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At least 145 records · Page 8

Deducing Wild 2 Components with a Statistical Dataset of Olivine in Chondrite Matrix

Introduction: A preliminary exam of the Wild 2 olivine yielded a major element distribution that is strikingly similar to those for aqueously altered carbonaceous chondrites (CI, CM, and CR) [1], in which FeO-rich olivine is preferentially altered. With evidence lacking for large-scale alteration in Wild 2, the mechanism for this apparent selectivity is poorly understood. We use a statistical approach to explain this distribution in terms of relative contributions from different chondrite forming regions. Samples and Analyses: We have made a particular effort to obtain the best possible analyses of both major and minor elements in Wild 2 olivine and the 5-30 micrometer population in chondrite matrix. Previous studies of chondrite matrix either include larger isolated grains (not found in the Wild 2 collection) or lack minor element abundances. To overcome this gap in the existing data, we have now compiled greater than 10(exp 3) EPMA analyses of matrix olivine in CI, CM, CR, CH, Kakangari, C2-ungrouped, and the least equilibrated CO, CV, LL, and EH chondrites. Also, we are acquiring TEM/EDXS analyses of the Wild 2 olivine with 500s count times, to reduce relative errors of minor elements with respect to those otherwise available. Results: Using our Wild 2 analyses and those from [2], the revised major element distribution is more similar to anhydrous IDPs than previous results, which were based on more limited statistics (see figure below). However, a large frequency peak at Fa(sub 0-1) still persists. All but one of these grains has no detectable Cr, which is dissimilar to the Fa(sub 0-1) found in the CI and CM matrices. In fact, Fa(sub 0-1) with strongly depleted Cr content is a composition that appears to be unique to Kakangari and enstatite (highly reduced) chondrites. We also note the paucity of Fa(sub greater than 58), which would typically indicate crystallization in a more oxidizing environment [3]. We conclude that, relative to the bulk of anhydrous IDPs, Wild 2 may have received a larger contribution from the Kakangari and/or enstatite chondrite forming regions. Alternatively, Wild 2 may have undergone accretion in an anomalously reducing region, marked by nebular condensation of this atypical forsterite. In [4], a similar conclusion was reached with an Fe-XANES study. We will also use similar lines of reasoning, and our previous conclusions in [5], to constrain the relative contributions of silicates that appear to have been radially transported from different ordinary and carbonaceous chondrite forming regions to the Kuiper Belt. In addition, the widespread depletion of Cr in these FeO-rich (Fa(sub greater than 20)) fragments is consistent with mild thermal metamorphism in Wild 2.

Frank, D. R.↗

Ion Exchange Technology Development in Support of the Urine Processor Assembly

The urine processor assembly (UPA) on the International Space Station (ISS) recovers water from urine via a vacuum distillation process. The distillation occurs in a rotating distillation assembly (DA) where the urine is heated and subjected to sub-ambient pressure. As water is removed, the original organics, salts, and minerals in the urine become more concentrated and result in urine brine. Eventually, water removal will concentrate the urine brine to super saturation of individual constituents, and precipitation occurs. Under typical UPA DA operating conditions, calcium sulfate or gypsum is the first chemical to precipitate in substantial quantity. During preflight testing with ground urine, the UPA achieved 85% water recovery without precipitation. However, on ISS, it is possible that crewmember urine can be significantly more concentrated relative to urine from ground donors. As a result, gypsum precipitated in the DA when operating at water recovery rates at or near 85%, causing the failure and subsequent re14 NASA Tech Briefs, September 2013 placement of the DA. Later investigations have demonstrated that an excess of calcium and sulfate will cause precipitation at water recovery rates greater than 70%. The source of the excess calcium is likely physiological in nature, via crewmembers' bone loss, while the excess sulfate is primarily due to the sulfuric acid component of the urine pretreatment. To prevent gypsum precipitation in the UPA, the Precipitation Prevention Project (PPP) team has focused on removing the calcium ion from pretreated urine, using ion exchange resins as calcium removal agents. The selectivity and effectiveness of ion exchange resins are determined by such factors as the mobility of the liquid phase through the polymer matrix, the density of functional groups, type of functional groups bound to the matrix, and the chemical characteristics of the liquid phase (pH, oxidation potential, and ionic strength). Previous experience with ion exchange resins has demonstrated that the most effective implementation for an ion exchange resin is a cartridge, or column, in which the resin is contained. Based on the results of equilibrium and sub-scale dynamic column testing, a possible solution for mitigating the calcium precipitation issue on the ISS has been identified. From an original pool of 13 ion exchange resins, two candidates have been identified that demonstrate substantial calcium removal on the sub-scale. The dramatic reduction in resin performance from published calcium uptake demonstrates the need for thorough evaluation of resins at the low pH and strong oxidizing environment present in the UPA. Chemical variations in the influent (calcium concentrations and pretreatment dosing) appear to have a noticeable impact on the calcium capacity of the resin. Low calcium concentrations and high pretreatment dosing will likely result in a decrease in calcium capacity. Conversely, low pre trea t - ment dosing will likely result in an increase in calcium capacity. In contrast, investigations at a variety of flow rates, length-to-diameter ratios, resin volumes, and flow regimes (continuous versus pulsed) show that changes in physical parameters do not have substantial impacts on resin performance in the very low specific velocity ranges of interest. This result is particularly useful because most commercial applications at higher specific velocities do show a relatively strong relationship between flow and capacity. The lack of a strong relationship will allow more flexibility in the implementation of an ion exchange bed for flight. Verification of subscale tests with flight-scale resin beds is recommended prior to implementation in the on-orbit UPA.

Mitchell, Julie↗

Compositions of Diverse Noachian Lithologies at Marathon Valley, Endeavour Crater Rim, Mars

Mars Exploration Rover Opportunity has been exploring Meridiani Planum for 11+ years, and is presently investigating the geology of rim segments of 22 km diameter, Noachian-aged Endeavour crater. The Alpha Particle X-ray Spectrometer has determined the compositions of a pre-impact lithology and impact breccias representing ejecta from the crater. Opportunity is now investigating the head (higher elevation, western end) of Marathon Valley. This valley cuts eastward through the central portion of the Cape Tribulation rim segment and provides a window into the lower stratigraphic record of the rim. At the head of Marathon Valley is a shallow (few 10s of cm), ovoid depression approximately 27×36 m in size, named Spirit of Saint Louis, that is surrounded by approximately 20-30 cm wide zone of more reddish rocks (red zone). Opportunity has just entered a region of Marathon Valley that shows evidence for Fe-Mg smectite in Compact Reconnaissance Imaging Spectrometer for Mars spectra indicating areally extensive and distinct lithologic units and/or styles of aqueous alteration. Rocks at the head of Marathon Valley and within Spirit of Saint Louis are breccias (valley-head rocks). In some areas, layering inside Spirit of Saint Louis appears continuous with the rocks outside. The valley-head rocks are of similar, generally basaltic composition. The continuity in composition, texture and layering suggest the valley-head rocks are coeval breccias, likely from the Endeavour impact. These local breccias are similar in non-volatile-element composition to breccias investigated elsewhere on the rim. Rocks within the red zone are like those on either side in texture, but have higher Al, Si and Ge, and lower S, Mn, Fe, Ni and Zn as compared to rocks on either side. The valley-head rocks have higher S than most Endeavour rim breccias, while red zone rocks are like those latter breccias in S. Patches within the rocks outside Spirit of Saint Louis have higher Al, Si and Ge indicating red-zone-style alteration extended beyond the narrow red zone. Rocks on either side of the red zone and patches within it have the multispectral signature (determined by Panoramic Camera) of red hematite indicating an oxidizing environment. The red zone appears to be a thin alteration zone marking the border of Spirit of Saint Louis, but the origin of this morphologic feature remains obscure.

Mittlefehldt, David W.↗

Inertial Weldment of Rhenium and Inconel 718

Inertia welding has been found to be a successful method for joining pure rhenium to Inconel 718, and with additional experimentation, this process may have great potential for rocket nozzle applications. Refractory metals are ideally suited to this application, where high temperatures and oxidizing environment survivability is required, but not all of the thruster must be made of these materials, only the areas that require them. A bolted joint between the two metals is not ideal, especially for small thrusters where the mess of a bolted join will come at a steep price. A welded joint would be preferred for flight thrusters.

Cavender, D. P.↗

Exceptional Thermal Properties of Polymer-Derived Ceramic Composites Reinforced with High Volume Fractions of Boron Nitride Nanotube at Elevated Temperature

We report for the first time the synthesis of boron nitride nanotube (BNNT) reinforced ceramic composites using the polymer derived ceramic (PDC) processing route. The nanocomposites had a BNNT loading of up to 35.4 vol.%. TGA results showed that the nanocomposites have good thermal stability up to 900 oC in air. BNNTs in the nanocomposites survived in an oxidizing environment up to 900 oC, revealing that the nanocomposites can be used for high temperature applications. Thermal conductivity of PDC reinforced with 35.4 vol.% BNNT was measured as 4.123 W/(m·K) at room temperature, which is a 2100 % increase compared to that of pristine PDC. The thermal conductivity value increases with the increase of BNNT content. A thermal conductivity percolation phenomenon appeared when the BNNT content increased to 36±5 vol.%. The results of this study showed that BNNTs could effectively improve the thermal conductivity of PDC materials. BNNT reinforced PDC could be used as thermal structural materials in a harsh environment at the temperature up to 900 deg C.

Yujun Jia↗

Jarosite Formation in Deep Antarctic Ice, an Earth Analogue to Unveil the Origin of Jarosite on Mars?

On Earth, jarosite is a weathering product forming in acidic-oxidative environments from the alteration of iron-bearing minerals in presence of liquid water. Typical settings where this iron-potassium hydrated sulphate is found, are weathering zones of pyrite-rich deposits, evaporative basins and fumaroles. Jarosite is not only known on Earth, it also occurs on Mars, where it has been identified by the Opportunity rover. The mineral was in fact recognized in the finely layered formations outcropping at Meridiani Planum and that were accurately investigated by the rover (Klingelhöfer et al. 2004). Since jarosite requires liquid water to form, its occurrence on Mars has been regarded as an evidence for the occurrence of liquid water in the geologic past of Mars (Elwood-Madden et al., 2004). Since then, many models have been proposed to describe the environments where the precipitation of Martian jarosite took place. The most accepted ones deal with evaporative basins similar to Earth’s playas, others concern volcanic activity and hydrothermal processes. An alternative proposal predicted that jarosite may have formed as a consequence of weathering of mineral dust trapped in massive ice deposits, i.e. the ice-weathering model (Niles & Michalsky, 2009). The hypothesis that jarosite formed on Mars because of low-temperature, acidic and water limited weathering, is not new (Burns, 1987), but until now no direct evidences were available to support it.A potential Earth analogue to investigate such processes is deep Antarctic ice. We present a first investigation of deep ice samples from the Talos Dome ice core (East Antarctica) aimed at the identification of englacial jarosite, so as to support the ice-weathering model. Evidences gathered through independent techniques showed that jarosite is actually present in deep Antarctic ice and results from the weathering of dust trapped into ice. The process is controlled by the re-crystallization of ice grains and the concurrent re-location of impurities at grain-junctions, which both depend on ice depth. This study demonstrates that the deep englacial environment is suitable for jarosite precipitation. Our findings support the hypothesis that, as originally predicted by the ice-weathering model, paleo ice-related processes have been important in thegeologic and geochemical history of Mars.

Lindsay P Keller↗

Oxidation behavior of TD-NiCr in a dynamic high temperature environment

The oxidation behavior of TD-NiCr has been studied in static and high-speed flowing air environments at 1100 and 1200 C. It has been found that the stable oxide morphologies formed on the specimens exposed to the static and dynamic environments were markedly different. The faceted crystal morphology characteristic of static oxidation was found to be unstable under high-temperature, high-speed flow conditions and was quickly replaced by a porous NiO 'mushroom' type structure. Also, it was found that the rate of formation of CrO3 from Cr2O3 was greatly enhanced by high gas velocity conditions. The stability of Cr2-O3 was found to be greatly improved by the presence of an outer NiO layer, even though the NiO layer was very porous. An oxidation model is proposed to explain the observed microstructures and overall oxidation behavior of TD-NiCr alloys.

Tenney, D. R.↗

Oxidation characteristics of 440 C CRES in gaseous oxygen (GOX) environments

The oxidation characteristics of 440 C corrosion-resistant steel are evaluated. The dependence of oxide color, type, and thickness, material hardness, and microstructure on temperature is examined. The effects of exposure time, passivation layer, and oxygen pressure on the oxide formation are investigated. A direct relationship between temperature and oxide color, formation, and thickness is detected. It is observed that the exposure time does not affect the microstructure or oxide color, type, or thickness; however, the passivation layer does affect oxide color and type.

Dennies, Daniel P.↗

Investigation of the oxidation behavior of dispersion stabilized alloys when exposed to a dynamic high temperature environment

The oxidation behavior of TD-NiCr and TD-NiCrAlY alloys have been studied at 2000 and 2200 F in static and high speed flowing air environments. The TD-NiCrAlY alloys preoxidized to produce an Al2O3 scale on the surface showed good oxidation resistance in both types of environments. The TD-NiCr alloy which had a Cr2O3 oxide scale after preoxidation was found to oxidize more than an order of magnitude faster under the dynamic test conditions than at comparable static test conditions. Although Cr2O3 normally provides good oxidation protection, it was rapidly lost due to formation of volatile CrO3 when exposed to the high speed air stream. The preferred oxide arrangement for the dynamic test consisted of an external layer of NiO with a porous mushroom type morphology, an intermediate duplex layer of NiO and Cr2O3, and a continuous inner layer of Cr2O3 in contact with the alloy substrate. An oxidation model has been developed to explain the observed microstructure and overall oxidation behavior of all alloys.

Tenney, D. R.↗

Corrosion of Silicon-Based Ceramics in Combustion Environments

The processes of passive oxidation, deposit-induced corrosion, active oxidation, scale/substance interactions, and scale volatility are presently studied in the case of high-purity SiC and Si3N4 in pure oxygen, giving attention to such secondary elements in the ceramics as water and CO2 oxidants, combustion environment impurities, and thermal cycling. Deposit-induced corrosion is discussed for the cases of NaSO4 as well as vanadate and oxide-slag deposits; issues associated with the active-to-passive oxidation transition are noted.

Jacobson, Nathan S.↗

Long Life Testing of Oxide-Coated Iridium/Rhenium Rockets

22-N class rockets, composed of a rhenium (Re) substrate, an iridium (Ir) coating, and an additional composite coating consisting of Ir and a ceramic oxide, were tested on gaseous oxygen/gaseous hydrogen (GO2/GH2) propellants. Two rockets were tested, one for nearly 39 hours at a nominal mixture ratio (MR) of 4.6 and chamber pressure (Pc) of 469 kPa, and the other for over 13 hours at a nominal MR of 5.8 and 621 kPa Pc. Four additional Ir/Re rockets, with a composite Ir-oxide coating fabricated using a modified process, were also tested, including one for 1.3 hours at a nominal MR of 16.7 and Pc of 503 kPa. The long lifetimes demonstrated on low MR GO2/GH2 suggest greatly extended chamber lifetimes (tens of hours) in the relatively low oxidizing combustion environments of Earth storable propellants. The oxide coatings could also serve as a protective coating in the near injector region, where a still-mixing flowfield may cause degradation of the Ir layer. Operation at MR close to 17 suggests that oxide-coated Ir/Re rockets could be used in severely oxidizing combustion environments, such as high MR GO2/GH2, oxygen/hydrocarbon, and liquid gun propellants.

Reed, Brian D.↗

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.↗

Metallic Concepts for Repair of Reinforced Carbon-Carbon Space Shuttle Leading Edges

The Columbia accident has focused attention on the critical need for on-orbit repair concepts for wing leading edges in the event that potentially catastrophic damage is incurred during Space Shuttle Orbiter flight. The leading edge of the space shuttle wings consists of a series of eleven panels on each side of the orbiter. These panels are fabricated from reinforced carbon-carbon (RCC) which is a light weight composite with attractive strength at very high temperatures. The damage that was responsible for the loss of the Colombia space shuttle was deemed due to formation of a large hole in one these RCC leading edge panels produced by the impact of a large piece of foam. However, even small cracks in the RCC are considered as potentially catastrophic because of the high temperature re-entry environment. After the Columbia accident, NASA has explored various means to perform on-orbit repairs in the event that damage is sustained in future shuttle flights. Although large areas of damage, such as that which doomed Columbia, are not anticipated to re-occur due to various improvements to the shuttle, especially the foam attachment, NASA has also explored various options for both small and large area repair. This paper reports one large area repair concept referred to as the "metallic over-wrap." Environmental conditions during re-entry of the orbiter impose extreme requirements on the RCC leading edges as well as on any repair concepts. These requirements include temperatures up to 3000 F (1650 C) for up to 15 minutes in the presence of an extremely oxidizing plasma environment. Figure 1 shows the temperature profile across one panel (#9) which is subject to the highest temperatures during re-entry. Although the RCC possesses adequate mechanical strength at these temperatures, it lacks oxidation resistance. Oxidation protection is afforded by converting the outer layers of the RCC to SiC by chemical vapor deposition (CVD). At high temperatures in an oxidizing environment, the SiC layer forms a protective SiO2 scale. However, CVD processing to form the SiC layer can result in the formation of small cracks in the outer surface. Hence, as a final fabrication step, a sodium silicate glass, known as "Type A," is applied as a sealant to fill any surface porosity and/or cracks in the coating and the outer portions of the RCC[1]. At relatively low temperatures, the Type A glass melts and flows into the cracks providing oxidation protection at the higher temperatures. In addition, the Type A coating, provides a "dark" coating with a high emissivity. This high emissivity allows the RCC to transfer heat by radiating outward to space as well as dispersing heat within the leading edge cavity. Lastly, the Type A possesses low catalycity which reduces surface temperatures by limiting oxygen recombination on the surface during re-entry.

Ritzert, Frank↗

Design, analysis, and fabrication of oxide-coated iridium/rhenium combustion chambers

Iridium-coated rhenium (Ir/Re) combustion chambers provide high temperature, oxidation-resistant operation for radiation-cooled liquid-fueled rocket engines. A 22-N (5-lb(sub f)) chamber has been operated for 15 hours at 2200 C (4000 F) using nitrogen tetroxide/monomethyl hydrazine (NTO/MMH) propellant, with negligible internal erosion. The oxidation resistance of these chambers could be further increased by the addition of refractory oxide coatings, providing longer life and/or operation in more oxidizing and higher temperature environments. The oxide coatings would serve as a thermal and diffusion barrier for the iridium coating, lowering the temperature of the iridium layer while also preventing the ingress of oxygen and egress of iridium oxides. This would serve to slow the failure mechanisms of Ir/Re chambers, namely the diffusion of rhenium to the inner surface and the oxidation of iridium. Such protection could extend chamber lifetimes by tens or perhaps hundreds of hours, and allow chamber operation on stoichiometric or higher mixture ratio oxygen/hydrogen (O2/H2) propellant. Extensive thermomechanical, thermochemical, and mass transport modeling was performed as a key material/structure design tool. Based on the results of these analyses, several 22-N oxide-coated Ir/Re chambers were fabricated and delivered to NASA Lewis Research Center for hot-fire testing.

Jang, Q.↗

Diffusion Limited Supercritical Water Oxidation (SCWO) in Microgravity Environments

Tests designed to quantify the gravitational effects on thermal mixing and reactant injection in a Supercritical Water Oxidation (SCWO) reactor have recently been performed in the Zero Gravity Facility (ZGF) at NASA s Glenn Research Center. An artificial waste stream, comprising aqueous mixtures of methanol, was pressurized to approximately 250 atm and then heated to 450 C. After uniform temperatures in the reactor were verified, a controlled injection of air was initiated through a specially designed injector to simulate diffusion limited reactions typical in most continuous flow reactors. Results from a thermal mapping of the reaction zone in both 1-g and 0-g environments are compared. Additionally, results of a numerical model of the test configuration are presented to illustrate first order effects on reactant mixing and thermal transport in the absence of gravity.

Hicks, M. C.↗

Records of our Early Biosphere Illuminate our Origins and Guide our Search for Life Beyond Earth

A scientific "mission of exploration to early Earth" will help us chart the distribution of life elsewhere. We must discriminate between attributes of biospheres that are universal versus those attributes that represent principally the outcomes of long-term survival specifically on Earth. In addition to the basic physics and chemistry of matter, the geologic evolution of rocky habitable planets and their climates might be similar elsewhere in the Universe. Certain key agents that drive long-term environmental change (e.g., stellar evolution, impacts, geothermal heat flow, tectonics, etc.) can help us to reconstruct ancient climates and to compare their evolution among populations of Earth- like planets. Early Earth was tectonically more active than today and therefore it exhaled reduced chemical species into the more oxidized surface environment at greater rates. This tectonic activity thus sustained oxidation-reduction reactions that provided the basis for the development of biochemical pathways that harvest chemical energy ("bioenergetics"). Most examples of bioenergetics today that extract energy by reacting oxidized and reduced chemicals in the environment were likely more pervasive among our microbial ancestors than are the presently known examples of photosynthesis. The geologic rock record indicates that, as early as 3.5 billion years ago (3.5 Ga), microbial biofilms were widespread within the coastal environments of small continents and tectonically unstable volcanic islands. Non oxygen-producing (non-oxygenic) photosynthesis preceded oxygenic photosynthesis, but all types of photosynthesis contributed substantially to the long-term increase in global primary biological productivity. Evidence of photosynthesis is tentative by 3.5 Ga and compelling by 2.7 Ga. Evidence of oxygenic photosynthesis is strong by 2.7 Ga and compelling by 2.3 Ga. These successive innovations transformed life from local communities that survived principally by catalyzing chemical equilibration to a globally dominant agent that created and sustained widespread chemical disequilibria in the environment and shallow crust. Major biogeochemical perturbations ca. 2.3 to 2.0 Ga, 1.3 Ga, and also 0.8 to 0.6 Ga, contributed to the irreversible oxidation of the global environment and perhaps also triggered evolutionary innovations (e.g., the development of multi-cellular biota) that became the foundations of our modern biosphere. Understanding the nature and timing of this ascent of life is crucial for discerning our o m beginnings. This understanding also empowers OUT search for the origins, evolution and distribution of life elsewhere in our solar system and beyond.

DesMarais, David J.↗