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By H. H. Storch

"INTRODUCTION The first paper of this series contained data concerning the behavior of polyhalite (K2S04.MgS04.2CaS04.2H20) upon calcination and subsequent leaching with water at 100° C. It was found that upon heating polyhalite to temperatures between 298 and 500° C. the water of crystallization is driven off, leaving, an amorphous mixture of K2S04, MgS04, and CaS04. Two transition points were located; one at 298° C. which coincides with the vigorous evolution of steam; and one at 551° C. which results in the formation of a hard mass of crystals. The latter probably consist of a solid solution If the compounds langbeinite (K2504, 2MgS04), potassium dicalcium sulphate (K2304. 2CaS04), and anhydrite (CaS04). The heat of decomposition of polyhalite at 298° C. was measured and found to be 66,000 ± 5,000 calories per mol. The optimum temperature of calcination with regard to subsequent extrac¬tion with two parts of water (at "" 0° C.) is 430 to 450° C. for 65 to 100 mesh material, if one half hour at the calcination temperature is allowed. The maximum concentration of K2S04 obtainable in the extraction of calcined polyhalite is 11.4 grams per 100 grams of water. This concentration of K2304 is considerably above the equilibrium value (3.6 g. per 100 L. of H20 at 83° C.) with respect to the solid phases polyhalite, potassium calcium pentasulphate, ¬and anhydrite. The figure 11.4 K. of K2804 per 100 g. of H20 is also somewhat than the equilibrium value (9,65 g. per 100 g, H20) with respect to the solid phases potassium calcium pentasulphate and syngenite."

Oct 1, 1930

By Loyal Clarke, H. H. Storch

"The discovery of large deposits of polyhalite (K2S04.MgS04.2CaSO4.2H2O) in Texas has led to an investigation of possible industrial proecsses for the extraction of potash from this material. This mineral was first discovored in small quantities in the European potash deposits in or about the year 1800. Chemists fire thought it to be a form of calcium sulphate, but a more accurate analysis by Strohmiyer indicated the composition as given by the above formula.The decomposition of polytalite by aster is very slow and results in the formation of a layer of gypsum at the surface of the polyhalite which retarts the solution of the potaseium and magnesium sulphates. To obtain a substantial yield of K2S04 in solution it is necessary to use large amounts of water at room temperature, for he concentration of K2S04 is limited by the low solubility of syngonite (K2S04.CaS04.H2O) whereas at 100º C. several days boiling are necessary to obtain more than a 6 per cent K2S04 solution even when finely powdered polyhalite is employed.In 1854 H. Rose discovered that calcination, followed by leaching with water, resulted in a larger extraction of the potassium and magnesium sulphates, as compared with leaching without precalcination. During the course of a series of investigations concerning formation of oceanic salt deposits, Van't Hoff and his pupils obtained sufficient data to construct the equilibrium diagram for the system K+Mg+SO4--Ca++.H2O for 25° C. and for 83° C. These data are very well summarized. in the International Critical Tables' and by Boeke and Eitel. From a consideration of the diagrams for 83º C. one would conclude that an extraction of polyhalite with moderate amounts of water at 33º C. would result in a solution whose maximum concentration of K2So4 would be about 3.6 grams per 100 grams of water and of M2SO; about 4.0 grams per 100 grams of water, corresponding to equilibriumwith the solid phases: Polyhalite potassiam-calcium pentasulphate and anhydrite.The fact that it has been found possible to obtain as high as 11.4 grams of K2S04 per 100 grams of water (see table 6) and an equivalent amount of MgSo4 (8.1 grams per 100 grams of water was obtained corresponding to a ratio K2/Mg of 0.98; indicates that the formation of these complex salts is very slow. To be sure, this results was obtained at 100° C. instead of 83º C. However, the work of Anderson and Nestall 9 on the double salts of calcium and potassium sulphates at 100º C. indicates that the diagram at 100º C. C. would not be greatly different from that at 83º C. This slow rate of approach to equilibrium when combined with precalcination of,of polyhzli-,a is the 17,asis of some of the more p:olisinE methods of extracting potash from polyhalite."

Jun 1, 1930

By W. D. Bensema, J. W. Adams

A portable, multichannel battery-operated mine-permissible measurement system was developed to measure the rms magnetic-field noise spectrum in the frequency range from 100 Hz to 375 kHz. During each measurement, the entire spectrum is measured simultaneously through the use of time-domain recordings which are later analyzed by Fast Fourier Transform processing. Dynamic ranges of 60 dB in a 125 Hz bandwidth are obtained for spectra covering the range from 100 Hz to 100 kHz. The method also allows a three-dimensional display of the way spectrum occupancy changes with time. Calibration and correction procedures allow absolute field strength measurement with an uncertainty of not more than 3 dB. We feel that further analysis of the system errors will allow this uncertainty to be reduced to less than 1 dB. Ambient magnetic field noise spectra covering frequencies from 100 Hz to 100 kHz are given for several underground coal mine locations. Examples are also given of magnetic field noise on the surface above the mine, noise in the mine face area, noise radiated by specific equipment, the voltage spectrum found on a 600 V dc trolley wire, and noise picked up simultaneously on loops and on roof support bolts.

Jan 1, 1973

By L. B. Pankratz, R. Barany, W. W. Weller

Experimental determinations were made of the heats of formation at 298.15 ° K of cuprous ferrite and cupric ferrite ; the heat capacity of cuprous ferrite was measured over the temperature range from 50 ° to 298 ° K and the entropy at 298.15 ° K was evaluated ; the heat contents of cuprous ferrite and cupric ferrite above 298.15 ° K were measured to 1,500 ° K and 1,100 ° K , respectively . These thermodynamic values were combined with other pertinent data to obtain heat and free energy of formation values at high temperatures . The stability of the two ferrites with respect to their constituent oxides is discussed . Thermodynamic values are included for the decomposition of cupric ferrite to form cuprous ferrite , magnetite , and oxygen .

Jan 1, 1964

By N. Fragen, H. H. Stroch

"INTRODUCTION A previous paper by H. H. Storch 4 described. three processes for the production of potassium sulphate from polyhalite (K2S01.MgSO1.2CaS04.2H2o), Since these processes depended upon calcination of polyhalite followed by leaching with water at 100°C., the fundamental reactions occurring in these steps were discussed in detail. This paper, which describes processes producing syngenite (K2S04.CaSO4.H2O) and potassium sulphate and gives data concerning the production of by-product magnesia, presents the results of work performed at the Non metallic Minerals Experiment Station of the U. S. Bureau of Mines, maintained at New Brunswick, N. J., in cooperation with Rutgers University.A study of the solubility relationships of the system 5 Ca++ -Mg++ -K+-SO4 = H20 at 25ºC. shows that syngenite is stable in the presence of a concentrated MgSO4 solution, the K2SO : equilibrium concentration being comparatively low (2.6 per cent), The processes described below, which involve the conversion of calcined polyhalite to syngenite, are based on the 25°C. equilibria. It has further been found that syngenite can be decomposed by water at 100ºC, yielding a 9 to 10 per cent K250 solution, the solid phase being potassium calcium pentasulphate (K2SO, 3CaSO.H2O, hereafter referred to as ""pentasulphate""). This latter compound is unstable in the presence of water at 25°C., its decomposition resulting in a solution containing about 3 per cent of K2SO4 and a solid phase consisting of gypsum. This behaviour of syngenite with water at 100°C. and of pentasulphate with water at 25ºC. constitutes the basis of processes for the production of K2SO4 by way of the conversion of calcined polyhalite to syngenite,Syngenite is a product which may be used as a fertilizer per se. As produced in the process to be described, it contains about 50 per cent of K2SO1, and will readily give up its potash content on treatment with water, although the limiting concentration at ordinary temperatures is approximately 3 per cent. This definite but limited solubility should make this product more desirable as a fertilizer then the more concentrated forms of potash salts which have higher solubilities and hence involve the danger or plant injury due to a high local concentration of potash."

Sep 1, 1931

By L. B. Pankratz

Heat content measurements were conducted for GaPo.996 and InPo.986 over the temperature range from 298° to 1,100° K, and for In2S2.897 over the range from 298° to 1,200° K. Both the actual experimental data and values adjusted to conform with the stoichiometric compositions (GaP, InP, and In2S3) were reported. Entropy increments above 298.15° K were calculated for the stoichiometric compounds, and heat content and heat capacity equations were derived.

Jan 1, 1965

By L. B. Pankratz

Enthalpies were determined for synthetic chalcopyrite (CuFeS2) between 298° and 1,050° K and for synthetic bornite (Cu5FeS4) between 298° and 1,100° K by copper-block drop calorimetry. Two transitions were found for each compound. The lower transitions were both crystal transformations from tetragonal (low-temperature form) to cubic (high-temperature form). The chalcopyrite transformation occurred at 830' K with a heat of transformation of 2,405 cal/mole; the bornite transformation was at 485° K with a heat of 1,430 cal/mole. The other transitions were of the second order and were presumed to be magnetic in character. The second-order transitions for chalcopyrite occurred at 930° K, and the one for bornite at 540° K. Enthalpy increments, entropy increments, and heat capacities are tabulated at even temperatures above 298.15° K. Equations of enthalpy are also given.

Jan 1, 1970

By Robert M. Doerr

The purpose of the investigation was to determine the oxidation behavior of selected tungsten-cobalt alloys. Specimens of Wand W-Co containing 0.7, 1.7, 3.4, and 9.7 weight-percent Co were subjected to pure 02 at 1,000° and 1,100° K, and specimens of W-Co containing 29.8 weight-percent Co, at 1,100° K. Reaction kinetics were determined volumetrically. For specimens other than those containing 29.8 percent Co, the reactions proceeded at about a constant rate at either temperature, indicating the formation of a scale of constant protectivity; the reaction rates were essentially independent of the Co concentration. The scales on these alloy specimens consisted principally of WO3 and CoWO4. Specimens of a 29.8 weight-percent Co alloy, consisting primarily of the W6CO7 phase, oxidized with only slight deviations from the parabolic rate law at 1,100° K. The protective scale on these specimens consisted chiefly of Co3O4, CoW04, and W1 8°49; Co3O4 was outermost, and the W18O49 was adjacent to the alloy. The results suggest that the Co-rich outer scale inhibited the inward transport of 0 to an extent sufficient to greatly limit the amount of the nonprotective WO3 formed, so that protective W18O49 formed instead.

Jan 1, 1967

By C. L. Karr

The U.S. Bureau of Mines is optimizing the design of an air-sparged hydrocyclone. This report summarizes the initial stage of the project-the prediction of collision efficiencies for use in a comprehensive air-sparged hydrocyclone model. The equations of motion are presented in nondimensional form and solved numerically for a small spherical particle passing around a larger bubble in an infinite fluid under the influence of a strong force field. Collision efficiencies are determined from the calculated particle trajectories for values of Stokes' number, K, between 0.01 and 100 and for values of the nondimensional force, W, between 0.0 and 100. These large values of K and Ware needed to model high-performance flotation devices like the air-sparged hydrocyclone; solutions for the required K and W values have not appeared in the literature prior to this study. Effects of changes in particle-to-bubble radius ratio are considered for both viscous and potential flows. The results help predict the improved recovery of fine particles when flotation is performed in a strong force field.

Jan 1, 1990

By Harold L. Rhodes

Vapor-liquid equilibria data for 65-34-1 and 25-27-48 mole percent helium-nitrogen-methane mixtures are presented for 12 temperatures from 76.5° to 164° K and pressures from 100 to 1,200 psia. These data were obtained in a windowed phase equilibria cell equipped with a vapor recirculating pump. Isobaric and isothermal K-values are plotted for both mixtures. Two isometric plots are included.

Jan 1, 1972

By L. B. Pankratz

The heat contents of the sesquioxides of erbium, holmium, thulium, and ytterbium (Er203, Ho203, Tm203, and Yb203) in the cubic crystalline form were measured over the temperature range from 298° to 1,800° K. The erbium and holmium sesquioxides gave regular heat content-temperature curves. Thulium sesquioxide had a minor thermal anomaly near 1,680° K, with a heat absorption of 310 cal/mole; similarly, ytterbium sesquioxide had a minor anomaly near 1,365° K, with a heat absorption of 150 cal/mole. The heat content results are presented in both tabular form (at 100° intervals) and in algebraic form. Entropy increments, corresponding to the tabulated heat content results, also are listed.

Jan 1, 1963

By J. W. Walkiewicz

The Bureau of Mines investigated alloys containing mischmetal (MM), cobalt, copper, magnesium, and iron for use in permanent magnets in place of the scarce samarium-cobalt alloys. The magnetic properties of MM-Co, MM-Co-Cu, MM-Co-Cu-Mg, and MM-Co-Cu-Fe-Mg alloys were evaluated. Magnets were fabricated by powder metallurgy consisting of arc-melting the metals, crushing and grinding the resultant alloys, alining and compacting the powder, and sintering the compacts. Magnetic values of MHc = 4.7 kOe, BHc = 4.07 kOe, Br = 6.81 kG, and (BH)max = 10.0 MGOe were obtained with a MM-Co alloy containing 36±0.5 wt-pct MM. By substituting copper and magnesium for part of the cobalt, the values for MHc and BHc were increased to 29.0 kOe and 5.89 kOe, respectively. This intrinsic coercivity value exceeded that of Sm-Co alloy obtained in our laboratory. The addition of iron to MM-Co-Cu-Mg alloys resulted in an increase of Br to 6.90 kG and (BH)max to 10.3 MGOe. Copper and magnesium contents of these alloys were optimized to obtain maximum values of MHc.

Jan 1, 1981

By Philip Thompson

The Bureau of Mines investigated a selective flocculation-flotation technique to remove insoluble slimes from low-grade potash ore in a continous 45-kilogram-per-hour (100-pound-per-hour) process investigation unit (PIU). This research is part of the Bureau's program to improve resource recovery from low-grade ores. Results showed that 84 percent of the insoluble slimes were removed from an ore containing 5.5 percent water-insolubles and 14 percent K20 using a Bureau-developed, cationic flocculant-glycol ester-diesel oil reagent. Subsequent potash flotation recovered 75 percent of the potash in a cleaner concentrate assaying 56 percent K20. Concentrate leaching upgraded the product to market specifications of 60 percent K2O. An economic evaluation by the Bureau suggested that the rate of return on investment, after taxes, should be about 20 percent for such an enterprise.

Jan 1, 1980

By D. G. Foot

The Bureau of Mines investigated energy-efficient methods for recovering potash values from process and waste brines. Laboratory pan evaporation of four chloride brines produced crude salts containing predominantly sylvite, halite, and carnallite. Six sulfate-chloride brines produced crude salts containing primarily schoenite, kainite, leonite, sylvite, carnallite, and halite. Potash grades ranged from 7.2 to 22.2 pct K20, and recoveries from 84 to 99 pct. Sylvite flotation from chloride evaporites, with amine collector, recovered 90 to 97 pct of the potash in a concentrate containing 54.3 to 60.3 pct K20. Fatty acid flotation of the high-sulfate evaporite recovered 78 pct of the sulfate minerals in a 27.8-pct-K20 concentrate. Flotation of the chloride minerals with amine collector recovered 80 pct of the potash in a 59.7-pct-K20 concentrate. Solar evaporation of 10,000 gal of brine recovered 99 pct of the potash in a crude evaporite containing 24.5 pct schoenite and 20 pct sylvite. Continuous flotation in a 100-lb/h process research unit recovered over 95 pct of the potash in schoenite and sylvite concentrates containing 28.0 and 62.3 pct K20, respectively. An economic evaluation suggested a rate of return of 3 pct for a new facility and 9 pct if. the process is adapted to fit an existing plant.

Jan 1, 1984

By R. K. Koch

The vapor pressures of liquid molybdenum and liquid zirconium were determined by the Langmuir free-evaporation method. An electron-beam furnace with a water-cooled copper crucible was used for melting. Temperature was measured with a two-color ratio pyrometer. The vapor-pressure data led to the following equations: [log p (atm) = 5.429 - 28,380 T for liquid molybdenum in the range 2,890° to 2,990° K, and log p (atm) = 6.521 - 30,940 T for liquid zirconium in the range 2,229° to 2,795° K.] Third-law evaluations of each data set gave mean heats of sublimation (298.15° K) of 157.6 ± 1.8 kcal/mole and 148.4 ± 2.4 kcal/mole for molybdenum and zirconium, respectively, where the uncertainties are two standard devia¬tions. Second-law standard heats of sublimation determined from sigma plots and tabulated enthalpies were 143.5 ± 2.7 kcal/mole and 149.2 ± 3.8 kcal/mole for molybdenum and zirconium, respectively. The better agreement in heats of sublimation for zirconium is attributed to the 566° K temperature range studied which permitted a more accurate definition of the vapor pressure curve than could be obtained from the 100° K span for molybdenum. This supposition was verified by making a sigma-prime plot which utilized solid vapor pressure data for molybdenum to extend the evaluation range by 800° K. This gave a standard heat of sublimation of 155.2 ± 1.6 kcal/mole which is in good agree¬ment with the third-law value. The plot also gave a standard entropy of sublimation (298.15° K) of 35.73 ± 0.48 eu.

Jan 1, 1968

By Robert E. Wood

[The temperature dependency of the low-density thermal conductivity coefficients, ?°T, of nitrogen, 100° to 1,200° K, is correlated with the Keyes' equation, ?T ½ -1 -12/T) WT = aT+ bT 10 The equation ?T,P = ?°T +a[ ]ß represented 509 experimental higher V pressure thermal conductivities in the temperature range 131.2° to 973.15° K for pressures to 500 atmospheres, with a mean absolute deviation of 2.35 percent. This equation was used to compute thermal conductivities of gaseous nitrogen for 47 pressures, 1 to 240 atmospheres, and 110 temperatures, 133° to 740° K, which are common to conditions encountered in Bureau of Mines helium purification processes. Isobaric heat capacities, CP, and viscosities, ?T,P, from previous work were combined with the present thermal conductivities, ?T,P, to compute Prandl1 numbers, C?T P / ?T ,P, of nitrogen. Tabular values of Prandtl num¬bers are presented for 49 pressures, 1 to 240 atmospheres, and 75 temperatures, 133° to 740° K. Estimated uncertainties are ±5 percent in the tabulated thermal conductivities and ±15 percent for the computed Prandtl numbers. However, the uncertainty may rise to ±10 percent for thermal conductivities and to ±30 percent for Prandtl numbers as the critical conditions of nitrogen are approached.]

Jan 1, 1971

By J. E. Murphy

A method is being developed by the Federal Bureau of Mines for recovering lead metal from galena without the generation of SO2. Lead chloride is obtained by leaching lead concentrate at a temperature of approximately 100° C with FeCl3 solution: PbS + 2FeCl. " PbC1 2 + 2FeC1 2 + S. Electrolysis of the PbCI 2 product in a fused-salt bath results in deposition of molten lead metal at the cathode and evolution of chlorine at the anode. The chlorine can then be absorbed in the spent leach solution to regenerate FeCl3 for recycling. Optimum electrolyte composition was a PbC12-LiCl eutectic containing 7.6 wt-pct LiCl. The PbCl2-NaCl eutectic also proved satisfactory. Electrolysis in the PbCl2-LiCl bath at 450° C yielded 99 pct current efficiency at a current density of 5 amp/in2 with an energy requirement of only 0.24 kW-hr/lb metal produced. This compares with 98 pct current effi¬ciency and 0.26 kW-hr/lb metal produced for the PbCI2-NaCI bath. A typical lead deposit contained less than 100 ppm total detectable metallic impurities. At the low temperature employed for electrolysis, there was essentially no vaporization of Pb or FbC12.

Jan 1, 1974

By D. G. Foot

The Bureau of Mines investigated two methods for recovering potash from carnallite ore in continuous 100-lb/h flotation units. In the insoluble-slimes flotation procedure, insoluble slimes were removed by flotation prior to potash flotation. In the direct flotation method, insoluble slimes were depressed and the potash floated directly without prior removal of the insoluble slimes. Seventy-three percent of the potash in the ore was recovered in a leached final KCl product contain-ing 59.1 pet K20 using the insoluble-slimes flotation method. The direct flotation method recovered 74.5 pct of the potash in a final product containing 60.2 pet K20. The rate of return on the investment was calculated at 13 pct for the insoluble-slimes flotation method and 15 pct for the direct flotation method, based on a Bureau economic evaluation.

Jan 1, 1984

By John W. Adams

The present status of the National Bureau of Standards program is that many magnetic tapes of analog data have been recorded in four major mines. Each mine uses different types of equipment. In addition, some surface measurements of noise have been made at two additional mines. Two types of recordings have been made: (1) broadband measurements for spectral plots and (2) narrowband measurements for amplitude probability density (APD) plots. Only data from one mine (Robena #4) has been processed and was, presented at this workshop. The short-term goals are: (1) finish processing data from the other mines, (2) establish or reduce measurement system uncertainties, (3) put Robella report into final form for distribution, and (4) hold a review to determine what has been done, to distribute and to interpret the preliminary data, and to determine what still needs to be done. Long-term goals are: (1) complete final reports on each of the mine trips, (2) establish techniques for predicting noise in mines already visited and establish uncertainty bounds for these predictions, and (3) establish techniques for predicting noise in mines that have not been visited (but that use similar equipment to those visited) and also establish uncertainty bounds for these predictions. Specific factors or formats to be presented include: (A) For underground broadband measurements: 1. 300 Hz to 100 kHz spectral plots 2. 300 Hz to 384 kHz spectral plots 3. 300 Hz to 192 kHz spectral plots 4. 300 Hz to 6kHz (subject to change to 3 or 12 kHz) spectral plots (B) For surface broadband measurements: 1. 300 Hz to 6 kHz (or 12 kHz) spectral plots 2. 300 Hz to 3 kHz spectral plots (C) For underground narrowband measurements : 1. APD plots at 12 frequencies from 10 kHz to 32 mHz of magnetic field strength 2. R. M.S. and average values will be calculated based on time averaging for these plots (D) Sample spectral measurements of: 1. Roof-bolt voltages 2. Trolley wire-to-rail voltages 3. Phone line currents

Jan 1, 1973

By J. P. Morris

A diphenyl ether calorimeter for measuring high-temperature heat contents of ferrous alloys and iron-and steelmaking slags was constructed and calibrated with specimens of molybdenum, alumina, and platinum that were heated to temperatures ranging from 1,720° to 1,875° K. The standard deviation of the calibration measurements was 0.37 percent. By measurements of the enthalpy of delta and liquid iron, the heat of fusion of iron was found to be 3,298 ±100 cal per mole.

Jan 1, 1966