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By Clark F. Grain

These investigations were undertaken as part of the Bureau of Mines program for the development and evaluation of high temperature nonmetallic materials. This report consists of thermal expansion and phase inversion measurements by high-temperature X-ray diffractometry on the principal oxides of beryllium (BeO), calcium (CaO), titanium (TiO2 ), zirconium (ZrO2 ), hafnium (HfO2), and thorium (ThO2); all were high-purity commercially available oxides. Thermal expansion values were calculated from unit cell dimensions measured at selected temperatures. Expansion was determined parallel to each major crystallographic axis for the anisotropic oxides: BeO, TOi2, ZrC2, and HfO2. Combined random and systematic errors in the thermal expansion values are considered to be less than 3 percent of the total expansion at 500° C. and approximately 2 percent at 1,000° C. No hysteresis in the expansion curves was noted between heating and cooling cycles. The Bureau's values were compared with published expansion measurements obtained by X-ray diffraction, dilatometric, interferometric, and telemicroscopic techniques. For anisotropic oxides, average linear expansion values were calculated from the volume expansion.

Jan 1, 1962

By J. Burlin Johnson

In small-scale blasting experiments conducted in the Bureau of Mines laboratory, small charges were used to produce craters in blocks of concrete mortar. The results are compared with larger scale experiments of other research workers, and the comparison demonstrates the similarity of the results obtained and indicates that small-scale blasting should be a useful tool for predicting large-scale blasting effects. INTRODUCTION The purpose at this investigation was to conduct blasting experiments in mortar in the laboratory and then, by comparing the results with those from larger scale field blasts in rock to determine to what extent, if any, the laboratory results resemble those in the field. The work described herein was the initial phase of a project aimed at evaluating small-scale blasting as a tool for use in improving blasting techniques. It is evident from the stand-point of control and cost that small-scale blasting would be valuable in the study of rock fragmentation by blasting in mines and quarries, if the extrapolation is valid.

Jan 1, 1962

By K. E. Tame

Pollution from radioactive nuclides, principally Ra226, in liquid waste from uranium mills can be minimized by reusing the waste solution within the mill. Such reuse of waste solution in the Vitro Chemical Co.-type process was investigated in the laboratory. Vitro employs an acid leaching process for dissolution of the uranium, countercurrent decantation for liquid-solid separation and washing, and amine solvent extraction for recovery of the uranium from solution. The simulated reuse of barren raffinate in the mill circuit was carried through two separate laboratory campaigns of 29 and 31 cycles. Conventional chloride stripping of the amine was employed in the first campaign, whereas nitrate stripping was used in the second campaign. Dissolution of uranium from the are in the acid leaching circuit averaged 96 percent. Washing efficiencies of 98 to 99 percent were attained by using 4 volume tons of combined raffinate and makeup water per ton of ore. Uranium recovery from the pregnant solution using a 5-percent solution of amine LA-1 in kerosine ranged from 99.3 to 99.9 percent.

Jan 1, 1962

By Ling Yang, John Henderson

Self-diffusion coefficients of copper in molten copper have been measured by the capillary reservoir method in the temperature range 1140o to 1260°C. The results can be represented by the equation D = [(1.46 * 0.01) x 10-3) exp [(-9710 * 710)/RT] cm2/sec. The energy of activation agrees within the limit of experimental uncertainty with that for viscous flow. The relationship between the diffusivity and coefficient of viscosity is best described by the equation D = kT/4pnr cm2/sec. MEASUREMENT was made of the self-diffusion coefficient of copper in molten copper in the temperature range 1413º to 1533ºK, using the capillary reservoir technique and CU64 as the radioactive tracer.The procedures for filling the capillaries, making the diffusion run and evaluating Dcu from the counting results were the same as described previously.1,2 All experimental operations involving the melt were carried out in a purified argon atmosphere. A graphite crucible, enclosed in a McDanel tube, was used as a container for the melt because of its satisfactory nature as a refractory material and the low solubility of carbon in copper. Graphite was also used for the capillary material. A McDanel thermocouple sheath, to which graphite radiation shields were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube, the capillaries could be lowered into or raised out of the melt. A Globar furnace with a constant temperature zone (± 2°C) of 2 in. was used to heat the assembly. The temperature of the furnace was the equilibrium value corresponding to a given setting of the transformer. Temperature was measured with a Pt-10 pct Rh/Pt thermocouple and varied during a run

Jan 1, 1962

By Alla D. Mah

The heat of formation of scandium sesquioxide (Sc203) has not been measured previously, and existing values for gallium sesquioxide (Ga203) are subject to large uncertainties. As a consequence, thermodynamic calculations involving these oxides hare lacked scientific exactness. This paper reports newly determined values of the heats of formation of gallium and scandium sesquioxides at 298.15° K., by combustion calorimetry. The corresponding free energies of formation are derived from heat and entropy data.

Jan 1, 1962

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

By J. L. Potter

An inert-gas fusion technique was applied by the Bureau of Mines to the oxygen analysis of mixed-fluoride electrolytes used in electrowinning uranium and the rare-earth metals. Method development included: (1) Thermodynamic and experimental evaluation of the temperature required to quantitatively remove oxygen from a fluoride melt; (2) installation of a water and an acid trap to entrain the volatilized fluorides; (3) development of a suitable sample-preparation technique for the heterogeneous fluoride baths in which both pulverizing and pelletizing were necessary to achieve reproducible results; (4) comparison of platinum flux and dry crucible techniques, which showed that the use of platinum was not necessary. The accuracy of the method was evaluated by analyzing fluoride baths containing known amounts of oxygen added as the metal oxide. In the 0.05-to 0.5-percent range, the relative error was about ±5 percent.

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 D. R. Rathburn

Jan 1, 1962

By Sara Jane Boles

In recent years the demand for products of greater refractoriness has placed an ever-increasing emphasis on ceramic materials, including the metallic oxides. Magnesia (MgO) is one of the most important of these oxides, exhibiting, as it does, high electrical resistivity, high slag resistance, and a melting point of 2,800° C. However, magnesia has a tendency to hydrate in the presence of water and to volatilize above 1,500° C. in certain kiln atmospheres and has a comparatively low resistance to thermal shock. Because of these disadvantages, the previously listed advantages inherent in this material have been largely overlooked, and research on magnesia has lagged behind that on oxides such as alumina and zirconia. This bibliography has been prepared in an effort to present to Government and industry a comprehensive picture of the prospects for greater utilization of magnesia as a refractory material in future research. To provide as selective and accurate a collection as possible, the references included cover magnesia in a pure state, not as an additive or in combination with other materials. However, several references discuss the effect of minor impurities (less than 5 percent of the total) on the properties of magnesia, as these papers are considered to be of special importance. A few references to articles on forming techniques are also included, as they are valuable additions to the overall treatment of the subject. The processes used in obtaining and refining the raw materials are adequately covered in earlier publications and are excluded. A number of references are omitted as being of questionable value in enhancing the cumulative study of pure magnesia as an ultra-high-temperature refractory material.

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 Jerry B. F. Champlin

The successful injection of liquids into subsurface permeable formations for production stimulation, storage, or waste disposal requires a rapid, precise, and accurate method of determining the permeability of porous solids. This report describes a method and apparatus, developed by the Bureau of Mines, that use the principle of specific-volume permeametry. Calibration of the apparatus over a wide range of permeabilities and standardization of several apparatus constants have eliminated many of the tedious calculations and problems of manipulation common to some other methods. Improvements in reproducibility and accuracy have resulted from reducing experimental measurements to one parameter--time. Specific permeabilities of reservoir rock samples are determined directly from a chart that relates elapsed time to a permeability equivalent to that determined by bubble-tube measurements.

Jan 1, 1962

By E. P. Abrahamson II

The effect of transition elements which form binary solid solution upon the recrystallization temperature of zirconium has been investigated. All additions raised the recrystallization temperature. A correlation is obtained between the logarithm of the rate of change of recrystallization temperature with atomic percent solute and the free atom ground state electron configuration of the solute element. ThE work of Abrahamson, et al., on dilute binary solid-solution alloys indicated a correlation between the free-atom ground state electron configuration of the solute and either the brittle-ductile transition or recrystallization temperature. These studies were carried out on bcc base materials. The implication is that the outer s and d electrons of the solute are the prime determinant of the absolute rate of change of recrystallization or transition temperature. Furthermore, the limit of linearity has been shown to be a function of solute electron configuration for recrystallization in iron and vanadium. To date no Complete systematic recrystallization study of dilute binary zirconium base alloys has been made. It is the purpose of this study to note whether the change in solvent structure from bcc to hcp will influence the correlation. It was also desired to learn more of the role of the electron configuration of the solvent on recrystallization temperature. PROCEDURE All alloys were made using 99.87 pct Zr with 0.01 Cr, 0.04 Fe, 0.006 Hf, 0.003 Mg, 0.003 Mn, 0.003 N, and 0.080 0 (132 BHN). The solute elements were 99.9 pct pure. According to the published binary phase diagrams6 and metallographic examinations at X750, all alloys used were solid solutions. The alloys were arc melted and remelted six times in the form of cubic 200-g buttons under an argon atmosphere. They were then hot pressed at 950°C to 0.450 in., upset pressed to 0.350 in., and annealed at 800°C for 1 hr. The specimens were then Blanchard ground to 0.250 in., removing 0.050 in. from each side. The grain size of the material at this stage was found to be 8000 100 grains per sq mm. The specimens were then cold rolled to 0.130 in. and cold pressed to 0.125 in., yielding 50 1 pct cold work. All alloys were then chemically analyzed for the principal addition. The interstitial contents remained at the values of the starting material when checked on random alloy specimens. The rolled sheet was cut into 6.75 by 0.25-in. lengths and heat treated in a gradient furnace for 1 hr. The gradient was 250o to 900°C over the 6-in. length, recorded continuously by six thermocouples resting on each specimen. Control was 3oC, accomplished at the hot end. The recrystallization temperature was determined metallographically using polarized light. The criterion chosen was the point on the specimen showing the first recrystallized grain at a constant magnification, X200. Specimens were repeated, and the agreement was found to be 3°C. RESULTS Three different pure zirconium specimens were tested, and the recrystallization temperature was

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 R. W. Stahl

The use of continuous mining machines has greatly minimized the necessity for blasting in coal mines, even during pillar recovery; however, explosives are still used to blast stumps. The use of improper blasting materials, improper procedures, or both has caused mine explosions and fires, with loss of life and property damage. Researchers and manufacturers are continuously improving explosives and blasting accessories; use of the more recently developed materials will make the blasting operation safer. Extreme caution is mandatory when blasting stumps, as the ignition of methane or coal dust may trigger an explosion or cause a fire. Since the blasting of stumps will no doubt continue, although often unnecessarily, this paper summarizes recent findings published by the Bureau of Mines and recommends safer methods.

Jan 1, 1962

By John K. Alley

Despite the extensive use of fluorphlogopite, investigators do not agree as to its exact melting temperature. Data on other fluormicas and on related fluorsilicate systems are largely nonexistent. A knowledge of the melting temperature is necessary for the effective synthesis and use of fluorphlogo¬pite or other fluormicas. The increasing use of two- and three-mica systems to yield polycrystalline ceramics has made more urgent the need for melting temperature information concerning these other fluormicas. This report is part of a program by the Bureau of Mines to synthesize large-size or large-crystal fluorphlogopite and develop a usable reconstituted fluormica sheet. The melting temperature of fluorphlogopite, K2Mg6A12Si6020F4, was found to be 1,383° ±2° C. This temperature was found by studying single crystals of fluorphlogopite, heating behavior of glass of fluorphlogopite composition, and the actual crystallization of fluorphlogopite from a melt that had been heated above 1,430° C. The formation of forsterite or norbergite was directly proportional to the loss of volatiles during the experimentation. Many trials revealed that the only reliable seal was a thick platinum sheet with welded seams. If no volatiles were lost, neither norbergite nor forsterite were formed; fluormica was then the only product. Excellently formed crystals of forsterite with an optical sign different from ordinary forsterite were obtained during the single crystal melting experiments. These crystals resulted from a slow loss of volatiles. A congruent melting of fluorphlogopite is indicated by the data of this report; however, incongruency within a small temperature range is not precluded. A more refined method using phase equilibria-quench methods would be necessary to settle the question absolutely.

Jan 1, 1962

By Leonard Obert

This report describes a gage which, when used with my procedure for producing strain relief, will measure the resulting borehole deformation, From the borehole deformation the magnitude and direction of the principal stresses in a plane normal to the axis of the borehole can be calculated. The design considerations, mechanical construction, sensitivity, and stability of the gage are discussed. INTRODUCTION During the past two decades an increasing mount of consideration has been given to the problem of measuring and evaluating stress in rock around underground openings. Several investigators have made theoretical and model studies of the stress and (or) strain concentrations around simulated mine openings or in structural members, such as mine pillars or immediate roof. Other investigators have developed gages for directly or indirectly measuring stress or strain, and a number of reports present the results of measurements made with these gages. Because various methods and instruments have been developed, factors involved in this type of measurement will be briefly considered.

Jan 1, 1962

By Harry Perry

One of the most notable achievements of the iron and steel industry in the United States in this century has been the general increase in productivity of individual blast furnaces and the reduction in coke rate. Most of the improvement in furnace operations has occurred within the past decade. During this time the output of the average furnace increased about one-third, while fuel rates decreased from 15 to 20 percent. For example, in 1949, the iron and steel industry produced 811.2 short tons of pig iron per blast-furnace day with a coke rate of 1,870.4 pounds per ton of pig iron, By 1960, the average production of pig iron per blast-furnace day had risen to 1,182.4 tons, while the coke rate had decreased to 1,497 pounds per ton of pig iron. These figures are averages for the entire industry; many furnaces produced over 2,000 tons per day and one furnace, operating on pellets, reached 2,700 tons of pig iron per day, Coke rates of individual furnaces varied, but some furnaces operated on less than 1,200 pounds per ton of pig iron. The significance of this decrease in coke rate is shown clearly when data on pig-iron production and coke consumption in 1959 are compared with 1948. In 1948, 57.3 million short tons of coke was charged into blast furnaces to produce 60.1 million tons of pig iron; in 1959 only 47.6 million tons of coke was needed to produce 60.2 million tons of pig iron. Thus, in 1959, nearly 10 million tons less coke was required to produce about the same amount of pig iron as was produced in 1948.

Jan 1, 1962

By H. C. Fuller

Rhodonite, a manganese silicate, occurs as an important component of extensive veins in the San Juan district of Colorado. Recent work by the Bureau of Mines has demonstrated that typical ores of the area can be upgraded to about 30-percent manganese content. Because of their siliceous nature, such concentrates require further processing to convert the manganese into more usable forms. The investigation described in this report demonstrates the technical feasibility of producing silicomanganese from a rhodonitic concentrate by electric smelting methods. The rhodonitic concentrate used in the smelting research was prepared by dry high-intensity magnetic separation of ore from the Silver Queen vein. The concentrate contained 29 percent manganese, 2 percent iron, and 41 percent silica. The principal minerals in the concentrate were 35 percent rhodonite, 30 percent rhodochrosite, and 25 percent quartz and chalcedony. Limestone was used as the flux and coal was used as the reductant. These minerals were crushed and screened to minus 1/2-inch plus la-mesh size.

Jan 1, 1962