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At least 19 records

Tracing the Source of Carbon Oxides on the Large Moons of Uranus

The Uranian moons Ariel, Umbriel, Titania, and Oberon are enriched in CO 2 mixed with CO, but the origin(s) of these carbon oxides, be they primarily native or radiolytic, remain(s) uncertain. Using data collected by NIRSpec on the James Webb Space Telescope (JWST), we measured the spectral signature of CO 2 and other carbon oxides to help disentangle these hypotheses. Through comparison to laboratory data, we find that many of the detected spectral features are consistent with CO 2 ice, including 12 CO2 scattering peaks (4.15–4.26 μm), multilobe 13 CO 2 bands (4.35–4.43 μm), and CO 2 biphonon and triphonon modes (4.80–5.25 μm). Our measurements show that CO 2 and CO are concentrated on the trailing hemispheres of the inner moons Ariel and Umbriel, potentially supporting a radiolytic production hypothesis, consistent with prior ground-based results. However, many of the identified spectral features are only observed in thick crystalline ice deposits measured in the laboratory, which may be difficult to form via radiolysis of carbon-bearing material mixed in icy regoliths. Similarly, the data exhibit weak 4.02 and 4.40 μm bands, hinting at the presence of carbonate minerals and 13 CO 2 clathrates, respectively, possibly formed in the interiors of these moons. Furthermore, JWST has revealed that CO 2 is widespread at Uranus, present in its system of rings, ring moons, and irregular satellites, consistent with its largest moons accreting CO 2 and other carbon oxides from the Uranian subnebula. We conclude that exposed carbon oxides are potentially native, with their surface distributions shaped by charged particle irradiation and seasonal sublimation–condensation cycles.

Ice spectroscopy↗

Pathways of organic carbon oxidation in three continental margin sediments

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

NASA Discipline Exobiology↗

Space Shuttle Orbiter carbon-carbon oxidation performance

Reusable, oxidation protected reinforced carbon carbon (RCC) has been successfully flown on forty Shuttle Orbiter flights. Thermal testing of the silicon carbide coated, reinforced carbon-carbon to determine its oxidation characteristics has been performed in both radiant and convective (plasma arc jet) heating test facilities. Subsurface oxidation of the RCC substrate as a result of oxygen penetrating micro cracks (fizzures) in the coating was characterized as a function of temperature and pressure for both convective and radiant environments. High temperature testing was performed to establish coating recession for over-temperature flight conditions experienced on abort trajectories. Suggested methods for using these test data to establish multi-mission reuse (i.e., mission life) and single mission limits are presented.

Curry, D. M.↗

Simulation of RCC Crack Growth Due to Carbon Oxidation in High-Temperature Gas Environments

The carbon wall oxidation technique coupled with a CFD technique was employed to study the flow in the expanding crack channel caused by the oxidation of the channel carbon walls. The recessing 3D surface morphing procedure was developed and tested in comparison with the arcjet experimental results. The multi-block structured adaptive meshing was used to model the computational domain changes due to the wall recession. Wall regression rates for a reinforced carbon-carbon (RCC) samples, that were tested in a high enthalpy arcjet environment, were computationally obtained and used to assess the channel expansion. The test geometry and flow conditions render the flow regime as the transitional to continuum, therefore Navier-Stokes gas dynamic approach with the temperature jump and velocity slip correction to the boundary conditions was used. The modeled mechanism for wall material loss was atomic oxygen reaction with bare carbon. The predicted channel growth was found to agree with arcjet observations. Local gas flow field results were found to affect the oxidation rate in a manner that cannot be predicted by previous mass loss correlations. The method holds promise for future modeling of materials gas-dynamic interactions for hypersonic flight.

Titov, E. V.↗

Hydrazines and carbohydrazides produced from oxidized carbon in earth's primitive environment

Whether abiological organic compounds can be formed from the interactions of energy sources with nitrogen, oxidized carbon and water is held to be of importance in geochemical models of the primordial earth atmosphere. It is reported that experiments using quenched spark discharges through molecular nitrogen on aqueous suspensions of CaCO3 and other reactants to simulate the hydrosphere/atmosphere interface yield hydrazine and carbohydrazine in significant but low yields. Such reactions in primitive aquatic environments may have supplied a pathway for chemical evolution and the origin of life, on a primitive earth in which fully oxidized states of carbon were available for the primary synthesis of organic matter.

Folsome, C. E.↗

Analysis of the Shuttle Orbiter reinforced carbon-carbon oxidation protection system

Reusable, oxidation-protected reinforced carbon-carbon (RCC) has been successfully flown on all Shuttle Orbiter flights. Thermal testing of the silicon carbide-coated RCC to determine its oxidation characteristics has been performed in convective (plasma Arc-Jet) heating facilities. Surface sealant mass loss was characterized as a function of temperature and pressure. High-temperature testing was performed to develop coating recession correlations for predicting performance at the over-temperature flight conditions associated with abort trajectories. Methods for using these test data to establish multi-mission re-use (i.e., mission life) and single mission limits are presented.

Williams, S. D.↗

Coupling Carbon Oxidation and Surface Recession in Direct-Simulation Monte Carlo Code, SPARTA

Ablative thermal protection system (TPS) materials for spacecraft are composites that are often made out of carbon-based reinforcement and a polymeric matrix. They endure high-temperature oxidation and surface recession when re-entering Earth’s atmosphere. Ablation is the result of many coupled and competing thermal, mechanical, and chemical phenomena, and it is difficult to isolate the role of each on the overall degradation of the TPS. Here we develop an ablation model for material recession coupled explicitly to finite rate carbon oxidation in complex microstructures. In this work, Stochastic PArallel Rarified-gas Time-accurate Analyzer (SPARTA), a direct-simulation Monte Carlo (DSMC) code, is modified to allow oxidation-driven ablation of implicitly defined carbon surfaces. In SPARTA, implicit surfaces are generated from the grid corner point values via a marching cubes algorithm, therefore creating a new set of surface elements every time ablation is performed. The finite-rate oxidation model developed by Gopalan et. al, was adapted to tally surface reactions and other surface data on a per-grid cell basis. The ablation functionality was also adjusted so once the reactions have occurred, the number of reactions leading to CO formation can be converted to corner point reduction values; therefore, carbon removal is directly proportional to surface recession. We also develop robust algorithms which handle the evolution of the flow cells and solid material regions, including split cells (flow cell divided in two by a solid surface). Finally, we demonstrate our implicit chemistry model for 2D and 3D geometries by producing reaction statistics and detailed visualization of oxidation-induced material recession at the microscale.

V Arias↗

Implementation of active sites to capture pitting of oxidizing carbon materials in DSMC.

In this work we demonstrate a newly developed capability to capture pitting of carbon fibers in DSMC simulations, specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code [1]. State-of-the-art reactive surface models in DSMC compute collision dependent carbon consumption rates (usually through desorption of CO) based on a set of surface reactions that has been derived from molecular beam experiments [2]. The reactivity on each carbon surface element is constant in those models, such that the carbon surface recedes uniformly as a result of ablation. However, it is well known that in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale [3]. These defective sites have a much higher reactivity than the average sites (2-3 orders of magnitude) and are first to react during ablation leading to its removal. This causes all the neighboring atoms to be defective and increase their reactivity, thus leading to the localized carbon removal around these ”active” sites (as shown in Fig. 1). In this manner, these highly reactive defective sites serve as nucleation sites for the formation and growth of etch pits with potentially detrimental effects on the structural integrity. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various reaction mechanisms such as adsorption, desorption, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms [4]. Within this framework, we have implemented the capability of a single surface having multiple site sets with different reactivities. Using this feature, we can simulate the presence of active sites on carbon surfaces, whose reactivity is much greater than an average site as a result of defects. We have implemented the active site fraction as a property of surface elements within SPARTA, which is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface, and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we are able to capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗

Implementation of Active Sites in DSMC to Capture Pitting of Oxidizing Carbon Materials

In this work we demonstrate a newly developed capability to capture pitting of carbon fibers in DSMC simulations, specifically using the Stochastic PArallel Rarefied-gas Time-accurate Analyzer (SPARTA) code. State-of-the-art reactive surface models in DSMC compute collision dependent carbon consumption rates (usually through desorption of CO) based on a set of surface reactions that has been derived from molecular beam experiments. The reactivity on each carbon surface element is constant in those models, such that the carbon surface recedes uniformly as a result of ablation. However, it is well known that in reality the carbon surface has locally different reaction rates due to the presence of defects at the atomic scale. These defective sites have a much higher reactivity than the average sites (2-3 orders of magnitude) and are first to react during ablation leading to its removal. This causes all the neighboring atoms to be defective and increase their reactivity, thus leading to the localized carbon removal around these ”active” sites. In this manner, these highly reactive defective sites serve as nucleation sites for the formation and growth of etch pits with potentially detrimental effects on the structural integrity. Recently a detailed surface chemistry framework was developed in SPARTA, capable of incorporating various reaction mechanisms such as adsorption, desorption, Eley-Rideal (ER) and Langmuir-Hinshelwood (LH) mechanisms. Within this framework, we have implemented the capability of a single surface having multiple site sets with different reactivities. Using this feature, we can simulate the presence of active sites on carbon surfaces, whose reactivity is much greater than an average site as a result of defects. We have implemented the active site fraction as a property of surface elements within SPARTA, which is directly proportional to the local reactivity of each surface element. By introducing an initial distribution of the active site fraction across the carbon surface, and propagating it in a manner that mimics the evolution of real reacting carbon surfaces, we are able to capture the formation and growth of etch pits as a result of surface consumption reactions such as oxidation.

DSMC↗

Reinforced carbon-carbon oxidation behavior in convective and radiative environments

Reinforced carbon-carbon, which is used as thermal protection on the space shuttle orbiter wing leading edges and nose cap, was tested in both radiant and plasma arcjet heating test facilities. The test series was conducted at varying temperatures and pressures. Samples tested in the plasma arcjet facility had consistently higher mass loss than those samples tested in the radiant facility. A method using the mass loss data is suggested for predicting mission mass loss for specific locations on the Orbiter.

Curry, D. M.↗

Parallelized Carbon Oxidation and Surface Recession Model in Direct-Simulation Monte Carlo Code, SPARTA

Ablative thermal protection system (TPS) materials for spacecraft are composites that often consist of a carbon-based reinforcement and a polymeric matrix. During Earth re-entry, they endure high-temperature oxidation and surface recession. Oxidation is an important mechanism for ablation, sometimes leading to the weakening, spallation, or failure of the oxidized fibers at the surface and in the char layer. However, more details are required including accurate material properties of the fiber microstructure, whether the fibers recede homogenously or localized at pits, and the role of pyrolysis outgassing in order to evaluate the role oxidation plays in the degradation and failure mechanisms of these materials. In this work, we demonstrate a parallelizable oxidation-driven ablation model developed for detailed, large-scale simulations in the DSMC code SPARTA. We also develop robust algorithms which handle the conservation of the surface state after an ablation step. Finally, we verify our model for both simple and more complex chemistry as well as microstructures with reaction statistics, oxidation depth calculations, and detailed visualization of oxidation-induced material recession at the microscale.

V Arias↗

Validation of CrIS Ozone and Carbon Oxide Products from CrIS Single-Field-of-View Retrievals

Single Field-of-view Sounder Atmospheric Products (SiFSAP) from Cross-track Infrared Sounder (CrIS) on S-NPP have been developed at NASA Langley Research center, and recently a significant improvement in its trace gases products has been made. These products are derived based on the Principal Component (PC)-based Radiative Transfer Model (PCRTM) and an optimal estimation retrieval method (PCRTM-RA). Use of the PCRTM in this method allows for fast and accurate calculations for thousands of spectral channels under clear and cloudy sky conditions. The use of principal component to compress information from all spectral channels into the PC domain enables to reduce the observational noise and use the information from all hyperspectral infrared channels. The retrieval is made on PC-domain, and temperature, water vapor, trace gases, cloud and surface parameters are retrieved simultaneously. This presentation will present some validation to the SiFSAP ozone (O3) and carbon monoxide (CO) products. Since the SiFSAP has a spatial resolution of about 14 km at nadir, which is better than most global weather and climate models and enables to make process-oriented analysis of the transport of these gases, this study will focus on validation of CO and O3 products under some extreme weather and/or climate events, such as CO emission and transport from large biomass burning, and O3 variation impacted by fire emission, stratospheric intrusion, and tropical cyclones. Data used in our validation include CO and O3 from NASA aircraft campaigns, plus other satellite products such as CO and O3 from AIRS, IASI and TROPOMI, MOPPIT CO and OMPS O3. Some comparison of SiFSAP O3 with the O3 from the fifth-generation ECMWF reanalysis (ERA5) data the NASA Modern-Era Retrospective Analysis for Research and Applications, Version 2 (MERRA-2) will also present. Such a validation not only helps to quantify the performance of the retrievals in these extreme conditions, but also displays the capability of satellite observation to capture the fine-scale spatial pattern of CO and O3 variation.

Xiaozhen Xiong↗

A Comparison of Oxidized Carbon Abundances among Comets

Comets contain relatively well preserved icy material remaining from the epoch of Solar System formation, however the extent to which these ices are modified from their initial state remains a fundamental question in cometary science. As a comet approaches the Sun, sublimation of the ices contained in its nucleus (termed " native ices") releases parent volatiles into the coma, where they can be measured spectroscopically. One means of assessing the degree to which interstellar ices were processed prior to their incorporation into cometary nuclei is to measure the relative abundances of chemically-related parent volatiles. For example, formation of C2H6 by hydrogen atom addition (e.g., to C2H2) on surfaces of ice-mantled grains was proposed to explain the high C2H6 to CH4 abundance observed in C/1996 B2 (Hyakutake) [1]. The large C2H6/CH4 abundance ratios measured universally in comets, compared with those predicted by gas phase production of C2H6, establishes H-atom addition as an important and likely ubiquitous process. CO should also be hydrogenated on grain surfaces. Laboratory irradiation experiments on interstellar ice analogs indicate this to require very low temperatures (T approx. 10-25 K), the resulting yields of H2CO and CH3OH being highly dependent both on hydrogen density (i.e., fluence) and on temperature ([2],[3]). This relatively narrow range in temperature reflects a lack of mobility below 8-10 K on the one hand, and reduced sticking times for H-atoms as grain surfaces are warmed above 20 K on the other. The relative abundances of these three chemically-related molecules in comets provides one measure of the efficiency of H-atom addition to CO on pre-cometary grains (Fig. 1).

DiSanti, M. A.↗

Investigation of low temperature carbon monoxide oxidation catalysts

Carbon monoxide generation rates related to the use of commerical equipment in Spacelab, added to the normal metabolic and subsystem loads, will produce carbon monoxide levels in excess of the maximum allowable concentration. In connection with the sensitivity of carbon monoxide oxidation catalysts to poisoning at room temperature, catalysts for an oxidation of carbon monoxide at low temperatures have been investigated. It was found that platinum and palladium are the only effective room temperature catalysts which are effective at 333 K. Hopcalite was ineffective at ambient temperatures, but converted CO with 100 percent efficiency at 333 K. Poisoning tests showed the noble metal catalysts to be very sensitive, and Hopcalite to be very resistant to poisoning.

Jagow, R. B.↗

Effect of chlorine purification on oxidation resistance of some mechanical carbons

Oxidation experiments were conducted with some experimental and commercial mechanical carbons at 650 C in dry air flowing at 28 cc/sec (STP). In general, purification of these carbon-graphites with chlorine at 2800 C improved oxidation resistance. Additional improvements in oxidation resistance were obtained from purification followed by an antioxidant (zinc phosphate) treatment. For the commercial materials, purification alone gave greater oxidation resistance than the antioxidant treatment alone. The reverse, however, was the case for the experimental materials.

Wisander, D. W.↗

The oxidation of carbon monoxide using tin oxide based catalysts

The preparation conditions for precious metal/tin oxide catalysts were optimized for maximum carbon monoxide/oxygen recombination efficiency. This was achieved by controlling the tin digestion, the peptization to form the sol, the calcination process and the method of adding the precious metals. Extensive studies of the tin oxide structure were carried out over the temperature range 20 to 500 C in air or hydrogen environments using Raman scattering and X ray diffraction. Adsorbed species on tin oxide, generated in an environment containing carbon monoxide, gave rise to a Raman band at about 1600 cm(exp -1) which was assigned to carbonaceous groups, possible carbonate.

Sampson, Christopher F.↗

Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Herz, Richard K.↗

Novel Carbon Dioxide Microsensor Based on Tin Oxide Nanomaterial Doped With Copper Oxide

Carbon dioxide (CO2) is one of the major indicators of fire and therefore its measurement is very important for low-false-alarm fire detection and emissions monitoring. However, only a limited number of CO2 sensing materials exist due to the high chemical stability of CO2. In this work, a novel CO2 microsensor based on nanocrystalline tin oxide (SnO2) doped with copper oxide (CuO) has been successfully demonstrated. The CuO-SnO2 based CO2 microsensors are fabricated by means of microelectromechanical systems (MEMS) technology and sol-gel nanomaterial-synthesis processes. At a doping level of CuO: SnO2 = 1:8 (molar ratio), the resistance of the sensor has a linear response to CO2 concentrations for the range of 1 to 4 percent CO2 in air at 450 C. This approach has demonstrated the use of SnO2, typically used for the detection of reducing gases, in the detection of an oxidizing gas.

Xu, Jennifer C.↗