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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 D. F. Smith

The thermodynamic data presented in the literature for zirconium compounds are incomplete. Among the compounds for which adequate data are Zacking are zirconium fluoride and sulfate. This paper reports experimental heat-content values determined by the Bureau of Mines for these two zirconium salts throughout the temperature range of 273° to 1,200° K. No crystalline transformations were found in the two compounds investigated, and neither of the compounds melted over the temperature range studied. MATERIALS TESTED The Oak Ridge National Laboratories, Oak Ridge, Tenn., supplied the two zirconium salts used in this investigation. The zirconium fluoride was high- purity reactor grade material. The zirconium sulfate contained between 0.01 and 0.10 percent hafnium and calcium, and other elements in concentrations below 0.01 percent, A spectrographic analysis of the two compounds is given in table 1. Before use the compounds were dried at 400° C. for several hours to removed adsorbed moisture.

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 R. R. Lowery

This project was proposed to provide information on the hazards associated with arc melting of thorium. A general air-sampling analysis was made to determine the separation, concentration, and distribution of thorium daughter (decay) products throughout arc melting, machining, and forging processes of a thorium handling facility. The value of well coordinated health physics program is stressed in connection with potential health hazards and personnel protection. Building, equipment, and exhaust ventilation requirements for such a facility are discussed. Special handling methods are described for thorium. INTRODUCTION The Bureau of Mines at the Albany Metallurgy Research Center has been involved in handling the naturally radioactive metals, uranium and thorium, for several years. Cooperative work for the Atomic Energy Commission has been carried out with thorium metal, and as a result the concerned laboratories of the Center have accumulated experience on the hazards associated with this metal. This report details the radioactive hazards arising from the arc melting, machining, and forging of thorium.

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

By A. M. Poston

Introduction of radioactive elements into ore samples and/or pregnant liquors and radiometric tracing thereof have greatly improved control of fusion and extraction studies on beryllium ores and products. Extractive metallurgical research on beryllium, normally guided by the usual laborious analytical methods, is both costly and slow. Recognition of this problem by the Bureau of Mines led to the development and application of radioisotope tracer techniques" as a substitute for chemical analysis at the Salt Lake City Metallurgy Research Center, The result was that much faster progress at significantly lower cost was achieved. This report discusses the problems encountered and resolved in using radioactive tracers and radiometric methods, defines the conditions and techniques for their effective use, and delineates the limitations and flexibility inherent in applying such methods in laboratory-scale beryllium research.

Jan 1, 1962

By John K. Alley

Despite the extensive use of fluorphlogopite, investigators do not agree as to its exact melting temperature. Data on other fluormicas and on related fluorsilicate systems are largely nonexistent. A knowledge of the melting temperature is necessary for the effective synthesis and use of fluorphlogo¬pite or other fluormicas. The increasing use of two- and three-mica systems to yield polycrystalline ceramics has made more urgent the need for melting temperature information concerning these other fluormicas. This report is part of a program by the Bureau of Mines to synthesize large-size or large-crystal fluorphlogopite and develop a usable reconstituted fluormica sheet. The melting temperature of fluorphlogopite, K2Mg6A12Si6020F4, was found to be 1,383° ±2° C. This temperature was found by studying single crystals of fluorphlogopite, heating behavior of glass of fluorphlogopite composition, and the actual crystallization of fluorphlogopite from a melt that had been heated above 1,430° C. The formation of forsterite or norbergite was directly proportional to the loss of volatiles during the experimentation. Many trials revealed that the only reliable seal was a thick platinum sheet with welded seams. If no volatiles were lost, neither norbergite nor forsterite were formed; fluormica was then the only product. Excellently formed crystals of forsterite with an optical sign different from ordinary forsterite were obtained during the single crystal melting experiments. These crystals resulted from a slow loss of volatiles. A congruent melting of fluorphlogopite is indicated by the data of this report; however, incongruency within a small temperature range is not precluded. A more refined method using phase equilibria-quench methods would be necessary to settle the question absolutely.

Jan 1, 1962

By Clark F. Grain

These investigations were undertaken as part of the Bureau of Mines program for the development and evaluation of high temperature nonmetallic materials. This report consists of thermal expansion and phase inversion measurements by high-temperature X-ray diffractometry on the principal oxides of beryllium (BeO), calcium (CaO), titanium (TiO2 ), zirconium (ZrO2 ), hafnium (HfO2), and thorium (ThO2); all were high-purity commercially available oxides. Thermal expansion values were calculated from unit cell dimensions measured at selected temperatures. Expansion was determined parallel to each major crystallographic axis for the anisotropic oxides: BeO, TOi2, ZrC2, and HfO2. Combined random and systematic errors in the thermal expansion values are considered to be less than 3 percent of the total expansion at 500° C. and approximately 2 percent at 1,000° C. No hysteresis in the expansion curves was noted between heating and cooling cycles. The Bureau's values were compared with published expansion measurements obtained by X-ray diffraction, dilatometric, interferometric, and telemicroscopic techniques. For anisotropic oxides, average linear expansion values were calculated from the volume expansion.

Jan 1, 1962

By E. C. Perkins

As part of a program for developing methods of using domestic titanium deposits, the Bureau of Mines investigated methods for chlorinating titanium slags prepared from titaniferous minerals by electrosmelting. Titaniferous slags were made from ilmenites in the following deposits: Valley County, Idaho; Trail Ridge, Fla.; Aiken, S. C.; and Maclntyre, N. Y.; titaniferous magnetite from Iron Mountain, Wyo., were also evaluated. The tests were made in two chlorinators, a 4-inch and a 36-inch unit. Preliminary testing was done in a 40-millimeter bench-type unit. Chlorine gas was contacted with a loose mixture of titaniferous slag and carbon at a high temperature to form titanium tetrachloride. The moving-bed system used in this work involved a downward movement of feed countercurrent to the chlorine flow, and residues continuously removed from the bottom of the reactor. The performance characteristics of these slags depended on their composition, which varied widely according to the geographic source of the ore. The results showed that all but two of the slags could be chlorinated as effectively as rutile, converting 70 to 80 percent of the titanium to the tetra-, chloride. The two slags that proved difficult were made from New York ilmenite and Wyoming titaniferous magnetite. These slags contained enough magnesium to cause clinkering, which necessitated that the bed be prematurely withdrawn before more than 70 percent of it could react. The iron content of the slags did not interfere with operating the chlorinators. The data from the 4-inch and the 36-inch units were in agreement on the relative amenability of the slags to chlorination.

Jan 1, 1962

By M. L. Bowser

Pulse-forming circuitry is described for use in explosives research that requires precise synchronization and control of events in order to investigate detonation parameters. Included are pulse generators for oscilloscope sweep control, counterchronograph actuators, and a raster-type oscillographic method for the determination of velocities of detonation that are applicable to studies on solid, liquid, and gaseous detonations. INTRODUCTION Prom time to time, requests have been received for information on electronic circuitry used in explosives work at the Explosives Research Laboratory, Bruceton, Pa. The methods used are not entirely original;4 5 6 however, modifications of earlier techniques and some novel design aspects have resulted in time-tested methods that warrant a more detailed description.

Jan 1, 1962