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By E. G. King

This paper reports measurements of low-temperature heat capacities and entropies at 298.15° K. of two copper ferrites (CUFe204 and CU0.75Fe2.2504). These substances, which occur in copper-smelting slags, have not been sujected to any previous direct thermodynamic investigation. The two copper ferrites are spinel minerals of the variate class. In previous investigations similar data were obtained for 13 other spinel minerals -7 of the normal class and 6 of the variate class. The entropies at 298.15° K. of these minerals have been compiled and revised as necessary in the light of present knowledge regarding structural randomness; entropy values, recommended for use in thermodynamic calculations, are listed.

Jan 1, 1959

By J. C. Fowler

The field testing of the Seismic Mine Monitor System is described. This system consists of nine geophones buried about 40 feet deep over a ten-square-mile area, the amplifiers and electronics needed to get the signals to the mine office, and a central processor unit to detect and locate explosions and large roof falls. Since the problems associated with the original installation were solved, this system has worked for 2 1/2 months. The system has detected roof falls in the pillar areas and has located blasts as small as 114 pound of dynamite. The location accuracy has, in general, been within 250 feet. The system is now being used to gather long-term data on the seismic activity of the mine.

Jan 1, 1974

By Seth C. Schaefer

The Federal Bureau of Mines studied the Gibbs free energies of formation of chromous fluoride (CrF2), chromic fluoride (CrF3), and chromium (II,III) fluorides (CrF2.40 and CrF2.45) with high-temperature galvanic cells employing calcium fluoride doped with 1 mole-pct yttrium fluoride as the electrolyte. Free-energy changes were obtained from open-circuit potential measurements for the following cells: Cr, CrF2 // CaF2 // NiF2, Ni (a) NiO, NiF2 // CaF2 // CrF3 , Cr203 (b) CrF2 , CrF2.40 // CaF2 // NiF2, Ni (c) and CrF2 ?45 , CrF3 // CaF2 // NiF2, Ni (d) with the following overall reactions Cr(s) + NiF2 (s) = Ni(s) + CrF2 (s) (1) 3NiO(s) + 2CrF3 (s) = 3NiF2 (s) + Cr203 (s) (2) 5CrF2 (s) + NiF2 (s) = 5CrF2.4O (s) + Ni(s) (3) and 3.64CrF2.45 + NiF2 (s) = 3.64CrF3 (s) + Ni (s) . (4) These results were combined with the best available literature values of ?Gf° of NiF2, NiO, and Cr203 to deduce Gibbs free energies of formation for the chromium fluorides expressed as follows: ?Gf°(CrF2) = -179.31 + 24.33 X 10-3T ± 0.43 kcal-mole. (5) (858.1 - 964.9 K) ?Gf° (CrF3) _ -226.16 + 1.82 X 10-3T ± 0.79 kcal/mole (6) (880.8 - 957.8 K) ?Gf°(CrF2.40) _ -213.65 + 32.14 X 10-3T ± 0.44 kcal/mole (7) (0053.9 - 936.8 K) and ?Gf°(CrF2.45) _ -176.17 - 12.67 X 10-3T ± 0.80 kcal/mole (8) (875.1 - 937.6 K). Free energies and equilibrium fluorine pressures for three univariant and one bivariant equilibria are illustrated.

Jan 1, 1976

By K. O. Bennington

The thermodynamic properties of two manganese silicates, pyroxmangite and fowlerite (zincian rhodonite), were experimentally determined by the Bureau of Mines. The standard enthalpies of formation were determined by hydrofluoric acid (HF) solution calorimetry, the low-temperature heat capacities by adiabatic calorimetry, and the high-temperature heat capacities by differential scanning calorimetry over the range 322 to 1,372 K. Data for the standard enthalpy of formation (AH298), the derived standard entropy (S298), and the standard Gibbs energy of formation (AGf 298) are as follows: Pyroxmangite [(Mn0.9554Cao,0446)(Si03)J- AHf298 319.668±0.46 kcal/mol AH298 (from oxides)... -7.215±0.11 kcal/mol 5295 23.785±0.048 cal/(mol'K) AGf298 -301.190±7.96 kcal/mol Fowlerite [(Mno.7o3Zno.0884Ca0.2086)(Sio3)]--AHf298 ?... -329.914±0.419 kcal/mol AH298 (from oxides)... -8.400±0.104 kcal/mol 5598 21.949±0.059 cal/(mol-K) AGf298 -310.716±7.99 kcal/mol These experimentally determined values were combined with data from the literature to calculate the Gibbs energies and equilibrium constants of formation over the temperature range of the measurements. Standard enthalpies, Gibbs energies, and equilibrium constants of formation are given as a function of temperature from both the elements and the constituent oxides.

Jan 1, 1987

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 D. A. Stanley

The Bureau of Mines is investigating a method of dewatering flocculated fine-particle waste that involves treating the waste with a high molecular-weight polymer such as polyethylene oxide (PED) followed by dewatering on a static screen and/or in a trommel. Dilution of the polymer solution used for dewatering and use of the ion-exchanged form of the montmorillonite clay were found to be major factors determining the amount of polymer required to dewater clay-containing slurries. The amount of polymer, A, required to dewater ion-exchanged montmorillonite can be described by the equation, An = kC + b where n, k, and b are empirical constants and C is the concentration of the polymer solution used for dewatering. Clays that require large amounts of polymer for dewatering also dewater to a lower solids content. The concentration of the polymer solution is important because it affects the radius of the polymer coil in solution and hence its ease of transfer to a bridging configuration by shear. The constant, n, a function of the charge to hydrated radius of the exchange ion, relates to the strength of the bond between the polymer and the surface of the clay through a water bridge. The constant k is related to the hydrated radi-us for sodium or to the unhydrated radius for the other exchange ions.

Jan 1, 1986

By M. J. Ferrante

Relative enthalpies of high-purity disodium hexatitanate (Na2Ti6013) were measured at the Bureau of Mines to provide new thermodynamic data needed to advance the technology of materials. Measurements from 298.15 to 1,478 K were made by drop calorimetry with a copper block. Tabulated values are listed for the standard relative enthalpy, heat capacity, en-tropy, and Gibbs energy function between 298.15 and 1,500 K. Enthalpy data are also given in equation form and are combined with thermodynamic data from the literature to derive values of standard enthalpies of formation, Gibbs energies of formation, and logarithms of the equilibrium constants of formation. Similar calculations were made for the reaction of Na20 with Ti02.

Jan 1, 1986

By R. K. Koch

The vapor pressures of liquid titanium and liquid platinum were studied under the Bureau of Mines program for the determination of thermochemical data on the transition elements. Beating was done in a 2-kw electron-beam furnace with a water-cooled copper crucible to contain the melt. Temperature was measured with a disappearing-filament brightness pyrometer. The vapor pressure data for liquid titanium in the range 2,008° to 2,379° K are represented by the least-squares derived equation [log p (atm) = 6.268 - 22, T] Two series of determinations were made on liquid platinum. Results of the first series are expressed by the least-squares derived equation [log p (atm) = 8.240 - 30,460T] for the range 2,0860 to 2,4200 K. Results of the second series are expressed by the least-squares derived equation [log p (atm) = 7.795 - 29,580 T] in the range 2,045° to 2,442° K. Third-law evaluations of each series gave mean standard heats of sublimation of 112.4 kcal/mole, 133.3 kcal/mole, and 133.8 kcal/mole for titanium first series on platinum, and second series on platinum, respectively. Second-law heats of sublimation and equations for heats, free energies, and entropies of vaporization were obtained from sigma plots of each data set.

Jan 1, 1969

RI 9527. Effective Hazard Recognition Training Using a Latent-Image, Three-Dimensional Slide Simulation Exercise, by E.A. Barrett and K.M. Kowalski. Pittsburgh, PA: U.S. Department of the Interior, Bureau of Mines, 1995. NTIS stock number: PB95-170379. Rl 9531). Computer Modeling and Analysis of The Greens Creek Mine, Admiralty Island, AK, by MJ. Beus and T.J. Orr. Spokane. WA. -U.S. Department of the Interior, Bureau of Mines. 1995. NTIS stock number: PB95-176418. RI 9600. Application of Field Measurements and Computer Modeling to Evaluate Deep Mine Shaft Stability in Northern Idaho, by M, J. Beus, T. J. Orr and J. K Whyatt. Spokane, WA: U.S. Department of the Inferior. Bureau of Minus. 1996. NTIS stock number: PB96-140181. [ ]

Jan 1, 1995

By [F. P. ] Stambaugh

Results of research on the hydrothermal precipitation of zirconium oxide from the Bureau of Mines' zirconyl chloride-sulfate strip liquors indicate that nuclear grade material can be prepared by this process. Greater than 99% of the zirconium value can be precipitated at 250-260°C in short (5-10 minutes) reaction time without consumption of acid value of the liquor. Thus, precipitation of zirconium dioxide on a continuous basis, i.e., the zirconium dioxide is precipitated in a continuous mode of operation by pumping the strip liquor through a heated pressurized reactor and recycle of the acidic (spent) liquor to the process stage are favored. The results of accompanying studies of liquod/solid separation, product washing and dewatering, product purity, and chlorination of the product are presented and discussed.

Jan 1, 1980

By Deborah A. Kramer

This Bureau of Mines report presents a cost estimate of the Bayer process, which is used for virtually all cell-grade alumina production. The report will serve as a reference point to determine the economic merits of processes that have evolved from Bureau of Mines investigations on technology for producing alumina from domestic nonbauxitic raw materials. The Bayer process involves dissolving the alumina present in bauxite in a caustic solution at high temperature and pressure. After the un- dissolved impurities are removed, the solution is seeded to produce an alumina trihydrate precipitate. This precipitate is filtered, washed, and calcined to produce the cell-grade alumina product. This cost estimate is for a plant producing 1 million tons of alumina per year. The estimated operating cost is approximately $250 per ton of alumina.

Jan 1, 1983

By H. V. Makar

An aluminizing dross which is accumulating as a waste material in substantial quantities was tested for possible use as a steel deoxidizer. This material, consisting mainly of aluminum, silicon, and iron, was used to deoxidize laboratory-scale melts ranging from 7 to 100 pounds. Oxygen analysis showed that the aluminizing dross was effective in reducing oxygen levels in steel. A direct comparison with aluminum wire showed the dross material to be at least as effective. Under similar test conditions with 7-pound melts, 3 grams of aluminum reduced the oxygen concentration from 210 to 175 ppm, while 4 grams of aluminizing dross (equivalent to approximately 2 grams aluminum) reduced the oxygen concentration from 250 to 170 ppm. An additional 4 grams of aluminizing dross produced a final oxygen concentration of 140 ppm.

Jan 1, 1972

By Grant R. Brown

The report provides guidance for determining those environmental impacts associated with the surface mining of steeply pitching coal seams. In addition to the environmental impacts, four additional issues are addressed, namely (1) Time and motion studies of those coal mining systems employed in mining seams which pitch in excess of 250, (2) Assessment of those mining techniques, (3) Development of rationale for the mining methods employed, (4) Identification of the reclamation practices and determine whether these practices were in compliance with appropriate Federal and State regulations. Five surface mines located in three geologically distinct basins of the United States were analyzed during the period of August through November 1979. The three basins include the Hanna Basin of Wyoming, the North Park Basin of Colorado and the Southern Anthracite Field of Pennsylvania.

Jan 1, 1980

By Jack C. White

As part of an investigation of the production of alumina by the nitric acid leaching of kaolinitic clay, the Bureau of Mines designed, built, and tested a fluidized-bed system for the calcination of aluminum nitrate nonahydrate to alumina, while recovering nitric acid. The calciner consisted of an 8-in-square by 36-in-tall vessel containing 18 in of fluidized solids. Molten aluminum nitrate, sprayed directly into the fluidized solids, formed sandy, granular alumina by growth of successive layers on fluidized particles. Solids were fluidized in a dense bed at temperatures of 250° to 500° C with steam, air, or mixtures thereof. Decomposition of nitrate ranged from 4 to 10 pet during single-pass steam or air fluidization, respectively. Alumina dust losses and low throughput are significant unsolved problem areas.

Jan 1, 1982

By P. L. Woolf

Oil was successfully injected into the tuyeres of the Bureau of Mines experimental blast furnace. Determinations were made for the minimum oil addition necessary to permit the maximum available blast temperature of 2,250° F. and the maximum oil rates at blast temperatures of 1,900°, 2,000°, and 2,100° F. From these tests, the upper and lower levels of high-temperature heat input, which limit the smoothly operating furnace, were established. Substantial coke saving was realized with maximum oil injection. Oil-to-coke replacement ratios have been calculated for various conditions, and oil is compared with natural gas and moisture in somewhat general terms. A study of the effect of variations in slag volume and basicity on the sulfur content of the metal at high sulfur loads was made.

Jan 1, 1963

By D. G. Kesterke

Research was conducted to determine the feasibility of extracting elemental oxygen from silicate-bearing melts by high-temperature electrolysis. The method was based on a modification of existing processes for electrowinning metals from their oxides dissolved in molten halide systems. Electrolyses were performed at temperatures ranging from 1,050° to 1,250° C in boron nitride cells that incorporated a silicon carbide cathode and an iridium anode. The electrolytes contained volcanic scoria as the oxygen source, plus mixtures of BaF2 and LiF as fluxing agents. Cell gases containing almost 14 volume-percent oxygen were obtained. The average anode current efficiency for several experiments of extended duration was calculated to be 55 percent. Cell design and operating conditions are described, and some of the problems associated with the process are discussed.

Jan 1, 1971

By Russell R. Trengove

Bureau of Mines exploration at the property of the Tulare County Tungsten Mines was by core drilling from the surface from May 16, 1950, to July 13, 1950. The property is in the western foothills of the Sierra Nevada Range, 18 miles northeast of Lindsay, Calif. It has been in almost continuous production since 1942 and has produced 40,831 units of tungsten trioxide (W03) with a grade of approximately 67 percent. The work performed comprised a study of the geology, mapping the area, sampling the outcrops, and diamond drilling the area adjacent to the mine workings. Ten holes were drilled for a total of 1,824 feet. Ore reserves were found to be confined to tactite zones in a surface area approximately 250 by 400 feet and extending downward about 350 feet.

Jan 1, 1956

By K. K. Kelley

Sodium-aluminum and potassium-aluminum silicates are among the more important rock-forming minerals of the earth's crust. They also appear as constituents of some metallurgical slags and of some refractory materials. Consequently, knowledge of their thermodynamic properties is interesting and valuable from several viewpoints. This paper reports experimental determinations of the low-temperature heat capacities and entropies at 298.16° K. of albite, jadeite, and nephelite it the sodium-aluminum silicate series and of adularia, ferriferous orthoclase, leucite and kaliophilite in the potassium-aluminum silicate series. Also high-temperature heat-content and entropy increments about 298.16° K. are reported for albite, jadeite, nephelite, and carnegieite in the sodium-aluminum silicate series. Except for a few high-temperature heat-content values for albite, all these data are available for the first time.

Jan 1, 1953

By E. G. King

Thermodynamic data for the hydrated varieties of alumina are sparse, and those for the common clay minerals are virtually nil. This paper partly fills the vacuum by reporting low-temperature heat-capacity measurements and entropy evaluations of diaspore (A10(OH)) and three clay minerals of the composition A12Si207?2H20 - kaolinite, dickite, and halloysite. The heat-capacity measurements were made in the temperature range 510 to 298.15° K., and the entropies were evaluated at 298.15° K. Diaspore has an unusually low heat capacity and entropy compared with boehmite (another mineral of the same chemical composition). The entropies of the three clay minerals differ too little for entropy to be the important factor relating to differences in the thermal stability of these substances.

Jan 1, 1961

By Alla D. Mah

Titanium forms several compounds with oxygen and also is able to dissolve interstitially about 33 atomic percent of oxygen. Starting with titanium dioxide, reduction becomes increasingly difficult as oxygen is removed; and the final step, be reduction of the titanium-oxygen interstitial solutions, is by far the most difficult. The possibility of reducing titanium oxide, or of purifying titanium containing oxygen, by treatment with certain more volatile metals has been a subject of considerable interest. Theoretical appraisal of the limitations of this possibility, however, has been hampered by lack of adequate information on the thermodynamic properties of the titanium-oxygen solutions. The purpose of the present work was to remedy this difficulty by expanding the thermodynamic knowledge regarding these solutions. The experimental work involved three types of calorimetry and furnished the following information: (1) Heats of formation of 11 titanium-oxygen solutions, in the range of 0 to 10 wt.-percent oxygen, were determined at 298.15° K. As a byproduct, an improved value of the heat of formation of rutile was obtained, which, in turn, led to improved values of the heats of formation of the lower titanium-oxygen compounds. (2) Low-temperature heat-capacity data and entropies at 298.15°K in were determined for 2 representative titanium-oxygen interstitial solutions. (3) High-temperature heat-content data were obtained for 2 titanium-oxygen interstitial solutions to about 1,600° K.

Jan 1, 1957