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By H. G. Iverson

Solid state reactions of manganese with silica were investigated in high-temperature tests. Reactions of 0.5 to 4.0 moles manganese (Mn) with 1 mole silica (SiO2) at 1,100° C and of 2.0 Mn:SiO2 mole-ratio mixtures at 1,000° to 1,150° C yielded products consisting of a slag phase and a metallic phase. At 1,100° C, the slag phase from reactions of the low Mn:SiO2 mole-ratio mixtures was composed of SiO2 and rhodonite (MnSiO3), and the slag phase from the high Mn:SiO2 mixtures was composed of MnSiOs and tephroite (Mn2SiO4). The metallic phase from the corresponding low Mn:SiO2 mole-ratio reactants consisted of two manganese silicides, Mn5Si3 and Mn3Si; from the high Mn:SiOg mixtures, it was Mn and the manganese silicide (Mn5Si). For the higher mole ratios of MnSiO2 the manganese content in the metallic phase increased, while the manganese and silica contents of the slag phase remained nearly constant. The slags did not contain free or uncombined manganese oxide (MuO). For the 2.5 to 4.0 Mn:SiO2 mole-ratio mixtures reacted at 1,100° C, the maximum quantities of silica reduced and of the manganese in the slag appeared to become asymptotical at about 41 and 48 percent, respectively. A brominating procedure was developed that was highly selective in removing the metallic constituents from the reaction product, leaving the slag phase as residue. X-ray diffraction patterns were obtained on prepared silicides Mn5Si, Mn3Si, and MnSi.

Jan 1, 1967

By H. Leitch

In laboratory experiments, the Bureau of Mines investigated melting, quenching, and sulfuric acid leaching of alumina from mixtures of albite and anorthite, and from anorthosites containing 26 to 32 percent alumina. Variations in pouring temperature, quenching and leaching conditions, were studied with respect to the extraction of alumina and impurities. Virtually all of the alumina was dissolved by leaching melted and quenched California anorthosite in boiling 16-percent sulfuric acid solutions for 15 to 30 minutes. The leach solutions were readily separable from the solid residue by conventional thickening and filtration techniques. Only 2 to 5 grams of SiO2, Fe2O3, or CaO dissolved per 100 grams of alumina. The quantity of SiOz in solution varied inversely with the duration of the leach and with the concentration of the H2SO4 solution used. Melted and quenched Wyoming and Minnesota anorthosites with SiO2:CaO weight ratios of 4.3 and 3.2, respectively, were less amenable to sulfuric acid leaching than California anorthosite with an SiO2:CaO weight ratio of 5.3. However, excellent results were obtained on the Wyoming and Minnesota anorthosites by the addition of SiO2 to these materials before melting, in quantities sufficient to adjust the SiO2:CaO weight ratios of the furnace charges to between 4 and 6.

Jan 1, 1966

By Clark F. Grain

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

Jan 1, 1962

By G. Richards Gwinn

"Mica" is a group name for a number of orthosilicates of aluminum with magnesium, ferrous iron, and the alkalies. They are characterized by their high reflection and a basal cleavage so well developed that they can be split into exceedingly thin laminae, which are more or less tough, elastic, and transparent, according to variety. Barium, manganese, lithium, chromium, titanium, boron, and ferric iron occur in same varieties. Eight distinct species of true mica, which appear in the following table, are recognized by mineralogists, but only the first five are of commercial importance. [Species General Formula Muscovite H2KA13 (SiO4)3 Phlogopite [H,K, (MgF)]) Mg3A1 (Si04)3 Biotite (H,K)2(Mg,Fe)2(Al)Fe)2 (S104)3 Lepidolite K,Li Al(OH,F)2 Al (5103)3 Ros coalite H8K(Mg,Fe) (A1,V)4 (S103)12 Paragonite H2NaAl3(S104)3 Zinnwaldite (K)Li)3 FeAl3 Si5016(OH,F)2 Lepidomelene HK2F3IIIFe6III A13 (S104)9]

Jan 1, 1951

By Ann G. Kim

The Bureau of Mines investigated factors that influence the formation of methane and other hydrocarbon gases in coal, which is an integral part of the coalification process. Coalification begins with a biogenetic stage in which plant debris decomposes and peat is formed; methane and CO2 are the predominant gases produced during this stage. During the diagenetic stage of coalification hydrogen and the hydrocarbon gases methane, ethane, ethylene, propane, propylene, butene, iso- and normal butane, and pentane are formed by dissociation of the organic material. Methane may also be produced by a secondary reaction of hydrogen with unsaturates or by the reduction of CO2. The gas contained in coalbeds is a mixture of methane, C2 through C5 alkanes, CO2, 02, N2, H2, and H2; its heating value is equivalent to that of natural gas. The gas content of coal depends on many variables, but an empirical relationship between adsorptive capacity, rank, and depth has been observed.

Jan 1, 1978

By Ann G. Kim

The Bureau of Mines investigated factors that influence the formation of methane and other hydrocarbon gases in coal, which is an integral part of the coalification process. Coalification begins with a biogenetic stage in which plant debris decomposes and peat is formed; methane and CO2 are the predominant gases produced during this stage. During the diagenetic stage of coalification hydrogen and the hydrocarbon gases methane, ethane, ethylene, propane, propylene, butene, iso-and normal butane, and pentane are formed by dissociation of the organic material. Methane may also be produced by a secondary reaction of hydrogen with unsaturates or by the reduction of CO2. The gas contained in coalbeds is a mixture of methane, C2 through C5 alkanes, CO2, O2, N2, H2, and He; its heating value is equivalent to that of natural gas. The gas content of coal depends on many variables, but an empirical relationship between adsorptive capacity, rank, and depth has been observed.

Jan 1, 1978

By Lindsay D. Norman

Four chloride and seven fixed-nitrogen processes for recovering manganese from domestic resources are described. The chloride processes are divided into two classes (leaching and chloridization) depending upon the major operation responsible for converting the manganese minerals to the chloride from which manganese oxide products are obtained. The fixed nitrogen processes, all of which yield high-grade manganese oxide products, are essentially either leaching or roasting processes. The 11 processes include HC1 leach, HC1 chloridization, HC1 chloride volatilization, CaC12 chloride volatilization, NO2 leach, HNO3 leach, HNO3 ?NO2 leach, H3 ?CO2-H2O system leach, (NH4)2SO4 leach, (NH4)2SO4 roast , and ammonium salt roast .

Jan 1, 1963

By Thomas E. Green

A gas volumetric method was developed for determining metallic aluminum at the 0.01-to 0.3-percent level in 100-gram samples of recycled glass. The method is based on the measurement of the change in gas volume produced by the reaction 2 Al + 2 NaOH + 2 H2O ? 2 NaAl02 + 3 H2 using a simple apparatus assembled from readily available glassware. Apart from sampling errors, the precision of the method is within ±5 percent. A minor modification of the apparatus would extend the method to larger samples or samples of higher metallic aluminum content. Metallic iron and metallic zinc do not interfere at the concentrations found in recycled glass recovered from incinerator residues.

Jan 1, 1971

By N. S. Dalal, Xianglin Shi

"The mechanism of vanadium(V) V ) toxicity is still not fully understood in spite of extensive current effort (1-3). The presence of a vanadium(V) V ) -dependent NAD ( P )H oxidase in cell membranes suggests that at least one of the pathways involves oxidation of NAD(P)H (1-3). Considerable effort has therefore been devoted to finding the mechanism of NAD ( P ) H-oxidation by va¬nadium( V ) (1-19). Recently Liochev and Fridovich (4, 16) provided a critical review of vanadium( V) -stimulated NAD (P )H oxidation by plasma membranes. They out¬lined a mechanism in which vanadium(V) V )-stimulated oxidation of NAD ( P )H by biomembranes involves an O2 - initiated free radical chain reaction (4 ). While the above may be the major pathway for the vanadium-me¬diated NAD (P )H oxidation in membrane-related sys¬tems, some recent results suggest that in the presence of NADPH the flavoenzyme glutathione reductase can function as a vanadium(V) V ) reductase (18). Because of the significance of this result in relationship to the mech¬anism of vanadium( V) metabolism and the novelty of the metal-reductase behavior of a flavoenzyme, we have car¬ried out additional studies on one-electron reduction of vanadium( V) by two other, related flavoenzymes: lipoyl dehydrogenase and ferredoxin-NADPH oxidoreductase. These two enzymes were selected because they are known to catalyze a one-electron reduction of Cr ( VI ) (19-21 ), which is isoelectronic with vanadium( V ).The present study also reports on the generation of hydroxyl ( • OH) radicals in the vanadium( V) -flavoen-zyme redox system without exogenous H2O2. The • OH study was undertaken because • OH radicals are known to be generated in reactions of vanadium( IV) with H2O2 (17,18,22-27). For example, Piette and co-workers (17, 22) have studied effects of vanadium(IV) IV ) on lipid per-oxidation and NADPH oxidation and suggested that va-nadium( IV) -induced • OH radical formation may play an important role in vanadium( V) toxicity. Carmichael (25, 26) investigated the reaction between a RNA /VO 2' complex and H2O2 with a view to probe the possible re-lationship between vanadium( IV) -mediated • OH radical generation and DNA damage. He has suggested that in this reaction the • OH radical adds to the C (5) carbon of uracil, causing nucleotide damage, similar to what occurs in the nucleotide /Fe2+ / H2O2 reaction (28) and in y-irradiated aqueous solutions of nucleic acids (29 ). To our knowledge, however, there is as yet no report on ·OH radical generation in any reaction involving the reduction of vanadium ( V) by a well-characterized enzyme, without exogenous H20 2 • The present study provides evidence that ·OH radicals can form in a flavoenzyme-mediated reduction of vanadium( V) to vanadium( IV) and that this process involves also the reduction of molecular oxygen ( 0 2 ) to H20 2 • The H20 2 thus generated reacts with vanadium( IV) to produce ·OH radical, in analogy with the Fenton reaction ( Fe2 + + H20 2 - Fe3 + + OH- + ·OH)."

Mar 1, 1992

By K. O. Bennington

[Thermodynamic properties of two amphibole asbestos minerals were determined by the Bureau of Mines. The enthalpies of formation were determined by the hydrofluoric acid solution calorimetry method. Heat capacity measurements were made with an adiabatic calorimeter over the range of 5 to 315 K. High-temperature enthalpies above 298 K were determined with a copper-block drop calorimeter to 852 K for amosite and to 902 K for crocidolite. Thermodynamic data determined for amosite of the composition Fe5+2.2766Mg1.5209 Fe+03.12Mn0.0825) Si7.9163Al0.0837022.0363)(OH)1.9637 are: S°298 = 168.8 ± 5 cal/deg-mole; ?Hf°298-15 (elements) = -2419.24 ± 2.95 kcal/mole; ?Hf298.15 (oxides) = -30.92 ± 2.47 kcal/mole; and ?Gf° -2260.1 kcal. Corresponding data found for s3 ,1s = crocidolite of the composition (Na1.9Ca0.1)(Fe2+.024Fe2.5 01Mg0.475) (Si7.9713024Fe+2 2.501Mg0.475) (Si7.971 Al0.029022.095) (OH)1.905 are: S2.98-15 - 161.1 ± 4 cal/deg-mole; ?Rf° 2 298.15 (elements) = -2433.56 ± 2.99 kcal/mole, 10298.1s (oxides) = -87.69 1.70 kcal/mole, and ?Gf°298.15 = -2269.8 kcal.] Calorimetric values from this investigation were combined with other data from the literature to calculate the Gibbs energies of formation and equilibrium constants of formation over the temperature range of the measurements. Tables of enthalpies of formation and Gibbs energies of formation are given as a function of temperature both from the elements and the constituent oxides.

Jan 1, 1978

By Lloyd R. Michels, Burke Cartwright, S. F. Ravitz

"INTRODUCTION Frequent attempts have be,made in the electrolysis of molten magnesium chloride to regenerate the electrolyte by allowing the chlorice generated at the anwdo to read with magnesium oxide and carbon within the melt according to the following reactions: (1) MgO + C + CL2 = MgCl2 + CO,(2) 2MgO + C + 2C12 = 2MgC12. + CO2.The principal advantages of such a procedure are that (1) the direct source of magnesium is magnesium oxide rather than the more expensive dehydrated magnesium chloride and (2) it is not necessary to handle or dispose of large quantities of chlorine or hydogen chloride.Grätzll 5/ proposed the use of an MgO carbon feed in a more or,less compact form in the anode compartment, of the cell. In a patent issued to Magall Aktiengecellschaft, 6/ a compact mixture of MgO and carbon is used as the anode itself. Kato 7/ and Backer 8/ add the feed in finely divided form to the surface of the anode compartment. The Bureau of Mines 2/ recently made a pilot-plant investigation of the electrolysis of suspension of MgO and carbon from chloride melts, in which it was found that although,current efficiencies of 60 to 70 percent were obtainable, the formation of sludges containing MgO, carbon, and magnesium seriously interfered with the operation of the cell,"

Apr 1, 1945

By E. G. Noble

The effects of hydrogen chloride (HCI) concentration and temperature on the solubility and hydration state of the alkali chlorides LiCI, NaCI, and KCI and the alkaline-earth chlorides, MgCI2, and CaCl2 were investigated by the Bureau of Mines. Saturated aqueous solutions of the chlorides were sparged with HCI gas at temperatures of 20°, 40°, and 60° C. Increased HCI concentration caused decreased salt solubility be-cause of the common ion effect. Aqueous solubilities for the chlorides of Ca, Li, Mg, K, and Na ranged from 42.6, 45.2, 35.2, 25.5, and 26.1 pct, respectively, at 20° C to 56.9, 49.4, 37.6, 31.0, and 27.0 pct, re-spectively, at 60° C. In solutions sparged to HCI saturation, solubili-ties for these chlorides ranged from 22.4, 26.5, 3.0, 1.3, and 0.05 pct, respectively, at 20° C to 53.2, 48.8, 28.3, 2.6, and 0.8 pct, respec-tively, at 60° C. The solubilities of LiCI and CaCl2 in HCI solution were high because HCI solubility is low in these solutions. The chlo-ride salts of Ca, Li, and Mg formed hydrates, which depended on tempera-ture and HCI concentration. Monohydrates for LiCI, tetrahydrates and hexahydrates for MgCI2, and dihydrates, tetrahydrates, and hexahydrates for CaCl2 were obtained.

Jan 1, 1985

By A. F. Jolly

As a part of ongoing research into the sulfidation partitioning of selected complex minerals, the U.S. Bureau of Mines conducted research designed to selectively recover Cu from sulfidized chalcopyrite (CuFeS2). Ferric chloride (FeCI3) solutions leached >90 pct of the Cu and <20 pct (sometimes < 10 pct) of the Fe in the sulfidized concentrates. Cupric chloride (CuCI2) leaches were even more selective, solubilizing essentially 100 pct of the Cu and < 5 pct of the Fe. In contrast, leaching non-sulfidized CuFeS2 with either FeCl3 or CuCl2 showed that somewhat more Fe than Cu dissolved. These studies demonstrate that Cu is substantially more leachable from sulfidized CuFeS2 than from nonsulfidized CuFeS2? The Cu-and Fe-bearing constituents generated as sulfidation products, CuS (covellite) and FeS2 (pyrite), respectively, are differentially dissolved. The solubility of Fe from pyrite in sulfidized CuFeS2 is much lower than the solubility of Fe from complex nonsulfidized sulfide where Fe and Cu are bound in the same crystal lattice. Thus, the Cu dissolves selectively, producing a high-Cu filtrate from which Cu can be recovered by cementation or by electrolysis. Flotation of CuS-FeS2 mixtures indicates partitioned phases can be physically separated if effective liberation can be achieved. Magnetic separation tests yielded less promising results.

Jan 1, 1991

By R. H. Lien

The Bureau of Mines investigated a roast-leach process for recovering a marketable lithium product from a montmorillonite-type clay deposit located on the Nevada-Oregon border. The clay sample treated in the investigation contained 0.6 wt pct Li. The lithium recovery process consisted of several unit operations. The lithium silicate compounds in the clay were converted to Li2SO4 by roasting a pelletized mixture of clay, limestone, and gypsum at 900° C in a direct-gas-fired rotary roaster. Water--leaching the calcine at 40 pct solids extracted the Li2SO4. Lithium recovery from the leach solution involved concentrating the solution by evaporation, adding Na2CO3 to the concentrated solution to precipitate Li2CO3 , and filtering the slurry to obtain the product. The product filtrate was recycled to the evaporator following a crystallization step. About 80 pct of the lithium in the clay was recovered as 99-pct-pure Li2CO3. Process operating costs were estimated at $2.12/lb Li2CO3 produced; the current Li2CO3 selling price is $1.48/lb. Raw materials. accounted for 30 pct of the total operating cost.

Jan 1, 1985

By B. R. Eichbaum

To develop technology to assure an ample supply of zinc and to reduce environmental pollution, the U.S. Bureau of Mines investigated alternatives to the roast-leach process for treating complex sulfide concentrates. Previous studies proved that low-grade zinc sulfide (ZnS) concentrates could be leached using chlorine-oxygen to produce zinc chloride (ZnCI2). The process involves high energy requirements for evaporating the pregnant solution to produce anhydrous ZnCl2 needed for electrolytic cell feed. An efficient hydrometallurgical process would facilitate treatment of lower grade ores than can be used in conventional processing and would render roasting unnecessary. An alternative method was devised for recovering ZnCl2 from solution. Zinc diammine chloride [Zn(NH3)2CI2] was precipitated from solution by adding ammonium chloride (NH4CI) and sparging with ammonia (NH3) to a pH of 6 to 7.5. The spent solution was treated with calcium hydroxide [Ca(OH)21 at 60° to 80° C for 1 to 4 h to remove remaining zinc and NH3. The Zn(NH3)2CI2 was heated to 300° to 400° C to remove NH3 and produce anhydrous ZnCI2. A possible flowsheet was devised and is included.

Jan 1, 1991

By Seth C. Schaefer

The Bureau of Mines studied the standard free energies2 of formation of ferrous fluoride (FeF2) and ferric fluoride (FeF3) with high-temperature galvanic cells employing calcium fluoride doped with 1 mole-pet yttrium fluoride as the electrolyte. A free-energy change for the cell reaction Fe (s) + NiF2 (S) = FeF2 (S) + Ni (s) together with the standard free energy of formation of nickel fluoride yields a standard free energy of formation of ferrous fluoride from the elements of ?GF° = -168.74 + 30.63 x 10-3T ± 0.41 kcal/mole (897-1,098 K). (2) Combining the standard free energies of formation of magnesium fluoride, ferric oxide, and magnesium oxide with the free-energy change for the overall cell reaction 3MgO(s) + 2FeF3 (s) = 3MgF2 (S) + Fe2 03 (S) (3) gives a standard free energy of formation of ferric fluoride from the elements as ?Gf° = -281.45 + 90.46 X 10-3T ± 0,67 kcal/mole (880-935 K). (4) Free energies and equilibrium fluorine pressures for the two univariant equilibria of the Fe-F system are tabulated and illustrated.

Jan 1, 1975

By P. E. Churchward

The Bureau of Mines developed a process using amines for recovering tungsten as ammonium paratungstate from alkaline leach liquors without producing synthetic scheelite as an intermediate product. Over 90 pct of the tungsten in low-grade scheelite or ferberite concen-trate was recovered as ammonium paratungstate by (l) autoclave leaching the concentrate with Na2CO3, (2) solvent extraction of the acidified leach liquor with kerosine solutions of either a quaternary amine (Aliquat 336) or a primary amine (Primene JM-T), (3) stripping the tungsten values from the quaternary amine with ammoniacal NH4C1 or from the primary amine with NH4OH, and (4) crystallization of ammonium paratungstate from the strip liquor. Reagent consumption in pounds per pound of W03 recovered was, for the quater¬nary amine, 3 Na2CO3, 3.5 H2SO4 , 2.2 NH4Cl, 1 NH3, and 0.4 glacial acetic acid; for the primary amine, it was 3 Na2CO3, 3.5 H2SO4, .06 NH4Cl, and 0.9 NH3. Both reagents extract molybdenum along with tungsten. Silicate and phosphate are partly extracted and contaminate the product; leach liquors containing these impurities require preliminary purification.

Jan 1, 1966

By John A. Johnson

The first report of investigations5/ in this series pertaining to the investigation of stemming at the Mount Weather testing adit dealt with dust produced from blasting. The present report discusses the effect of stemming on eases generated by blasting, describes the test procedure, and analyzes the results from, blasting 61 standard rounds. Following care the types of stemming that -,re being investigated: 1, No stemming. 2. Sand in 2 paper cartridges. 3. Clay in 2 paper cartridges. 4. Commercial hydrated lime in 2 paper cartridges. 5. Combustible blasting plugs. 6. Ceramic is blasting plugs with clay in 2 paper cartridges.

Jan 1, 1940

By John A. Johnson

The first report of investigations5/ in this series pertaining to the investigation of stemming at the Mount Weather testing adit dealt with dust produced from blasting. The present report discussed the effect of stemming on eases generated by blasting, describes the test procedure, and analyzes the results from, blasting 61 standard rounds. Following care the types of stemming that are being investigated: 1, No stemming. 2. Sand in 2 paper cartridges. Clay in 2 paper cartridges. Commercial hydrated lira in 2 paper cartridges. 5. Combustible blasting plugs. 6. Ceramic is blasting plugs with clay in 2 paper cartridges.

Jan 1, 1940

By Joan C. Biordi

[Composition profiles for atomic, radical, and stable species, as well as temperature and area expansion ratio profiles, have been determined for a nearly stoichiometric CH4-02-Ar flame and one to which 0.3 percent CF5Br inhibitor had been added. Net reaction rate profiles were calculated for all the observed species. For the normal flame, these and the mole fraction profiles gave rate coefficient information about the elementary reactions in the methane flame, for example, CH. + 0 4- H2CO 0 H, k4 = 1.05 X 1014CM3 mole-1sec-1 for 1,550§T 0,725&apos; K; CO + OH 4 C02 + H, k6= 4.7 X 1011 for 1,350{T X1,750° K. Comparison between the inhibited and normal flame showed that A] and [CH3] were significantly reduced at the lower temperatures in the inhibited flame even though in the hot gas region the [E] [OH!, and [0] were essentially the same in both flames. The CF3Br disappears very early in the flame, relative to the fuel, and the reaction primarily responsible for its disappearance is H v CF3Br 4 HBr + CF3, where k7 is found to be 2.2 X 1014 exp(-9460/RT) for 700-1,550° K. Reaction of the inhibitor with methyl radicals provides for the relatively small amounts of CH3Br observed, but CH3 + Br2 - CHs Br + Br must also occur. The HBr formed reacts rapidly with H atoms to form H2 and Br, but the reaction is soon "balanced" in the flame as may be demonstrated by calculation of the equilibrium constant at various temperatures. The fluoro-carbon fragment produced in reaction (7) also reacts rapidly, in part with methyl radicals to give the observed elimination product CH2CF2 Later in the flame, above -1,400&apos; K, F2CO is formed from the reaction CH2CF2 + 0 P F2CO + CH2 and k., -1.5 X 1013 at 1,600° K. The rather slow decay of carbonyl fluoride is attributed to reaction with H atoms according to the sequence F2CO I H - HF + FCO and FCO + H HF + CO.]

Jan 1, 1975