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At least 415 records · Page 23

Supercritical waste oxidation of aqueous wastes

For aqueous wastes containing 1 to 20 wt% organics, supercritical water oxidation is less costly than controlled incineration or activated carbon treatment and far more efficient than wet oxidation. Above the critical temperature (374 C) and pressure (218 atm) of water, organic materials and gases are completely miscible with water. In supercritical water oxidation, organics, air and water are brought together in a mixture at 250 atm and temperatures above 400 C. Organic oxidation is initiated spontaneously at these conditions. The heat of combustion is released within the fluid and results in a rise in temperature 600 to 650 C. Under these conditions, organics are destroyed rapidly with efficiencies in excess of 99.999%. Heteroatoms are oxidized to acids, which can be precipitated out as salts by adding a base to the feed. Examples are given for process configurations to treat aqueous wastes with 10 and 2 wt% organics.

Modell, M.↗

Oxidation and emittance of superalloys in heat shield applications

Recently developed superalloys that form alumina coatings have a high potential for heat shield applications for advanced aerospace vehicles at temperatures above 1095C. Both INCOLOY alloy MA 956 (of the Inco Alloys International, Inc.), an iron-base oxide-dispersion-strengthened alloy, and CABOT alloy No. 214 (of the Cabot Corporation), an alumina-forming nickel-chromium alloy, have good oxidation resistance and good elevated temperature strength. The oxidation resistance of both alloys has been attributed to the formation of a thin alumina layer (alpha-Al2O3) at the surface. Emittance and oxidation data were obtained for simulated Space Shuttle reentry conditions using a hypersonic arc-heated wind tunnel. The surface oxides and substrate alloys were characterized using X-ray diffraction and scanning and transmission electron microscopy with an energy-dispersive X-ray analysis unit. The mass loss and emittance characteristics of the two alloys are discussed.

Wiedemann, K. E.↗

Pretreatment effects on the morphology and properties of aluminum oxide thermally grown on NiCoCrAlY

The effect of pretreatments on the morphology and properties of aluminum oxide thermally grown from NiCoCrAlY was investigated. The goal was to optimize process steps to produce a highly adherent, continuous, and insulating aluminum oxide. Two pretreatments were carried out, one in vacuum (about 0.0001 Torr) at 1350 K for 5 h, and the other consisting of deposition of a 1-micron thick Al2O3 film by activated reactive evaporation. Samples were subsequently oxidized thermally at 1000 C for 50 h at 0.5 Torr oxygen pressure. The two pretreatments were carried out on electron-beam evaporation NiCoCrAlY, about 120 microns thick, deposited on a superalloy turbine blade substrate. The results showed that the thermally grown oxide was significantly different in microstructure, surface topography and in its adherence to the NiCoCrAlY for the two pretreatments. Optimum results were obtained by combining the two pretreatments to produce an adherent, continuous, and insulating oxide film on the NiCoCrAlY-coated superalloy substrate.

Prakash, S.↗

Thermal and sputtered aluminum oxide coatings for high temperature electrical insulation

Aluminum oxide coatings have been investigated as electrically insulating layers for mounting thin film Pt-Pt/Rh thermocouples on gas turbine blade and vane alloys (MAR M200 + Hf and MAR M509). Thermal oxides were grown directly onto NiCoCrAlY and FeCrAlY coatings on these alloys at temperature between 1300 and 1400 K in oxygen partial pressures 10 to the -7th to 2 x 10 to the 4th Pa. Although these thermal oxides exhibited good adherence, analytical characterizations using electron and optical microscopy, as well as X-ray photoelectron spectroscopy showed that they had defects and impurities which limited their insulating ability. The insulating quality of the coating was greatly improved however by reactively sputtering an aluminum oxide film over the thermal oxide. Results are presented on the electrical performance of the 2-5 micron thick composite layers for temperatures up to 1300 K.

Kreider, K. G.↗

Wet oxidation of a spacecraft model waste

Wet oxidation was used to oxidize a spacecraft model waste under different oxidation conditions. The variables studied were pressure, temperature, duration of oxidation, and the use of one homogeneous and three heterogeneous catalysts. Emphasis is placed on the final oxidation state of carbon and nitrogen since these are the two major components of the spacecraft model waste and two important plant nutrients.

Johnson, C. C.↗

Oxidation and embrittlement of Ti-6Al-2Sn-4Zr-2Mo alloy

A thermogravimetric analysis monitoring study has been conducted for Ti-6Al-2Sn-4Zr-2Mo in the 593-760 C range, with a view to its total oxidation kinetics in laboratory air. In addition, tensile elongation was obtained for selected foil specimens after their exposure to simulated Space Shuttle reentry conditions. The total weight gain with time exhibited two parabolic stages separated by a transient region which is the result of a simultaneous increase in the parabolic growth rate constant for the oxide and in oxygen solubility at the oxide-metal interface. A model for the total oxidation kinetics accounting for the two individual components (oxide growth and solid solution formation) is proposed; the activation energy for oxygen diffusion in the alpha-solid solution is shown to approximate the activation energy for the degradation of tensile elongation of the alloy in its foil gage condition.

Shenoy, R. N.↗

A review of tin oxide-based catalytic systems: Preparation, characterization and catalytic behavior

This paper reviews the important aspects of the preparation, characterization and catalytic behavior of tin oxide-based catalytic systems including doped tin oxide, mixed oxides which contain tin oxide, Pt supported on tin oxide and Pt/Sn supported on alumina. These systems have a broad range of applications and are continually increasing in importance. However, due to their complex nature, much remains to be understood concerning how they function catalytically.

Hoflund, Gar B.↗

Oxidation of commercial purity titanium

The oxidation kinetics of commercial purity Ti-A55 exposed to laboratory air in the 593-760 C temperature range were continuously monitored by thermogravimetric analysis. The oxide thickness was measured by microscopy, and the substrate contamination was estimated from microhardness measurements. The microhardness depth profiles were converted to oxygen composition profiles using calibration depth. The oxygen diffusion coefficient in alpha-Ti appears to be approximately concentration-independent in the 1-10 at. pct oxygen range. Diffusion coefficient for oxygen in TiO2 has been estimated as a function of temperature and is found to be about 50 times the value in alpha-Ti. The metallographically prepared cross sections of the oxidized specimens revealed a 'moving boundary' in the substrate, parallel to the oxide-metal interface. This boundary was associated with a specific oxygen level of 5.0 + or - 0.5 at. pct. It occurred at a distance from the oxide-metal interface which was correlatable with temperature and time of exposure. The diffusion coefficient corresponding to the composition of this moving boundary is in excellent agreement with the effective diffusion coefficient for the substrate contamination.

Unnam, J.↗

Fracture of flash oxidized, yttria-doped sintered reaction-bonded silicon nitride

The oxidation behavior of a slip cast, yttria-doped, sintered reaction-bonded silicon nitride after 'flash oxidation' was investigated. It was found that both the static oxidation resistance and flexural stress rupture life (creep deformation) were improved at 1000 C in air compared to those of the same material without flash oxidation. Stress rupture data at high temperatures (1000 to 1200 C) are presented to indicate applied stress levels for oxidation-dependent and independent failures.

Govila, R. K.↗

Pyrite oxidation and reduction - Molecular orbital theory considerations

In this paper, molecular orbital theory is used to explain a heterogeneous reaction mechanism for both pyrite oxidation and reduction. The mechanism demonstrates that the oxidation of FeS2 by Fe(3+) may occur as a result of three important criteria: (1) the presence of a suitable oxidant having a vacant orbital (in case of liquid phase) or site (solid phase) to bind to the FeS2 via sulfur; (2) the initial formation of a persulfido (disulfide) bridge between FeS2 and the oxidant, and (3) an electron transfer from a pi(asterisk) orbital in S2(2-) to a pi or pi(asterisk) orbital of the oxidant.

Luther, George W., III↗

Influence of alloying elements on the oxidation behavior of NbAl3

NbAL3 is one candidate material for advanced aeropropulsion systems because of its high melting point, low density, and good oxidation resistance. Although NbAl3 has the lowest oxidation rate among the binary Nb-Al alloys, it does not form exclusive layers of protective Al2O3 scales. Recently Perkin et al., have shown the feasibility of forming alumina scales on Nb-Al alloys at greatly reduced Al contents. However, the objective was to maintain the high Al content, and hence low density, while achieving the capability of growing protective alumina scales. Alloy development followed approaches similar to those used successfully for superalloys and oxidation resistant MCrAlY coatings. Among the three elements examined (Ti, Si, and Cr) as ternary additions to Nb-Al3, Cr was the most effective in favoring the selective oxidation of Al. Nb-41Al-8Cr formed exclusive layers of alumina and had a k sub p value of 0.22 mg squared/cm (sup 4)/hr at 1200 C. The addition of 1 wt percent Y to this alloy was also beneficial, resulting in nearly an order of magnitude decrease in K sub p at 1200 C. Further improvements were achieved by adding about 1 wt percent Si to the quaternary alloy. The k sub p value of 0.012 mg squared/cm (sup 4)/hr for Nb-40Al-8Cr-1Y-1Si at 1200 C was identical to the best NiAl + Zr alloys. These NbAl3 alloys also exhibited excellent cyclic oxidation resistance for 100 hr at 1200 C, being nearly equivalent to NiAl + Zr.

Hebsur, M. G.↗

The oxidation of Ni-rich Ni-Al intermetallics

The oxidation of Ni-Al intermetallic alloys in the beta-NiAl phase field and in the two phase beta-NiAl/gamma'-Ni3Al phase field has been studied between 1000 and 1400 C. The stoichiometric beta-NiAl alloy doped with Zr was superior to other alloy compositions under cyclic and isothermal oxidation. The isothermal growth rates did not increase monotonically as the alloy Al content was decreased. The characteristically ridged alpha-Al2O3 scale morphology, consisting of cells of thin, textured oxide with thick growth ridges at cell boundaries, forms on oxidized beta-NiAl alloys. The correlation of scale features with isothermal growth rates indicates a predominant grain boundary diffusion growth mechanism. The 1200 C cyclic oxidation resistance decreases near the lower end of the beta-NiAl phase field.

Doychak, Joseph↗

High temperature isothermal and cyclic oxidation behavior of a single crystal Ni base superalloy

High-temperature oxidation behavior of a Ni-base superalloy, PWA1480, developed for use as single-crystal blades and vanes in advanced gas turbines, has been assessed. Isothermal and cyclic oxidation tests up to 200 hours were conducted at 1323, 1410, and 1473 K. The alloy was evaluated as to sample weight change, type of scale formed, type and amount of spall, and microstructural changes. The oxidation attack was more severe in cyclic as compared with isothermal oxidation. Also, enormous growth of the gamma-prime precipitate was observed at 1423 K during cyclic oxidation.

Hebsur, M. G.↗

Effect of 0.1 at. pct Zirconium on the cyclic oxidation resistance of beta-NiAl

The effect of 0.1 at. pct Zr on the cyclic oxidation of hipped beta-NiAl was studied. Oxidation testing was performed in static air at 1100-1200 C, using 1-hr exposure cycles for test times up to 3000 hr. The weight change versus time data were modeled with the COSP computer program to analyze and predict cyclic-oxidation behavior. Zr additions significantly change the nature of the scale-spalling process during cooling, so that the oxide spalls near the oxide-air interface at a relatively low depth within the scale. Without Zr, the predominantly alpha-Al2O3 scale tends to spall randomly to bare metal at relatively high effective-scale-loss rates, particularly at 1150 C and 1200 C. This leads to higher rates of Al consumption for the Zr-free aluminide and much earlier depletion of Al, leading to eventual breakaway (i.e., failure).

Barrett, Charles A.↗

Oxidation of silicon with a 5 eV O(-) beam

A silicon wafer has been oxidized at room temperature in vacuum using a pure, ground-state beam of O(-) ions. The beam was of sufficiently low energy that no displacement damage or implantation was energetically possible. The resulting SiO2 films were analyzed with X-ray photoelectron spectroscopy. A logarithmic dependence of oxide thickness on dose was observed, with an extrapolated oxidation efficiency of unity for the clean silicon surface. A distinct initial oxidation phase was observed, with an anomalously high level of silicon suboxides. In addition, the valence-band offset between the silicon and the oxide was unusually small, suggesting a large interfacial dipole.

Hecht, M. H.↗

Oxidation state in chondrites

An evaluation is made of extant data on chondrite oxidation states and intrinsic O fugacities. A variety of oxidation states are exhibited by the chondritic meteorites; petrologic and chemical data may be used to arrange the major chondrite groups in order of oxidation state. The intrinsic O fugacity measurements on chondrite whole-rock samples are noted to display a corresponding ordering of oxidation states. Metamorphosed chondrites and igneous meteorites that were substantially altered by metamorphic reactions, outgassing, and igneous processes may preserve information on the oxidation state and size of their parent bodies.

Rubin, Alan E.↗

Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

Kilduff, Jan E.↗

Analysis of Pt/SnO(sub x) during catalysis of CO oxidation

Temperature-programmed reduction using 6kPaH2 suggests that a sample consisting of 3 percent Pt supported directly on SnO2 is, under conditions of catalysis of CO oxidation used here, best represented as 3 percent Pt/SnO sub x, since the support is likely to partially reduced, probably in the vicinity of the metal/oxide interface. Catalytic measurements at 421 to 424 K show that this 3 percent Pt/SnO sub x is significantly more active per unit area of Pt than 6 percent Pt/SiO2 in catalyzing the oxidation of CO. In situ micro-FTIR reveals that while the latter has predominantly linearly bound CO on the surface under reaction conditions, the Pt/SnO sub x also has a species absorbing at 2168 cm(exp -1) which may be CO upon Pt in a positive oxidation state or weakly chemisorbed CO on zero-valent Pt. This may be directly involved in the low temperature oxidation of CO on the Pt/SnO sub x, since being weakly held the activation energy for its surface diffusion to the metal/oxide interface will be low; such mobile species could allow the high rates of surface transport and an increase in the fraction of the surface over which the CO oxidation occurs. FTIR also reveals carbonate-type species on the P/SnO sub c surface.

Sermon, Paul A.↗