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By J. R. Welty

High-temperature thermodynamic data have, in recent years, become increasingly important for the extractive metallurgist. The extraction of metals from their ores previously was based on trial and error methods, involving hours of testing and often costly equipment fabrication. Using thermodynamic data it is frequently possible to predict the feasibility of a proposed metallurgical process as well as the optimum operating conditions for the process with reasonable accuracy. Such predictions can save consider-able tim~ and expense. Widespread use of thermodynamic analyses has been handicapped by lack of dependable experimental data. Investigators, notably K. K. Kelley (4)4. have devoted many years to determining and compiling such data. These investigators, although prolific in their production of thermodynamic values, have been unable to meet all the needs of industry and other branches of science. This becomes obvious when one considers the aeronautical and nuclear fields, in which previously unimportant, therefore uninvestigated, substances have become of prime importance.

Jan 1, 1962

By Louis P. Domingues

As part of a study on high-temperature ceramic materials, the ammonium sulfate, carbonate, nitrate, oxalate, and sulfate salts of yttrium, lanthanum, and cerium were analyzed thermogravimetrically. The temperature ranged from room temperature to 1,500° C. Each salt was decomposed by heating at a rate of 2.5° C. per minute, and some of the salts were subjected to additional rates of 5° C. per minute or 10° C. per minute. The decomposition sequences have been identified, and the temperatures of formation of intermediate compounds and of the oxides have been determined. The minimum oxide formation temperature of a given lanthanum salt exceeds that for the similar salt of yttrium, and both exceed that for the same salt of cerium except for one cerium carbonate. Variation of the heating rate indicates a thermal lag in the materials and produces the shift of formation temperatures to higher values and loss of resolution in the weight-loss distribution as the heating rate increases.

Jan 1, 1962

By L. B. Pankratz

Present-day interest in the rare-earth elements and their compounds, for both metallurgical and ceramic uses, makes it highly desirable to accumulate basic thermodynamic data that can be applied to theoretical considerations of the processing of these substances. Such data still are seriously lacking. This Bureau of Mines paper reports the results of high-temperature heat content measurements of the sesquioxides of four rare-earth elements--europium, gadolinium, neodymium, and samarium--and of the closely related element, yttrium. The temperature ranges covered by the measurements are as follows: Monoclinic Eu2O3, 298°-1,802° K. Cubic Eu203, 298°-1,350° K. Monoclinic Gd203, 298-1,802° K. Cubic Gd203, 298°-1,550° K. Hexagonal Nd203, 298°-1,795° K. Monoclinic Sm203 298°-1,798° K. Cubic Sm203, 298°-1,149° K. Cubic Y203, 298°-1,799° K.

Jan 1, 1962

By Alla D. Mah

The need for more and better basic thermodynamic data for the oxides of many of the rare metals is evident to anyone who attempts thermodynamic calculations involving these substances. In continuation of a Bureau of Mines program to meet this need, this paper reports new experimental values of the heats of formation at 298.15° K. of the hexagonal crystalline variety of germanium dioxide and germanium dioxide glass. The values were obtained by means of combustion calorimetry and sodium hydroxide-solution calorimetry. The calorimetric results also made possible the derivation of values for the heat and entropy of fusion of hexagonal germanium dioxide at its melting point. The newly measured data were combined with previously known entropy and high-temperature heat content values to obtain heats and free energies of formation of germanium dioxide (in the hexagonal crystalline, glassy, and liquid states) over the temperature range from 298.15° to 2,000° K.

Jan 1, 1962

By Robert F. Stewart

The oxidation of structural materials at high temperatures in gas-cooled systems can be greatly retarded by the addition of small amounts of hydrogen to the inert coolant. In experimental equipment for gasifying coal with heat transferred by helium, the oxidation of graphite and metals (molybdenum, tungsten, and certain stainless steels) by trace impurities in the coolant helium was virtually eliminated by adding 0.1 to 1.0 percent hydrogen. The reaction of hydrogen with praphite does not preclude its use to retard oxidation; at 2,400° F. only 0.2 pound of graphite per square foot per year is lost for each percent of hydrogen in the helium. The addition of hydrogen appeared to prevent the mass transfer of carbon often associated with oxidation of graphite, without causing noticeable embrittlement of stainless steels and molybdenum or other damaging effects. This method has been tested in precision gas-recycle systems and applied successfully for more than a year in a pilot-scale unit operating at 250 pounds per square inch gage and 2,400° F. It is now used routinely and can be applied to many gas-cooled systems operating at high temperatures.

Jan 1, 1962

By E. G. King

As low-temperature heat-capacity and entropy data were available for only one sesquisulfide (cerium sesquisulfide), it appeared desirable to augment the information for this class of compounds by measuring the sulfides of antimony and indium. In addition a pressing need existed for data on indium sulfide to supplement vaporization studies in progress in the Department of Mineral Technology, University of California. This Bureau of Mines paper reports low-temperature heat-capacity measurements and entropy evaluations at 298.15° R. of antimony sesquisulfide of stoiehiometric composition (Sb2S3) and of indium sesquisulfide which was somewhat deficient in sulfur (In2S2.93). The data for the latter substance were adjusted to correspond to the stoichiome tric composition (In2S3 ) . Indium sesquisulfide has a lower entropy at 298.15' K, than either antimony sesquisulfide or cerium sesquisulfide, in line with the higher atomic density of the indium compound.

Jan 1, 1962

By J. P. Capp

The Bureau of Mines conducted field-scale experiments in underground gasification of coal with oxygen-enriched air. A path about 140 feet long was linked at the rate of LO feet per day through a coalbed hydraulically fractured with a mixture of starch gel and sand. During the best gasification period, which extended for 2-1/2 days, 785,000 std. c.f. per day of 124-B.t.u. gas was produced. In other periods the heating value at times was almost 300 B.t.u. per std, c.f,, but sustained production of such gas was not achieved. During gasification, a total of 50 tons of coal was gasified and 114 tons of coal was carbonized. Approximately 12 million B, t .u. per foot of nominal path was recovered at the surface.

Jan 1, 1962

By W. A. McKinney

The segregation process consists of heating crushed oxidized or mixed oxide-sulfide copper are with a copper-volatilizing salt and carbonaceous material at about 750° C. to produce metallic copper which is recovered from the furnace calcines by conventional sulfide flotation. The Bureau of Mines made a number of bench-scale laboratory tests on two copper ores to determine the relative merits of using halogen salts, potassium chlorate, or various salt mixtures as volatilizing agents in segregation of the copper. Laboratory investigation of typical siliceous and calcareous oxidized ores revealed that sodium chloride was a better segregating agent than the other salts. Calcium chloride, magnesium chloride, sodium fluoride, or potassium chlorate gave nearly as good segregation as the sodium chloride on the siliceous ore. Segregation of the calcareous ore with calcium chloride was nearly as good as that obtained with sodium chloride, but inferior segregation resulted when magnesium chloride, sodium bromide, or potassium chlorate was employed. The use of sodium bromide or sodium iodide on the siliceous ore, and of sodium fluoride or sodium iodide on the calcareous are, gave appreciably poorer segregation than sodium chloride or the other salts. Other tests of the ores, using mixtures of sodium chloride and the other halogen salts or potassium chlorate, gave segregation approaching that obtained with sodium chloride.

Jan 1, 1962

By H. P. LeVan

The aced for reliable reserves of the essential element, manganese, has been a continuing concern of the Federal Government for more than three decades. Because of the increasing vulnerability of outside sources of supply efforts have been intensified to find a means for beneficiating United States domestic deposits. The deposits of most interest would of necessity be near, or have access to, suitable transportation to processing plants. The Georgia manganiferous iron deposits represent some 10 million tons4 of ore readily available to southern iron and steel industries, if a manganese recovery process capable of functioning in the presence of large quantities of iron can be developed. In addition, a successful method for beneficiating the Georgia ore could produce a significant quantity of high-grade iron concentrate. The Differential sulfatization process developed 47 the Bureau of Mines5 seemed to be well suited for this application, particularly because it results in low concentrations of iron in the leach liquors with relatively complete extractions of manganese. In this process, manganese in the presence of iron is preferentially reacted with sulfur dioxide at elevated temperatures and subsequently extracted with water.

Jan 1, 1962

By A. Gene Collins

Potassium, lithium, strontium, barium, and manganese are present in many oilfield brines, None of them except barium is determined routinely in brine analyses. Therefore, sensitive and accurate flame-spectrophotometric methods were developed. Potassium, lithium, and strontium were determined by a standard-addition technique in ethyl alcohol solutions. Barium and manganese were determined in ethyl alcohol and normal propyl solutions, respectively, after interfering substances were removed.

Jan 1, 1962

By E. G. King

The literature contains little thermodynamic information regarding inter-oxidic compounds of the ferroalloy elements and, as a result, thermodynamic considerations of extractive and utilization processes involving these elements have been hampered. As part of a Bureau of Mines program to improve this situation, this paper reports the heats of formation of three calcium vanadates and two magnesium vanadates. There were no previous similar data for any of these compounds. The experimental method was hydrochloric acid solution calorimetry, using calorimetric reaction schemes involving the vanadates and their component oxides. The results were expressed as heats of formation from the component oxides and from the elements. Corresponding free energy of formation values were calculated. The data show that the calcium and magnesium vanadates are stable with respect to all possible decompositions in which vanadium remains pentavalent. This conclusion is similar to the one drawn by Koehler6 for three sodium vanadates.

Jan 1, 1962

By John J. S. Sebastian

A laboratory-scale investigation was made of the basic problems involved in developing a ceramic heat exchanger to operate at high temperatures for using nuclear heat from gas-cooled process-heat reactors. Technical data were obtained on transferring heat by forced-convection from helium to air in a single-tube vitreous-alumina heat exchanger. Coolant air was passed through the annulus parallel with, and either concurrently or counter to, the flow of helium inside the tube. The data obtained pertain to removing heat from the helium. Average inside film coefficients were determined at mean surface temperatures of 200° to 1,570° F., inlet-gas temperatures of 1,450° to 2,665° F., and Reynolds numbers up to 560. The gas-to-surface temperature ratios were varied from 1.05 to 7.6. The tabulated results are shown in the appendix at the end of this report. The film coefficients of heat transfer were correlated by taking into account the physical properties of the helium at the average fluid temperature. With experimental conditions pointing to a laminar flow, the Nusselt number was found to decrease as the ratio of gas-to-wall temperature was increased to a value of 3. However, within the range tested, gas-to-wall temperature ratios above 3 did not affect the Nusselt number, regardless of the value of the Graetz number. Thus, beyond this point any increase in this ratio ceased to influence the heat-transfer relationship.

Jan 1, 1962

By Roy L. Wilfong

The thermal decomposition of the ammonium sulfate, carbonate, nitrate, oxalate, and sulfate salts of praseodymium, neodymium, and samarium was investigated thermogravimetrically in the temperature range 25° to 1,500° C. Each salt was decomposed at a heating rate of 2.5° C, per minute. The pyrolytic sequences have been identified and the temperatures of formation of inter-mediates, the minimum oxide formation temperatures, and values for loss on ignition have been determined. The nonstoichiometric ranges between Pr6011 and Pr203 and the extent of these ranges have been determined for oxides derived from the carbonate, nitrate, and oxalate salts of praseodymium. The alum and sulfate salts of praseodymium produced the sesquioxide without forming the intermediate non-stoichiometric oxides. The temperature limits of formation and regions of stability for the alums and sulfates were better defined than were those for the carbonates, nitrates, and oxalates. The minimum oxide formation temperature increased in the order of samarium, neodymium, and praseodymium irrespective of the anion.

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. O. Bacon

This Bureau of Mines report summarizes the results of laboratory work in the design of instrumentation for obtaining the dynamic tensile strength of rock at minimum loading. Minimum loading is defined as the lowest tensile loading by pulse reflection to cause fracturing. The instrumentation for obtaining dynamic tensile strengths of rock cores evolved into the use of a compressed-air pellet gun to impact one end of a rock core, suspended by wires, at increasing increments of air pressure. Maximum strain was measured on most or all of the impacts, and the strain at fracture of the core was obtained by extrapolating the pellet velocity-strain curve to the pellet velocity at fracture. Stress at tensile fracture was obtained from the maximum s train, and the dynamic Young's modulus was calculated from the rod velocity by using simple rod theory.

Jan 1, 1962

By Eugene L. Grumer

High-expansion foam was applied to the flames of six fuels burning in a 1-foot-diameter tray. The flames of three hydrocarbon fuels were more readily extinguished than the flames of methanol, acetone, or unsymmetrical dimethyl hydrazine. The result is rationalized on the basis that heat transfer from flame to fuel surface is primarily radiative with the hydrocarbons and more largely convective with the nonhydrocarbons. INTRODUCTION Equipment for producing high-expansion foams has been developed by the Bureau of Mines to control coal mine fires.5 Recently such equipment has been redesigned for portability and has now been produced commercially for other fire-fighting applications. In May 1961, a 50-by 50-foot gasoline fire was extinguished within 2 minutes by a trailer-mounted foam unit that produced 12,000 cu.ft./min. of high-expansion (1,000:1) foam.6

Jan 1, 1962

By E. Morrice

High-purity lanthanum metal was prepared by electrolysis of La003 in a LaF3-LiF-BaF2 bath at 950° C. The requisite bath temperature for the deposition of molten metal was maintained by supplying the heat as current directly to the electrodes. A current efficiency of about 60 percent was obtained. The lanthanum nodules contained carbon and oxygen as major impurities. The total impurity content was from about 0.1 to 0.2 percent.

Jan 1, 1962

By R. L. Crosby

From studies of wrought magnesium alloys containing rare-earth elements, data are presented on the mechanical properties of the alloys at room temperature and at temperatures of 100°, 200°, and 300° C. Results of studies of the solid-solubility of cerium and zirconium in magnesium as determined by electrical resistance measurements are also discussed and are compared with those of other investigators. The strength of magnesium-cerium alloys did not increase with the addition of vanadium and titanium dioxide. The addition of zirconium increased the tensile strength of the alloys as much as 10,000 p.s.i. at room temperature, but this increase diminished above 100° C.

Jan 1, 1962

By G. H. Gronhovd

This report describes the design and initial operation of a slagging gasification pilot plant installed by the Bureau of Mines at the Lignite Research Laboratory, Grand Forks, N. Dak., in 1958-59. The tests covered in this report were conducted over a period of about 2 years, beginning in April 1959. The pilot plant was designed for eventual operation at pressures ranging from 400 to 600 p.s.i.g. (pounds per square inch gage); however, for the preliminary test reported here, the gasifier was fitted with a low-pressure slagging section and operated at atmospheric pressure and at 80 p.s.i.g. The reason for using a low-pressure slagging section for initial operation was to facilitate modifications in design during the development of a reliable slagging procedure.

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