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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

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 J. G. Eberhort

ThE literature of surface phenomena shows that, except for most of the rare-earth elements, surface tensions have now been determined for almost every liquid metal. The situation for liquid metal oxides is, in contrast, characterized by a great scarcity of surface-tension data. A surface-tension correlation between these two classes of substances has been found which provides a means of estimating unknown liquid-oxide surface tensions from the corresponding known liquid-metal surface tension. Lf the surface tension of the liquid metal is a(M) and that of the liquid metal oxide is o(M,Oy), then oxides of all stoichiometries can be brought into one correlation if is plotted against with the surface tensions taken at the respective melting points. The available data is displayed in this fashion in Fig. 1 where the relationship between the surface tensions of the two classes of liquids is found to be The correlation in Fig. 1 is based on data found for nine liquid metal oxides and the corre- sponding liquid metals In cases where several sur-face-tension determinations were available on the same substance, higher values were generally favored over lower ones because they usually indicate greater Sample purity. All of the metal-metal oxide pairs are in good agreement with Eq. [I] except for B-Bz03. The reason for the departure of this pair from the correlation is not understood. To estimate the surface tension of other liquid metal oxides the corresponding liquid-metal surface tension must be found. A nearly complete bibliography of the surface tension of liauid elements is available in the 46th edition of the Handbook of Chemistry and physics. Some additional references on metals are included here for convenience Se,26Sr,'?ThanduZ5). It is also possible to estimate the surface tension of a solid metal oxide or metal from the corresponding liquid-state data. As a liquid material is cooled through its melting point the surface tension increases abruptly by an amount Ao. bondi' has estimated that the maximum value of Aa at the melting point is Ao = Ahf/A [2] where Alzf is the heat of fusion per atom and A is the area per atom in the interface. Thus with heat of fusion and crystallographic data the surface tension of a solid at the melting point can be estimated as o + Ao.

Jan 1, 1967

Jan 1, 1967

Detailed petrographic analyses of coal seams from the Newcastle, Illawarra, and Lithgow Coal Measures were made for a number of localities for each of twelve seams. From these analyses characteristic standardprofiles were derived for each seam. Two broad types of profile were found; one in which vitrite-poor and vitrite-rich layers alternate, and another in which there is a steady decrease in vitrite from the base to the top of the seam. From comparison of the petrographic profiles it was concluded that the Great Northern Seam in the Northern Coalfield is a possible equivalent to the BulIi in the Southern; and likewise the Fassifern to the Balgowni...

Jan 1, 1967

By W. H. Eddy

The Bureau of Mines conducted laboratory batch flotation tests and continuous pilot plant flotation tests on a complex calcareous fluorspar ore from Cave-in-Rock, Ill., to determine the technical feasibility of producing commercial-grade concentrates by the sodium fluoride-calcium lignin sulfonate-fatty acid method of concentrating fluorspar previously developed by the Bureau. The continuous flotation tests, treating about 150 pounds of ore per hour, produced fluorspar concentrates assaying 96.4 percent CaF2; 90 percent of the fluorspar was recovered.

Jan 1, 1967

The flolation behaviour of some Australian uranium ores was investigated. Although uraninite and pitchblend float readily with fatty acids, selective concentration to produce an economically discardable tailing has not yet been achieved. This is attributed to the presence in the ores of a quantity of uranium mineral in finely dispersed form which is very difficult to liberate. For some of the ores, at least, the proportion of this material decreases with increase in head assay.Flotation may be a useful concentrating method for some Australian ores if uranium oxide is to be sold in a free competitive market.

Jan 1, 1967

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

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. H. Larson, L. G. Twidwell

DURING the roasting of zinc sulfide concentrates and by-product recovery from flue dusts, the zinc sul-fate phase may occur in various stages of the processes. In addition to zinc sulfide, other sulfide phases are usually present such as CdS, PbS, CuzS, and FeS. Consequently, the effect of these sulfides on the thermal decomposition of ZnS04 was investigated. Merck high-purity, anhydrous zinc sulfate was used as the starting material. The sulfate was heated under an argon atmosphere, at a rate of 10°C per min. With the first slight indication of decomposition as determined by gas analysis, the sample was removed from the furnace and allowed to cool. X-ray patterns showed no other phase present. It is estimated that less than 0.05 pct of the ZnS04 decomposed. The metal sulfides were also heated under an argon atmosphere to drive off any adsorbed water. The materials were then sized (-200 to +270 mesh), mixed in predetermined mole ratios, and pressed into pellets. The experimental measurement of the reaction rate consisted of purifying the argon carrier gas, continuous flushing of the heated reacting mixture with argon, and collection and analysis of the SOn product gas. The reaction system was heated to 600°C and al-

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,' 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

By Robert E. Barieau

This report gives the principles of the method used by the Helium Research Center of the Bureau of Mines when solving nonlinear-regression problems and contains the mathematical equations necessary to accomplish the following objectives: the evaluation of the parameters in such a way that the sum of the weighted squares of the residuals of an experimental observable is a true minimum, regardless of the functional relationship between the variables and these parameters; and the evaluation of all variances and covariances of the parameters by means of the usual approximation of the law for the propagation of errors.

Jan 1, 1967

By H. R. Cooper

Beginning from the point of view that process control of ore flotation can be approached by on-line analysis of processing behavior, an equation was developed which has characteristics useful for a multi-variable feedback loop. The application of this equation to optimizing control with a data acquisition system will be discussed in Part 11. OBJECTIVE OF CONTROL The purpose of developing a feedback method for concentrator control is to provide a means for determining ore processing behavior in order that data describing the ore can be used to make appropriate changes in control conditions while the ore continues to flow through the flotation circuit. In absence of simple linear relationships between pairs of variables in the flotation process, attention is directed to the need for a generalized relationship which possibly would incorporate all pertinent variables. It would be possible to apply such an equation to the control of variables in a concentrator in real time according to operational requirements as ore gradually changes in quality and processing behavior. To meet this objective, it is necessary to define relationships describing flotation performance in terms of performance variables capable of being measured on-line, either with on-line instruments and analyzers or with manual methods lending themselves to quick determination of meaningful information. Relationships derived to meet this objective form a model for the flotation process. The evaluation of flotation parameters of the ore and the execution of control on the basis of the derived information while the ore is continuing through the process would constitute a feedback control system. Data for the following control and performance variables can be made available: 1) ore feed rate, 2) collector addition rate, 3) lime addition rate, 4) pulp density, 5) assay or multiple assays in feed, tails, or concentrate sufficient for material balancing, 6) particle size distribution in flotation feed, 7) froth height, and 8) frother addition rate. Other process variables, such as flotation air input and mechanical agitation intensity, are usually not considered as control variables and were not taken into account in this analysis. Other data, such as that describing the ore, would be useful for concentrator process control. However, information of this type (such as ore hardness, grain size of the mineral, chemical species of the mineral, and ore surface properties) being not presently measurable in the on-line sense, has the effect of causing disturbances in the system which can be detected only indirectly. The process control system being sought must recognize disturbances by their effect on measured performance followed by determining control changes to compensate for them in meeting the objectives of improved performance (perhaps higher throughput, maximum return, etc.). A suitable model for the process having capability of recognizing the effects of ore disturbances should provide the means for introducing proper compensation through control changes. This would be done by processing on-line data with the model to calculate coefficients reflecting ore characteristics. This procedure can only be applied in a typical flotation system when on-line data can be processed at faster rates than the usual rate at which the ore in flotation feed takes on significantly different characteristics. For example, material balance data can be accumulated in approximately 5-min intervals using on-line X-ray fluorescence analysis. The flotation system time constant might be 15 min including grinding. Ore changes having time constants longer than 1 hr could be accommodated using on-line feedback control by this procedure. FORM OF A FLOTATION MODEL A suitable form for mathematical expression of the flotation process is an equation involving rates, when each of the components entering into the separation can be treated independently by a rate equation. A first-order, kinetic rate equation can be written on

Jan 1, 1967

Jan 1, 1967