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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 R. W. Van Dolah

A premature detonation of an explosive charge occurred on January 30, 1961, at a face being prepared for blasting in the underground Jefferson Island Salt Mine, Diamond Crystal Salt Co., Jefferson Island, Iberia Parish, La. The accidental blast injured the powderman fatally; his helper was injured also, but recovered. The accident represents the first fatality reported to the Bureau of Mines in connection with the use of ammonium nitrate-fuel oil (AN-FO) blasting agents in underground mining in the United States. Representatives of the Bureau of Mines Explosives Research Laboratory, Pittsburgh, Pa., and field representatives of the Bureau's Health and Safety Activity conducted the investigation, upon request of the manufacturer of the ammonium nitrate being used and with concurrence by the mine management.

Jan 1, 1962

By Charles B. Kenahan

Vanadium is subject to only light corrosion in phosphoric acid at temperatures up to 60° C. and has a moderate corrosion rate in this acid at 100° C. It is relatively corrosion resistant in sulfuric and hydrochloric acids up to 60° C, but corrodes rapidly at 100° C. It corrodes rapidly in dilute nitric acid at 35° C. Vanadium is almost inert in 10-percent solutions of formic, acetic, lactic, tartaric, and citric acids; in 9-percent oxalic acid it corrodes slowly up to 60° C. and rapidly at 100° C. Vanadium is resistant to corrosion in substitute ocean water, tapwater, and in 3-percent sodium chloride and 10-percent sodium hydroxide solutions. It is readily attacked, however, by 20-percent ferric chloride, 20-percent cupric chloride and 5-percent mercuric chloride solutions. Vanadium is protected by contact with magnesium, aluminum, and steel SAE 4130 in substitute ocean water, by magnesium and aluminum in 3-percent sodium chloride solution, and by magnesium in tapwater. Vanadium protects copper in substitute ocean water. When vanadium and stainless steel are coupled in sulfuric acid solutions, both metals are usually unaffected by contact, whereas the corrosion rate of titanium in sulfuric acid is greatly reduced by contact with vanadium.

Jan 1, 1962

By R. S. Warfield

Following World War II, the rapid increase in both military and civilian activity in the area served by the Alaska Railroad stimulated interest in the availability of local sources of nonmetallic minerals that might be used for building materials. Except for abundant sand and gravel and some pumice, the construction industry of the area depended entirely on high-cost imports for building materials of mineral origin. Because continued rapid growth was anticipated, development and use of local sources of such materials was advocated by both military and civil authorities to reduce the high costs of con¬struction and bolster the unstable economy of the area. The U.S. Department of the Interior began a program On included examining the numerous deposits of nonmetallic minerals accessible to the Alaska Railroad to determine their possible use as raw materials for the construction industry. Preliminary field investigations were made by the Geological Survey. The more promising deposits were subsequently examined and sampled by Bureau of Mines engineers, and the samples were subjected to the laboratory tests necessary to indicate the chemical and physical characteristics of the raw materials or their products. Such field and laboratory investigations were conducted on clay, shale, argillite, limestone, gypsum, and pumice taken from various parts of the area. In initial phasees of the work, done irate 1948 through 1952, many of the deposits examined were suitable for proctoring building materials. Results of the work completed during that period have been published in a Bureau of Mines report3 giving general information and detailed data on more than 35 deposits that were investigated.

Jan 1, 1962

By Willard L. Hunter

The research described in this Bureau of Minus report was conducted to improve the chromium-iron ratio of offgrade chromite. Two methods were used: (1) Iron was selectively reduced from chromite by carbothermic reduction in an electric-arc furnace, and (2) a mixture of carbon, chromite, and sometimes fluorspar was chlorinated to remove a substantial part of the iron. Chromite concentrate from the Mouat deposit in Montana and from northern California was used in the test work. Chromium-bearing slag and chromite that had been beneficiated by a roast-leach process were each smelted to produce high-carbon ferrochromium. Iron was selectively reduced in a laboratory-scale., electric-arc furnace. Carbon additions to the smelting charges varied from 40 to 100 percent of the stoichiometric requirement, and slag basicities were varied from 0.4 to 1.0 chromium-iron ratios of more than 4:1 were obtained with 89 percent recovery of chromium in a chromium-bearing slag.

Jan 1, 1962

By Charles W. Huggins

A study of the high magnification of some inorganic fibers which are found in nature or produced in the laboratory, has been conducted with the electron microscope. This series of electron microqraphs shows the important morphological differences exhibited by potassium-lead silicate, lead-aluminum silicate, chrysotile, wollastonite, silicon nitride, potassium titanate, cobalt chrysotile, magnesio-fluor-richterite, fluor-richterite, refractory oxide fiber, silicon carbide, massive serpentine, and palygorskite. A ribbon or a thin lath 250-2500 A. wide is the structural form of potassium-lead silicate and lead-aluminum silicate. Chrysotile, cobalt chrysotile, and massive serpentine all have a tubular structure and a fairly uniform (150-300 A.) diameter. Wollastonite, potassium titanate, fluor-richterite, and magnesio-richterite crystals have a lath shape, and potassium titanate laths are laminated ribbons. Single fibers of silicon nitride and palygorskite are ribbons, and the silicon nitride sample contains many twins (branching fibers). Palyqorskite fibers are highly flexible and have cross-sectional measurements of 150-300 A. Silicon carbide fibers differ from other fibers because their structure consists of several different forms. The sample used in this study had, predominately, a margarite-type structure. The refractory oxide fiber lost, all its apparent fibrosity after being prepared for electron microscopic examination, and only irregular fragments are visible in the electron micrographs.

Jan 1, 1962

By M. E. Tyrrell

Lightweight basic refractories suitable for use in some sections of the all-basic furnace were developed. Potential advantages of such refractories are lower weight, improved resistance to thermal shock, and less tendency to spall off the working face. Plant trials in positions not subject to heavy loading or severe erosion seem warranted. Forsterite (2MgO.SiO2), stabilized dolomite (2Ca0?SiO2 + MgO), and chrome-spinel [(Fe,Mg)0?(Cr,Al) 031 refractories were fabricated using bubbles as the principal component in the brick mixtures. Bubbles were blown from melts of the basic raw materials as they were tapped from a conducting-hearth arc-resistance furnace. The bubbles were graded, bonded with synthetic Forsterite plus mineralizers, dry-pressed, and fired to temperatures of 1,600° C. or over in a gas-fired kiln. Refractory properties of the bubble brick were compared with those of insulating refractories made by burning combustibles out or dense brick mixtures. Lightweight refractories fabricated of bubbles were one-third lighter in weight than dense bricks of like materials. Their mechanical strength was satisfactory, and their resistance to thermal shock was excellent. In tolerance to open-hearth slag and in resistance to thermal shock, the chrome-spinel bubble bricks wore the best of the refractories tested. Basic refractories of the insulating type were about 40 percent lighter in weight than dense commercial refractories, but they were mechanically weak and not suitable for superduty service.

Jan 1, 1962

By Raymond W. Hiteshue

Experiments were conducted al temperatures of 480° to 800° C. and hydrogen pressure of 6,000 p.s.i.g. to determine the effect of coal residence time on the conversion of a high-volatile bituminous C coal to liquid and gaseous products when using a semicontinuous apparatus designed fur rapid heating and cooling of reactants. The objective of the studies at high temperatures was to determine if appreciable quantities of coal could be converted to gaseous hydrocarbons and low-boiling liquid hydrocarbons. Experiments at lower temperatures were designed to indicate shifts in product distribution with respect to temperature and to learn more about the general mechanism of the reaction when using close control of coal residence time. One percent molybdenum, based on m.a.f. (moisture-and ash-free) coal, was used throughout this investigation. At 800° C., 6,000 p.s.i.g., and "zero" residence time) the yield of gaseous hydrocarbons was about 38 percent and the yield of oil about 4.5 percent, based on m.a.f. coal. With IS minutes residence time, under the same conditions, the yield of gaseous hydrocarbons was approximately 80 percent with no increase in yield of oil. Apparently at 800° C., and hydrogen pressure of 6,000 p.s.i.g. coal was rapidly carbonized to char with expulsion of volatiles. Char was then slowly hydrogenated to gaseous hydrocarbons without production of oil.

Jan 1, 1962

By E. R. Palowitch

Two samples of the Lower Hartshorne (Spadra) bed were collected: A sample of the raw coal with the machine cuttings excluded, and a sample of the machine cuttings exclusively. Analysis of the 5-inch by 200-mesh size fraction of the raw coal, excluding machine cuttings, showed that a product meeting minimum quality specifications could be produced by washing at 1.60 specific gravity, yielding a theoretical 93.7 percent of clean coal. A negligible amount of near-gravity material at the separation gravity indicated an easy washing problem. The sample of machine cuttings had a maximum size of 2 inches and contained about 50 percent ash. Washability tests of the 2-inch by 200-mesh size fraction indicated that a theoretical yield of 30.0 percent of specification-grade coal could be achieved by washing at 1.49 specific gravity. As the machine cuttings represent an estimated 10 percent of the total coal mined, their inclusion in the mine output would increase the theoretical net yield of salable coal by only 3.7 percent. Because the machine cuttings contained a high percentage of sink 1.80 specific-gravity material, they had neither an effect on the separating gravity required to clean the raw coal nor on the difficulty of separation. Gabbing underground versus transporting the cut-tings to the surface for disposal or washing either separately or combined with the raw coal involves a number of practical, economic; and intangible factors; hence, no specific recommendations could be made. A discussion of some of the factors involved in dealing with a similar problem is given by Gandrud and Riley.4

Jan 1, 1962

By Henry M. Harris

Low-carbon shales from 65 deposits and 11 sources of coal-mine waste in western Oregon and Washington were tested in a rotary kiln for their suitability as raw material for expanded aggregate. Shales from 41 sources bloated enough to produce crushed, expanded aggregates, weighing less than 65 pounds per cubic foot in the preliminary tests. The samples were judged on the basis of processing qualities, physical properties, and size and uniformity of the source. Nine low-carbon shale deposits and three coal-mine waste sources were selected for more extensive bloating tests and for examination of the expanded aggregates in concrete shapes. Composite samples from these 12 sources and from 2 commercial operations, when processed for testing in concrete shapes, had bulk densities ranging from 37.S to 72.9 pounds per cubic foot. Damp-cured concrete shapes made with these aggregates had bulk densities ranging from S6 to 119 pounds per cubic foot, and all but three of the lightweight concretes had crushing strengths ranging from 3,270 to 6,810 p.s.i. Properties of the lightweight concretes were compared with those of concrete shapes made with commercial aggregates, and with sand and gravel.

Jan 1, 1962

By L. H. Banning

This investigation was undertaken to obtain basic information necessary for the design and operation of a plant for recovering metallic values from nickeliferous laterite and serpentine of the Philippine Islands. It was divided into three parts: (1) Mineralogical studies and preliminary mineral dressing tests; (2) electric smelting of the ores, upgrading of ferronickel by blowing with oxygen, smelting laterite slag to produce crude iron, and the production of mild steel; and (3) nickel and cobalt recovery from upgraded ferronickel. Results of the investigation indicate that it should be feasible to recover nickel, iron, and possibly cobalt products from the laterite and ferro-nickel from the serpentine. Mineralogical studies were made on representative fractions of the laterite and serpentine tonnage samples and on five selected samples; mineral dressing tests were made only on laterite. The nickel occurs principally associated with hydrous iron oxides and chemically combined with serpentine; garnierite was the only discrete nickel mineral identified, and it was found in a highly decomposed serpentine. The bulk of the cobalt was found in wadlike manganese oxide material. Approximately twice as much chromite was found in the laterite as in the serpentine, By mineral dressing techniques, laterite was separated into two fractions: one fraction contained over 90 percent of the nickel and cobalt, and 83 percent of the iron; the other fraction contained 74 percent of the chromium. A cobalt concentrate (1.1 percent Co) was produced by a scrubbing and sizing procedure.

Jan 1, 1962

By John D. Bardill

Data from extensive tests was obtained on friction-head losses of various sand slurries, composed of materials of different specific gravities and under varying transport conditions, to provide useful information for designing hydraulic transport systems. The tests were run in a pilot plant through 2-, 3-, and 4-inch lines with slurries composed of relatively pure barite and limestone solids. Available grinding and classification equipment did not permit attaining a comparable size distribution in the two materials tested, thus preventing direct correlation of friction-head loss values to physical properties or mineral composition. A total of 495 measurements were made of limestone slurries in the 2-, 3-, and 4-inch pipe test sections at flow velocities from 6 to 14 feet per second and pulp densities from 40 to 70 percent solids. A total of 640 measurements of barite slurries were made in the 3-and 4-inch pipe test sections at flow velocities between 7 and 14 f.p.s. and pulp densities ranging from 40 to 80 percent solids.

Jan 1, 1962

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grindability index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions 5/ issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor and, if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous sampling of coal as delivered is a check on the practical results obtained in burning the coal.

Jan 1, 1962

By H. R. Babitzke

The purpose of this investigation was to evaluate the potential of columbium-hafnium alloys as structural materials for use at elevated temperatures. The work described in this report was conducted to determine the properties of columbium-hafnium alloys and to select the more promising ones for further improvement. Properties determined in this report were machinability, hardness, workability, tensile strength, and oxidation resistance. Ten ingots, ranging from 100 percent columbium to 70 atomic-percent hafnium, were prepared and subjected to tests. The test results showed that the alloys with 33 and 50 atomic-percent hafnium were superior in workability, strength, and oxidation resistance. For the alloy series tested, the strength and hardness values increased with the increasing hafnium content. Maximum values were reached with 50 atomic-percent hafnium. The oxidation resistance was poorest at the 1 atomic-percent hafnium level but improved with increasing hafnium content through 70 atomic-percent. Eight of the ten ingots were fabricable at room temperature. The two remaining ingots, those with 5 and 10 atomic-percent hafnium, required hot-working.

Jan 1, 1962

By A. G. Starliper

The report covers studies by the Bureau of Mines on the removal of metallic values in two waste products from the Longhorn tin smelter at Texas City, Tex. One product was a slag that contained tin, tungsten, iron, tantalum, and columbium. The other product was a spent acid solution that contained tin, tungsten, iron, lead, copper, zinc, and silver and that came from presmelting treatment of impure tin concentrates. Molten slag was treated with sulfur or sulfur compounds and with coke, calcium carbide, or gaseous reductants to form tin sulfide that volatilized from the charge and to reduce tungsten along with iron and silicon to form a carbon-bearing metallic layer. The metallic layer was treated by an oxidizing alkali roast and then was water-leached to extract the tungsten. The waste acid was used in other experiments to dissolve an iron-tin- tungsten alloy (hardhead) obtained by direct reduction of the slag. An insoluble fraction containing tungsten, silver, silicon, columbium, and tantalum was removed, and copper was cemented on metallic iron, Tin was recovered by cementation on zinc plates, and lead was precipitated by adding sulfate ion. Iron was precipitated by increasing the pH which left a solution containing principally zinc. Slabs of hardhead were electrolyzed in an electrolyte consisting of waste acid to plate out groups of metals at different pH?s. The time did not permit thorough exploration of this method of treatment.

Jan 1, 1962

By Leonard Obert

Between 1927 and 1957, sodium borate minerals were mined by underground methods in the Kramer District, Kern County, Calif. In 1957, surface mining methods were initiated, and during the next two or more decades it is probable that most of the production from the district will be obtained from open pits. However, part of this borate deposit is sufficiently deep that surface mining may not be economical and, hence, at some future date underground methods may again be employed. This report was prepared to document the underground mining methods employed in the district before 1957. The general geology of the district and the detailed geology of each of four mine sites are presented, together with a mineral and mechanical description of the ore and enveloping rock. The report also describes the stoping, extraction, pillar support, methods of artificial support, and other factors that affect the structural characteristics of these mines.

Jan 1, 1962

By William J. Campbell

Evaluation by the Bureau of Mines of published expansion values for magnesium oxide shows significant variation in values, which may be attributed to sample variables, experimental errors, or systematic differences between measuring techniques. To eliminate the sample variable in measuring expansion, thermal expansion characteristics of a high-purity polycrystalline magnesium oxide were determined by 21 cooperating laboratories using one or more of the following techniques; X-ray camera, X-ray diffractometer, dilatometer, interferometer, and telemicroscope. All expansion values were corrected by the author to a single reference temperature of 25° C. Linear expansion was expressed as a power series in the form of the following equation. Expansion (percent) = [[ A + B (?t) + C (?t)2] ?t 104] The constants, A, B, and C, were determined by least square techniques for X-ray camera, X-ray diffractometer, and dilatometer data separately, and for combined data of all five techniques. Expansion values are tabulated from 26° C. to 1,400° C. in 2° C. intervals using constants derived from X-ray camera data. Below approximately 500° C., expansion values obtained by dilatometric and interferometric methods are significantly lower than those by X-ray methods; above 500° C., this bias decreases rapidly. Comparison of results within methods showed the least variance for X-ray camera results; dilatometer and X-ray diffractometer results have about the same variance. The average deviations, in percent, between observed and calculated expansion values among methods were approximately 10 percent from 100°C. to 300°C., 5 percent from 300°C. to 500°C., and 2 percent from 500°C. to 1,400°C. Maximum deviations were approximately twice as large in most instances.

Jan 1, 1962

By A. A. Cochran

Methods of preparing small heats of steel containing radioisotopes were developed, and the techniques of stripping film autoradiography were used to detect and study the carbide and sulfide phases in titanium-bearing steels. Metallography had revealed areas of titanium sulfide and ferrite or pearlite adjacent to areas of titanium carbide and ferrite, and unidentified, irregular phases at the boundaries between these two areas. Sulfur 35 was used to deter-mine the extent of the titanium sulfide inclusions, and carbon 14 was used to delineate the titanium carbide phase. Individual radioactive areas were located with a resolution of approximately 10 microns. A general background exposure that was not correlated with microscopically visible phases was observed in the carbon 14 autoradiographs. The evidence from both sulfur 35 autoradiographs and carbon 14 autoradiographs indicated that the unidentified inclusions were sulfides rather than carbides. INTRODUCTION The use of radioisotopes to facilitate the work at the Rolla Metallurgy Research Center was expanded in fiscal year 1959 when the Bureau of Mines authorized the installation of an intermediate-level radioactivity laboratory. Before this time, sealed cobalt 60 sources had been employed for radiography, but no tracer work was done. The primary objective of the first experiments conducted in the new laboratory was to supplement physical metallurgy investigations of selected problems in steel research.

Jan 1, 1962

By James H. Gary

Data regarding the composition and physical properties of Florida land-pebble phosphate-waste slime are presented, and the feasibility of dewatering and beneficiating the slime by several different methods is discussed. Chemical analyses, electron micrographs, and X-ray diffraction data showed that principal constituents of the slime included quartz, attapulgite, and flaorapatite. Viscosity of the slime changed with pH; thixotropic, Newtonian, and rheopectic states were observed as the pH increased. Use of various flocculating agents was not effective in improving thickening properties of the slime. Dewatering tests using pressure filtration showed that temperature influenced the filtration rate more than pressure; the filtration rate at 165° C was tenfold that at room temperature. Selective flotation of the slime, using two different processes, gave promising results. About 25 pct of the phosphate was recovered in a concentrate assaying 31 pct P205, Other tests demonstrated that the slime could be successfully fractionated at 20-microns using a hydrocyclone. In hydrometallurgical tests about 80 pct of the phosphorus and alumina were chemically extracted from the slime using sulfuric acid. Limited bacteriological studies made of the slime showed that several types of microorganisms were present and grew in the material despite the presence of fluorine-bearing minerals.

Jan 1, 1963

By W. E. Robinson

Samples of raw oil shale and kerogen concentrates were oxidized by alkaline potassium permanganate, air, nitric acid, oxygen, and ozone to obtain information about the chemical structure of organic kerogen in oil shale. In one test, oil shale and oil-shale products were oxidized exhaustively with alkaline potassium permanganate, and the distribution of the organic carbon in the final oxidation products was determined. Comparing results of this oxidation with those obtained from other carbonaceous materials and known compounds gave information about the structure of kerogen. Alkaline potassium permanganate oxidation also was used partly to degrade kerogen into soluble products for characterization purposes. Structures present in these degradation products were indicative of type structures originally present in the kerogen. Nitric acid, oxygen, and ozone were used also for partly degrading kerogen to soluble oxidation products. Carbon-balance oxidation tests using alkaline potassium permanganate showed that Colorado oil-shale kerogen differs from many other carbonaceous materials such as coal and kerogens from other areas. Composition of the degradation products indicated that Colorado oil-shale kerogen is predominantly cycloparaffinic and saturated heterocyclic structures with some long-chain paraffinic and aromatic structures present. The ring systems may be connected through short carbon chains or bridges containing oxygen, nitrogen, and sulfur.

Jan 1, 1963