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At least 217 records · Page 12

A Novel Approach for Modeling Chemical Reaction in Generalized Fluid System Simulation Program

The Generalized Fluid System Simulation Program (GFSSP) is a computer code developed at NASA Marshall Space Flight Center for analyzing steady state and transient flow rates, pressures, temperatures, and concentrations in a complex flow network. The code, which performs system level simulation, can handle compressible and incompressible flows as well as phase change and mixture thermodynamics. Thermodynamic and thermophysical property programs, GASP, WASP and GASPAK provide the necessary data for fluids such as helium, methane, neon, nitrogen, carbon monoxide, oxygen, argon, carbon dioxide, fluorine, hydrogen, water, a hydrogen, isobutane, butane, deuterium, ethane, ethylene, hydrogen sulfide, krypton, propane, xenon, several refrigerants, nitrogen trifluoride and ammonia. The program which was developed out of need for an easy to use system level simulation tool for complex flow networks, has been used for the following purposes to name a few: Space Shuttle Main Engine (SSME) High Pressure Oxidizer Turbopump Secondary Flow Circuits, Axial Thrust Balance of the Fastrac Engine Turbopump, Pressurized Propellant Feed System for the Propulsion Test Article at Stennis Space Center, X-34 Main Propulsion System, X-33 Reaction Control System and Thermal Protection System, and International Space Station Environmental Control and Life Support System design. There has been an increasing demand for implementing a combustion simulation capability into GFSSP in order to increase its system level simulation capability of a liquid rocket propulsion system starting from the propellant tanks up to the thruster nozzle for spacecraft as well as launch vehicles. The present work was undertaken for addressing this need. The chemical equilibrium equations derived from the second law of thermodynamics and the energy conservation equation derived from the first law of thermodynamics are solved simultaneously by a Newton-Raphson method. The numerical scheme was implemented as a User Subroutine in GFSSP.

Sozen, Mehmet↗

Methylhopane Biomarker and Carbon Isotopic Evidence for Late Archean Aerobic Ecosystems

Molecular fossils are particularly valuable in early Earth studies because they provide information about microbial sources and ecology. Here we report on the distribution of 2- methyl and 3-methylhopanes preserved in a 2.72-2.56 billion-year-old section of shallow and deepwater sediments of the Hamersley Province [Eigenbrode et aI., submitted]. These biomarkers are mostly from cyanobacteria and oxygen-respiring methanotrophs, respectively. The relative abundance of 2-methylhopanes increases with carbonate abundance in shallow-water facies indicating cyanobacteria were key microbes in shallow ecosystems and suggesting they supplied both molecular oxygen and fixed carbon. The relative abundance of 3-methylhopane strongly correlates with kerogen-carbon isotopic values, and is more abundant in the samples with 13C-enriched signatures. Thus, molecular data provides evidence for cycling of methane in shallow settings, even though the anoxic deeper environments bear stronger 13C-depletion, which together suggests a more complex methane cycle than previously envisioned. Detailed facies analysis of the Hamersley carbon-isotope record reveals temporal changes suggesting continued oxidation of shallow settings favoring the expansion of aerobic ecosystems and respiring organisms [Eigenbrode et aI., 2006, PNAS, 103: 15759]. Similar analysis of published carbon-isotopic records suggests similar, but diachronous, expansion of oxygenated habitats in shallow then deep waters as anaerobic microbial communities gave way to respiring communities fueled by oxygenic photosynthesis before the post 2.45-Ga atmospheric oxygenation event [Eigenbrode et aI., 2006]. The robust relationships observed provide geochemical support for methanogenesis, aerobic methanotrophy, and oxygenic photosynthesis in the late Archean, as well as major ecological shifts linked to biogeochemical reorganization.

Eigenbrode, Jennifer L.↗

A molecular beam mass spectrometric study of the formation and photolysis of C(lc)lO dimer

A study of the chlorine oxides present at temperatures and pressures typical of the Antarctic stratosphere was carried out. A series of low temperature flow reactors was constructed and used in conjunction with molecular beam mass spectrometric techniques to identify species and characterize their kinetic behavior at temperatures of -20 to -70 C and pressures of from 30 to 130 Torr. It was found that the gas phase chlorine-oxygen system was quite complex at low temperatures. ClO dimer was identified and found to be thermodynamically very stable under stratospheric conditions. It was also found that any system which contained ClO also contained a larger oxide. The oxide was identified as Cl2O3. A survey of possible higher oxides, which have been postulated as possible chlorine sinks in the stratosphere, was also carried out. The rate of formation of ClO dimer was measured as a function of temperature and pressure. Measurements were made of both the decay of ClO and the formation of the dimer. By comparing these rates it was determined that virtually all of the ClO was converted to the dimer under stratospheric conditions, and that the other ClO reactions were not important under these conditions.

Greene, Frank T.↗

TEM Analysis of Interfaces in Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

Silicon Carbide (SiC) is a promising material for thermo-structural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, and Mo-B. In this presentation, the result of microstructural analysis obtained by TEM observations and the influence of metallic interlayers and fiber orientation of SA-THX on the joint microstructure will be discussed.

Silicon Carbide↗

TEM Analysis of Diffusion-Bonded Silicon Carbide Ceramics Joined Using Metallic Interlayers

Silicon Carbide (SiC) is a promising material for thermostructural applications due to its excellent high-temperature mechanical properties, oxidation resistance, and thermal stability. However, joining and integration technologies are indispensable for this material in order to fabricate large size and complex shape components with desired functionalities. Although diffusion bonding techniques using metallic interlayers have been commonly utilized to bond various SiC ceramics, detailed microstructural observation by Transmission Electron Microscopy (TEM) of the bonded area has not been carried out due to difficulty in preparing TEM samples. In this study, we tried to prepare TEM samples from joints of diffusion bonded SiC ceramics by Focused Ion Beam (FIB) system and carefully investigated the interfacial microstructure by TEM analysis. The samples used in this study were SiC fiber bonded ceramics (SA-Tyrannohex: SA-THX) diffusion bonded with metallic interlayers such as Ti, TiMo, Mo-B and TiCu. In this presentation, we report the microstructure of diffusion bonded SA-THX mainly with TiCu interlayers obtained by TEM observations, and the influence of metallic interlayers on the joint microstructure and microhardness will be discussed.

Ceramics↗

Hydrogen Plasma Reduction

Hydrogen plasma increases efficiency by strategically using energy to break bonds within the regolith to liberate oxygen instead of heating the entire bed of regolith. The energy used by the plasma system would be imparted into the H2 gas, forming highly energetic ions, electrons, and neutrals that would interact with the regolith surface. The energized atomic and ionic H2 provide the energy needed to make reduction of SiO2 (Silicon Dioxide) and other regolith mineral oxides favorable. What’s more, the high-energy plasma interaction occurs in a small, localized volume, and thus requires relatively little energy. The lunar regolith is well-suited for the process as the fine particles naturally available provide a high surface area for the plasma to interact with. The process would require a system to collect the regolith composed of metal oxides (MxOy) and load it into a reactor. An H2 plasma would pass over the surface (potentially at a low pressure, reducing complexity of the system as it would not require large increases in pressure from the lunar vacuum), then the gases from the plasma reaction would be collected and processed, and the spent regolith would be carried away. The gross reaction temperature would be near ambient (due to the localized nature of the plasma), eliminating the necessity of a regolith heating mechanism or handling of molten regolith. Also, the H2 used in the plasma could be subsequently recovered from the water produced by the plasma reaction. Thus, this approach would not require significant amounts of added commodities.

Elspeth Petersen↗

Photochemistry of monodentate and bidentate carbonato complexes of rhodium (3)

A scheme for the photochemical fixation of water is proposed which involves a five-step reaction sequence; the first step involves the 2 electron reduction of a metal by a coordinated carbonate ligand, with corresponding oxidation of the carbonate to CO2 and O2. Ligand field photolysis of trans- (RH(en)2 H2O CO3) ClO4, and (Rh(en)2 CO3) CLO4 have been studied in the solid state and in aqueous solution at various pH values. Both salts are photoinert in the solid phase, but are quite photoreactive in aqueous solution. In solution, the monodentate ion undergoes efficient isomerization to a mixture of cis and trans - (Rh(en)2 H2O CO3)+, presumably with water exchange. A minor pH increase upon photolysis is evidence of inefficient carbonate (CO3 =) release, with formation of (Rh(en)2 (H2O)2)3+. In contrast, aqueous solutions of the bidentate carbonato complex undergo efficient pH decrease upon ligand field photolysis. Changes in the electronic spectrum (200-500 nm) and pH changes indicate that the desired redox is occurring. The pH increase is due to the aqueous behavior of CO2.

Sheridan, P. S.↗

Thermal Design for Extra-Terrestrial Regenerative Fuel Cell System

The Advanced Exploration Systems (AES) Advanced Modular Power Systems (AMPS) Project is investigating different power systems for various lunar and Martian mission concepts. The AMPS Fuel Cell (FC) team has created two system-level models to evaluate the performance of regenerative fuel cell (RFC) systems employing different fuel cell chemistries. Proton Exchange Membrane fuel cells PEMFCs contain a polymer electrolyte membrane that separates the hydrogen and oxygen cavities and conducts hydrogen cations (protons) across the cell. Solid Oxide fuel cells (SOFCs) operate at high temperatures, using a zirconia-based solid ceramic electrolyte to conduct oxygen anions across the cell. The purpose of the modeling effort is to down select one fuel cell chemistry for a more detailed design effort. Figures of merit include the system mass, volume, round trip efficiency, and electrolyzer charge power required. PEMFCs operate at around 60 C versus SOFCs which operate at temperatures greater than 700 C. Due to the drastically different operating temperatures of the two chemistries the thermal control systems (TCS) differ. The PEM TCS is less complex and is characterized by a single pump cooling loop that uses deionized water coolant and rejects heat generated by the system to the environment via a radiator. The solid oxide TCS has its own unique challenges including the requirement to reject high quality heat and to condense the steam produced in the reaction. This paper discusses the modeling of thermal control systems for an extraterrestrial RFC that utilizes either a PEM or solid oxide fuel cell.

thermal modeling↗

Clustered DNA damages induced in isolated DNA and in human cells by low doses of ionizing radiation

Clustered DNA damages-two or more closely spaced damages (strand breaks, abasic sites, or oxidized bases) on opposing strands-are suspects as critical lesions producing lethal and mutagenic effects of ionizing radiation. However, as a result of the lack of methods for measuring damage clusters induced by ionizing radiation in genomic DNA, neither the frequencies of their production by physiological doses of radiation, nor their repairability, nor their biological effects are known. On the basis of methods that we developed for quantitating damages in large DNAs, we have devised and validated a way of measuring ionizing radiation-induced clustered lesions in genomic DNA, including DNA from human cells. DNA is treated with an endonuclease that induces a single-strand cleavage at an oxidized base or abasic site. If there are two closely spaced damages on opposing strands, such cleavage will reduce the size of the DNA on a nondenaturing gel. We show that ionizing radiation does induce clustered DNA damages containing abasic sites, oxidized purines, or oxidized pyrimidines. Further, the frequency of each of these cluster classes is comparable to that of frank double-strand breaks; among all complex damages induced by ionizing radiation, double-strand breaks are only about 20%, with other clustered damage constituting some 80%. We also show that even low doses (0.1-1 Gy) of high linear energy transfer ionizing radiation induce clustered damages in human cells.

NASA Discipline Radiation Health↗

Thermal System Modeling for Lunar and Martian Surface Regenerative Fuel Cell Systems

The Advanced Exploration Systems (AES) Advanced Modular Power Systems (AMPS) Project is investigating different power systems for various lunar and Martian mission concepts. The AMPS Fuel Cell (FC) team has created two system-level models to evaluate the performance of regenerative fuel cell (RFC) systems employing different fuel cell chemistries. Proton Exchange Membrane fuel cells PEMFCs contain a polymer electrolyte membrane that separates the hydrogen and oxygen cavities and conducts hydrogen cations (protons) across the cell. Solid Oxide fuel cells (SOFCs) operate at high temperatures, using a zirconia-based solid ceramic electrolyte to conduct oxygen anions across the cell. The purpose of the modeling effort is to down select one fuel cell chemistry for a more detailed design effort. Figures of merit include the system mass, volume, round trip efficiency, and electrolyzer charge power required. PEMFCs operate at around 60 degrees Celsius versus SOFCs which operate at temperatures greater than 700 degrees Celsius. Due to the drastically different operating temperatures of the two chemistries the thermal control systems (TCS) differ. The PEM TCS is less complex and is characterized by a single pump cooling loop that uses deionized water coolant and rejects heat generated by the system to the environment via a radiator. The solid oxide TCS has its own unique challenges including the requirement to reject high quality heat and to condense the steam produced in the reaction. This paper discusses the modeling of thermal control systems for an extraterrestrial RFC that utilizes either a PEM or solid oxide fuel cell.

thermal modeling↗

Vacuum Packaging of MEMS With Multiple Internal Seal Rings

A proposed method of design and fabrication of vacuum-packaged microelectromechanical systems (MEMS) and of individual microelectromechanical devices involves the use of multiple internal seal rings (MISRs) in conjunction with vias (through holes plated with metal for electrical contacts). The proposed method is compatible with mass production in a wafer-level fabrication process, in which the dozens of MEMS or individual microelectromechanical devices on a typical wafer are simultaneously vacuum packaged by bonding a capping wafer before the devices are singulated (cut apart by use of a dicing saw). In addition to being compatible with mass production, the proposed method would eliminate the need for some complex and expensive production steps and would yield more reliable vacuum seals. Conventionally, each MEMS or individual microelectromechanical device is fabricated as one of many identical units on a device wafer. Vacuum packaging is accomplished by bonding the device wafer to a capping wafer with metal seal rings (one ring surrounding each unit) that have been formed on the capping wafer. The electrical leads of each unit are laid out on what would otherwise be a flat surface of the device wafer, against which the seal ring is to be pressed for sealing. The resulting pattern of metal lines and their insulating oxide coverings presents a very rough and uneven surface, upon which it is difficult to pattern the sealing metal. Consequently, the seal is prone to leakage unless additional costly and complex planarization steps are performed before patterning the seal ring and bonding the wafers.

Hayworth, Ken↗

Vacuum Plasma Spray of CuCrNb Alloy for Advanced Liquid - Fuel Combustion Chambers

The copper-8 atomic percent chromium-4 atomic percent niobium (CuCrNb) alloy was developed by Glenn Research Center (formally Lewis Research Center) as an improved alloy for combustion chamber liners. In comparison to NARloy-Z, the baseline (as in Space Shuttle Main Engine) alloy for such liners, CuCrNb demonstrates mechanical and thermophysical properties equivalent to NARloy-Z, but at temperatures 100 C to 150 C (180 F to 270 F) higher. Anticipated materials related benefits include decreasing the thrust cell liner weight 5% to 20%, increasing the service life at least two fold over current combustion chamber design, and increasing the safety margins available to designers. By adding an oxidation and thermal barrier coating to the liner, the combustion chamber can operate at even higher temperatures. For all these benefits, however, this alloy cannot be formed using conventional casting and forging methods because of the levels of chromium and niobium, which exceed their solubility limit in copper. Until recently, the only forming process that maintains the required microstructure of CrNb intermetallics is powder metallurgy formation of a billet from powder stock, followed by extrusion. This severely limits its usefulness in structural applications, particularly the complex shapes required for combustion chamber liners. Vacuum plasma spray (VPS) has been demonstrated as a method to form structural articles including small combustion chambers from the CuCrNb alloy. In addition, an oxidation and thermal barrier layer can be formed integrally on the hot wall of the liner that improve performance and extend service life. This paper discusses the metallurgy and thermomechanical properties of VPS formed CuCrNb versus the baseline powder metallurgy process, and the manufacturing of small combustion chamber liners at Marshall Space Flight Center using the VPS process. The benefits to advanced propulsion initiatives of using VPS to fabricate combustion chamber liners while maintaining the superior CuCrNb properties are also presented.

Zimmerman, Frank↗

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.↗

Hibonite: Crystal Chemistry and Origin of Blue Coloration in Meteoritic Assemblages

The blue color and optical spectra of hibonite, a common constituent of refractory inclusions in carbonaceous chondrites, are discussed. Because they may be manifestations of exotic cation species stabilized in unusual coordination sites in the hibonite crystalstructure. Hibonite, ideally CaAl12O19, is conducive to atomic substitution of host Ca2+ and Al3+ ions by a variety of lanthanide and first series transition elements. The latter cations are responsible for the colors of many rock-forming minerals as a result of intraelectronic or intervalence transitions. The visible-region spectra of most oxide and silicate minerals are generally well understood. Assignments of absorption bands in meteoritic hibonite optical spectra due to uncertainties of cation valencies and complexities in the crystal structure are examined. The crystal chemistry of hibonite is reviewed, Mossbauer spectral measurements of iron-bearing hibonite and electronic transitions that may be responsible for the blue coloration of meteoritic hibonites are discussed.

Burns, R. G.↗

A review of tin oxide-based catalytic systems: Preparation, characterization and catalytic behavior

This paper reviews the important aspects of the preparation, characterization and catalytic behavior of tin oxide-based catalytic systems including doped tin oxide, mixed oxides which contain tin oxide, Pt supported on tin oxide and Pt/Sn supported on alumina. These systems have a broad range of applications and are continually increasing in importance. However, due to their complex nature, much remains to be understood concerning how they function catalytically.

Hoflund, Gar B.↗

Elevated initial Sr-87/Sr-86 in ordinary chondrite metal

The metal phase of ordinary chondrites has been found to contain a complex assemblage of non-metal phases, evidently formed when elements such as Si, Cr and P, originally dissolved in the metal, were subsequently oxidized and exsolved. We have investigated the Rb-Sr isotopic system in samples of H-chondrite metal, finding small but nontrivial amounts of Sr, apparently concentrated toward the surface of metal grains, and characterized by pronounced excesses of Sr-87/Sr-86 in chondritic metal can plausibly account for the characteristically elevated initial Sr-87/Sr-86 found in ordinary chondrite phosphates, but it remains unclear when and where the metal experienced the high Rb/Sr environment needed to account for such high Sr-87/Sr-86. We have previously reported Rb-Sr data for separated metal from Dhajala (H3), Forest Vale (H4) and Estacado (H6). Here we report data for two size fractions (80-160 and 280-450 microns) of separated metal from the H4 chondrite Ste. Marguerite. These samples were etched twice (.5N HCl for one hour) before dissolution (6N HCl). Aliquots of the solutions were spiked for Fe, Ca and Rb + Sr. The results for Ste. Marguerite metal are presented; errors are two-sigma and elemental concentrations are stated in terms of total sample weight.

Podosek, F. A.↗

Impact of Evolving Isoprene Mechanisms on Simulated Formaldehyde: An Inter-comparison Supported by in Situ Observations from SENEX

Isoprene oxidation schemes vary greatly among gas-phase chemical mechanisms, with potentially significant ramifications for air quality modeling and interpretation of satellite observations in biogenic-rich regions. In this study, in situ observations from the 2013 SENEX mission are combined with a constrained O-D photochemical box model to evaluate isoprene chemistry among five commonly used gas-phase chemical mechanisms: CBO5, CB6r2, MCMv3.2, MCMv3.3.1, and a recent version of GEOS-Chem. Mechanisms are evaluated and inter-compared with respect to formaldehyde (HCHO), a high-yield product of isoprene oxidation. Though underestimated by all considered mechanisms, observed HCHO mixing ratios are best reproduced by MCMv3.3.1 (normalized mean bias = -15%), followed by GEOS-Chem (-17%), MCMv3.2 (-25%), CB6r2 (-32%) and CB05 (-33%). Inter-comparison of HCHO production rates reveals that major restructuring of the isoprene oxidation scheme in the Carbon Bond mechanism increases HCHO production by only approx. 5% in CB6r2 relative to CBO5, while further refinement of the complex isoprene scheme in the Master Chemical Mechanism increases HCHO production by approx. 16% in MCMv3.3.1 relative to MCMv3.2. The GEOS-Chem mechanism provides a good approximation of the explicit isoprene chemistry in MCMv3.3.1 and generally reproduces the magnitude and source distribution of HCHO production rates. We analytically derive improvements to the isoprene scheme in CB6r2 and incorporate these changes into a new mechanism called CB6r2-UMD, which is designed to preserve computational efficiency. The CB6r2-UMD mechanism mimics production of HCHO in MCMv3.3.1 and demonstrates good agreement with observed mixing ratios from SENEX (-14%). Improved simulation of HCHO also impacts modeled ozone: at approx. 0.3 ppb NO, the ozone production rate increases approx. 3% between CB6r2 and CB6r2-UMD, and rises another approx. 4% when HCHO is constrained to match observations.

isoprene↗