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By M. E. Tyrrell

Despits its high melting point (2,135° C.), resistance to attack by molten metals, and its hardness (8), spinel (MgO?Al203) synthesized by the fusion of alumina (Al 2 0.) and magnesia (MgO) is not used on a large scale as a commercial furnace lining, mainly because of the prohibitive cost. This investigation by the Federal Bureau of Mines was prompted by the possibility of producing synthetic spinel from inexpensive raw materials by methods outlined in U.S. Patent 2,029,773, "Process for Obtaining Products Containing Spinets," dated February 4, 1936. In this patent Ture B. Haglund described a process for recovering crystalline spinels from melts in the system Mg0?Al203-2CaO-SiO2, a system well suited to the use of starting materials such as dolomite CaMg(C03)2, olivine [2(Mg?Fe)0.Si02], and bauxite (Al203?2H20) which are abundant in the southeastern United States. Compositions, ranging from a low content in the eutectic mixture of 35 percent spinal and 65 percent dicalcium silicate (2 CaO?SiO2) to a high of 75 percent spinel and 25 percent dicalcium silicate, were fused in electric furnaces of the arc-resistance and internal-resistance types. So long as members of the system were in proper chemical balance, "dusting" slags could be produced over the entire range of spinel concentration.

Jan 1, 1961

By A. W. Decora

Gas-liquid chromatography has been applied to separating basic nitrogen compounds, such as pyridines and amines. Close-boiling compounds have been separated by exploiting structural and polarity differences, using selective liquid substrates dispersed on specially prepared solid supports. Development of these special supports was necessary in order to obtain symmetric peaks for basic nitrogen compounds; solution of this problem was important in applying gas-liquid chromatography to the analysis of basic nitrogen compounds found in shale oil. Attempts to analyze shale-oil tar bases by conventional gas-liquid chromatographic techniques, using Chromosorb4/ or Celite 545 as the support for a nonpolar liquid substrate, resulted in asymmetric peaks. These asymmetries were caused by adsorption of sample vapors on the solid support. Symmetric peaks were obtained when strongly polar liquid substrates were used on either Chromosorb or Celite. However, a solid support giving symmetric peaks only with strong polar substrates restricts the choice of substrate, and frequently, desired separations cannot be achieved.

Jan 1, 1961

By Michael G. Zabetakis

The process of ?gasfreeing? has been defined3/ as "* * * the removal of oil and vapors from tanks, pipelines, and compartments to render such spaces safe for the intended work," Generally, part or all of a vessel is gasfreed for one of several reasons: Periodic cleaning; tank inspection or repairs; shipyard overhaul or major repairs; or change of cargo, Curing the gas- freeing, flammable or explosive4/ mixtures (mixtures through which a flame can propagate after ignition by an open flame, heated object, electrical charge, or other means) may be produced. These mixtures create an explosion hazard, as the pressures produced after their ignition are often great enough to completely demolish the vessel and kill all those aboard, This paper outlines a study by the Federal Bureau of Mines of the gas explosion hazards likely to be encountered while gasfreeing a vessel compartment. To better understand these hazards it will first be necessary to review the language used in gas- explosions work. This language is considered in the following sections. Inert gases such as carbon dioxide, nitrogen, water vapor, and others can be used to decrease the range of combustible-vapor concentrations in which flammable mixtures are formed. Sufficient quantities of such gases can often be added to cause a mixture that originally was flamable to become nonflammable. Unfortunately, the use of water vapor in this application is complicated by the fact that elevated temperatures are required to keep the water in the vapor state. In practice, it may be difficult to maintain these elevated temperatures throughout the space (such as a cargo tank) to be inerted for any length of time. Accordingly, where other inert gases are not available, it may be desirable to gasfree a Lank by using heated air. To do this, the combustible vapors should be flushed as quickly as possible from the space to be gasfreed. In a properly designed system, large tanks were gasfreed with a littlee as 6 volumes of air per volume of tank capacity.

Jan 1, 1961

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean's equation (Eq. [4] of Gifkins' paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean's equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"' on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins' work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins' results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins' results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author's reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

By David M. Gullikson

Since publication of the paper on the composition of California oilfield waters by Jensen (6)3/ in 1934 the only other information on the subject was published recently by Chave (4). To supply needed information on the composition of California waters in areas of current drilling activity, the Federal Bureau of Mines collected formation water samples for analysis. Thirty-eight samples from oil-and gas-producing formations in 12 fields located in Ventura, Kern, Glenn, and Colusa counties were analysed by the Bureau's San Francisco Petroleum Research Laboratory. The samples were selected particularly from fields where the water composition was not well known or where interpretation of electrical logs has been difficult and the interpretation may be affected by unusual composition of the water. These samples were obtained from rocks ranging in geologic age from Cretaceous to Upper Pliocene. Fifteen constituents of these waters were determined including sodium, potassium, calcium, magnesium, strontium, barium, lithium, chloride, iodide, bromide, carbonate, bicarbonate, sulfate, borate, and residual acidity. These analyses are the first to be published on California oilfield waters in which determinations for potassium, strontium, bromide, iodide, boron) and naphthenates were made on a significant number of samples. The electrical resistivities of tae samples were determined at 75° F. and 175° F.

Jan 1, 1961

By I. H. Warren, Forward F. A

The reduction of aqueous slurries of uranyl carbonate at elevated temperature with compressed hydrogen m the presence of metal catalysts and certain organic promoters has been shown. to yield uranium dioxide. The reduction takes place in a sequence of steps. The purity and sintering properties of the dioxide make it of interest as a starting material for fuel element production. Simple control can be exercised over the surface area and oxygen/uranium ratio of the product during reduction. URANIUM dioxide for fueling atomic power reactors 1s conventionally produced as a powder by simultaneously decomposing and reducing ammonium diuranate with hydrogen in a furnace at high temperature. Fuel elements are then generally made from this powder by compacting and sintering ( 1). In order that elements approaching theoretical density may be obtained,

Jan 1, 1961

By H. W. Manley

SULPHUR, like the minerals of coal, iron and petroleum, is one of the essential materials in our modern expanding industrial civilization. Before discussing the salient features of the production of sulphur from the Canadian sour gas, it seems appropriate to outline the historical past and probable future utilization of sulphur. The ancient Greek writer Homer spoke of its "pest-averting sulphur" and the "divine purifying fumigation". Ancient alchemists found sulphur to be a fascinating and baffling material. The discovery of gun powder in the year of 1250, and its application to the art of war a, century later, made sulphur an important commodity in the progress of mankind. The initial manufacture of sulphuric acid in the year of 1736 by the Englishman Joshua Ward, established the basis of a chemical industry that today utilizes 80 per cent of the consumption of elemental sulphur. Commercial production of the chemical soda ash ( N a2C03) discovered in 1787 by the famous Leblanc Process, in-creased international demand for the element sulphur and marks the birthday of the Sicilian sulphur industry.

Jan 1, 1961

By M. G. Zabetakis

The use of liquid hydrogen as a high-energy fuel introduces numerous hazards not ordinarily associated with the use of other more conventional fuels. These hazards are attributable to the unique properties of hydrogen in the liquid and gas states (table 1). Since little work has been conducted on explosion and related hazards of cryogenic fuels, a research program was undertaken to obtain basic data on such dangers for hydrogen and other combustibles under these conditions. These data were used to outline emergency procedures for protecting personnel and equipment when an accidental spillage of liquid hydrogen occurs and to establish a quantity-distance table for the storage of this fuel. The vaporization of liquid hydrogen from a surface is treated as a prob¬lem in heat transfer theory. Two extreme cases are briefly considered: (1) The transfer of heat occurs at constant temperature drop between, the boiling liquid and the hot surface, and (2) the transfer of heat is limited by the rate at which it can flow to the surface from a hot insulating medium. The available data indicate that the former case (1) is applicable when vaporizing from a conducting surface and, initially, when vaporizing from an insulating medium; the latter case (2) is applicable after initial flash vaporization has occurred from the insulating medium. The vaporization rate determines in part the rate at which flammable hydrogen vapor-air mixtures are formed above a spill area. However, the rates at which heat is transferred to the vapor, and air is brought in contact with it also are of importance. Accordingly, the distribution of flammable mixtures above a spill area was determined experimentally. In general, flammable mixtures were found to be both above and within the visible vapor cloud.

Jan 1, 1961

By William J. Campbell

This study was a part of two programs: The first, to develop and evaluate high-temperature refractories; the second, to investigate reaction-rate kinetics and phase equilibria in the sinter step of the lime-soda process for the recovery of alumina. High-temperature X-ray diffractometer techniques are to be used extensively in both programs. This paper summarizes developments in the field of high-temperature X-ray diffractometers through 1959, evaluates various furnace designs, and describes briefly the X-ray diffraction facilities of the Federal Bureau of Mines. A more detailed description of the equipment and its calibration is planned in a future paper on thermal expansion and phase inversion of rare-earth oxides.

Jan 1, 1961

By K. K. Kershner

The purpose of this research by the Federal Bureau of Mines was to investigate the recovery of tin from mine-run ores and low-grade concentrates. Over 95 percent of the total tin in such materials was volatilized to tin chlorides at temperatures ranging from 520° to 565° C. Gaseous mixtures of hydrogen and hydrogen chloride were used for reducing cassiterite to stannous oxide and for converting this compound to tin chlorides. The chlorides were swept from the reaction zone of an oscillating kiln by a rapid flow of reactant gases and collected in a condensing system. Losses of tin that occur in current metallurgical processing were prevented. Approximately the same time of treatment was required for minus 35-mesh mine-run ores and low-grade concentrates. In a continuous process, the circulating gases would require some enrichment.

Jan 1, 1961

By Dr. Ralph W. Edie

The limestone reef reservoir at Swan Hills consists essentially of a "buildup" of successively smaller atoll-like layers. Precipitation of calcium carbonate within the lagoonal area of each layer essentially kept pace with growth of the outer organic lattice. Within the reef mass, six de-positional environments characterized by specific suites of fossils (or fossil fragments) and associated limestone textures are recognized as follows: ( 1) Aerated moderately agitated water of normal marine salinity (widespread shelf or submerged reef-built platform). Thamnopora-type corals, Amphipora, "pancake" stroma-toporoids, crinoids, articulate bra-chiopods, rare rugose cup corals, and ostracods occurs in light gray-buff skeletal microgranular limestone of low permeability. (2) Semi-stagnant quiet water of normal marine salinity (leeward side of reef). Crinoids, articulate brachio-pods, rare thamnopora-type corals, Amphipora, pancake and bulbous stromatoporoids, rugose cup corals, ostracods and gastropods occur in impermeable dark brown argillaceous skeletal calcilutite with thin black bituminous shale beds and rare dark chert nodules.

Jan 1, 1961

The paper outlines the development of a solvent extraction process for the recovery of scandium, yttrium, thorium, and heavy lanthanides from waste sulphate liquor at the Port Pirie uranium treatment plant. A summary is given of known solvents for these elements, including the recently developed alkyl-phosphoric acid esters which are applicable to sulphate solutions.A kerosene solution of di- (2'-ethylhexyl) phosphoric acid (EHPA) has been suggested by some workers as a suitable solvent for fractionation of the lanthanides. Experimental work with this solvent showed that it could be used for initial recovery of the above elements from low concentrations in the complex sulphate liquor. In particular, scandium could be recovered as a high grade product by extraction with 0·lM EHPA, followed by a purification strip with 9N sulphuric acid, and final stripping of scandium with sodium hydroxide solution.To enable alkaline stripping to be used successfully, the kerosene solution of the reagent was modified by the addition of a small proportion of nonanol. Experimental work included laboratory scale batch tests and small pilot scale continuous tests.A proposed extension of the process for the separate recovery of individual heavy lanthanides, yttrium, and thorium is described.INTRODUCTIONAt the Port Pirie uranium treatment plant of the South Australian Government, large volumes of "barren liquor", free from 'uranium, are at present run to waste. This "barren liquor" results from sulphuric acid leaching of Radium,Hill uranium concentrate, followed by separation of solid residues and removal of uranium from the clear solution by ion exchange. The mineral davidite, from which the uranium is derived, contains other potentially valuable components, notably vanadium, chromium, thorium, yttrium, scandium, and the lanthanides. These constituents are...

Jan 1, 1961

By J. T. McCartney

Thin sections of coal have been prepared for many years either by cutting on a microtome (1,2)5 or by grinding and polishing (2,1). Specimens of most coals had to be demineralized in hydrofluoric acid and softened in caustic solutions before they could be successfully cut with a conventional microtome. Some lignites could be cut without pretreatment. Jeffrey (1) obtained sections from coals of all ranks, although long and tedious pretreatment was required for anthracite. His sections were less than 1 cm.2 in area (probably much less for high rank coals) and about 5 microns thick. Thiessen (2) also cut sections of softened coals, mostly of low rank. His sections were a few square millimeters in area and about 3 microns thick. However, Thiessen preferred ground and polished sections for detailed studies because they were larger and had not been chemically attacked by softening media. He prepared ground sections as large as 4 cm.2 in area and usually 5 to 10 microns thick. Thousands of such sections, covering complete column samples of many coal beds, were studied for a number of years (4). With the development of the electron microscope and increased interest in quantitative optical studies of coals, a need for much thinner sections arose. However, no suitable technique for preparing such sections was known until Fernández-Morán developed a diamond knife for cutting ultrathin sections of hard materials (5). Workers at the Centre d'Etudes et Recherches de Charbonnages de France applied this new tool to the cutting of coal sections and have recently described their technique to the Burg, of Mines. Using their methods, with some modifications, researchers of the Bureau of Mines have succeeded in cutting ultrathin sections of coals ranging in rank from lignite to

Jan 1, 1961

By James E. Mauser

This report deals with the investigation of a continuous process for producing pure zirconium. It covers the construction, operation, and maintenance of the semicontinuous reactor. The report covers a study of test variables, such as reactor temperature and reluctant charge weights, and evaluates the results, such as billet metal hardness, residual billet salt content, and suitability of a purified billet as a consumable electrode for arc melting. The purpose of this project was to develop an inexpensive and continuous process for producing pure zirconium. The process developed, termed the semicontinuous reactor process, produced billets of compacted zirconium sponge. The metal was produced by reducing zirconium tetrachloride with sodium and magnesium beneath molten byproduct salt. Hydraulic rams at each end of a vertical reaction tube compacted the sponge and ejected it as a billet. These billets were purified by heat under vacuum to remove entrapped salt. The goal was to utilize the purified billet directly as a consumable electrode for arc melting.

Jan 1, 1961

By Beverly W. Dunning

The effect of vacuum melting on the elimination of gases and nonmetallic inclusions for six low-alloy steels was investigated. The purpose of these studies was the analysis and comparison of differences in gas content and inclusions in air-melted and vacuum-melted steel. Data obtained from melts of 1-1/4 to 20 pounds indicate that vacuum melting decreases the number and size of nonmetallic inclusions and at the same time increases the degree of dispersion of the remaining inclusions. These improvements are undoubtedly related to the elimination of approximately 80 percent of the nitrogen and 90 percent of the oxygen as well as most of the undesirable metallic trace impurities.

Jan 1, 1961

By H. J. Heinen

This report summarizes preliminary research studies by the Bureau of Mines in electrowinning molybdenum directly from pure or impure molybdenum trioxide (MoO3) by fused-bath electrolysis in an open graphite cell without need of a protective inert atmosphere. A formulated electrolyte of the tertiary system containing 41.6 percent sodium pyrophosphate, 16.7 percent sodium tetraborat, 33.3 percent sodium chloride, and 8,4 percent molybdenum trioxide, by weight, electrolyzed at 1,000° C,, gave excellent results. Current density studies were made over a range from 20 to 260 amperes per square decimeter. Current efficiencies of 80 to 90 percent were obtained over the entire range. Yields up to 500 grams of molybdenum per kilowatt-hour were obtained. Higher current densities, however, reduced yields and produced a finer grained metal. The two most important facets in electrowinning molybdenum from MoO3, in an open cell, are temperature and electrode spacing to minimize or eliminate the formation of the suboxide MoO2, the major source of oxygen contamination. At temperatures of 1,000° C. and higher, together with the proper spacing of the electrodes, formation of oxides are practically eliminated. Molybdenum metal electrowon from pure MoO3 was 99.9 percent pure and contained 0,056 percent oxygen and 0,007 percent carbon. This metal, when arc-melted, had a Vickers hardness number of 175 and contained 50 parts per million oxygen and less than 10 parts per million carbon. Molybdenum metal electrowon directly from an impure MoO3 containing 90 percent MoO3 resulted in a metal of 99.8 percent purity.

Jan 1, 1961

By John C. Machisak

Injury data and experience, with related employment statistics, at coal mines in the United States for 1959 are presented in this publication under the following general sections: (A) General injury experience: Tables 1 to 6: Current data on number of injuries degree of injury, frequency and severity rates, average severity, and related employment and production data by work location. (B) Selected injury experience: Tables 7 to 38: Current data on principal agencies of injuries, distribution of injuries by part of body injured, days of disability, extent of hand and machine loading, experience by employment and production groups, and various other operating factors and physical conditions related to the occurrence of injuries at the Nation's coal mines.

Jan 1, 1961

By Marvin L. Whisman

This report describes the preparation of tritium-labeled organic compounds to be used by the Federal Bureau of Mines in studying the role of certain gasoline constituents in gum-forming mechanisms. The gasoline constituents that have been investigated boil within a range of approximately 90 to 230° C. and can be classified as paraffins. naphthenes, olefins, diolefins, monocyclic aromatics, polycyclic aromatics, and organic sulfur, nitrogen,: and oxygen compounds. The technique of Wilzbach has been applied to more than 50 samples. Purification techniques have been developed that accomplish rapid and effective purification as well as removal of labile tritium in a one-step operation. Data are presented to show the rate of exchange between tritium and hydrogen that can be expected for a variety of compounds common to a full-boiling-range gasoline. These values should be useful to other investigators using tracer programs involving tritium labeled compounds.

Jan 1, 1961

By K. K. Kershner

Sulfide ore concentrates containing cobalt, nickel, copper, lead, and iron were salt roasted and leached on a laboratory scale. More than 95 percent of the cobalt, nickel, and copper was recovered. Heating patterns for salt roasting different concentrates were established. More cobalt, nickel, and copper were recovered from a bulk concentrate composed of a mixture of copper concentrate and iron concentrate. This mixture corresponded roughly with the mixture of these materials in stockpiles in southeastern Missouri. A temperature range of 375° to 400° C. was best for salt roasting. Metal chlorides were leached at a pH of 1 from chloridized charges of concentrates, Although the amounts of cobalt, nickel, and copper extracted were high, the amount of iron dissolved simultaneously interfered with subsequent separation and recovery of these metals. The amount of dissolved iron was reduced substantially by steam treating chloridized charges of bulk concentrate at 300° C. In this way, the ratios of cobalt, nickel, and copper to iron in leach liquors permitted satisfactory separation and recovery of these metals. INTRODUCTION The Federal Bureau of Mines is experimenting with chloridizing reactions.4 5 6 7/ Salt roasting of sulfide ores and concentrates, or their calcines, to form metal chlorides has certain advantages. Chlorides of

Jan 1, 1961

By H. F. Yancey

Traditionally the Pacific Northwest has relied on hydroelectric power, which has been both abundant and cheap. However, comparatively few hydroelectric sites capable of providing low-cost power remain, therefore the need for supplemental thermal generation, perhaps within the next decade, is generally recognized. Based on the present cost and availability of competing fuels, coal seems to be the logical choice for projected thermal power plants. Power companies and public utilities have become interested in establishing reserves of coal for future use. One deposit explored in 1958-59 lies in southern Thurston and northern Lewis Counties, Wash., near Centralia. Drilling, totaling 22,700 feet, proved the existence of 70 million tons of strippable coal--an ample reserve for the projected power plant. The coal, like most others and particularly those of Washington and Oregon, when mined in full seam section by mechanical methods, would require cleaning to make it suitable for use. The amount and nature of the impurities in this coal dictated a thorough investigation of its cleaning characteristics to establish economic factors and to insure proper preparation-plant design. Therefore, arrangements were made through a cooperative agreement to conduct such work at the Seattle Coal Research Laboratory of the Bureau of Mines. This report describes that investigation. The results are of interest primarily in connection with the utilization of this particular deposit, but some of the information developed is applicable to other deposits of low-rank coals in the West, because the impurities in these coals differ greatly in behavior from those generally associated with the higher rank coals of the Appalachian field.

Jan 1, 1961