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At least 1,459 records · Page 81

Static and dynamic oxidation of Ti-14Al-21Nb and coatings

The oxidation of Ti-14Al-21Nb (wt pct) was studied under static conditions at 649 to 1093 C for as long as 120 hr, and under simulated hypersonic flight (dynamic oxidation) conditions at 982 C for as many as 16 half-hour cycles. Under simulated hypersonic flight conditions heavy oxidation and spalling of the oxide was observed. It was concluded that titanium aluminides used in hypersonic applications must have oxidation-protective coatings. In this preliminary study coatings about 1 micron thick were applied by sputter deposition, from solutions, and from sol-gels. It was found that, because of cracks and porosity, the sputter-deposited coatings did not have sufficient film integrity to shield the alloy. Some of the coatings applied from sol-gels demonstrated film integrity in 1 hr exposures at 982 C.

Wiedemann, K. E.↗

Development of a regenerable metal oxide CO removal system

A regenerable metal oxide carbon dioxide (CO2) removal system was developed to replace the current means of a nonreusable chemical, lithium hydroxide, for removing the metabolic CO2 of an astronaut in a space suit. Testing indicates that a viable low-volume metal oxide concept can be used in the portable life support system for CO2 removal during Space Station extravehicular activity (EVA). A canister of nearly the same volume as that used for the Space Shuttle, containing 0.10 cu ft of silver-oxide-based pellets, was tested; test data analysis indicates that 0.18 cu ft of the metal oxide will result in an 8-hour EVA capability. The testing suggests that the metal oxide technology offers a low-volume approach for a reusable CO2 removal concept applicable for at least 40 EVA missions. The development and testing of the breadboard regeneration package is also described.

Cusick, Robert J.↗

Heterogeneous photocatalytic oxidation of atmospheric trace contaminants

The following subject areas are covered: (1) design and construction of continuous flow photoreactor for study of oxidation of trace atmospheric contaminants; (2) establishment of kinetics of acetone oxidation including adsorption equilibration, variation of oxidation rate with acetone concentration and water (inhibitor), and variation of rate and apparent quantum yield with light intensity; (3) exploration of kinetics of butanol oxidation, including rate variation with concentration of butanol, and lack of inhibition by water; and (4) exploration of kinetics of catalyst deactivation during oxidation of butanol, including deactivation rate, influence of dark conditions, and establishment of photocatalytic regeneration of activity in alcohol-free air.

Ollis, David F.↗

Bolide impacts and the oxidation state of carbon in the earth's early atmosphere

A one-dimensional photochemical model was used to examine the effect of bolide impacts on the oxidation state of earth's primitive atmosphere. The impact rate should have been high prior to 3.8 Ga before present, based on evidence derived from the moon. Impacts of comets or carbonaceous asteroids should have enhanced the atmospheric CO/CO2 ratio by bringing in CO ice and/or organic carbon that can be oxidized to CO in the impact plume. Ordinary chondritic impactors would contain elemental iron that could have reacted with ambient CO2 to give CO. Nitric oxide (NO) should also have been produced by reaction between ambient CO2 and N2 in the hot impact plumes. High NO concentrations increase the atmospheric CO/CO2 ratio by increasing the rainout rate of oxidized gases. According to the model, atmospheric CO/CO2 ratios of unity or greater are possible during the first several hundred million years of earth's history, provided that dissolved CO was not rapidly oxidized to bicarbonate in the ocean.

Kasting, James F.↗

Oxidation behavior of cubic phases formed by alloying Al3Ti with Cr and Mn

Gravimetric, SEM, and XRD data are presented which document the significant improvement obtainable in the oxidation resistance of Al3Ti-containing alloys through additions of Cr. The L1(2) Al(67)Cr(8)Ti25 alloy exhibited excellent cyclic oxidation resistance at 1473 K, with the primary oxide formed being the ideally protective alpha-Al2O3. The Al(67)Mn(8)Ti(25) alloy also tested for comparison exhibited poor cyclic oxidation resistance, with substantial occurrence of TiO2 in the protective scales. Catastrophic oxidation was also encountered in the quaternary alloy Al(67)Mn(8)Ti(22)V(3).

Parfitt, L. J.↗

Ecosystem approach to a global nitrous oxide budget

An approach using relationships among soil fertility, nitrogen cycling, and nitrous oxide production is presented in order to estimate nitrous oxide flux from humid tropical forests. The effects of human disturbance are also investigated. It is noted that recent estimates suggest that 6-10 million ha. of tropical forest are cleared permanently each year. The results of measurements of nitrous oxide flux from cleared and burned sites in Costa Rica and Brazil, in conjunction with satellite-based classifications of ecosystem types, are used to calculate average hourly fluxes for a given region. In the NASA intensive site near Manaus, Brazil, it was found that although pasture areas cover only 11 percent of the region they account for 40 percent of the nitrous oxide flux. This analysis of the fluxes of trace gases through consideration of the gradients of factors that control both fluxes and ecosystem properties and processes will prove useful for extrapolating fluxes and for calculating budgets of nitrous oxide, methane, nonmethane hydrocarbons, and carbon dioxide.

Matson, P. A.↗

Sliding durability of two carbide-oxide candidate high temperature fiber seal materials in air to 900 C

A test program to determine the friction and wear properties of two complex carbide oxide ceramic fibers for high temperature sliding seal applications is described. The fibers are based on Si, C, O, and Ti or Si, C, N, and O ceramic systems. Pin on disk tests using ceramic fiber covered pins and Inconel 718 disks, were conducted in air from 25 to 900 C to evaluate potential seal materials. This testing procedure was used in a previous study of oxide ceramic fibers which were found to exhibit wear behavior based predominantly on their mechanical properties. Like the oxide fibers tested previously, these carbide oxide ceramic fibers, show an increase in friction and wear with increased test temperature. At room temperature, the wear behavior seems to be based upon mechanical properties, namely tensile strength. At 500 and especially 900 C, the fibers wear by both mechanical fracture and by oxidative type wear. Based upon post test microscopic and x ray analyses, interaction between the fiber constituents and elements transferred from the counterface, namely Ni and Cr, may have occurred enhancing the tribochemical wear process. These results are interpreted.

Dellacorte, Christopher↗

Oxidation characteristics of Beta-21S in air in the temperature range 600 to 800 C

The metastable beta-Ti alloy Beta-21S, Ti-15Mo-2.7Nb-3Al-0.2Si (weight percent), has been proposed as a candidate for use in metal matrix composites in future hypersonic vehicles. The present study investigated the oxidation behavior of Beta-21S over the temperature range 600 C to 800 C. Oxidation weight gain was evaluated using thermogravimetric analysis. Oxidized specimens were evaluated using x ray diffraction techniques, scanning electron microscopy, energy dispersive x ray analysis, and electron microprobe analysis to identify oxidation products and evaluate oxidation damage to the alloy.

Wallace, Terryl A.↗

An XPS study of the stability of Fomblin Z25 on the native oxide of aluminum

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum and sapphire surfaces, and their behavior at different temperatures was studied using x ray photoelectron spectroscopy (XPS) and thermal desorption spectroscopy (TDS). It was found that the interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. Our conclusion is that the native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At high temperatures (150 C) degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formulation of a debris layer.

Herrera-Fierro, Pilar↗

Oxidation-chlorination of binary Ni-Cr alloys in flowing Ar-O2-Cl2 gas mixtures at 1200 K

Nickel-chromium alloys are resistant to oxidation because of the selective oxidation of chromium to form a protective Cr2O3 scale. In chlorine-containing environments, volatile corrosion products can also be formed. The mixed oxidation-chlorination of Ni-4.5Cr, Ni-13.8Cr, and Ni-26.5Cr (by weight) alloys in Ar-O2-Cl2 gas mixtures is investigated using thermogravimetric analysis and atmospheric-pressure-sampling mass spectrometry, followed by examination of the corrosion products using scanning electron microscopy and X-ray diffraction analysis. The overall kinetics of the corrosion are affected by the relative amounts of oxides and chlorides formed and the composition of the oxide corrosion products.

Mcnallan, M. J.↗

Thermal barrier coating life and isothermal oxidation of low-pressure plasma-sprayed bond coat alloys

The paper investigates the isothermal oxidation kinetics of Ni-35Cr-6Al-0.95Y, Ni-18Cr-12Al-0.3Y, and Ni-16Cr-6Al-0.3Y low-pressure plasma-sprayed bond coat alloys and examines the effect of these alloys on the thermal barrier coating (TBC) cyclic life. TBC life was examined by cycling substrates coated with the different bond coats and a ZrO2-7 wt pct Y2O3 TBC in an air-rich burner rig flame between 1150 C and room temperature. The oxidation kinetics of the three bond coat alloys was examined by isothermal oxidation of monolithic NJiCrAlY coupons at 1083 C. The Ni-35Cr-6Al-0.95Y alloy exhibits comparatively high isothermal oxidation weight gains and provides the longest TBC life, whereas the Ni-16Cr-6Al-0.3Y alloy had the lowest weight gains and provided the shortest TBC life. The results show that, although bond coat oxidation is known to have a strong detrimental effect on TBC life, it is not the only bond coat factor that determines TBC life.

Brindley, W. J.↗

Effect of fiber reinforcement on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermooxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. The polyimide PMR-15 was the matrix material used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-4OR graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces.

Bowles, K. J.↗

The oxidizing capacity of the earth's atmosphere - Probable past and future changes

A number of critical atmospheric chemical problems depend on the earth's oxidizing capacity, which is essentially the global burden of oxidants in the lower atmosphere. There is limited direct evidence for changes in the earth's oxidizing capacity since recent preindustrial times when, because of industrial and poulation growth, increasing amounts of O3 precursor trace gases (carbon monoxide, nitrogen oxides, and hydrocarbons) have been released into the atmosphere. The concentrations of O3 and possibly H2O2 have increased over large regions. Models predict that tropospheric O3 will increase about 0.3-1.0 percent per year over the next 50 years with both positive and negative trends possible for OH and H2O2. Models and the observational network for oxidants are improving, but validation of global models is still at an early stage.

Thompson, Anne M.↗

Nonequilibrium synthesis of NbAl3 and Nb-Al-V alloys by laser cladding. II - Oxidation behavior

Isothermal oxidation behaviors of NbAl3 alloy synthesized by laser cladding were investigated at temperatures between 800 and 1400 C, and the effect of vanadium microalloying on the oxidation of the laser-clad alloy was examined. The oxidation kinetics of the two alloys were monitored using thermal gravimetric weight gain data, and the bulk and surface chemistries were analyzed using XRD and XPS, respectively. It was found that NbAl3 did not form an exclusive layer of protective Al2O3. The oxidation products at 800 C were found to be a mixture of Nb2O5 and Al2O3. At 1200 C, a mixture of NbAlO4, Nb2O5, and Al2O3 formed; and at 1400 C, a mixture of NbAlO4, Al2O3, NbO2, NbO(2.432), and Nb2O5 formed. The addition of V led to a dramatic increase of the oxidation rate, which may be related to the formation of (Nb, V)2O5 and VO2, which grows in preference to protective Al2O3.

Haasch, R. T.↗

Determination of the oxidative stability of perfluoropolyalkyl ethers and correlation with chemical structure

The oxidative stabilities of several perfluoropolyalkyl ethers (PFPAE) with related chemical structures were determined by thermal gravimetric analysis and correlated with their chemical structures. These results show that oxidative stability increases as the number of difluoroformal groups decreases and as trifluoromethyl substituents are added. They are also consistent with a recently proposed intramolecular disproportionation reaction mechanism involving coordination of successive ether oxygens to a Lewis acid. Since polytetrafluoroethylene contains no oxygen, it provides an indication of the upper limit to oxidative stability of PFPAE fluids. These results also show that oxidative decomposition of PFPAE fluids requires the presence of an active metal as well as air. Consequently, it may be possible to minimize decomposition and thus improve oxidative stability by passivating reactive metal surfaces.

Helmick, Larry S.↗

X-ray photoelectron spectroscopy study of the stability of Fomblin Z25 on the native oxide of aluminum

Thin films of Fomblin Z25, a perfluoropolyalkylether lubricant, were vapor deposited onto clean, oxidized aluminum, and onto sapphire surfaces, and their behavior at different temperatures was studied using X-ray photoelectron spectroscopy and temperature desorption spectroscopy (TDS). The interfacial fluid molecules decompose on the native oxide at room temperature, and continue to decompose at elevated temperatures, as previous studies had shown to occur on the clean metal. TDS indicated that different degradation mechanisms were operative for clean and oxidized aluminum. On sapphire substrates, no reaction was observed at room temperature. The native oxide of aluminum is neither passive nor protective towards Fomblin Z25. At higher temperatures (150 C), degradation of the polymer on sapphire produced a debris layer at the interface with a chemical composition similar to the one formed on aluminum oxide. Rubbing a Fomblin film on a single crystal sapphire also induced the decomposition of the lubricant in contact with the interface and the formation of a debris layer.

Herrera-Fierro, Pilar↗

Predicting the oxidative lifetime of beta NiAl-Zr alloys

Nickel aluminides containing 40 to 50 at. pct Al and 0.1 at. pct Zr were studied following cyclic oxidation at 1400 C. The selective oxidation of Al resulted in the formation of protective Al2O3 scales on each alloy composition. However, repeated cycling eventually resulted in the gradual formation of less-protective NiAl2O4, first appearing on the 40Al alloys followed at longer times on the 45Al alloys. The appearance of the NiAl2O4, signaling the end of the protective scale-forming capability of the alloy, was related to the presence of gamma-prime (Ni3Al) which formed as a result of the loss of Al from the sample. A diffusion model, based on finite-difference techniques, was developed to predict the protective life of beta Ni-Al alloys. This model predicts Ni and Al concentration profiles after various oxidation exposures. The model can predict the oxidative lifetime due to Al depletion when the Al concentration decreases to a critical concentration. Measured Al concentration profiles on two alloys after various oxidation exposures are compared to those predicted by the diffusion model. The time to the appearance of the NiAl2O4 and that predicted by the diffusion model are compared and discussed.

Nesbitt, J. A.↗

Acetate concentrations and oxidation in salt marsh sediments

Acetate concentrations and rates of acetate oxidation and sulfate reduction were measured in S. alterniflora sediments in New Hampshire and Massachusetts. Pore water extracted from cores by squeezing or centrifugation contained in greater than 0.1 mM acetate and, in some instances, greater than 1.0 mM. Pore water sampled nondestructively contained much less acetate, often less than 0.01 mM. Acetate was associated with roots, and concentrations varied with changes in plant physiology. Acetate turnover was very low whether whole core or slurry incubations were used. Radiotracers injected directly into soils yielded rates of sulfate reduction and acetate oxidation not significantly different from core incubation techniques. Regardless of incubation method, acetate oxidation did not account for a substantial percentage of sulfate reduction. These results differ markedly from data for unvegetated coastal sediments where acetate levels are low, oxidation rate constants are high, and acetate oxication rates greatly exceed rates of sulfate reduction. The discrepancy between rates of acetate oxidation and sulfate reduction in these marsh soils may be due either to the utilization of substrates other than acetate by sulfate reducers or artifacts associated with measurements of organic utilization by rhizosphere bacteria. Care must be taken when interpreting data from salt marsh sediments since the release of material from roots during coring may affect the concentrations of certain compounds as well as influencing results obtained when sediment incubations are employed.

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