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By C. S. Tout

While investigating methods for determining the best temperatures for hot-working experimental stainless steels, the Bureau of Mines Albany Metallurgy Research Center developed a machine in which hot-twist tests could be made in a few minutes. This machine is similar to some used previously except that specimens are heated by induction instead of by radiation, and their temperature is measured by a calibrated radiation-detection unit instead of by a thermocouple. In. developing the technique for using the new machine, tests were made on specimens of medium-carbon steel, mild steel, and AISI (American Iron and Steel Institute) type 304 stainless steel. Tests also were made on as-cast specimens and preworked specimens of experimental AISI type 202, low austenitic stainless steel, and as-cast specimens of AISI type 301 experimental stainless steel. The optimum hot-working temperatures were determined for all types of steel tested. Also, data were gathered on the effects of test speed and temperature on torsional strength and the effect of twisting on tensile stress in the specimen.

Jan 1, 1962

By A. A. Berk

The Bureau of Mines devised a test nipple for the field study of corrosion in the condensate-return lines of Federal heating plants. Corrosion surveys, made with this device, showed that the deterioration of the piping was caused principally by carbonic acid in the steam condensate. Corrosion problems were brought under control when the carbonic acid concentration in the condensate was decreased. In many instances, this was effected by decreasing the total carbon dioxide content of the feedwater; in others, the condensate acidity was neutralized with volatile, alkaline chemicals. Filming treatment with octadecylamine, reported successful in controlling return-line corrosion in industry, was much less effective in Federal area-heating plants. Laboratory study by the Bureau disclosed that octadecylamine is unstable in heating systems. Analytical methods were developed for this chemical and its degradation products in heating-plant condensate. Field surveys, in using these methods, confirmed the instability of the filming material. Laboratory tests showed that the degradation products are not useful film formers. Since filming treatment has little effect on condensate corrosivity, the piping was corroded where it was not coated by the treatment chemical.

Jan 1, 1962

By D. W. Scott

Thermodynamics is a powerful tool for investigating rotational isomerism in substituted ethanes and related molecules. Accurate calorimetric data can be interpreted to give information, not only about the energy difference between conformations, but also about the shape of the potential barrier hindering rotation from one conformation to another. However, a deterrent to this use of thermodynamics is the labor required to calculate the contributions to the thermodynamic functions for assumed potential functions. Tables of thermo-dynamic contributions for appropriate potential functions can eliminate that labor and greatly facilitate the thermodynamic study of rotational isomerism. In this research, tables of contributions to the thermodynamic functions were compiled for two potential functions typical of some commonly encountered examples of rotational isomerism. TYPES OF POTENTIAL FUNCTIONS Potential function 1, illustrated in figure 1, A, has two equal minima higher than the third. It has the general shape of the barrier to internal rotation in n-butane, for example. The trans conformation of n-butane has the lowest energy, and the two skew or gauche conformations have equal but higher energy. Potential function2, illustrated in figure 1, B, has two equal minima lower than the third. It has the general shape of the barrier in 2-methylbutane, for example. The two C1 conformations of 2-methylbutane have equal energy much lower than the assumed Cs conformation, which has not been observed spectroscopically.

Jan 1, 1962

By W. H. Ode

An investigation of standard methods for determining ash in low-rank* coals showed that generally 60 to 95 percent of the total sulfur in the coal is retained in the ash as SO3. This large sulfur retention causes a positive error in the determined mount of ash of as much as 6 percentage points for the coals examined, although it usually is 2 to 3 percentage points for lignites and about 1 for subbituminous coals. Unless the sulfur content is low or unless a correction is made for the SO3 retained, the fixed carbon and oxygen have an equivalent negative error when determined by difference; also other inaccurate analytical values occur when the data are calculated on an ash- free bas is. No simple modification of the ashing procedure was found that would reduce the sulfur retention to a point where its effect on the ash determination would not be significant, Therefore, for accurate analytical work on law-rank coals, the SO3 should be deducted from the determined ash to obtain a "corrected" ash value.

Jan 1, 1962

By John Ward Smith

The potential economic value of oil shale depends on the products from thermal degradation of the rock, because no other practical method for producing valuable material from oil shale has been found. Detailed study of thermal degradation behavior can aid in characterizing oil shales and their deposits and in evaluating oil-shale processing methods, Numerous publications describe various pyrolysis properties of oil shales (see surveys 3, 9, 11 and articles 1, 2, 4-8, 10, 12),4 but they do not describe a generally applicable analytical procedure for detailed evaluation of thermal degradation products. The analytical method presented here for such evaluations is designed to provide for: 1. Control of retorting conditions--temperature, heating, rate, reaction atmosphere--plus some control over retort pressure and carrier-gas flow, 2. Precise direct gravimetric measurement of the thermal degradation products--oil, water, gas, and spent charge (residue after thermal treatment of the charge). 3. Samples of all products. 4. Determination of the identities and amounts of gaseous compounds produced. 5. Elemental analysis and gross heating value of all products. 6. Determination of the distribution in the retorting products of the elements present in the original samples.

Jan 1, 1962

By Gerald W. Elger

This report compares the quality of zirconium metal prepared by batch reduction of zirconium tetrachloride by (1) sodium, (2) magnesium, and (3) mixtures of sodium and magnesium. Criteria for quality are based on chemical analyses and hardness testing of zirconium arc-melted from sponge. The best quality zirconium with respect to low oxygen content and hardness numbers was prepared by reaction of zirconium tetrachloride with a mixture of sodium and magnesium. It was found that this reaction could be successfully carried out by two methods: (1) addition of sodium and magnesium before the initial reaction and (2) periodic injection of sodium during reaction of zirconium tetrachloride with magnesium. The largest quantity of metal was found to be recovered from experiments in which a mixture of sodium and magnesium was used. Magnesium appeared to be a better reductant than sodium because magnesium-reduced zirconium contained less oxygen and exhibited lower hardness numbers than sodium-reduced metal.

Jan 1, 1962

By T. T. Campbell

This investigation was undertaken by the Bureau of Mines to determine if high-purity ductile molybdenum of uniform quality can be prepared by bomb reduction techniques. Molybdenum trioxide (Mo03) and mixtures of molybdenum dioxide (Mo02) and trioxide were reduced by magnesium in closed steel bomb reactors. Very high pressures in excess of 5,000 p.s.i. developed during magnesium reductions of Mo03. The addition of calcium oxide to the bomb charges caused a significant reduction in pressure. Reaction efficiencies higher than 95 percent were obtained during magnesium reductions of either Mo03 or mixtures of Mo02 and Mo03, but high pressures were encountered when the charges contained from 30 to 60 percent Mo02. Reaction efficiencies were usually low (less than 80 percent) when the bomb charges contained more than 40 percent Mo02. The charges with the best composition considering operating pressure, yield, and purity contained from 10 to 30 percent Mo02. The addition of small amounts of carbon to the reaction charges was helpful because some deoxidation occurred during the reduction and also during subsequent arc-melting of the regulus metal. The purity of the bomb-reduced, arc-cast molybdenum metal ranged from 99.2 to 99.8 percent and in some instances the metal contained as little as 5 parts per million oxygen.

Jan 1, 1962

By Gerald V. Gibbs

As a part of the Bureau of Mines long-range program in asbestos, synthetic asbestiform compounds and minerals were prepared and described. Fundamental structural data on two such compounds are given in this report. Crystallographic data are provided for the synthetic isotypic compounds potassium-lead silicate, K2.Pb4 -Si8021 (I), and lead-aluminum silicate, Pb2. Pb4 .Al2Si6O21 (II). The space group symmetry 14/mmm was assigned provisionally to I and II on evidence of single crystal and piezoelectric measurements. A statistical evalua¬tion of indexed powder diffraction data revealed the cell edtes of I to be a 11.816 and c 7.932A and those of II to be a 11.723 and c 8.044A. The phases are uniaxial with observed refractive indices eD 1.790, an ?D,699 and eD 1.884, cusp 1,807, respectively. The atomic structure of I and II may be based on a complex of chains of silicon-oxygen tetrahedra lying along the c cell edge similar to the type of chain structure postulated by Pauling for scapolite. K2.Pb4.Si8021 and Pb2.Pb4 Al2Si6021 were first described by Geller and Bunting (5, 6)4 as fibrous compounds similar in crystal habit to asbestos. These authors gave powder diffraction data, although no attempt was made to find the cell edges or to index the powder diffraction patterns. Later, Shell and others (9) conducted a crystallochemical study of these fibrous silicates in search of a substitute for strategic asbestos. Their single crystal data revealed K2.Pb4 -Si8021 to be tetragonal body-centered with cell edges a 11.66, c 7.95 A. Pb2.Pb4 Al2Si6021 was concluded to be isotypic with K2.Pb4 -Si8021 on the basis of similar powder diffraction patterns, chemistry, and physical properties. No attempt was made, however, to index the powder diffraction record nor to determine the appropriate space group of either compound.

Jan 1, 1962

By G. Asai

The purpose of this Bureau of Mines investigation was to determine the properties of arc-melted iron-chromium alloys ranging in chromium content from 12 to 50 wt.-pct. Alloys were prepared by consumable-electrode arc melting of electrodes composed of high-purity chromium and high-purity iron. Alloys were fabricated to rod and sheet, and the following data were obtained: Electrical resistivity, hardness, tensile strength, and impact strength at room temperature; and creep-rupture life at 650° C. (1,200° F.). As the chromium content of the annealed alloys varied from 12 to 50 pct., the properties varied as follows: The electrical resistivity increased proportionally from 41 to 53 microhm-cm,; the Rockwell hardness varied from A 38 to A 58; the tensile strength ranged from 52,000 to 96,000 p.s.i.; the impact strength of V-notched charpy specimens varied from 140 to 405 ft.-lb., and the 100-hour creep rupture life at 1,200° F. varied from 5,000 to 16,000 p.s.i.

Jan 1, 1962

By C. J. Chindgren

Upgrading of commercial red cake and recovery of vanadium oxide from uranium-vanadium mill solutions were investigated by the Bureau of Mines. Alternative procedures potentially useful for manufacture of high-quality vanadium oxide at the mill site were explored and developed. The simplest and best procedure for converting commercial red cake containing about 10 percent combined sodium and potassium oxides (Na20) (K20) into a 98- to 99-percent vanadium pentoxide (V205 product appeared to be a metathesis in an ammoniacal solution of ammonium sulfate. Molybdenum, as well as the alkali metal oxides, was removed from the red cake by this procedure at a modest expenditure of labor and reagents. When preparing vanadium oxide of higher grade, it was necessary to dissolve the red cake and reprecipitate the vanadium as ammonium metavanadate. Calcination at 450° C, decomposed the metavanadate and yielded oxide of about 99.5 percent V205. By recyrstallizing the metavanadate before decomposition, an oxide product approaching 99.9-percent purity was obtained.

Jan 1, 1962

By E. L. Singleton

This Bureau of Mines investigation was initiated to study and establish some of the chemical and physical characteristics of the condensed Mno-Si02 system. To prevent oxidation of the manganous ion, I atmosphere of purified helium was used in the furnaces. Solidus-liquidus curves and invariant points were established from melting-point determinations and were supplemented from data obtained by the static-quenching method. Experimental findings and data are for the intermediate compounds of tephroite and rhodonite with their respective eutectics represented at 25.5 and 37.2 weight-percent silica. Tephroite melts congruently at 1,347° C., and rhodonite melts incongruently at 1,286° 8.. A metastable transformation was determined to exist at the 1,347° C. isotherm, the congruent melting point of tephroite. A composite X-ray-diffraction pattern was formulated for synthetic rhodonite. This investigation contributes fundamental data leading toward a better understanding of the more complex slag systems.

Jan 1, 1962

By V. E. Edlund

Pyrometallurgical studies by the Bureau of Mines demonstrated the feasibllity of sintering and smelting a low-grade flotation concentrate made by pilot-plant processing 10-percent manganese ore from the Maggie Canyon deposit, Mohave County, Ariz. Under optimum conditions 85 percent of the manganese in a flotation concentrate that assayed 36 percent manganese was recovered as standard ferromanganese. A blend of this flotation concentrate with high-grade dithionate pilot plant precipitate was similarly processed with a recovery of 90 percent of the manganese. Thorough mixing and pelletizing of the charge before treatment on the sinter hearth was necessary to produce a well agglomerated product by single pass sintering. Although satisfactory sinter was produced from a variety of material combinations, best results were obtained on a charge that contained 80 percent flotation concentrate and 20 percent return sinter fines. This combination was mixed with 6 percent coke, based on weight of concentrate; and 12 percent moisture. Sintering such a charge yielded a well agglomerated product containing over 80 percent coarse material, The results of standard crushing tests showed that the product was physically comparable to iron ore sinters and manganese nodules.

Jan 1, 1962

By K. C. Dean

A flotation method was developed by the Bureau of Mines for concentrating pollucite, a cesium-aluminum-silicate mineral that may contain from 20 to 40 percent cesium oxide. Separation of the pollucite from three typical ores was achieved by froth flotation of the associated micas, feldspars, and other gangue minerals, using sulfuric and hydrofluoric acids and a cationic-type collector. A low-tenor, 8 percent cesium ore from Maine was upgraded to 20 percent cesium with recovery of 87 percent of the cesium. Relatively high- grade ores from Canada and Southern Rhodesia were beneficiated at lower ratios of concentration to 28 and 29 percent cesium content respectively with recovery of over 92 percent of the cesium. In addition to concentrating the cesium content of ores, the method also effectively separates cesium from sodium, potassium, and lithium, and in certain ores from rubidium. This is accomplished by selective froth flotation of the alkali metal-bearing gangue minerals such as lepidolite, other micas, and feldspars. Since the alkali metals, especially potassium and rubidium, are difficult to separate chemically or thermally from cesium to prepare high- purity cesium products, separation by physical mans is important.

Jan 1, 1962

By R. O. Dannenberg

This report describes aperiments by the Bureau of Mines and reviews theoretical aspects of the use of organophosphate solvent extraction for recovering beryllium from sulfate leach liquors. The leach liquors were prepared by sulfuric acid leaching of lime-sintered low-tenor beryl flotation concentrates. The experimental work on sulfate leach liquors showed that the acidic esters of organophosphates extracted beryllium slowly but in preference to aluminum. Three common alkylphosphoric acids, di- (2-ethylhexyl) (EHPA), heptadecyl (HDPA), and dodecyl (DDPA), in order of decrmsing selectivity, yielded a partial separation of beryllium from aluminum.

Jan 1, 1962

By D. J. Bauer

A pure scandium solution was concentrated from 10-4 mole per liter to 0.5 mole per liter by continuous foam fractionation in a spaced, packed column. Recovery in the foam was 77 percent using a spaced, packed draining column with sodium n-methyl-n-"coconut oil acid" taurate as the surfactant. The technique was first studied batchwise in a small unpacked column to determine the more important variables. Optimum surfactant concentration was found to depend on scandium concentration. Extraction and, in general, enrichment ratios were highest in the 2.5 to 3.5 pH range at temperatures ranging from 50° to 70° C. An airflow rate of 136 ml./min. was satisfactory in the equipment used.

Jan 1, 1962

By Heinz W. Sternberg

The literature on electrochemical treatment of coal is reviewed, and possible avenues of further research in this field are discussed in this report. Electrolytic reduction of finely distributed coal resulted in the addition of as many as 9 atoms of hydrogen to 100 atoms of carbon. Reduction of coal extracts at controlled potentials indicated the presence of condensed aromatic hydrocarbons and reducible quinones in coal. As much as 65 percent of low-rank coal can be made alkali soluble by electrochemical treatment. Higher rank coals gave smaller yields of alkali-soluble products. However, the nature of this reaction is not clear. The difficulty of reducing coal electrolytically is probably due to the insolubility of coal and not to any structural peculiarity. Reduction of coal by electrolytically generated radical anions appears to be a promising approach for further research.

Jan 1, 1962

By M. E. Tyrrell

Magnesia spinel (MgO.Al203) recovered from dusting slags in the system MgO.Al203-2Ca0.SiO2 is in the form of single crystals most of which will pass 35-mash. This investigation was undertaken by the Bureau of Mines to evaluate the concentrates as a refractory raw material. Three specific types of refractory bricks were studied: (1) dense, (2) lightweight bubble, and (3) insulating. Test specimens ware fabricated 1 by dry pressing, fired to 1,675° C., and tested by procedures common to the industry. The concentrates produced a refractor, having satisfactory density and mechanical strength; however, spinal is sensitive to thermal shock and the possibility of producing a spall-resistant brick using aggregate of such small grain-size must be considered remote. Lightweight refractorias fabricated of spinel bubbles were the most promising of the types tested. They were 30 percent lighter in sight than the dense refractory, their mechanical strength was good, and definite superiority in thermal shock resistance was indicated.

Jan 1, 1962

By D. J. Stoops

The object of the research described in this paper was to investigate the effect of metallurgical and surface treatments on the corrosion behavior of arc-melted reactor-grade zirconium in cupric or ferric chloride solutions. An apparatus was constructed and specimens of various metallurgical conditions and surface treatments were tested for 6 days at 35° C., with aeration. Some correlations were observed between corrosion rate and the metal's condition and treatment, Specifically, the unattacked or least attacked specimens were those that had been etched as a final treatment before testing. The most severely attacked specimens were those that had been vacuum-annealed as a final treatment before testing. The moderately attacked specimens were those neither vacuum-annealed nor etched, but having a final surface treatment which left a cold-worked surface. Attack by cupric and ferric chloride was by pit- ting with no preference for grain boundaries, The corrosion scale was cow posed predominately of very fine zirconim particles, Particles from the FeC1,-corroded specimens were more pyrophoric than those from CuCl2-corroded specimens, and appeared to have a higher surface area to volume ratio. Comparison of results to those of previous investigators showed that at certain salt concentrations the more pure, reactor-grade zirconium was quite resistant to attack while the less pure, graphite-melted zirconium was severely attacked.

Jan 1, 1962

By Edwin E. Maust

In response to the ever- increasing demand for high temperature materials, the Bureau of Mines instituted a program for the study and development of superrefractories, One of the major tools obtained for use in this research was an image furnace of the double-paraboloidal mirror type. Although extensive theoretical analyses of solar furnace performance may be found in the literature, comparable detailed information on the double-paraboloidal-mirror image furnace has been nonexistent. This report presents an analysis based on an investigation undertaken to ascertain the limitations and characteristics of the furnace so that it can be used most effectively. The quantitative determination of the energy available at the image, the control of this energy by mans of a 60-inch iris diaphragm, and its variation with position and time relative to the heat source used have all been dealt with in detail. The quantitative results were obtained using a specially designed waterflow calorimeter and these measurements, in conjunction with the theoretical analysis, are used to present a fairly complete description of the furnace and its capabilities.

Jan 1, 1962

By G. L. Hopps

Various chemicals, including compounds of copper and lead, were added to a mixture of No. 2 and No. 6 fuel oils that was fired in an experimental furnace. Tests were made to determine (1) the effectiveness of these chemicals in removing soot deposits on probes devised to simulate heat-transfer surfaces in boilers and (2) the effectiveness of the chemicals in preventing the deposition of soot on the probe surface. Test conditions were regulated so that the temperature of the products of combustion adjacent to the probes was in the range of 625° to 700° F. The clean-metal temperatures of the air-cooled probes were comparable with the water-tube temperatures in boilers operated at 40 to 100 p.s,i.g. The dosages of the fuel oil additives used in these tests were generally larger than those usually recommended for most proprietary compounds.

Jan 1, 1962