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By J. B. Zink

The Bureau of Mines developed a spectrochemical method to determine six constituents in coal ash in the following concentration ranges: silica 9 to 63 percent, alumina 7.5 to 35 percent, ferric oxide 2 to 30 percent, calcium oxide 1 to 29 percent, magnesium oxide 0.5 to 6 percent, and titanium oxide 0.5 to 4 percent. Samples of coal ash are fused with a mixture of lithium tetraborate and vanadium pentoxide. The resulting beads are crushed, mixed with powdered graphite, and briquetted. The pellets are analyzed spectrographically, using controlled high-voltage spark excitation. Vanadium serves as the internal standard. Effects due to matrix variations are minimized by fusion with lithium tetraborate. Intensity ratios of selected analytical lines are determined photometrically, Concentrations are read from analytical curves, prepared from synthetic standards, relating log intensity ratios to log concentration. A combustion procedure is used to determine sulfur tri-oxide. The method is most useful when large numbers of coal ashes must be analyzed but a high degree of accuracy is not essential.

Jan 1, 1967

By K. A. Jackson, J. D. Hunt

A new classification of eutectics is proposed, based on tlze entvopies of wzelting of the tuio eutectic phases. The clnssification was used to predict suitable tvansparent analogs of the metallic systems. Experimental confir?nation loas obtained for the theovetical shape of the lamellar solid-liquid interface, fov the fault mechanisms of lanzellar spacing changes, and for the development of low-energy solid-solid boundaries between the lamellae. An explanation is presented to account jov the irvegular and coinplex regular structures zrhich are found in some eritectic systems. FrOM experimental observations, single-phase materials can be divided into two groups according to their solidification characteristics, those that grow as faceted crystals and those that do not. acksonl' showed from thermodynamic reasoning that the type of growth depended on a factor a which was almost thg entropy of melting. Most nonmetals have high entropies of melting (a greater than 2) and grow with crystalline facets. Most metals have low entropies of melting (CY less than 2) and grow almost isotropically with no facets. The authors propose that eutectics may be classified in a similar manner. There are three groups of eutectics, those in which both phases have low entropies of melting, those in which one phase has a high and the other phase has a low entropy of melting, and those in which both phases have high entropies of melting. Lamellar or rodlike structures are formed in systems in which both phases have low entropies of melting. In these alloys dendrites of either phase may be formed, when the alloy is rich in the relevant component. Examples are Pb-Sn, Sn-Cd, Pb-Cd, Sn-Zn, Al-Zn. Irregular, Fig. 14((), or complex regular, Fig. 14(b), structures are formed in alloys in which one phase has a high entropy of melting and the other has a low entropy of melting. Examples are A1-Si, Zn-MgzZnll, Pb-Bi, Sn-Bi. When the alloys are rich in the low entropy of melting phase, dendrites are formed; when the alloys are rich in the high entropy of melting phase, faceted primary crystals are produced. These crystals are sometimes called hoppers or pseudodendrites. In this work the term dendrite will only be used to describe nonfaceted primary crystals. Dendrites are not formed during solidification in high entropy of melting single-phase materials. The third group of eutectics includes alloys in which both phases have high entropies of melting. Each phase grows with a faceted solid-liquid interface. Since most metals do not have high entropies of melting, metallic examples in this eutectic group are rare. However they may occur between some intermetallics and semiconductors or semimetals such as silicon, germanium, and bismuth. Attempts have been made to study eutectic solidification visually by watching the growth process.374 Since metals are not transparent, the observations had to be made on external surfaces. This difficulty can be overcome by using transparent analogs of the metallic systems. As was mentioned earlier, most single-phase compounds have entropies of melting greater than 2 and so grow as faceted crystals. Recently organic materials with entropies of melting less than 2 were investigated.' These materials grow in exactly the same way as the low entropy of melting metals. When the materials are pure, they grow with a solid-liquid interface parallel to an isotherm; when they are impure, cells or dendrites are formed. Since these materials are transparent, have low melting points, and even have cubic structures, they should be ideal for making up transparent analogs of the metallic eutectics. The purpose of the present work was to investigate these organic eutectics and to see whether this quite different series of eutectics could be classified in the same way as the metallic systems. The observations made on the organic alloys are also discussed with reference to the current theories of lamellar growth. Explanations are proposed to account for the structures formed in the other eutectic groups. EXPERIMENTAL Thin cells containing the organic alloys were uni-direction ally solidified on a specially constructed microscope stage.' Uniform growth rates were obtained by moving the cells, with a motor drive, through a fixed temperature gradient, so that the solid-liquid interface remained stationary with respect to the microscope objective lens. The cells were made by fusing two microscope cover slides 7/8 by 7/8 by 1/100 in. together on three sides, leaving a gap of 1 to 3 mils between the slides, and these were filled by surface tension. A preliminary investigation of the phase diagram between two components could be made very rapidly. One side of the cell was filled with component A and the other side with component B. Since only a small amount of mixing could occur every composition from pure A to pure B was present in the cell. When the cell was placed in the temperature gradient a pictorial representation of the phase diagram was obtained. Eutectics, peritectics, "interorganics", and solid -solid transformations could be readily detected. Fig. 1 shows part of a eutectic phase diagram. The Sample was first grown slowly then stopped. The two

Jan 1, 1967

By R. A. Guereca

The Bureau of Mines conducted an analysis to determine criteria for steady-state, laminar flow boundary conditions for a coiled-tube gas viscosimeter by comparing experimental data from a thick-walled, stainless steel capillary in a horizontal, straight-tube condition, with similar data taken after the same capillary was formed into a helix. Overlapping volumetric f10wrates and pressure drops are covered for both configurations at pressure levels of 28, 225, and 1,000 psia at 3000 K. Friction factor, Reynolds number, and Dean number correlation plots show conditions where the coi1ed-tube flow deviates from straight-tube flow. The coiled-tube data indicate departure from Poiseui11e steady-state laminar flow at a Reynolds number close to 390 and a Dean number of about 15. Below these conditions and consistent with the data reported, Dean's circulation appears negligible. For the particular coil used, a conservative upper limit of 10 is chosen for the Dean number corresponding to an upper limit of about 250 for the Reynolds number.

Jan 1, 1967

By Lowell Stroud

Ten natural gases containing from 0.023 to 8.4 percent helium were investigated. In seven high-helium samples, the isotopic abundance of Ne21 was greater than in the atmosphere, being supplemented by 33 to 85 percent of "excess" or "radiogenic" Ne21. The ratio of He4/Ne21(rad) in these gases was evaluated and found to vary between 2.9 x 107 and 5.9 x 107 , a factor of approximately 2. Argon concentrations were determined by the isotope dilution method. The isotopic ratios of Ar40/Ar36 in the high-helium gases were from 5 to 75 times the atmospheric value, with the Ar40 being about 80 to 99 percent radiogenic in nature. The ratios of He4/Ar40(rad) in all 10 gases were evaluated and found to range from 4 to 18. The isotopic ratio of N14/N15 in four of the high-helium gases was essentially the same as in the atmosphere; in three cases it was approximately 5 percent higher than the atmospheric value of 272.0. The genesis of nitrogen and the relationship of nitrogen to helium in natural gases were reviewed and are discussed in terms of a theory for the concurrent generation of nitrogen, helium, radiogenic neon 21, and petroleum (hydrocarbon gases and liquids).

Jan 1, 1967

By Theodore Kessler

The purpose of this Bureau of Mines investigation was to determine what new organic compounds or high concentrations of a particular organic species can be formed by exposure of coal derivatives to ultrasonic energy. Tetralin, l-methylnaphthalene, and pyridine were used as model compounds. Gaseous and solid reaction products resulting from the ultrasonic irradiation of these coal derivatives were determined using mass spectrometry. Products from the irradiation of tetralin were studied as a function of time, atmosphere, and sample size. The sonolysis (chemical reactions produced by ultrasonic energy) of tetralin and l-methylnaphthalene produced C2H2, HCN, CH4, H2, CO, and CO2, depending upon the experimental conditions. The ultrasonic irradiation of tetralin also produced diacetylene under certain experimental conditions. The cleavage of organic chemical bonds by ultrasonic cavitation in the absence of water was also observed in this study.

Jan 1, 1967

S. Tandanand, Twin Cities Mining Research Center, U. S. Bureau of Mines As an addition to the fine reviews on drilling presented in the foregoing papers, we feel it would be appropriate to mention briefly some work in this area by the U. S. Bureau of Mines. The Bureau has had under way for several years at its Twin Cities Mining Research Center studies directed toward a better understanding of basic drilling mechanisms. The work includes drillability investigations with diamond rotary, and with percussive drilling systems, as well as fundamental studies of rock behavior under drill bit types of loading. Results of our work to date have contributed the following to the state of the art. MECHANISM OF ROCK FAILURE-Rock fragmentation through use of mechanical energy systems, including drilling systems, consists of two major components-machine and rock. The two components are related to each other by their functional behavior and their resultant motion which the components mutually influence. Forces in the systems are transmitted directly to the bit which in turn induces stresses in the rock. When the induced stresses exceed the strength of the rock, the rock fails resulting in penetration. Rock strength is a function of the forces applied to the rock. Stresses under a drill bit, regardless of bit configurations, are essentially compressive, resulting in a condition where the rock has the highest resistance to failure. The ratio of principal stresses induced under drill bits is an indication of the mode of failure in the rocks. Initially, compressive stresses under the drill bit cause rock to undergo inelastic deformation. The impression observed at the first stage of crater formation under the drill bit shows that rock is no longer elastic. Associated subsurface failure at this stage precedes total rupture which subsequently appears at the rock surface. Thus, explanation of crater formation, by applying theory of elasticity alone, is likely to be over-simplified. ENERGY VERSUS VOLUME OF ROCK REMOVED-Experimental results show that energy per unit volume of rock removed is constant for a particular rock and bit type. Rock offers a definite resistance to penetration, depending on the method of the energy application; this may be defined as the drilling strength of a rock. Energy consumption in a drilling system may be divided into two components: 1) Energy required to move the machine parts; and 2) energy consumption in breaking rock. Component 1 is dependent on the type of the machine. Component 2 is dependent on the strength properties of rock and the efficiency of the bit in rock cutting. The sum of the energy required in both components determines the total energy required in breaking rock. Our work in this area has included consideration of both diamond and percussive drilling systems. PENETRATION RATE-For a drilling rate expression to be useful in predicting field performance, it should include the operating characteristics of the drilling machine. Eq. 37, for example, is simply a statement of the fact that the drilling rate is determined by the power output of the machine (2pNT) and the power requirements to break the rock in the hole (AER). In order to predict the performance of a particular drill and the effect, for example, of the rotary speed, on the drilling rate, R, Eq. 37 must be modified to include the

Jan 1, 1967

By Jonnie M. Estes

A two-constant equation is presented for helium from 30° = T = 1,473° K. This equation is developed by modifying a generalized equation of state originally presented by Redlich and Kwong (20).3 The modification consists of setting B = 0.06372 Tc/PeT. This modified equation represents the compressibility factors of each of 80 isotherms tested in this temperature range to less than 1 percent average deviation.

Jan 1, 1967

By D?Arcy R. George

A survey of the copper mining industry in Western United States revealed that uranium is almost universally present in the solutions resulting from leaching the waste ore dumps to recover copper. The U308 content ranges from about 2 to 15 ppm and a potential production of up to 1,000 tons of U3O8 per year is indicated. A six-week pilot plant test at the Bingham Canyon mine of Kennecott Copper Corporation showed that the uranium is readily recoverable by ion exchange techniques. The design of the new types of countercurrent ion exchange columns and operation of the pilot plant are described.

Jan 1, 1967

By A. A. Brant

"Improving geological and geophysical evaluation should serve to reduce the early-stage risk assessment and there-by contribute to exploration expenditure stimulation. The limitations of present-day methods are reviewed, particularly as to anomaly causes, depth penetration and quantitative physical interpretative abilities. Some of the problems now under study are discussed. Future developments expected include the treatment of quantitized geologic and geophysical data, as well as continuing attempts toward computerized interpretation."

Jan 1, 1967

By Webster S. Anderson

The design, development, and testing of hydraulic props to provide a lightweight, high strength, recoverable unit is described. Modifications in design incorporating threaded components resulted in the development of a lightweight hydraulic prop fabricated from aluminum alloy tubing. This new design facilitates interchange and replacement of component parts, and the physical properties of the material are not changed as they are when welding is required. The new prop is 65,000 pounds and has a maximum load capacity of a lower weight-to-load capacity ratio than the hydraulic props now available.

Jan 1, 1967

By E. L. Litchfield

Descriptions are given of the techniques and apparatus used by the Bureau of Mines for determinations of flat plate ignition quenching distance and minimum spark ignition energy. The descriptions include discussions of reaction vessel materials, shapes, and sizes and discussions of electrode configurations. Spherical, hemispherical, or flat plate electrodes are recommended. The preferred metal in electrodes and electrode supports is stainless steel; the flat plate electrodes incorporate flanges of low electrical conductivity which are most frequently formed from glass. Various aspects of the electrical energy supply system are discussed and suitable arrangements of components are indicated. The concept of a thermal relaxation time is introduced as a basis for the choice of a minimum interspark time during the testing of a gas mixture. The following indicate the varied conditions under which these tech were utilized: Mixture pressures between 10 mm Hg and 45 psig, initial temperatures between -78° and +198° C, and gaseous mixtures representing wide ranges of cL.. D reactivity and corrosiveness. Minimum ignition energies were determined which varied from about 10-7 joule to nearly 103 joule.

Jan 1, 1967

By A. A. Cochran

Bureau of MinesThe Bureau of Mines studied the development of practical methods for recovering manganese from the extensive domestic resources of low-grade ores and open hearth slags. A one-step operation was developed on a laboratory scale in which manganese and iron compounds are treated with chlorine, volatilized, and separated by selective condensation. Manganese recoveries of 90 to nearly 100 percent were obtained from 9 of the most important domestic ores. Analyses of the manganese chloride product indicated that it was suit-able for aqueous electrolysis with little additional purification. A complete, integrated process that provides for the recovery and recycling of chlorine is proposed. This process appears to have distinct advantages over previously proposed manganese recovery processes, and, in sharp contrast to leaching procedures, it is applicable to practically any manganese-bearing material.

Jan 1, 1967

By John E. Miller

Absolute viscosity values for gases usually are determined with a capillary tube viscosimeter, One of the correction factors applied to the experimental data is that for nonuniformity of the capillary bore. This report contains useful analytic expressions of the nonuniformity correction for the following cases: ellipse, cone, sine wave, sawtooth wave, square wave, and the general case. The methods herein described are applied to estimate the nonuniformity of a section of stainless steel capillary tubing to be used at the Bureau of Mines Helium Research Center. Several other examples are given to illustrate the usefulness of the present results.

Jan 1, 1967

By A. D. McMaster, M. L. Gimpl, N. Fuschillo

There is interest in the use of rhenium metal films as resistive elements in thin-film circcits, and already some zvork has been done using er)aporated rhenium films. It has been found that rheniim films protected from the atmosphere by an evaporated layer of silicon monoxide show excellent electrical stability. Unprotected films, however, are subject to aging- effects, notably the increase in electrical resistivity as a function of time. This phenomenon can be understood as primarily one of oxidation of the thin films. This paper is concerned with the study of the oxidation and crystallization behavior of such unprotected films. It has been found that the oxidation rates are a function of the substrate temperatures used during the deposition of Lhe metal films. The strictures observed in the films are correlated with the film resistivities and some data are presented to establish the existence of the various types of oxides of rhenium. ThERE is some interest in the use of thin films of rhenium metal as resistive elements in monolithic, thin-film integrated circuits. Some work has been done using evaporated films and it has been found that such films, if protected from the atmosphere by an evaporated layer of silicon monoxide, show excellent electrical stability up to temperatures of 500"." Rhenium films unprotected from the atmosphere tend to age and the electrical resistivity of the films increases as a function of time. Rhenium films, of the order of <100A thick, prepared by electron-beam evaporation techniques are found to oxidize very readily when exposed to dry air at room temperature. It would seem, therefore, that this aging phenomenon could be attributed to the oxidation of the metal films. In this investigation, the oxidation and crystallization behavior of thin films of rhenium evaporated onto silicon monoxide substrates were studied as a function of the substrate temperatures used during the evaporation. The films were examined using electron-microscopy and electron-diffraction techniques. EXPERIMENTAL RESULTS Rhenium metal was evaporated onto suitable prepared substrates which were heated to various temperatures. The evaporations were performed in a vacuum of approximately 5 x 1CT5 torr. The evaporation was carried out at a rate of approximately 10A per omin. The final film thickness was approximately lOOA and the resistance ranged from 5000 to 10,000 ohms per square. The substrates used for supporting the metal films were made by evaporating 75A of silicon monoxide onto freshly cleaved mica. The silicon monoxide film was then floated off the mica by immersing the composite in water. The film could then be picked up on a clean nickel grid. Silicon monoxide substrates were chosen because of their similarity to quartz and glass substrates commonly used for making thin-film resistors. Fuschillo, Gimpl, and McMas-ter have also shown that silicon monoxide films have only minor structural changes at temperatures up to 800°C. This fact simplified the interpretation of any changes observed in the electron micrographs or electron-diffraction patterns obtained from the deposited rhenium films. After the evaporations were completed, the substrates were cooled to room temperature, except where noted differently, before the coated substrates were removed from the vacuum system. All aging of the deposited films was done in a desiccator. The evaporated films were examined in an electron microscope equipped with a hot stage that would permit continuous observations of the samples up to temperatures of 1000°C. RESULTS A series of electron micrographs of the rhenium films deposited on the silicon monoxide substrates are shown to Figs. 1 to 3. In all cases, the metal films are approximately 100A thick and the micrographs were taken 1 hr after the deposition was completed. here was no apparent structure in the films deposited on the substrates held at the higher temperatures. The

Jan 1, 1967

By F. G. Loper

Simulation as a mathematical technique is not new. However, recent increases in digital computer speeds and the ease of programming with languages such as Fortran have centered a good deal of attention around simulation in the last few years. By ignoring all but the relevant characteristics of a process, a mathematical simulator may be constructed which, when fed operating data, should react as the process would. The output becomes numbers, instead of tons, however. Thus, a trial-and-error operation of such a simulator will permit management to study a major system change at little cost.

Jan 1, 1967

By Harry Perry

By 1980, the free world's need for economic sources of energy is expected to double. As a result, there will be a tremendous potential for all energy sources working together to supply the demand. For coal to continue its dominant role as a low-cost energy source, means must be found for it to meet the challenge of nuclear power and to overcome obstacles placed on its use by air and water pollution regulations. As the more limited reserves of gas and oil diminish, economic ways are also required for converting coal to synthetic liquid and gaseous fuels, and to chemicals, thus resulting in optimum utility of the most abundant low-cost fuel resource. The means for accomplishing these ends can only come about by a vigorous research and development program. Successful efforts by industry and government working together, both in America and abroad, will assure the continued use of coal to meet the world's energy demands. This paper discusses the emerging patterns of energy sources throughout the world and the role that research and development on coal will play in supplying future energy requirements.

Jan 1, 1967

By H. J. Gerritsen

From presently available components a portable, rugged, reliable apparatus can be built which will be able to detect methane concentrations of 0.1% and lower in air. Sensitivity and design considerations of the apparatus are given. Ways to build even simpler and cheaper apparatus in the future are indicated. Traditionally the problem of detecting and monitoring the presence of dangerous gases present in small concentrations in air has been a difficult one. Whether canaries,&apos; or sophisticated chemical or thermal conductivity methods are used, they seem to be either slow, cumbersome, or otherwise not completely satis factory. A seemingly natural way of gas detection is to measure the strength of absorption undergone by light of a wavelength that the gas to be detected absorbs. This method has been difficult to apply in view of the low power output over a narrow wavelength range in the infrared from traditional glow bar light sources. Besides, the apparatus to select such a narrow band of wavelengths is quite costly and complex. The use of a laser solves these problems simultaneously. Although a variety of lasers are available to detect a variety of gases (such as carbon monoxide or methane) whose early detection would be desirable, this paper deals exclusively with the use of lasers for methane detection. ABSORPTION SPECTRUM OF METHANE IN AIR The absorption spectrum of pure methane is very well known.2-4 There are four fundamental vibrations, all occurring in the infrared of which only two absorb strongly. They occur at 3.3 µ and 7.7 µ. The absorption spectrum is quite complicated due to the fact that the methane molecule can rotate in a variety of rotational quantum states. These rotational states are furthermore split by anharmonic forces such as the Coriolis force.4 When methane is present in air at atmospheric pressure, much of the very fine structure due to the anharmonic force is washed out since the pressure broadening is of the same magnitude as the splitting due to anharmonicity. For most of the spectrum at 3.3 µ, the rotational lines are typically separated by 0.01µ while the individual linewidth is 0.0001 µ. It is thus very important that the laser emit at a wavelength that coincides with one of these rotational lines. Before elaborating on the point that such a laser exists and how it performs, it is necessary for later discussion to point out that in the

Jan 1, 1967

By William H. Lehr

A 4200 ton-per- hour marine transfer terminal, where river and oceangoing vessels simultaneously exchange cargos of coal and phosphate rock, is now in operation near the mouth of the Mississippi. Its materials handling machinery includes a bucket ladder barge unloader; a rope operated clamshell bucket unloader; a coal loader; and a rail mounted bucket wheel machine. The design and operation of this equipment is described as are the docks and conveying, breasting and barge-haul systems in use at the facility. Design considerations imposed by soil and river conditions, geography, operating needs and investment requirements are discussed. The economic significance of design and shipping innovations introduced by this facility is noted.

Jan 1, 1967

By R. Stauffer, S. Lindsay

"Sherritt Gordon Mines Limited utilizes pressure hydro-metallurgical techniques to recover nickel, copper and cobalt from su1phidic concentrates, mattes and various other metal-bearing materials.A brief description of the nickel refinery operation is given. In the nickel refinery process, an ammonia pressure leach is employed to treat the feed materials to dissolve the non-ferrous metals as their respective ammine complexes. The resulting leach solution goes through a series of steps which removes copper as copper sulphide and further purifies the solution prior to nickel precipitation by hydrogen reduction. The reduction end solution, containing the cobalt which was originally present in the leach solution as well as residual nickel, is treated with hydrogen sulphide. The resulting nickel-cobalt sulphide precipitate feeds the soluble cobaltic ammine process, which separates the nickel and cobalt and recovers the cobalt as a pure powder.A detailed description of the cobalt recovery process is given. Included are the various steps, comprising: acid leaching of the mixed sulphides, solution purification, ammine complex formation and cobaltous oxidation, two-stage nickel precipitation, cobalt conversion and reduction. A brief description of cobalt powder handling is included, along with typical physical properties and chemical analyses of the cobalt product. In general, the purpose of this paper is to describe the present plant practices employed in the recovery of cobalt as a by-product of the nickel refinery operations."

Jan 1, 1967

By Robert E. Barieau

General expressions for evaluating various thermodynamic properties applicable to the van der Waals equation of state have been derived. These formulas were subsequently used to evaluate various thermodynamic functions in the two-phase region. The results indicate that, for a van der Waals fluid, there is a finite discontinuity in the second derivative of the vapor pressure curve, in the second derivative of the chemical potential or Gibbs free energy at the critical point, and in the heat capacity at constant volume measured at the critical density. Numerical values are tabulated and graphs are presented for all functions calculated.

Jan 1, 1967