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By R. D. Ladoo

"At the beginning of 1920 a general feeling of optimism was noted in many talc-producing districts. The industry seems to have recovered from the temporary depression of the first half of 1919 and many mills are running at capacity production with their entire output for 1920 contracted for. The imports of talc for 1919 were only slightly larger than in 1918 by weight and probably no more by value. Thus foreign competition has not begun to be seriously felt. Several new companies in this country have been organized, some to operate new deposits and others to continue the work done by others.An interesting phase of the present situation is the possibility of increased use of talc in paint. There is a shortage of barium sulfate used as,paint filler. Since, for some uses, talc is considered second only to BaSo4 as a filler for paint, it is possible that part of the shortage could be relieved by an increased use of talc.A series of physical tests upon all pigment materials used in the manufacture of paints is being conducted for the Paint Manufacturers Association of the United States. It is important that all types of talc be represented in these tests. Producers of finely ground talc, 200 mesh and finer, are urged to submit samples of at least two pounds each of these grades that are available to paint makers with trade name and quality data, to the Institute of Industrial Research, 19th & B Streets, Washington, D. C., where the tests are being conducted.The Talc Products Company, Inc., Washington Building, Los Angeles, California, has recently been organized to develop a large body of talc one mile north of Riggs, San Bernardino County, California, This deposit contains a compact, white talc which can be sawed into crayons. The company's mill, at Los Angeles) is equipped with a unit of the Raymond system of grinding and air separation, and pencil sawing machines. It is reported that the pencils are being successfully used in Pacific Coast ship yards.The mining of talc where no mill is owned by the operator and the consequent sale of talc in its crude massive state has not proved profitable in a number of cases recently noted. Under exceptional circumstances, where mining costs are low and the product can be sold to a mill near the mine, the operation maybe profitable, but this condition is not common. One mine of this type has recently closed down, at least temporarily; but a second, more fortunately situated, in another district, is continuing operations, although plans are being made to erect a mill in the early spring. Most satisfactory results are ordi¬narily obtained where the mine and mill are owned by the same company.The sale of the Balmat mine of the International Pulp Company, near Gouverneur, N. Y., to J. H. McLear, Gouverneur, and H. G. McLear of New York, has been reported. It is stated that a large part of the property has been already leased to the Sylvia Lake Company, who will operate it. ""Cement, Hill, and Quarry""* states that ""the first mining done on this property was for silver and lead, but it developed into a good zinc producing property and later it was worked for its talc deposits. It has passed through several hands, the American Pulp Co., the Union Talc Co., and the International Pulp Co., all having had it in successive periods since 1891."""

Jan 1, 1920

By CHARLES L. WRIGHT

Previous work.-The general plan of work outlined for the Government fuel-testing plant erected at the Louisiana Purchase Exposition, at St. Louis, Mo., in 1904, included investigations relative to the briquetting of coals found in the United States. These investigations embraced the possibility of making satisfactory commercial fuels from lignite or low-grade coals which do not stand shipment well; of benefiting culm or slack coals that are wasted or sold at unremunerative prices; and of improving the furnace efficiency or ability to withstand transportation of good coals. This work was begun in 1904 and was continued in 1905, 1906, and 1907 as an essential part of investigations looking to the determination of methods for reducing waste and increasing efficiency in the utilization of the fuel resources in the United States. The initial briquetting tests at St. Louis, which included examination into the behavior of different coals or mixtures of coals in the briquetting press, experimental study of the merits of various substances used as binders, and consideration of the physical properties and resistance to weather and abrasion of the briquets, have been described.a They demonstrated that satisfactory briquets could be made from most coals, and that by briquetting the commercial value of many low-grade coals and lignites could be raised enough to more than cover the cost of manufacture. Norfolk plant.-The briquetting plant of the Geological Survey was moved from St. Louis, Mo., to Norfolk, Va., in 1907, along with the steam boiler and producer-gas equipment of the fuel-testing plant, as the closing out of the affairs of the Louisiana Purchase Exposition and the consequent removal of the buildings from Forest Park made a change of location necessary. Norfolk was selected largely with a view to the testing of coals for naval purposes, and because of facilities in the way of buildings and materials offered by the Jamestown Exposition Company. The work at Norfolk was chiefly devoted to making steaming and briquet tests of coals which reach the Atlantic seaboard at Norfolk and Newport News and are used by the navy and merchant marine. Two briquet machines were installed at the Norfolk plant, one being the English machine used in briquetting tests by the Geological Survey at St. Louis in 1905 and 1906, and the other an American machine. The briquets made at this plant were tested on locomotives of several railroads entering Norfolk and on the United States torpedo boat Buldle in comparison with the run-of-mine coal used in making them. Some of the tests were conducted by the railroads on their own locomotives, but those on the Biddle and on the locomotive of the Seaboard Air Line Railway were carried on by W. T. Ray and Henry Kreisinger, of the United States Geological Survey. Personnel.-Charles T. Malcolmson continued in general charge of the briquetting section after the removal to Norfolk until January 1, 1908. Walter J. Chapman continued in charge of operation of the briquet machines and of the observations reported under the heading "Details of manufacture." Charles L. Wright supervised the installation of the English briquet machine and later in the year continued the physical tests of briquets and the analyses in the chemical laboratory of the section until January 1, 1908, on which date he was placed in general charge of the work of the section. G. E. Ryder and Ralph Galt also continued with the staff, but the former was obliged to resign soon after the plant was in operation on account of ill health; the latter continued with the section as computer until the close of work on December 1, 1908.

Jan 1, 1911

By WILLIAM F. McMURRAY, James O. Lewis

The Bureau of Mines is investigating the technology of petroleum and its products, the investigation including well-drilling methods and the transportation, treatment, and utilization of petroleum and of natural gas, with especial reference to the prevention of waste and to increased efficiencyin the development of oil and gas resources in land belonging to or controlled by the Government. During. the winter of 1912-13 the enormous waste of the gas encountered while drilling for oil in the Cushing field, Oklahoma, called forth protests from various sources, and appeal was made to the President of the United States and to the Secretary of the Interior in behalf of the landowner and of the public in general. The facts were wanted regarding the amount of waste and the technical conditions that were responsible for practices causing it. An investigation was ordered and conducted under the direct supervision of the late J. A. Holmes, the first Director of the Bureau of Mines. R. S.Blatchley was sent to investigate the amount of waste going on in the Mid-Continent flelds.s In the latter part of March, 1913, J. A. Pollard and A. G. Heggem were sent to Oklahoma to study well-drilling methods with reference to the waste of gas from wells on Indian lands and to suggest means of preventing the waste of natural gas on such lands. Pollard and Heggem decided that the mud-laden fluid process, which had been used successfully for some years in Texas, Louisiana, and California was the method that would meet the situation most efficiently and economically. The method was accordingly demonstrated in Oklahoma. In 1914 Congress provided for the employment of six oil and gas inspectors to supervise oil and gas mining operations on lands of the Five Civilized Tribes in Oklahoma and to conduct investigations with a view to the prevention of waste. Positions under this appropriation have been held by William F. McMurray, James O. Lewis, Harry D. Aggers, Ralph R. "Weed,George W. McPherson, James C. Fowler, Louis W. Courtney, and Carl H. Beal, the technical work of these men being directed "byW. A. Williams, chief of the petroleum division, Bureau of Mines. After careful and impartial investigation of conditions in Oklahoma, these men also decided that the mud-laden fluid process was the one best adapted to prevent further wastes. In 1915 laws were passed by the State of Oklahoma that provide for the conservation of natural gas and oil, authority being given to the corporation commission to make rules and regulations and to employ agents to enforce them. After hearings and investigations, the corporation commission reached substantially the same conclusions as the Federal agents regarding the importance of the wastes and the best methods of conserving the gas. Technical Papers 66a and 68b were published by the Bureau of Mines in December, 1913, and January, 1914, respectively. Technical Paper 66 deals with the mud-laden fluid process in general and No. 68 with its application in Oklahoma. The interest aroused by these publications has been so widespread that within two years the first editions have been practically exhausted. Rather than reprint these publications, it has been considered advisable to replace them with the present report, which includes the results of more recent investigations. The methods of using the mud-laden fluid are an outgrowth of the rotary drilling system, which was developed in Texas and later employed in Louisiana and California. Some of the principles of the use of mud fluid had been observed and used to a limited extent for a long time in cable-tool drilling. So far as known it was first used successfully with a circulator and cable tools in the Coalinga field, California, in 1906,Harry D. Aggers, one of the contributors to this paper, working on the well. The part of the Bureau of Mines has been to call attention to its merits and to demonstrate its practical use in fields like those of the Mid-Continent.

Jan 1, 1916

Rock property tests were performed on NX-size diamond drill core from the roof, floor, and coal from the longwall mining section of Federal No. 2 mine, West Virginia. The purpose of these tests was to determine the engineering properties of the various strata as part of a ground control study of the longwall operation. The following tests were performed: 1. Uniaxial compressive strength, Young's modulus, and Poisson's ratio 2. Triaxial compressive strength 3. Brazilian tensile strength 4. Modulus of rupture 5. Specific gravity Thirteen boxes of core delivered to the University on April 1, 1974 were identified as follows: 2 PTR 1 -2 boxes of roof rock 2 PTF 1 -2 boxes of floor rock 2 PTR 2 -2 boxes of roof rock 2 PTF 2 -2 boxes of floor rock with approximately 3 ft of coal in Box 2 (designated 2 PTC 2) 2 PTR 3 -2 boxes of roof rock 2 PTF 3 -2 boxes of floor rock 1 PC 5 -1 box of coal

Jan 1, 1976

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 Robert M. Doerr

Isothermal oxidation kinetics were determined for three grades of Ni and for 99.99 percent Co in Ca and in air from 800° to 1,200° C. The oxidation reactions followed approximately the parabolic rate law. For 99.99 percent Ni in 02 at 1,200° C, the parabolic rate constant was 2 mg cm-2 hr-2. For 99.99 percent Co in dry air, the constant ranged from 1 mg cm-2 hr-2 at 800° C to 18 mg cm-2 hr-2 at 1,200° C; for 99.99 percent Co in 02 the constant was 2 mg cm -2 hr-2 at 800° C and 10 mg cm-2 hr-2 at 1,000° C. For 99 percent Ni in dry air, the constant ranged from 0.2 mg cm 2 hr-2 at 800° C to 3 mg cm 2 hr-2 at 1,200° C. By X-ray diffraction measurements, only divalent oxides were found in the scales. Volumetric and quartz-helix gravimetric methods were used. The volumetric apparatus was designed to permit less stringent restrictions on the corrosion specimens; it was also more convenient to use. The agreement between the weight gain determined gravimetrically and the 02 consumption determined volumetrically was not good enough for direct comparison of gravimetric and volumetric results.

Jan 1, 1963

By Richard J. Mainiero, Michael J. Sapko, James H. Rowland III, Marcia L. Harris

All explosive materials produce a cloud of reaction products, the most toxic of which is nitrogen dioxide (NO2). In the study reported here, 4.5-kg (10-lb) charges of blasting agent confined in either thin-wall 10-cm (4-in) diameter galvanized pipe or 10-cm (4-in) schedule 80 seamless steel pipe were detonated in a closed chamber. The detonation gases were analyzed for NO2, nitric oxide (NO), ammonia (NH3), hydrogen (H2), carbon monoxide (CO), carbon dioxide (CO2), nitrogen (N2), oxygen (O2), and methane (CH4). Data were evaluated to determine the kinetics of the oxidation of NO to NO2. Analysis revealed that the only mechanism for NO loss for the conditions existing in the chamber was the reaction 2NO + O2 6 2 NO2. The rate constant was 2.08 @ 10-38 cm6 molecules-2 sec-1 for the rate equation -½d [NO]/dt = K @ [NO]2 @ [O2] for NO concentrations up to 100 ppm. The rate constant is in agreement with that recommended by Baulch, Drysdale, and Horne (1973).

By Mary H. Brown

The heats of formation of oxalic acid and sodium, potassium oxalates, and lithium oxalates were related by solution calorimetry to the heat of formation of (COOH)2.2H20, a value believed to be reliable as reported in the literature. The following heats of formation were determined: (COOH)2(a), -198.1±0.1; (COOH)2(ß), -197.8±0.1; UAW,, -328.7±0.4; Na2C204 -316.2±0.1; K2C204, -321.9±0.2; and K2C204-H20, -393.5±0.2 kcal/mole. The heat of the crystalline transformation (COOH)2(a) ? (COOH)2(ß) was determined to be 0.30±0.02 kcal/mole at 298.15° K.

Jan 1, 1970

By E. G. Noble

The effects of HBr concentration and temperature on the solubility and hydration state of AlBr3,' CoBr2, PbBr2, MnBr2, KBr, and NaBr were investigated by the Bureau of Mines. Saturated aqueous solutions of the AI, Pb, K, and Na bromides were sparged with HBr gas at 20°, 40°, and 60° C, and saturated solutions of Co and Mn bromides were sparged at 20° C. Increased HBr concentration caused decreased salt solubility because of the common ion effect for all the investigated bromides except PbBr2. Aqueous solubilities at 20° C were, in percent, 51.7 for AlBr3, 53.2 for CoBr2, 1.1 for PbBr2, 59.6 for MnBr2' 39.5 for KBr, and 47.4 for NaBr. At 60° C, the solubilities were, in percent, 53.3 for AlBr3, 2.2 for PbBr2' 46.0 for KBr, and 53.8 for NaBr. Solubilities in solutions sparged to HBr saturation at 20° C were, in percent, 0.5 for AlBr3, 42.0 for CoBr2, 32.2 for PbBr2, 21.0 for MnBr2, 0.6 for KBr, and 0.3 for NaBr. At 60° C, the solubilities at HBr saturation were, in percent, 1.8 for AlBr3, 41.4 for PbBr2, 1.3 for KBr, and 0.4 for NaBr. CoBr2 precipitated out to a minimum solubility of 27.2 pct at 28.7-pct-HBr concentration. Further increases in HBr concentration increased CoBr2 solubility because of the formation of bromide complexes. PbBr2 in-creased in solubility as HBr concentration increased.

Jan 1, 1988

By R D. Fleming

A single-cylinder research engine was operated on pure hydrocarbons and simple (two-component) mixtures of pure hydrocarbons to study the effect of fuel composition on exhaust emissions from a spark-ignition engine. Used as fuels were three pure hydrocarbons that represented the primary hydrocarbon types present in commercial motor fuels: A paraffin (2,2,4-trimethylpentane), an olefin (2,4,4-trimethylpentene-2), and an aromatic (meta-xylene). The engine was operated at the same equivalence ratio for all of the fuels used in the experiment. Exhaust gas samples were collected and quantitatively analyzed for carbon monoxide, carbon dioxide, hydrogen, nitrogen oxides, aldehydes, and hydrocarbons. Exhaust hydrocarbons were separated and quantitatively measured with a chromatographic system employing a flame-ionization detector. Unknown hydrocarbons and oxygenated materials in the exhaust were identified with a Time-of-Flight mass spectrometer coupled to a chromatographic system. The results of the exhaust gas analyses showed that ethylbenzene, l-methyl-3-ethylbenzene, and l-methyl-3-vinylbenzene were more abundant in the exhausts from either 2,2,4-trimethylpentane--m-xylene or 2,4,4-trimethylpentene-2--m-xylene fuel mixtures than in exhaust produced from m-xylene. Also, the pure 2,4,4-trimethylpentene-2 fuel produced smaller amounts of C2 to C7 olefins in the exhaust than that produced by the pure 2,2,4-trimethylpentane fuel. The exhaust from pure m-xylene fuel contained aromatic hydrocarbons of higher molecular weight than the parent fuel. The amount of total hydrocarbon (moles of exhaust hydrocarbon per mole of fuel used) in the exhaust from the three pure fuels decreased in the following order: 2,2,4-trimethylpentane > 2,4,4-trimethylpentene-2 > m-xylene. The hydrocarbon mole-fractions of unreacted fuel in the exhausts produced from each of the pure fuels were 0.20 for 2,2,4-trimethylpentane, 0.13 for 2,4,4-trimethylpentene-2, and 0.66 for m-xylene.

Jan 1, 1970

By K. P. V. Lei

The Bureau of Mines investigated molten salt electrorefining 'n helium atmosphere cells as a means for the production of ductile vanadium. 'Electrolytes composed of NaCl-VCl2, LiCl-NaCl-VCl2, BaCl2-KCl-NaCl-VCl2 KCl-LiCl-VCl2, and CaCl2-NaCl-VCl2 were tested. Two electrolytes, KCl-LiCl-VCl2 and CaCl2-NaCl-VC12, were selected for laboratory-scale production tests. A molten salt electrorefining process was developed for the production of ductile 99.6 percent vanadium from a commercial 90-percent grade. Using the CaCl2-NaCl-VC12 electrolyte, an 87-percent recovery of ductile vanadium was made; an 85-percent recovery was made with the KCl-LiCl-VCl2 electrolyte.

Jan 1, 1967

By H. A. Doerner

From thermodynamic calculations3 Maier predicted that zinc oxide Land methane would react at specified temperatures substantially according to equation (1). (1) ZnO + CH; = Zn (gas) + CO + 2H2 Other reactions that may take place are: (2) CH4 = C + 2H2. (3) ZnO + CO = Zn (gas) + CO2 (4) ZnO + H 2 = Zn (gas) + H2O . Maier predicted that 870°C. would be the critical temperature above which reaction (1) would take precedence over reaction (2) and that reaction (1), at equilibrium, would be substantially complete at or above 927°C.

Jan 1, 1931

By Doerner H. A.

From thermodynamic calculations Maier predicted that zinc oxide and methane would react at specified temperatures substantially according to equation (1). (1.) ZnO + CH4 = Zn (gas) + CO + 2H2. Other reactions that may take place are (2.) CH4 = C + 2H2. (3.) ZnO + CO = Zn (gas) + CO2. (4.) ZnO + H2 = Zn (gas) + H2O. Maier predicted that 870°C would be the critical temperature above which reaction (1) would take precedence over reaction (2) and that reaction (1), at equilibrium, would be substantially complete at or above 927°C. Theoretical considerations indicate that reaction (1) is reversible: this is supported, but not proved, by experimental data. The other reactions are known to be reversible. At low temperatures reaction (2) requires a catalyst and it is slow below 1000°C. Reactions (3) and (4) are rapid, but the equilibrium constants are such that only small concentrations of CO2 or H2O can be produced below 1000°C. Maier calculated that CO2 should not exceed 0.5 per cent at 870°C., and the calculation for water vapor gives a still smaller order of magnitude.

Jan 1, 1931

By Joan C. Biordi

In this research by the Bureau of Mines, slightly lean CH4-O2-Ar flames at 0.042 atm with and without small amounts of the inhibitor CF3Br were probed using molecular beam and mass spectrometric techniques. Ratios of product concentrations to reactant concentrations were formed and compared with the equilibrium constant for seven reactions--(l) H+O2 = OH+O, (2) O+H2 = OH+H, (3) OH+H2 = H2O+H, (4) OH+OH = H2O+O, (5) CO+OH = CO2+H, (6) Br+HBr = Br2+H, and (7) H+HBr =H2+Br--to determine to what extent they may be considered balanced in various regions of the flame. With the possible exception of reaction 4, none of the reactions are completely balanced until maximum flame temperature is reached. Once the reactions become equilibrated, their balance is maintained as the temperature and radical concentrations falloff in the secondary reaction zone. Reaction 7, in inhibited flames, is balanced at relatively low temperatures, comparable to reaction 4. Reaction 6 was found not to balance in either the secondary or primary reaction zones. Radical decay in the secondary reaction zone was analyzed using the pool-decay concept. The important recombination reactions were judged to be H+OH+M~H2O+M, and H+O2+M?HO2+M. A rate coefficient of 2x1016 cm6 mole-2 sec-1 is calculated for M = the burnt gas mixture of Ar, HaO, CO2, and 5x1015 cm6 mole-a sec-1 is calculated for M = Ar (both for T = 1,750±150 K).

Jan 1, 1977

By D. E. Banks, J. K. H. Ma, Y. Rojanasakul, J. Y. C. Ma, C. J. Malanga

There is evidence to suggest that cell injury induced in alveolar macrophages (AM) following phagocytic activation by silica particles may be mediated through changes in intracellular free calcium [Ca 2+}. However, the mechanism of silicainduced cytotoxicity relative to [Ca2+], overloading is not yet clear. To provide a better insight into this mechanism, isolated rat AMs were exposed to varying concentrations of crystalline silica (particle size< 5 µm in diameter) and the fluctuation in their [Ca2+]; and cell integrity were quantitatively monitored with the fluorescent calcium probe, Fura-2 AM, and the membrane integrity indicator, propidium iodide (Pl). Results from this study indicate that silica can rapidly increase [Ca2+]; in a dose-dependent manner with a characteristic transient calcium rise at low doses (<0.1 mg/ml) and an elevated and sustained rise at high doses (>0.1 mg/ml). Depletion of extracellular calcium [Ca 2+]0 markedly inhibited the [Ca2+]; rise (˜90%), suggesting that Ca2+ influx from extracellular source is a major mechanism for silica-induced [Ca2+]; rise. When used at low doses but sufficient to cause a transient [Ca2+]; rise, silica did not cause significant increase in cellular Pl uptake during the time of study, suggesting the presevation of membrane integrity of AMs under these conditions. At high doses of silica, however, a marked increase in Pl nuclear fluorescence was observed. Depletion of [Ca 2+] 0 greatly inhibited cellular Pl uptake, induced by 0. 1 mg/ml or higher doses of silica. This suggests that Ca 2 + influx, as a result of silica activation, is associated with cell injury. Indeed, our results further demonstrated that the low dose effect of silica on Ca 2+ influx is inhibited by the Ca2+ channel blocker nifedipine. At high doses of silica (>0.1 mg/ml), cell injury was not prevented by nifedipine or extracellular Ca2+ depletion, suggesting that other cytotoxic mechanisms, i.e., nonspecific membrane damage due to lipid peroxidation, are also responsible for the silica-induced cell injury. Silica had no significant effect on cellular ATP content during the time course of the study, indicating that the observed silicainduced (Ca2 ... ); rise was not due to the impairment of Ca2 + -ATPase pumps, which restricts Ca2+ efflux. Pretreatment of the cells with cytochalasin B to block phagocytosis failed to prevent the effect of silica on [Ca2+]; rise. Taken together, these results suggest that the elevation of [Ca2+]; caused by silica is due mainly to Ca2+ influx through plasma membrane Ca2+,channels and nonspecific membrane damage (at high doses). Neither ATP depletion nor Ca2+ leakage during phagocytosis was attributed to the silica-induced [Ca2+]; rise.

Nov 1, 1995

By L. C. George

The Bureau of Mines measured the vapor pressures of selected mixtures in the binary systems CdCl2 ?SnCl2, CdCl2 -ZnC12, PbCl2 ?SnCl2, and PbCl2 -ZnCl2 by the static pressure method. These data were evaluated by the second-law (sigma-plot) method. Equations expressing the vapor pressures and the heats and free energies of vaporization as functions of temperature are given.

Jan 1, 1969

By H. E. Perlee

Autoignition temperatures and limits of flammability of nine halogenated hydrocarbons in atmospheres of air, oxygen, and nitrogen tetroxide were measured in a modified standard autoignition apparatus and limit-of-flammability apparatus previously developed at the Bureau of Nines. Of the nine halogenated hydrocarbons investigates--bromochloromethane, bromotrifluoromethane, bromochlorodifluoromethane, 1,1,2-trichlorotrifluoroethane, 1-bromo-l-chloro-2,2,2-trifluoroethane, dibromodifluoromethane, l,2-dibromo-1,1,2,2-tetrafluoro-ethane, 1,1,1,3,3-pentachlorotrifluoropropane, and l-bromo-2,4-dichloro-1,1,2, 3,3,4-hexafluorobutane--two formed flammable mixtures with nitrogen tetroxide and six with oxygen; none formed flammable mixtures with air. Three of the halogenated hydrocarbons formed no flammable zones with any of the three oxidizing atmospheres. For those halogenated hydrocarbons that supported combustion in oxygen atmospheres, explosion pressures developed during constant-volume burning of mixtures near the middle of the flammable zone were observed to range from about 6 psig for dibromodifluoromethane to 158 psig for 1-bromo-1-chloro-2,2,2-trifluoroethane. In all cases, the calculated burning velocities of these mixtures were less than 8 in/sec.

Jan 1, 1966

By Stanley C. Rhoads

The Bureau of Mines investigated the complete ternary system K2 HfF6¬K2ZrF6-l.25 weight-percent HF at 40° C. In addition, solubility curves have been established at 25°, 30°, 500, 60°, and 70° C. These solubility data implemented a study of hafnium enrichment in feed solutions for liquid-liquid extraction processes.. Selected K2HfF6-K2 ZrF6-1.25 weight-percent HF mixtures were equilibrated in a constant temperature bath. Compositions of the equilibrated solutions and wet residues were established from combined hafnium and zirconium oxide and total fluorine analyses. All solubility curves were essentially parallel on triangular coordinates. At 40° C, the solid phase of the K2HfF6-K2ZrF6-1.25 percent HF system is a series of solid solution hydrates with K2HfF6-H20 and K2ZrF6.3H2O segments existing at the respective extremes. Since this system contains K2HfF6-H20 and K2ZrF6.3H20 segments, it is not ideal for simple separation of high-purity K2HfF6 from K2HfF6-K2ZrF6 mixtures by recrystallization. However, it would be useful for producing hafnium-enriched feed solutions from zircon concentrates for liquid-liquid extraction of hafnium from zirconium.

Jan 1, 1973

By L. B. Pankratz

Heat contents were measured for Na2CaSi04 and Na2Ca2S02 between 298° and 1,300° K, for Na2Ca2Si309 between 298° and 1,500° K, and for Na4CaSi3O9 between 298° and 1,350° K. Copper-block drop calorimetry was employed. Reversible, first-order transitions were found for Na2CaSi04 and Na2Ca2Si309. The transition for Na2CaSi04 is at 830° K with a heat absorption of 160 cal/mole; that for Na2CagSi309 occurs at 750° K with a heat absorption of 1,550 cal/mole. Results for the other two silicates showed no irregularities. A table of heat content and entropy increments above 298.15° K and heat con-tent equations are included for use in thermodynamic calculations.

Jan 1, 1968

By H. G. Iverson

An investigation was conducted on the conditions affecting the precipitation of aluminum by autoclaving synthetic solutions containing Na2SO4, Al2(SO4)3, H2SO4, and H2O. Virtually all of the alumina could be precipitated as natroalunite (NaAl3(SO4)2 (OH)6). This product could be readily filtered and dried. Results are reported in terms of alumina precipitated in this compound and not in terms of alumina itself. Solutions of ~ 0.30, ~ 0.60, and ~ 0.80 mole/liter A1203 and various concentrations of H2SO4 and Na2S04 were investigated. The optimum time and temperature for autoclaving were 20 to 30 minutes at 200° C. The highest yields of natroalunite were obtained from solutions containing little H2SO4 and ~ 2 moles Na2SO4 per mole A1202. Acid in quantities of 0.3 to 0.5 mole/mole of alumina in solution depressed the yield to 90 percent or less. In differential thermal analysis, at 1,000° C the natroalunite precipitate decomposed without melting to yield SO, and SO2 gases, a solid composed of Na2SO4, and gamma and alpha Al203. Continued heating to 1,200° C produced No SO, and alpha A1303. Water-leaching of this product removed the Na2S04 and left a final residue of alpha A1203.

Jan 1, 1968