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NASA NTRS1982

Supercritical water oxidation for wastewater treatment Preliminary study of urea destruction

Supercritical water oxidation is being investigated as a method of treating spacecraft wastewater for recycle. In this process, oxidation is conducted in an aqueous phase maintained above the critical temperature (374 C) and pressure (215 bar) of water. Organic materials are oxidized with efficiencies greater than 99.99 percent in residence times of less than 1 minute. This paper presents preliminary results for urea destruction. Above 650 C, urea can be completely broken down to nitrogen gas, carbon dioxide and water by supercritical water oxidation, without the use of a specific catalyst.

Timberlake, S. H.↗

NASA NTRS1983

Interfacial layers in high-temperature-oxidized NiCrAl

The utility of Auger electron spectroscopy combined with ball cratering for depth analysis of oxide and diffusion layers produced in a Ni-14Cr-24Al alloy by oxidation in air at 1180 C for 25 hr is demonstrated. During postoxidation cooling, the oxide layers formed by this alloy spalled profusely. The remaining very thin oxide was primarily Cr2O3 with a trace of Ni. The underlying metal substrate exhibited gamma/gamma-prime and beta phases with a metallic interfacial layer which was similar to the bulk gamma/gamma-prime phase but slightly enriched in Cr and Al. These data are compared to electron microprobe results from a nominally identical alloy. The diffusion layer thickness is modelled with a simple mass balance equation and compared to recent results on the diffusion process in NiCrAl alloys.

Larson, L. A.↗

NASA NTRS1984

Effect of alloy chemistry and exposure conditions on the oxidation of titanium

Multiwall is a new thermal protection system concept for advanced space transportation vehicles. The system consists of discrete panels made up of multiple layers of foil gage metal. Titanium is the proposed candidate metal for multiwall panels in the reentry temperature range up to 675 C. Oxidation and embrittlement are the principal concerns related to the use of Ti in heat shield applications. The results of a broad study on the oxidation kinetics of several titanium alloys subjected to different exposure conditions are described. The alloys include commercially pure titanium, Ti-6Al-4V, and Ti-6Al-2Sn-4Zr-2Mo. Oxidation studies were performed on these alloys exposed at 704 C in 5-760 torr air pressure and 0 to 50% relative humidity. The resulting weight gains were correlated with oxide thickness and substrate contamination. The contamination depth and weight gains due to solid solutioning were obtained from microhardness depth profiles and hardness versus weight percent oxygen calibration data.

Unnam, J.↗

NASA NTRS1984

Coupling Between the Thermosphere and the Stratosphere: the Role of Nitric Oxide

In order to understand the lower ionosphere and its probable control by dynamical processes, the behavior of nitric oxide below 100 km was investigated. A two dimensional model with coupled chemical and dynamical processes was constructed. Calculations based on the model reveal that the chemical conditions at the stratopause are related to the state of the thermosphere. This coupling mechanism can be partly explained by the downward transport of nitric oxide during the winter season, and consequently depends on the dynamical conditions in the mesosphere and in the lower thermosphere (mean circulation and waves). In summer, the photodissociation of nitric oxide plays an important role and the thermospheric NO abundance modulates the radiation field reaching the upper stratosphere. Perturbations in the nitric oxide concentration above the mesopause could therefore have an impact in the vicinity of the stratopause.

Brasseur, G.↗

NASA NTRS1985

Effects of chromium and aluminum on mechanical and oxidation properties of iron-nickel-base superalloys based on CG-27

The effects of chromium and aluminum on the mechanical and oxidation properties of a series of gamma-prime-strengthened alloys based on CG-27 were studied. Gamma-prime dispersion and solid-solution strengthening were the principal modes of alloy strengthening. The oxidation attack parameter K sub a decreased with increasing Cr and Al contents for each alloy group based on Al content. As a group, alloys with 3 wt % Al had the lowest attack parameters. Therefore, 3 wt % is the optimum level of Al for parabolic oxidation behavior. Spalling, due to diffusion-induced grain growth, was controlled by the overall Cr and Al levels. The alloy with 4 wt % Cr and 3 wt % Al had stress-rupture properties superior to those of the base alloy, CG-27, and maintained parabolic oxidation behavior while the Cr content was reduced by two-thirds of its value in cast CG-27.

Schuon, S. R.↗

NASA NTRS1985

Oxidation states of iron in the terrestrial planets: Evidence and implications for accretion models

Analyses of Mars spectra reveal that primary minerals may be more iron rich than average basalts on Earth, and the oxidation state of iron in the pyroxines suggests equally high or higher oxygen fugacities on Mars than Earth. Analysis of Mercury spectra reveal that silicate iron contents are substantially lower than those on Mars. Mercury, however, probably has a substantial iron core. This is consistent with a lower oxidation state of iron on Mercury than on Mars. These findings are consistent with predictions of models of equilibrium condensation and homogeneous accretion. Those models predict that Mercury would have negligible Fe(2+) in silicates (Fe/Fe+Mg approx. 0.5). For Mercury iron should be virtually all metallic, while for Mars the iron would be all oxidized as FeS and silicate. Surface measurements of Fe/Fe+Mg on Venus, Earth, and Mars further support the predicted relative increase in Fe/Fe+Mg ratio (increased oxidation state) with distance from the Sun. The implied high oxygen fugacities on Mars (Fe(3+) in silicates) provide additional consistence with the model predictions.

Huguenin, R. L.↗

NASA NTRS1985

Photoenhanced thermal oxidation of InP

The growth rate of laser-photoenhanced thermally grown native oxides of InP in a N2O ambient and its dependence on growth condition are presented. Increased laser power, substrate temperature, and N2O pressure are observed to increase the growth rate. The topography and the composition of these oxides have been studied using secondary electron microscopy and X-ray photoemission spectroscopy, respectively. The oxide layers contain In2O3 and a phosphate, probably InPO4. The enhanced growth appears to be caused by both excited oxidizing species and a photon-enhanced surface reaction.

Fathipour, M.↗

NASA NTRS1985

Satellite observations of the nitric oxide dayglow Implications for the behavior of mesospheric and lower-thermospheric odd nitrogen

The solar backscattered ultraviolet spectral radiometer on the Nimbus 7 satellite routinely measures fluorescence emissions from the nitric oxide (1, 4) gamma band that are imposed on the large Rayleigh-scattered signal in the wavelength range 255-256 nm. The gamma band feature, when isolated from the background radiance, provide information on the seasonal and latitudinal variations in the nitric oxide column abundance over the altitude region from 40 to 45 km upward through the thermosphere. At latitudes from 30 deg to 45 deg in the Northern Hemisphere the measurements show an annual cycle with maximum nitric oxide abundance in summer. The Southern Hemisphere pattern is qualitatively similar to this, although the amplitude of the seasonal variation is substantially smaller. The most prominent feature of the data base is a large maximum in nitric oxide emission that develops poleward of 45 deg latitude in both Hemispheres during late autumn and early winter. These maxima dissipate rapidly as spring approaches and are no longer evident in the data for Northern Hemisphere March and Southern Hemisphere September.

Frederick, J. E.↗

NASA NTRS1985

Electrical characterization of plasma-grown oxides on gallium arsenide

Plasma-grown GaAs oxides and their interfaces have been characterized by measuring the electrical properties of metal-oxide-semiconductor capacitors and of Schottky junctions. The current transport mechanism in the oxide at high electrical field was found to be Frankel-Poole emission, with an electron trap center at 0.47 eV below the conduction band of the oxide. The interface-state density, evaluated from capacitance and conductance measurements, exhibits a U-shaped interface-state continuum extending over the entire band gap. Two discrete deep states with high concentration are superimposed on this continuum at 0.40 and 0.70 eV below the conduction band. The results obtained from measurements on Schottky junctions have excluded the possibility that these two deep states originate from plasma damage. Possible origins of these states are discussed in this paper.

Hshieh, F. I.↗

NASA NTRS1986

Wet-oxidation waste management system for CELSS

A wet oxidation system will be useful in the Closed Ecological Life Support System (CELSS) as a facility to treat organic wastes and to redistribute inorganic compounds and elements. However at rather higher temperatures needed in this reaction, for instance, at 260 deg C, only 80% of organic in a raw material can be oxidized, and 20% of it will remain in the liquid mainly as acetic acid, which is virtually noncombustible. Furthermore, nitrogen is transformed to ammonium ions which normally cannot be absorbed by plants. To resolve these problems, it becomes necessary to use catalysts. Noble metals such as Ru, Rh and so on have proved to be partially effective as these catalysts. That is, oxidation does not occur completely, and the unexpected denitrification, instead of the expected nitrification, occurs. So, it is essential to develop the catalysts which are able to realize the complete oxidation and the nitrification.

Takahashi, Y.↗

NASA NTRS1986

Slip casting and extruding shapes of rhenium with metal oxide additives. 1: Feasibility demonstration

The feasibility of fabricating small rhenium parts with metal oxide additives by means of slip casting and extrusion techniques is described. The metal oxides, ZrO2 and HfO2 were stabilized into the cubic phase with Y2O3. Additions of metal oxide to the rhenium of up to 15 weight percent were used. Tubes of 17 mm diameter with 0.5 mm walls were slip cast by adapting current ceramic oxide techniques. A complete cast double conical nozzle demonstrated the ability to meet shapes and tolerances. Extrusion of meter long tubing lengths of 3.9 mm o.d. x 2.3 mm i.d. final dimension is documented. Sintering schedules are presented to produce better than 95% of theoretical density parts. Finished machining was found possible were requried by electric discharge machining and diamond grinding.

Barr, F. A.↗

NASA NTRS1986

Grain boundary oxidation and fatigue crack growth at elevated temperatures

Fatigue crack growth rate at elevated temperatures can be accelerated by grain boundary oxidation. Grain boundary oxidation kinetics and the statistical distribution of grain boundary oxide penetration depth were studied. At a constant delta K-level and at a constant test temperature, fatigue crack growth rate, da/dN, is a function of cyclic frequency, nu. A fatigue crack growth model of intermittent micro-ruptures of grain boundary oxide is constructed. The model is consistent with the experimental observations that, in the low frequency region, da/dN is inversely proportional to nu, and fatigue crack growth is intergranular.

Liu, H. W.↗

NASA NTRS1986

The effect of Cr, Co, Al, Mo and Ta on a series of cast Ni-base superalloys on the stability of an aluminide coating during cyclic oxidation in Mach 0.3 burner rig

The influence of varying the content of Co, Cr, Mo, Ta, and Al in a series of cast Ni-based gamma/gamma'superalloys on the behavior of aluminide coatings was studied in burner rig cyclic oxidation tests at 1100 C. The alloys had nominally fixed levels of Ti, W, Cb, Zr, C, and B. The alloy compositions were based on a full 2(sup 5)-fractional statistical design supplemented by 10 star point alloys and a center point alloy. This full central composite design of 43 alloys plus two additional alloys with extreme Al levels allowed a complete second degree estimating equation to be derived from the 5-compositional variables. The weight change/time data for the coated samples fitted well to the paralinear oxidation model and enabled a modified oxidation attack parameter, K'(sub a) to be derived to rank the alloys and log K' (sub a ) to be used as the dependent variable in the estimating equation to determine the oxidation resistance of the coating as a function of the underlying alloy content. The most protective aluminide coatings are associated with the highest possible base ally contents of CR and Al and at a 4 percent Ta level. The Mo and Co effects interact but at fixed levels of 0, 5, or 10% Co. A 4% Mo level is optimum.

Zaplatynsky, I.↗

NASA NTRS1986

Supercritical water oxidation of products of human metabolism

Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

Tester, Jefferson W.↗

NASA NTRS1987

Chemical engineering design of CO oxidation catalysts

How a chemical reaction engineer would approach the challenge of designing a CO oxidation catalyst for pulsed CO2 lasers is described. CO oxidation catalysts have a long history of application, of course, so it is instructive to first consider the special requirements of the laser application and then to compare them to the characteristics of existing processes which utilize CO oxidation catalysts. All CO2 laser applications require a CO oxidation catalyst with the following characteristics: (1) active at stoichiometric ratios of O2 and CO, (2) no inhibition by CO2 or other components of the laser environment, (3) releases no particulates during vibration or thermal cycling, and (4) long lifetime with a stable activity. In all applications, low consumption of power is desirable, a characteristic especially critical in aerospace applications and, thus, catalyst activity at low temperatures is highly desirable. High power lasers with high pulse repetition rates inherently require circulation of the gas mixture and this forced circulation is available for moving gas past the catalyst. Low repetition rate lasers, however, do not inherently require gas circulation, so a catalyst that did not require such circulation would be favorable from the standpoint of minimum power consumption. Lasers designed for atmospheric penetration of their infrared radiation utilize CO2 formed from rare isotopes of oxygen and this application has the additional constraint that normal abundance oxygen isotopes in the catalyst must not exchange with rare isotopes in the gas mixture.

Herz, Richard K.↗

NASA NTRS1987

The oxidation degradation of aromatic compounds

A series of experiments were conducted which focused on understanding the role that the O atom addition to aromatic rings plays in the oxidation of benzene and toluene. Flow reactor studies of the oxidation of toluene gave an indication of the amount of O atoms available during an oxidation and the degree to which the O atom adds to the ring. Flow reactor studies of the oxidation of toluene and benzene to which NO2 was added, have shown that NO2 appears to suppress the formation of O atoms and consequently reduce the amount of phenols and cresols formed by O atom addition. A high temperature pyrolysis study of phenol has confirmed that the major decomposition products are carbon monoxide and cyclopentadiene. A preliminary value for the overall decomposition rate constant was also obtained.

Brezinsky, Kenneth↗

NASA NTRS1986

Analysis of thermomechanical oxidation fields in thermal barrier coatings

This paper considers the problem of the thermomechanical oxidation response of thermal barrier coatings. Overall, this involves the formulation of the requisite field equations and their associated boundary conditions, including the effects of oxide scale developing either on external surfaces or at interlaminar regions. To establish the potential effects of growing scale layers, the solution to the thermomechanical oxidation response of a cylindrically configured thermal barrier coating is developed. This includes handling the overall thermomechanical oxidation history.

Padovan, J.↗

NASA NTRS1986

Grain boundary oxidation and fatigue crack growth at elevated temperatures

Liu, H. W.↗