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By W. S. Sanner

Anthracite was used extensively as a fuel in iron metallurgy from 1840 to 1880. In 1874, 226 of the 680 blast furnaces in the United States were operating on anthracite and producing almost one-half of the Nation's pig iron. However, by 1890, railroad expansion, the development of western iron-ore reserves, and the growing use of coke decreased the importance of anthracite as a metallurgical fuel. As a result, the last blast furnace designed exclusively for anthracite use was built in 1891. Because of the increased energy requirements of our expanding national economy, the abnormally high demands during national emergencies, and the proximity of anthracite deposits to eastern steel-producing areas, interest has grown in again using anthracite in iron metallurgy. Estimates of anthracite reserves indicate a 300-yr. supply at a production rate of 30 million tons per year. These large reserves dictate the development of an adequate technology for the use of anthracite by the metallurgical industry.

Jan 1, 1961

By L. R. Fisher

The purpose of this investigation was twofold: (1) To devise a rapid method for determining quantitatively the porphyrin-carboxylic acid content of a particular crude-oil porphyrin aggregate, and (2) to isolate porphyrins in the crystalline state from crude-oil porphyrin aggregates. The first purpose was accomplished by applying adsorption chromatography. In fulfillment of the second aim three different crystalline porphyries were isolated by methods which involved both adsorption chromatography and fractionation of benzene solutions with hydrochloric acid of varying strength. The three porphyrins had etio, rhodo-, and phyllo-type absorption spectra, respectively. INTRODUCTION Many samples of petroleum have, as interesting minor constituents, chemical compounds known as metalloporphyrins. Their presence in crude oil and other bituminous materials was first discovered by Treibs a quarter century ago. Much experimental work has been done on metalloporphyrins because of their importance to the petroleum industry. They have a deleterious effect on refining catalysts. The ash resulting from the burning of heavy fuel oil is very reactive, We to the presence of metallic constituents, particularly vanadium. In oil-fired gas turbines, the ash may build up on the blades, causing imbalance of the rotors and, in addition, severe corrosion. In industrial boilers, the ash residue is responsible for severe damage to boiler tubes and to the refractory brickwork (15).4 Through study of the chemical constitution of the various metalloporphyrins found in petroleum, much can be learned concerning the origin, migration, and history of crude oils.

Jan 1, 1961

By J. E. Miller

This paper reports experimental determinations by the Bureau of Mines of compressibility factors to 4,000 pounds per square inch absolute (p.s.i.a.) for helium at temperatures from -10° to 130° F. and for 16 helium-nitrogen mixtures at 70° F. This information is needed for computing accurate discharge volumes and is necessary for determining an average-density value for use in orifice-meter formulas. In thermodynamic calculations, several functions of the compressibility factor with pressure and temperature are required. The data in the original publications (6, 8)5 of this study have been reexamined and have been given a more comprehensive treatment. The recalculated compressibility factors are higher by approximately 0.2 percent because in the earlier work a linear relationship between the compressibility factor of helium and pressure was assumed.

Jan 1, 1961

By Donald W. Mitchell

Studies were made in the Bureau of Mines Experimental coal mine to evaluate the effectiveness of a few extinguishing agents and techniques for controlling a fire on a simulated mining machine. The investigation showed that water containing an alkali-metal salt or a surface-active (wetting) agent was more effective than water alone. For close attack, fog applications was the most effective technique studied; high rates of agent application controlled the fire more quickly than low rates. The ability to control the fire increased as the distance of attack decreased. Dry powders controlled the fire when applied by shovel but not when applied airborne by rock-dust distributor or by hand fire extinguishers. Dry alkali-metal salt powders (potassium and sodium bicarbonates and sodium tetraborate) quenched the fire more readily than limestone dust. In each instance the finer powder, the greater its effectiveness. In an open ventilated entry, smoke and hot gases backed against the air currents. An airspeed of 230 feet per minute was required to permit approach to within 10 feet of the fire. At lower airspeeds, approach could be made by extending the brattice across the bottom two-thirds of the entry, by pushing the smoke ahead with water sprays, or by discharging dust from a rock-dust distributor. In a dead-end entry, the fire was approached to within 30 feet by coursing fresh air along an airtight line brattice; however, it was safer, easier, and less time-consuming to attack the fire from a fresh-air base 100 feet away with a solid stream or by high-expansion foam; the latter method was more effective.

Jan 1, 1961

By Stephan Stecura

One of the principal objectives of the Bureau of Mines program for development of superrefractory ceramic materials is to obtain fundamental data on the physical properties of refractory oxides. Elements of particular interest to research workers in the Bureau include groups III and IV of the Periodic Table and the rare-earth group. This report contains thermal expansion and phase inversion measurements on oxides of scandium, yttrium, lanthanum and 12 lanthanide series elements (promethium and terbium omitted) up to 1,350°C, made by high-temperature X-ray diffractometer techniques. Thermal expansion values were calculated from unit cell dimensions measured at selected temperatures; with anisotropic oxides expansion was determined parallel to each major crystallographic axis. The 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 difference in expansion coefficients was observed between heating and cooling cycles for oxides that did not undergo phase inversion. Tabular data of linear expansion, in percent, linear expansion coefficients, and graphical presentation of linear expansion as a function of temperature are presented.

Jan 1, 1961

By Martin H. Stanczyk

The direct dissolution of a typical zinc sulfide flotation concentrate by elevated temperature and pressure leaching was investigated. The concentrate assayed about 55 percent Zn, 32 percent S, 6 percent Fe, and 1 percent Pb and contained minor quantities of copper and precious metals. The influence of various factors on the dissolution of the zinc in acidic and ammoniacal pulps when using oxygen as the oxidant was determined. The tests revealed that the sphalerite was difficult to oxidize. Complete dissolution of the mineral required vigorous and intimate nixing of the gaseous, liquid, and sold phases. The addition of pyrite or sulfuric acid to water slurries of the concentrate was required to obtain a high zinc extraction when leaching under acidic conditions. The quantity of pyrite and acid used was about 0.125 and 0.25 pound, respectively, per pound of zinc sulfide contained in the leach charge. In tests with acid, about 96 percent of the zinc was extracted from the concentrate in 1 hour at 200° C. when the oxygen partial pressure was 75 pounds per square inch gage or higher. Leaching with a continuous flow of air as the oxidant gave results that were almost as good as those obtained when oxygen was used, In tests with air fed through the autoclave at 320 liters per hour, 95 percent of the zinc was dissolved in 1 hour, Acid leach solutions assaying approximately 58 grams Zn per liter and containing Fe, Ni, Cr, and Cu impurities were produced in the better tests. The leached residue consisted essentially of red iron oxide together with substantially all of the lead and precious metals.

Jan 1, 1961

By Benjamin Petkof

Production quarry blasts in three rock types were photographed with a high-speed camera. Analysis of the films showed that step increases sometimes occur in the horizontal velocity of the broken rock. These step velocity increases were observed only in the first foot or so of rock movement. This observation indicates that the gaseous products of the explosion do additional work on the rock after it is crushed and cracked by the initial compressive-stress pulse and the reflected tensile-stress pulse. The observed initial fly-rock velocity is compared with the calculated fly-rock velocity for reflection spalling. A mechanism possibly causing the velocity increases is discussed. INTRODUCTION When a small concentrated charge of explosive is detonated at the bottom of a drill hole near a free surface, two modes of rock failure have been observed; both are associated with the stress pulse generated in the rock by the detonating explosive. The first mode of failure is the crushing and radial tensile cracking associated with the initial passage of the compressive-stress pulse as it propagates outward from the explosion. This type of rock failure is usually confined to the immediate vicinity of the charge hole. The second mode of failure is the tangential and radial tensile cracking associated with the tensile-stress pulse that is reflected from the free surface. This mode of failure is commonly called scabbing or spalling and has been shown to be a primary cause of rock failure in crater formation at one free surface. (3).4

Jan 1, 1961

By M. I. Copeland

The investigation of the zirconium-gadolinium equilibrium diagram was part of a program to investigate rare:earth alloys for use as nuclear reactor control materials. Investigation of the zirconium-gadolinium equilibrium diagram revealed a eutectic system with limited terminal solubilities and one peritectoid reaction. The eutectic composition occurs at about 82 percent gadolinium, and the eutectic isotherm, which occurs at 1,220 ±5° C., extends from about 12 to 99+ percent gadolinium. A peritectoid isotherm occurs at 890 ±5° C. and extends from about 2 to 99+ percent gadolinium. The solubility of gadolinium in beta zirconium decreases from about 12 percent at 1,220 ±5° C. to about 2 percent at 890 ±5° C. The solubility of gadolinium in alpha zirconium decreases from approximately 5 percent at 890 ±5° C. to between 2 and 3 percent at 600° C. Vary little solubility of zirconium in gadolinium was indicated. An allotropic transformation of gadolinium was observed at 1,260 ±5° C. A change of the gadolinium transformation temperature on alloying with zirconium was not observed.

Jan 1, 1961

By J. R. Nettle

The purpose of these studies by the Federal Bureau of Mines was to determine the feasibility of refining low-grade hafnium by an inert-gas-shielded molten-salt electrorefining technique to produce a hafnium metal meeting reactor specifications. The techniques were adapted from those used success-fully for titanium electrorefining. Three electrolytes containing hafnium chlorides were developed from which deposits having a Brinell hardness of 170 or below were recovered. A KC1 + NaC1 + HfC14 electrolyte produced deposits in the hardness range of 140 to 165 Brinell. Deposits with a hardness range of from 132 to 152 Brinell were pro-duced from an electrolyte composed of KC1 + LiC1 + HfC14. A third electrolyte composed of NaC1 + K3HfC17 produced deposits with a hardness as low as 139 Brinell. In a fourth electrolyte, composed of NaC1 + K2HfF6, a measure of refining was accomplished, but under the test conditions no metal meeting specifications was recovered; none was softer than 174 Brinell. A number of metallic impurities were reduced in quantity by the electro-refining process, notably iron, which normally was reduced from 250 p.p.m. to less than 50 p.p.m. Magnesium generally was reduced from 680 p.p.m. to less than 80 p.p.m. Manganese content was also reduced by the electrorefining process. Sponge containing 90 p.p.m. Mn yielded deposits containing a maximum of 50 p.p.m.; some deposits contained only 10 p.p.m.

Jan 1, 1961

By J. B. Gayle

Although heated circuits frequently have been employed in the conditioning stases of certain flotation processes, particularly the flotation of fluorite, the control of temperature is not generally considered economically feasible for the flotation of coal. This viewpoint, although widely held, can neither be substantiated nor refuted by reference to published data. Some evidence is available, however, that temperature is an important variable in the floatability of coal as well as other minerals. For example, Gayle and Swelley4 found that contact angles for coal and related substances were definitely dependent on temperature. Bailey and Whalan5 showed that changes in pulp temperature may exert a pronounced influence on recoveries of coal in batch flotation tests. The present laboratory-scale investigation was undertaken to obtain information about the effects of changes in pulp temperature on coal flotation recovery and also on the selectivity of separation possible using different reagents. The results indicated that flotation recoveries were markedly affected by temperature variations when certain reagents, particularly simple aliphatic alcohols, were used. For other reagents, particularly kerosine, flotation recoveries were substantially independent of variations in pulp temperature. Release-analysis results indicated that temperature variations did not greatly affect the selectivity of separation possible with the reagents tested.

Jan 1, 1961

By J. W. Jensen

Alloys of manganese and copper containing from 65 to 80 percent manganese possess mechanical strength and vibration-damping capacity in an unusually high degree. The success of their use in reducing vibration in structures depends, to some extent, on their fatigue properties. This report describes the results of fatigue tests on alloys of four compositions. Three metallurgical conditions were investigated for each alloy. Or the basis of the data in this report, the general rule that vibration-damping manganese-copper alloys are comparable to mild steel in hardness and strength may be extended to include fatigue strength. Methods for casting and fabricating these alloys were described in a previous report,4 which contained data on the mechanical and damping properties of the solid-solution alloys, and on alloys aged for 2 hours at 450° C. The aging heat treatment of solution-treated alloys results in optimum mechanical and damping properties throughout the range of specified composition. However, in the present work, measurements also were made on alloys aged for 2 hours at 500° C., because it was theorized that the additional precipitation of a-manganese under these conditions might have a pronounced effect on the fatigue strength of the alloy.

Jan 1, 1961

By W. M. Dressel

The objective of the research reported in this publication of the Federal Bureau of Mines was to devise a mineral dressing procedure that would concentrate zinc silicate minerals from certain deposits in southwestern Missouri. The best flotation results were obtained by batch laboratory flotation using sulfidizing agents and ethoxylated cocoamine. The flotation concentrate contained 70 percent of the zinc at a grade of 47.8 percent. Gravity concentration tests showed that 55 percent of the zinc could be recovered at a grade of 48.3 percent.

Jan 1, 1961

By E. G. King

Sodium-aluminum and calcium-aluminum silicates are important rock-forming minerals. While many of them are of only theoretical interest, several are of practical importance--as ceramic raw materials and as potential future sources of aluminum. Heretofore, thermodynamic data for these minerals were incomplete; and in many instances missing data were difficult to estimate reliably. This has seriously hampered thermodynamic calculations pertaining both to the natural formations of these minerals and to their decomposition in sintering and fluxing reactions. This paper reports the results of the Federal Bureau of Mines measurements of low-temperature heat capacities of four crystalline silicate minerals--dehydrated analcite (NaAlSi2O6), hexagonal anorthite (CaA12 Si208), lawsonite (Ca2Al2Si2080?2H20), and leonhardite (Ca2Al4Si8C24?7H2O). It augments previous similar measurements of related minerals, which were summarized recently.4 The measured heat-capacity data were used to derive entropy values for the four minerals at 298.15° K. Some relations between these entropy values and those of other similar minerals were discussed. These relations illustrate the difficulty of estimating entropy values of tertiary (or higher) silicates.

Jan 1, 1961

By H. D. Hess

This report presents the results of laboratory mineral evaluations conducted by the federal Bureau of Mines under the joint sponsorship of the U.S. Atomic Energy Commission (AEC) and the Bureau a! Ships, U. S. Department of the Navy. The major purpose of this investigation was to examine and evaluate zirconium minerals representing sizeable deposits in an effort to locate com¬mercial sources of high-hafnium ores. Although determination of the hafnium content was the principal objective, each of the zirconium minerals also was analyzed for combined zirconium-hafnium oxide, silica, uranium, thorium, yttrium, and cerium. The general laboratory procedure involved microscopic examination of the test samples, concentration of the hafnium-bearing zirconium mineral by standard laboratory techniques, and analysis of the derived concentrate by quantitative microscopic, chemical, and X-ray spectrographic methods. Of the several hundred samples tested under this program, 147 are discussed in this report, including 94 from domestic occurrences and 53 from widespread foreign sources.

Jan 1, 1962

By E. G. King

Many of the rare-earth oxides are now commercially available in pure form and they have a variety of potential technical uses. Thermodynamic data for these oxides, however, are rather sparse. It is one of the functions of the Bureau of Mines to fill the need for this type of information. This report gives the results of low-temperature heat-capacity and high-temperature heat-content measurements by the Bureau of Mines of lanthanum sesquioxide. The entropy at 298.15° K. was evaluated and heat-content and entropy increments above 298.15° K. were obtained to 1,800° K. The results were combined with the known heat of formation at 298.15° K. to derive heats and free energies of formation at higher temperatures. Sufficient information is now available to permit reliable thermodynamic calculations involving lanthanum sesquioxide within the temperature range 298° to 2,000° K.

Jan 1, 1961

By Mah Alla D.

Previously existing heat-of-formation values for the oxides of vanadium were rudimentary. They were subject to uncertainties of 1 to 5 kilocalories per gram-atom of contained oxygen. This fact has been the only adverse influence on the accuracy of thermodynamic calculations involving these substances, as the requisite entropy and high-temperature heat-content data are known with reasonable accuracy. This report presents new heat-of-formation data for four oxides of vanadium (VO, V203, V02, and V205), obtained by combustion calorimetry. It is believed that the uncertainties have been reduced to 0.1 to 0.3 kilocalorie per gram-atom of contained oxygen. The new heat-of-formation data were combined with existing entropy and high-temperature heat-content values to obtain free energies of formation of the four oxides at temperatures up to 2,000° K.

Jan 1, 1961

By G. E. Walden

The Bureau of Mines is currently engaged in a continuing investigation of the thermodynamic properties of certain inorganic compounds. As a part of this investigation, the heat contents of bismuth and cerous chlorides were measured throughout the temperature ranges of 370° to 630° K. and 370° to 1,200° K., respectively. Equations representing heat contents as a function of temperature were derived from the data by the method of least squares. These equations were used to calculate heat contents at selected temperature intervals ranging from the ice point to 650° K. for bismuth chloride and to 1,200° K. for cerous chloride; also, the heats of fusion of both compounds were calculated at their respective melting points. EXPERIMENTAL Materials The cerous chloride used in this investigation was supplied by the National Carbon Company of Cleveland, Ohio. A chemical analysis indicated Ce 56.57 percent and Cl 43.39 percent. No attempt was made to purify the compound or identify impurities since the analysis showed only about 0.04 percent total impurities. Reagent grade bismuth chloride was used without additional purification.

Jan 1, 1961

By V. T. Dow

In April 1957 the Bureau of Mines instituted a reconnaissance of titanium-and zirconium-bearing heavy sandstone deposits in the Four-State area of Utah, Wyoming, New Mexico, and Colorado. This report summarizes the study. Eighty-two deposits or groups of deposits, containing an estimated 27,920,000 tons of titaniferous sandstone, were examined in the Four-State area; 16 in southern Utah, 19 in Wyoming, 33 in New Mexico, and 14 in southwestern Colorado. The 16 deposits examined in Utah contain an estimated 1,043,000 tons with an average grade of 17.98 percent TiO2, 5.67 percent ZrO2, 20.98 percent Fe, and 0.09 percent equivalent Th02. The 19 deposits investigated in Wyoming are estimated to contain 21,873,000 tons of titaniferous sandstone having a weighted grade of 5.22 percent 702, 0.55 percent ZrO2, 24.8 percent Fe, and 0.01 percent equivalent Th02.

Jan 1, 1961

By P. C. Good

The work reported here was undertaken by the Federal Bureau of Mines to investigate new methods of preparing high-purity metal. Tungsten hexachloride was prepared by direct chlorination of scrap tungsten metal and by treating tungstic oxide with carbon and chlorine. The resulting tungsten hexachloride was purified by distillation and reduced win: sodium, magnesium, or hydrogen. The metal prepared by these techniques was at very high purity after arc melting but of variable quality prior to arc meIting. Metal recovery ranged from about 40 to 90 percent of theoretical values, It was found possible to deposit a smooth, dense coating of high-purity tungsten on the inside of a heated tube by vapor-phase reduction of tungsten hexachloride at reduced pressure.

Jan 1, 1961

By S. L. May

Procedures for separating columbium and tantalum have been developed by the Bureau of Mines as part of a broad research program on the utilization of low-grade ores of columbium and tantalum, Columbium and tantalum compounds of greater than 99 percent purity have been obtained by application of the solvent extraction separation system: Hydrofluoric acid-sulfuric acid-methyl iso-butyl ketone. This system is unique in that it not only separates columbium from tantalum, but also separates these two metals from other metallic impurities. The system is effective for separating the metals irrespective of the tantalum and columbium ratio of the starting materials. Investigations in which the spent feed obtained from the initial coextraction step was recycled to the system indicated that efficiency was increased, and cost was reduced without impairing product purity. Continuous tests demonstrated that this solvent extraction system could be used in large-scale equipment without loss in efficiency or in purity of products. The separation of columbium and tantalum has been difficult because of the similarity in their chemical bahavior. Many methods have been proposed for separating these two elements, but most methods either did not achieve satisfactory separation or were tedious and time consuming. The Marignac process (3, 4)4 developed in 1866 was the only method used commercially until recently. This separation procedure is based on the difference in solubility in aqueous solution of potassium tantalum fluoride and potassium columbium oxyfluoride. Current commercial practice appears to favor solvent extraction as a method for separating tantalum from columbium (1). Several efficient methods for separating columbium from tantalum by solvent extraction (2, 9, 8) were reported earlier from this laboratory.

Jan 1, 1961