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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Oxidation of the Mantle Wedge by H+ in Aqueous Fluids: A New Interdisciplinary Approach

The observation that arc magmas are the most oxidized on Earth have led petrologists to question whether the subduction process might cause oxidation of the sub-arc mantle source. A strong correlation between the input of slab-derived aqueous fluid and Fe3(+)/ΣFe in arc magmas has led to the hypothesis that slab fluids may facilitiate the transfer of redox potential from oxidized slab material to mantle wedge and subsequently to primary arc melts. Despite this intuitive link, identifying an efficient and ubiquitous chemical process to transfer oxidation state in slab fluids has been challenging. Pure H2O alone is an inefficient oxidizer in the mantle, necessitating another oxidant within the fluid. Commonly invoked components include S or C, which are likely heterogeneously distributed within subducting slabs, and direct transfer of Fe3(+), which is only possible in very solute-rich fluids. Here we present a new mechanism to explain the oxidation of the sub-arc mantle by slab-derived aqueous fluid, wherein dissolved H(+)(aq) is reduced to H2(aq). Redox equilibrium is satisfied by electron transfer from Fe2(+)(s), which is oxidized in the rock to Fe3(+)(s) in the reaction: 2Fe2(+)(s) + 2H(+)(aq) = 2Fe3(+)(s) + H2(aq). This simple reaction was previously overlooked due to the assumption that all H must be bound by H2O molecules (i.e., no dissolved H), applicable to a pure H2O fluid, but not one with a solute load as addressed here. The application of thermodynamic modeling tools from aqueous geochemistry (DEW, EQ3/6) to mantle petrology predicts this reaction between mantle rock and slab fluid with our own experimentally constrained chemistry and fO2 (QFM+2). Mass transfer model results show an increase in Fe3(+)/ΣFe in mantle rock from MORB- like (0.15) to arc-like (0.2–0.3) values at reasonable fluid fluxes, co-incident with increasing H2 activity in the fluid. This can explain the stark correlation between slab fluid input into the mantle wedge and the observed fO2 of arc magmas. Moreover, it does not require diffusion of hydrogen out of the system. Instead, H2 remains dissolved in fluid in equilibrium with oxidized mantle rock.

Iacovino, Kayla↗
NASA NTRS1990

Characterization of Iridium Coated Rhenium Used in High-Temperature, Radiation-Cooled Rocket Thrusters

Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.

Stulen, R. H.↗
NASA NTRS1972

Improved oxidation-resistant carbon and graphite materials

A variety of silicon-carbide treated carbon and graphite products were prepared, and oxidation and strength properties determined. Carbon and graphite materials used in the preliminary study include fiber, tape, felt, foam, bulk, and laminar configurations. The silicon-carbide treatment used in preparing the oxidation resistant specimens employs either vacuum or ultrasonic impregnation of various silicone-silicon mixtures into the matrix material. The impregnation phase is followed by controlled thermal reaction at which time the silicon carbide is synthesized and takes the form of an integral protective boundary layer. Thickness of the layer ranges from a fraction of a mil to 10 mils, depending on the matrix material and processing parameters. Oxidation resistance of all the silicon-carbide-treated specimens investigated was found to be significantly improved. Mechanical strengths of the laminar composites were also found to be somewhat improved. At room temperature the specific strength of the silicon-carbide treated fibers and tapes was degraded to some extent; however, their relative strengths were significantly increased at elevated temperatures in oxidizing atmosphere.

Muir, H. M.↗
NASA NTRS1977

Further developments in oxidation of methane traces with radiofrequency discharge

The radiofrequency discharge, previously shown to oxidize trace levels of methane in oxygen, was studied with contaminated air at 50, 600, and 760 torr. As with oxygen, the concentration of methane traces could be reduced by several orders of magnitude, and no organic reaction products were detected in the effluent; however, substantial concentrations of NOx (0.1-6%) were formed during treatment. The concentration of NOx was decreased by using a large diameter electrode. There is evidence that the process will oxidize N2 and NO as well as organic impurities in oxygen or oxygen/inert gas atmospheres.

Flamm, D. L.↗
NASA NTRS1979

Compound oxidized styrylphosphine

A process is described for preparing flame resistant, nontoxic vinyl polymers which contain phosphazene groups and which do not emit any toxic or corrosive products when they are oxidatively degraded. Homopolymers, copolymers, and terpolymers of a styrene based monomer are prepared by polymerizing at least one oxidized styrylphosphine monomer from a group of organic azides, or by polymerizing p-diphenylphosphinestyrene and then oxidizing that monomer with an organoazide from the group of (C6H5)2P(O)N3, (C6H5O)2P(O)N3, (C6H5)2C3N3(N3), and C6H5C3N3(N3)2. Copolymers can also be prepared by copolymerizing styrene with at least one oxidized styrylphosphine monomer.

Paciorek, K. J. L.↗
NASA NTRS1978

Nitric oxide production by Tunguska meteor

The nonequilibrium chemical processes of nitric oxide formation are computed for the wake of the Tunguska meteor of 1908. The wake characteristics are derived by carrying out an optically-thick radiation field analysis for ablation of the meteoroid. The wake flow field is approximated by a one-dimensional, well-stirred reactor model. Known characteristics of the Tunguska event are imposed as constraints, and three controlling parameters - chemical composition, density, and velocity - are varied over a range around the values derived by Korobeinikov et al. (1976) and Petrov and Stulov (1975). The calculation shows that at least 19 million tons of nitric oxide is produced between the altitudes of 10 and 50 km. The anomalous atmospheric phenomena following the event are attributed to the reactions involving nitric oxide thus produced and atmospheric ozone. It is speculated that the nitric oxide produced by the event fertilized the area near the fall, causing the observed rapid plant growth.

Park, C.↗
NASA NTRS1985

Catalytic distillation water recovery subsystem

An integrated engineering breadboard subsystem for the recovery of potable water from untreated urine based on the vapor phase catalytic ammonia removal was designed, fabricated and tested. Unlike other evaporative methods, this process catalytically oxidizes ammonia and volatile hydrocarbons vaporizing with water to innocuous products; therefore, no pretreatment of urine is required. Since the subsystem is fabricated from commercially available components, its volume, weight and power requirements are not optimized; however, it is suitable for zero-g operation. The testing program consists of parametric tests, one month of daily tests and a continuous test of 168 hours duration. The recovered water is clear, odorless, low in ammonia and organic carbon, and requires only an adjustment of its pH to meet potable water standards. The obtained data indicate that the vapor phase catalytic ammonia removal process, if further developed, would also be competitive with other water recovery systems in weight, volume and power requirements.

Budininkas, P.↗
NASA NTRSDate not supplied

Supercritical Water Oxidation and a Preliminary Concept for Lunar Application

Abstract: Water is a critical resource for crewed space exploration missions and reclamation of aqueous waste streams presents the only long-term viable option. Although early Artemis missions are considering water as part of the payload manifest, it would be extremely advantageous if follow-on missions were supplied—either in total or in part—by a reclamation technology that would operate autonomously between missions. An attractive technology is currently under ongoing research at NASA Glenn Research Center (GRC) that employs a Supercritical Water Oxidation (SCWO) process to destroy all hydrocarbons in the waste stream. Testing of an aqueous waste stream simulant, typical of what is generated on the International Space Station (ISS), has shown reductions in Total Organic Carbon (TOC) of greater than 99% with reactor residence times less than 30 s. Recent effort has been directed toward developing a conceptual design based on the current tubular reactor used in the evaluation of the conversion of SCWO. This conceptual design along with the results of recent SCWO conversion experiments will be presented. Recent design enhancements to achieve shorter residence times along with “production simulation” tests will be presented. The diagnostics used in assessing the extent of the waste conversion include a total organic carbon (TOC) analysis, Raman analyses, and measurements of pH, turbidity, and conductivity. Results obtained from the modified reactor configuration will also be compared to those of the Phase I configuration presented in earlier work.

SCWO↗
NASA NTRS1965

Nitrogen dioxide produced by self-sustained pyrolysis of nitrous oxide

Apparatus is developed for achieving continuous self-sustaining pyrolysis reaction in the production of nitrogen dioxide from nitrous oxide. The process becomes self-sustaining because of the exothermic reaction and the regenerative heating of the gases in the pyrolysis chamber.

Sabol, A. P.↗
NASA NTRS1971

Alloyed coatings for dispersion strengthened alloys

Processing techniques were developed for applying several diffusion barriers to TD-Ni and TD-NiCr. Barrier coated specimens of both substrates were clad with Ni-Cr-Al and Fe-Cr-Al alloys and diffusion annealed in argon. Measurement of the aluminum distribution after annealing showed that, of the readily applicable diffusion barriers, a slurry applied tungsten barrier most effectively inhibited the diffusion of aluminum from the Ni-Cr-Al clad into the TD-alloy substrates. No barrier effectively limited interdiffusion of the Fe-Cr-Al clad with the substrates. A duplex process was then developed for applying Ni-Cr-Al coating compositions to the tungsten barrier coated substrates. A Ni-(16 to 32)Cr-3Si modifier was applied by slurry spraying and firing in vacuum, and was then aluminized by a fusion slurry process. Cyclic oxidation tests at 2300 F resulted in early coating failure due to inadequate edge coverage and areas of coating porosity. EMP analysis showed that oxidation had consumed 70 to 80 percent of the aluminum in the coating in less than 50 hours.

Wermuth, F. R.↗
NASA NTRS1973

Study for identification of Beneficial Uses of Space (BUS), phase 2. Volume 2: Technical report. Book 2: Section 5, appendices A through D

An investigation of the technology and programmatics involved in the development of four of the products selected as capable of benefitting from space manufacturing was conducted. The four activities selected are as follows: (1) levitation heating and melting of tungsten, (2) free suspension processing of oxides to form amorphous oxide materials, (3) crystals for surface wave acoustic substrates, and (4) space manufacturing of surface acoustic wave devices.

Source record↗
NASA NTRS1975

Theoretical description of the 2A/double prime/ and 2A/prime/ states of the peroxyformyl radical

Simple orbital ideas are used to describe the lowest two states of the peroxyformyl radical, and ab initio Hartree-Fock calculations in these states are reported. It is found that both states may be formed exothermically by association of O2 and HCO in their ground states; however, the excited state may decompose readily to OH and CO2. The possible role of such processes in oxidation of aldelydes is discussed.

Winter, N. W.↗
NASA NTRS1975

Tunnel injection into gate oxide traps

An experimental method is described for measuring the density of oxide traps in the gate oxide of an MOS transistor as a function of energy and position near the silicon interface. Measurements are obtained from different oxide growth processes and after Co-60 irradiation. The results are related to long-term drift of threshold voltage.

Maserjian, J.↗
NASA NTRS1978

Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

Fielder, W. L.↗