resulted in their coprecipitation with the mercury when the aluminum was added From 95 to 99 percent of both the arsenic and antimony were precipitated as metal, which amalgamated with the mercury.

Jan 1, 1962

By H. F. Yancey

About 65 percent of the more than 400 million tons of coal produced annually in the United States is mechanically cleaned to remove the inorganic impurities before being sent to market. The impurities, principally shale and clay with some pyrite, average about 20 percent of the raw coal treated. Nearly 95 percent of the tonnage is treated by wet processes, in which water, suspensions of solids in water, or occasionally calcium chloride solutions are employed. Difference in density of coal and impurity is the basis of these processes. Of major importance in the separation is the competency of the impurities, that is, the resistance of the impurities to size disintegration in water. In general, the impurities are more resistant in geologically older coals or those in effect made older by metamorphism. If the impurities suffer reduction in particle size when immersed in water, the separation of organic from inorganic material becomes more difficult, Recently the Scientific Department of the National Goal Board (Great Britain) undertook fundamental research into the interaction of shale and water and also developed an empirical method of assessing shale breakdown or disintegration. 6

Jan 1, 1962

By J. M. Riley

This report summarizes Bureau of Mines experiments in purifying sulfate leach liquors, which were prepared from low-tenor beryl concentrates by modifying the Degussa process. The leach liquor was prepared from a beryl concentrate containing 2.7 percent BeO by (1) sintering the beryl concentrate with limestone in a rotary kiln at about 1,150° C. and by (2) treating the sinter first with sulfuric acid and then with water to form and extract beryllium sulfate. About 80 percent of the beryllium was dissolved. The resulting leach liquor contained 2.4 grams of BeO, 20 grams of Al203, and 6 grams of Fe203 per liter. The laboratory solution contained much more aluminum and iron than a solution derived from treating 10 percent BeO concentrate, which is the standard raw material used by industry. Tests were made to determine the behavior of the solution toward alum purification and limestone neutralization both of which were employed industrially in conventional Degussa procedure.

Jan 1, 1962

By Alla D. Mah

The heat of formation of scandium sesquioxide (Sc203) has not been measured previously, and existing values for gallium sesquioxide (Ga203) are subject to large uncertainties. As a consequence, thermodynamic calculations involving these oxides hare lacked scientific exactness. This paper reports newly determined values of the heats of formation of gallium and scandium sesquioxides at 298.15° K., by combustion calorimetry. The corresponding free energies of formation are derived from heat and entropy data.

Jan 1, 1962

By William J. Campbell

The purpose of this investigation was to extend the analytical services which are required for Bureau of Mines programs in developing and evaluating high-purity materials. Determination of trace elements in minerals and ores as an aid in geochemical evaluation and prospecting was considered. Serious consideration should be given to the merits of using the avail- able fluorescent X-ray spectrographic instrumentation and techniques for determining trace elements. Limits of detectability for trace elements in metal, oxide, solution or mineral samples range from 0.1 to 100 p.p.m, depending on the element being determined, overall sample composition, and the complexity of the X-ray spectra; limits of detectability range from 0.01 to 1 microgram for elements that have been preconcentrated by a chemical or physical process, for example, by ion-exchange membrane.

Jan 1, 1962

By A. R. Taylor

In recent years, thermodynamic data have been used to a greater degree than ever by the chemical and metallurgical engineer as a means of predicting and controlling chemical reactions. To satisfy the spiraling demand for basic physical data needed for the calculations, the Bureau of Mines is studying the heat capacities of a variety of chemical compounds at high and low temperatures. This paper is one of a series presenting such data. The heat capacities of two alkaline earth compounds, strontium bromide and strontium nitrate, were measured in a temperature range of 60° to 300° K. in an adiabatic calorimeter and at temperatures of 300° to about 1,200° K. in a Bunsen ice calorimeter. The construction and operation of the calorimeters are discussed in other reports.3 4 The heat-capacity data presented in this report were extrapolated to 0° K., and smooth values of heat capacity, entropy, enthalpy function, and free-energy function were calculated and tabulated at even 10-degree intervals. The enthalpy data were fitted with algebraic equations by applying the method of least squares; calculations a£ heat-capacity values, entropy, enthalpy function, and free-energy function were made at even 50-degree intervals. The heat and entropy of fusion of strontium bromide were calculated from the enthalpy measurements.

Jan 1, 1962

By Wilbur I. Duvall

In a review of so 40 papers on damage to residential structures resulting from blasting, only 3 were found that present data on the observed amplitude and frequency of the vibration levels produced by blasting together with an observed degree of damage to a residential structure. The data from these three reports have been analyzed statistically to determine if one of the quantities, displacement, velocity, or acceleration, is more reliable than the others for estimating the degree of damage to a residential structure. From this analysis the conclusion is drawn that a given degree of damage to a structure is most closely related to the magnitude of the particle velocity of the wave motion passing thru the earth at the structure location. On the average, only minor damage it observed for peak particle velocities of 5.4 inches per second, and major damage is observed for peak particle velocities of 7.6 inches per second. When the spread of the data is taken into consideration, the following statement can be made: Wave motions that have a peak particle velocity in excess of 2 inches per second have a fair probability of producing some damage to structures, whereas wave motions that have a peak velocity less than 2 inches per second have a very low probability of causing any damage. Therefore, the recommendation is made that vibration levels in the vicinity of residential structures should be maintained below a peat particle velocity of 2 inches per second. The above criterion for safe blasting is considered to hold over a wide variety of soil and rock conditions because the original data were obtained for a wide range of soil and rock conditions and on various types of residential structures. INTRODUCTION Ever since explosives were discovered and developed for mining purposes, there has existed the problem of what effects the air and ground vibrations resulting from blasting have on structures of various types. This problem is

Jan 1, 1962

By Murray Jacobson

Facts obtained by the Bureau of Mines on the dust-explosion hazard in air of materials used in the plastics industry are presented for 313 samples studied in the laboratory. Information is given on ignition temperature of dust clouds and layers, minimum explosive concentration, minimum energy required for ignition, explosion pressure and rates of pressure rise, amount of inert dust required to prevent ignition and flame propagation, and, in some instances, on the limiting oxygen concentration in an atmosphere to prevent ignition by spark and by heated surface. The effects of particle shape, additives, and resin structure on explosibility are discussed. Relative explosibility of the materials is related to the ignition sensitivity and explosion severity and is denoted by an empirical index. Recognition of the degree of hazard will facilitate adoption of adequate measures for preventing ignition and explosion during manufacturing or processing.

Jan 1, 1962

By Mary F. Koehler

Continuing a program of thermochemical investigation of compounds of to ferroalloy elements, this paper contains ins values of the heats of formation of two sodium molybdates (Na2Mo04 and Na2Mo207) and three sodium tungstates (NO2W4, Na2W207, and NA2W207, and Na2W4013). The experimental method was solution calorimetry. The solution medium was sodium hydroxide solution, except that hydrofluoric acid solution was used for sodium tetratungstate. The heat of formation values are given with reference both to the constit¬uent elements and to the constituent oxides. These data are of prime impor¬tance in the thermodynamic consideration of these substances, as their accumulation includes the most difficult and time-consuming steps toward evaluating the free energies of formation and thus the potential reactivities and thermal stabilities. Except for values for sodium monomolybdate and monotungstate, no previous similar data were contained in literature sources.

Jan 1, 1962

By R. Lincoln

A surplus of vanadium has resulted from the tremendous output of uranium, of which vanadium is a byproduct. More knowledge of the properties and characteristics of vanadium as a pure metal has been needed so that industry can take advantage of its availability and use it according to the best principles of conservation. Besides the problem of utilization, there is the ever present need of finding new materials which will satisfy specific and demanding requirements of science and engineering; vanadium or one of its alloys may possess the latent potential for filling some of these needs. Thus this? research project was undertaken by the Bureau of Mines to determine and examine some of the physical and mechanical properties of pure vanadium. A corallary investigation was the determination of the effect of the interstitial contaminants, oxygen, nitrogen, and carbon, on unalloyed vanadium. The vanadium used for these determinations was principally the product of experimental production of the Bureau. The evaluation of this material, as small quantities became available, provided most of the data that have been obtained.

Jan 1, 1962

By Charles Zahn

Direct mass spectrometric determination of alcohols in the presence of hydrocarbons has not been possible because of the similarity of hydrocarbon and alcohol mass spectra. Experiments have demonstrated that by converting the alcohols to their trimethylsilyl derivatives, characteristic mass spectra are obtained free of interference from hydrocarbon ion fragmentation. Hexa- methyldisilazane is the reagent selected for the conversion, An improved method of preparing the reagent is given, Mass spectrometric determination of alcohols as trimethylsilyl ethers now is not only possible without prior separation from other materials, but the range of the room-temperature mass spectrometer is also extended to include the C10 alcohol region. Water does not interfere because it is converted to hexamethyldisiloxane, which has its own distinctive mass spectral peak, Experience indicates that other compounds such as glycols, amines, and phenols probably could also be determined by mass spectrometry of their trimethylsilyl ethers. Studies on the similar detemination of phenols in coal oils have been started, When mass spectrometry is not available, gas-liquid chromatography of alcohols before and after their conversion to the trimethylsilyl derivatives probably could be performed. The preparation and properties of the trimethylsilyl derivatives of 23 alcohols, 2 glycols, 3 amines, and 1 mercaptan are detailed. INRODUCTION During investigations by the Bureau of Mines at the Pittsburgh Coal Research Center relative to the development of Fischer-Tropsch processes, complications were encountered in the mass spectrometric analysis of alcohols in hydrocarbon oils. The fragmentation peaks of the alcohols and the hydrocarbons were so similar that an accurate analysis was not possible, Since involved separation techniques are necessary to isolate alcohols from hydro-carbons for separate determinations, efforts were turned to the search for a

Jan 1, 1962

By Leonard Obert

This report describes a gage which, when used with my procedure for producing strain relief, will measure the resulting borehole deformation, From the borehole deformation the magnitude and direction of the principal stresses in a plane normal to the axis of the borehole can be calculated. The design considerations, mechanical construction, sensitivity, and stability of the gage are discussed. INTRODUCTION During the past two decades an increasing mount of consideration has been given to the problem of measuring and evaluating stress in rock around underground openings. Several investigators have made theoretical and model studies of the stress and (or) strain concentrations around simulated mine openings or in structural members, such as mine pillars or immediate roof. Other investigators have developed gages for directly or indirectly measuring stress or strain, and a number of reports present the results of measurements made with these gages. Because various methods and instruments have been developed, factors involved in this type of measurement will be briefly considered.

Jan 1, 1962

By D. Bienstock

As part of the development of the hot-carbonate scrubbing process by the Bureau of Mines, the corrosion rates of steel in boiling solutions of potassium carbonate saturated with carbon dioxide and hydrogen sulfide were determined, and the effectiveness of various inhibitors was evaluated by Bureau researchers. The highly corrosive solution of carbonate saturated with carbon dioxide can be inhibited with a 0.2-percent concentration of either potassium chromate or sodium metavanadate. Solutions of carbonate saturated with carbon dioxide and hydrogen sulfide are mildly corrosive, 0.01 inch per year. Complete absence of corrosion is obtained with 0.2 percent sodium metavanadate or 0.15 percent vanadium pentoxide. Oxidizing inhibitors such as potassium chromate are destroyed in the alkaline sulfide mixture, N-alkyl trimethylene diamines, at a concentration of 0.1 percent, lower the corrosion rate to about 0.005. Sodium metasilicate, at a concentration of 0.6 percent, completely inhibits the corrosion but may deposit free silica in the system. Commercial cladding materials such as the epoxy coatings also prevent corrosion.

Jan 1, 1962