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At least 253 records · Page 14

Calcium-Magnesium-Alumino-Silicates (CMAS) Reaction Mechanisms and Resistance of Advanced Turbine Environmental Barrier Coatings for SiC/SiC Ceramic Matrix Composites

Environmental barrier coatings (EBCs) and SiC/SiC ceramic matrix composites (CMCs) systems will play a crucial role in future turbine engines for hot-section component applications because of their ability to significantly increase engine operating temperatures, reduce engine weight and cooling requirements. The development of prime-reliant environmental barrier coatings is an essential requirement to enable the applications of the 2700-3000 F EBC - CMC systems. This presentation primarily focuses on the reaction mechanisms of advanced NASA environmental barrier coating systems, when in contact with Calcium-Magnesium Alumino-Silicates (CMAS) at high temperatures. Advanced oxide-silicate defect cluster environmental barrier coatings are being designed for ultimate balanced controls of the EBC temperature capability and CMAS reactivity, thus improving the CMAS resistance. Further CMAS mitigation strategies are also discussed.

Environmental barrier coatings (EBCs)↗

Development of a lightweight body-mounted solar cell array with a high power to weight ratio.

Three lightweight solar cell arrays have been fabricated with a high power-to-weight ratio. These arrays incorporate resistance welded interconnections, improved antireflection coating on the solar cell and lightweight substrates. Two of the substrates were constructed of magnesium with different structural geometry, while the third substrate was conventional aluminum honeycomb. All arrays utilized thin solar cells having a titanium-palladium-silver contact system and an antireflection coating of titanium oxide. The cells were welded with silver plated molybdenum interconnections. The two arrays having magnesium substrates exhibited a power/weight of 70.4 W/kg (32 W/lb.) and 81 W/kg (36.8 W/lb.), while the conventional array demonstrated a power/weight of 45.2 W/kg (20.6 W/lb.).

Somberg, H.↗

Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis

Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

Francois, P.↗

Mineralogic and petrologic implications of Viking geochemical results from Mars - Interim report

Chemical results from four samples of Martian fines delivered to Viking landers 1 and 2 are remarkably similar in that they all have high iron; moderate magnesium, calcium, and sulfur; low aluminum; and apparently very low alkalies and trace elements. This composition is best interpreted as representing the weathering products of mafic igneous rocks. A mineralogic model, derived from computer mixing studies and laboratory analog preparations, suggests that Mars fines could be an intimate mixture of about 80% iron-rich clay, about 10% magnesium sulfate (kieserite), about 5% carbonate (calcite), and about 5% iron oxides (hematite, magnetite, maghemite, goethite). The mafic nature of the present fines (distributed globally) and their probable source rocks seems to preclude large-scale planetary differentiation of a terrestrial nature.

Baird, A. K.↗

Advancing Development of Environmental Barrier Coatings Resistant to Attack by Molten Calcium-Magnesium-Aluminosilicate (CMAS)

Ceramic matrix composites (CMCs) are a leading material system to replace metal-based parts in the hot-section of air-breathing turbine engines to improve fuel efficiency in aircraft engines. CMCs have higher temperature capabilities and lower density compared with traditional metallic structural materials. However, silicon-based CMCs are susceptible to oxidation in the harsh combustion environment encountered in turbine engines. Consequently, environmental barrier coatings (EBCs) are being developed to protect CMC components to improve durability and extend service life of CMCs. Sand, volcanic ash and other particulate debris, which are generally comprised of calcium-magnesium-aluminosilicate (CMAS) and other trace oxides, are routinely ingested by aircraft engines. At temperatures above 1200°C, CMAS particulates melt. Near target operating temperatures (~1500°C) of future CMC-based aircraft engines, molten CMAS behaves like a viscous melt that can infiltrate and chemically interact with protective coatings. These interactions can cause premature failure of the EBC system and ultimately the overall CMC engine component. Degradation of candidate EBC materials by molten CMAS will be presented with a focus on recent work, as well as methods of evaluating the complex high-temperature materials interactions, underway at NASA Glenn Research Center.

Wiesner, Valerie L.↗

Thin-film ultraviolet detector and spectrometer

Typical metal-insulator-metal detector device is formed on quartz substrate. Base electrode is 3 to 6 nm aluminum layer, overcoated with 3 to 6 nm aluminum oxide or aluminum nitride, and capped with counter electrode of gold, lead, magnesium, or aluminum. Photoelectric yield data are given for Al-AlN-Au structure.

Lewicki, G. W.↗

Use of thin film light detector

A photovoltaic cell device with a trapezoidal barrier is described. An aluminum, magnesium, or tantalum base is vapor deposited on a quartz substrate. An oxide or nitride film of the base metal is produced as an insulator by reaction in a glow discharge plasma to a thickness of less than 100 Angstroms. A metal, preferably gold, conter-electrode is vapor deposited on the insulating layer. A bias generator of high impedance is used to set and shift or modulate the spectral response of the device.

Lewicki, G. W.↗

Analysis of Siderite Thermal Decomposition by Differential Scanning Calorimetry

Characterization of carbonate devolitilization has important implications for atmospheric interactions and climatic effects related to large meteorite impacts in platform sediments. On a smaller scale, meteorites contain carbonates which have witnessed shock metamorphic events and may record pressure/temperature histories of impact(s). ALH84001 meteorite contains zoned Ca-Mg-Fe-carbonates which formed on Mars. Magnetite crystals are found in the rims and cores of these carbonates and some are associated with void spaces leading to the suggestion by Brearley et al. that the crystals were produced by thermal decomposition of the carbonate at high temperature, possibly by incipient shock melting or devolitilization. Golden et al. recently synthesized spherical Mg-Fe-Ca-carbonates from solution under mild hydrothermal conditions that have similar carbonate compositional zoning to those of ALH84001. They have shown experimental evidence that the carbonate-sulfide-magnetite assemblage in ALH84001 can result from a multistep inorganic process involving heating possibly due to shock events. Experimental shock studies on calcium carbonate prove its stability to approx. 60 GPa, well in excess of the approx. 45 GPa peak pressures indicated by other shock features in ALH84001. In addition, Raman spectroscopy of carbonate globules in ALH84001 indicates no presence of CaO and MgO. Such oxide phases should be found associated with the magnetites in voids if these magnetites are high temperature shock products, the voids resulting from devolitilization of CO2 from calcium or magnesium carbonate. However, if the starting material was siderite (FeCO3), thermal breakdown of the ALH84001 carbonate at 470 C would produce iron oxide + CO2. As no documentation of shock effects in siderite exists, we have begun shock experiments to determine whether or not magnetite is produced by the decomposition of siderite within the < 45GPa pressure window and by the resultant thermal pulse to approx. 600 C experienced by ALH84001. Here, we report thermal and compositional characterization of unshocked siderite and its transition to magnetite. Additional information is contained in the original extended abstract.

Bell, M. S.↗

Mechanical Properties and Durability of Advanced Environmental Barrier Coatings in Calcium-Magnesium-Alumino-Silicate Environments

Environmental barrier coatings are being developed and tested for use with SiC/SiC ceramic matrix composite (CMC) gas turbine engine components. Several oxide and silicate based compositons are being studied for use as top-coat and intermediate layers in a three or more layer environmental barrier coating system. Specifically, the room temperature Vickers-indentation-fracture-toughness testing and high-temperature stability reaction studies with Calcium Magnesium Alumino-Silicate (CMAS or "sand") are being conducted using advanced testing techniques such as high pressure burner rig tests as well as high heat flux laser tests.

Miladinovich, Daniel S.↗

High Temperature Solar Reflector, Its Preparation and Use

A coating-substrate combination having high specular reflectivity at high temperatures reaching 8000 C in a vacuum is described. The substrate comprises pure nickel metal or a nickel-containing metal alloy such as stainless steel having a highly polished reflective surface. The coating is a layer of silver deposited on the substrate to a thickness of 300 A to 3000 A. A 300 A to 5000 A protective coating of silica, alumina or magnesium fluoride is used to cover the silver and to protect it from oxidation. The combination is useful as a parabolic shaped secondary concentrator for collecting solar radiation for generating power or thermal energy for satellite uses. The reflective layer and protective coating preferably are applied to the reflective surface of the substrate by electron beam evaporation or by ion sputtering.

Jaworske, Donald A.↗

Optimization and purification of magnesium borides fabricated by combustion synthesis and by high-temperature sintering

Hydrogen as a fuel provides several benefits over the use of fossil fuels; however, one challenge in utilizing hydrogen as an energy carrier revolves around its storage. Achieving sufficient volumetric hydrogen density in a storage solution will facilitate hydrogen’s adoption for use in both stationary and mobile applications. Solid-state hydrogen storage provides a promising pathway to solving this problem. However, the hydrogenation of these materials is characterized by slow kinetics and extreme thermodynamic conditions. Magnesium borohydride (Mg(BH4)2) is a promising material in hydrogen storage due to its reversible properties and a theoretical hydrogen capacity of 14.9 wt.%. To synthesize this material, combustion synthesis of magnesium borides (MgBx) has been implemented with the aim to further lower thermodynamic requirements for direct hydrogenation. A drawback of this process is the potential formation of oxide contaminants, which decrease hydrogenation/dehydrogenation and recyclability performance. The present work focuses on identifying parameters useful for reducing contamination and evaluating potential pathways to the purification of magnesium borides with the goal of improving their quality.

Camarena, Miguel Joaquin↗

Investigating Fifth Oxide Effect on CMXAS Glass Properties

Coatings for hot section aero turbine engine structural materials are subject to thermochemical degradation after interacting with calcium-magnesium-aluminosilicates (CMAS). Molten CMAS viscosity is the primary glass property of importance, correlating with coating infiltration and reaction depth. CMAS viscosity was measured using a spindle-dipped viscometer at temperatures between 1300-1550°C in 25°C increments. Experimental data were compared to Thermo-Calc and FactSage computational models, which showed good agreement with experimental trends. CMXAS compositions, where X denotes a fifth oxide, of Ca30.75-Mg9-X5-Al13-Si42.25 (single cation oxide mol%) for X = Fe2+, Fe3+, Gd3+, Hf4+, Na1+, Ti4+, Y3+, Yb3+, Zr4+ additions were used. Oxide precipitation was observed in X = Hf4+ , Zr4+ CMXAS specimens, indicating coating dissolution is an increased threat for T ≥ 1390°C. Molten CMAS and CMXAS viscosity measurements were shown to correlate with net cation field strength, offering an alternative in property prediction where thermodynamic data are unavailable.

Clark Avery Luckhardt↗

A proposed optical pumping system requiring no electric power

A method for optically pumping a fluid without electrical power is described. The method is based on utilizing the radiation from a metal oxidant combustion reaction that is contained within a transparent tube that is immersed in the medium to be pumped. The reaction initiation and maintenance occurs by gas dynamically induced resonance within the transparent cavity. All that is required is a supply of high pressure oxidant and metallic powder. Materials that were successfully evaluated to date include aluminum, steel, magnesium, and titanium.

Phillips, B. R.↗

Atomic Oxygen Effects on Materials

One objective of this investigation has been to offer recommendations on the selection of metal samples to be exposed to ambient atomic oxygen on the STS-8 flight presently scheduled for August 30, 1983. (These samples constitute a small subgroup of a very large group of test specimens prepared by A. Whitaker and other members of the Physical Sciences Branch for this mission.) The metals selected and prepared for STS-8 are silver, lead, copper, nickel, tungsten, molybdenum, magnesium, platinum, and alloys of FeCrAl and NiCr. Literature data are reviewed concerning the oxidation properties of these materials with a view towards understanding which oxides might be formed, the state of the oxide (surface film or volatile form), and the reaction rate. In addition, various techniques for characterizing the parent metals and the surface oxides are reviewed.

Fromhold, A. T.↗

Ignition and Combustion of Bulk Metals in a Microgravity Environment

Results of a study of heterogeneous and homogeneous combustion of metals in reduced gravity are presented. Cylindrical titanium and magnesium samples are radiatively ignited in pure-oxygen at 1 atm. Qualitative observations, propagation rates, and burning times are extracted from high-speed cinematography. Time-resolved emission spectra of gas-phase reactions are acquired with an imaging spectrograph. Lower propagation rates of the reacting mass on titanium and of ignition waves on magnesium are obtained at reduced gravity. These rates are compared to theoretical results from fire-spread analyses with a diffusion/convection controlled reaction. The close agreement found between experimental and theoretical propagation rates indicates the strong influence of natural-convection-enhanced oxygen transp6rt on burning rates. Lower oxygen flux and lack of condensed product removal appear to be responsible for longer burning times of magnesium gas-phase diffusion flames in reduced gravity. Spherically symmetric explosions in magnesium flames at reduced gravity (termed radiation-induced metal explosions, or RIME) may be driven by increased radiation heat transfer from accumulated condensed products to an evaporating metal core covered by a porous, flexible oxide coating. In titanium specimens, predominantly heterogeneous burning characterizes the initial steady propagation of the molten mass, while homogeneous gas-phase reactions are detected around particles ejected from the molten mixture. In magnesium specimens, band and line reversal of all the UV spectral systems of Mg and MgO are attributed to the interaction between small oxide particles and the principal gaseous emitters.

Branch, Melvyn C.↗

Calcium and Magnesium Distribution Between Sulfide and Silicate Melts: Thermodynamic Modeling and Insights into Mercury's Mantle-Crust Differentiation

Mercury stands out as the terrestrial planet with the lowest degree of oxidation among all planets of our solar system. It is characterized by a high abundance of sulfur, which is expected to replace oxygen in silicate melts. This sulfur enrichment could lead to sulfide saturation in its mantle, potentially resulting in the formation of sulfides rich in calcium and magnesium. Utilizing experimental data from the literature, we constructed a thermodynamic model to explore the partitioning of calcium and magnesium between sulfide and silicate melts. This model aims to improve our comprehension of the chemical equilibria driving the process of mantle-crust differentiation on Mercury. Our models indicate that increased temperature, decreased pressure, and low concentrations of iron, oxygen, and carbon within the sulfide phase, along with low sulfur concentrations in the silicate phase, favor calcium’s partitioning into the sulfide. Additionally, magnesium partitioning into the sulfide melt is favored with decreased pressure, decreased temperature, low concentrations of iron and calcium within the sulfide, and low concentrations of sulfur within the silicate. Our results suggest that up 9.4% and 5.6% Ca and Mg, respectively, can be present in sulfides equilibrated with sulfide-saturated silicate melts during mantle-crust differentiation. Further investigation will focus on the distribution of sulfide phases within the mantle and crust to better constrain Mercury’s internal structure.

Taylor McCombs↗

Characterization and Petrologic Interpretation of Olivine-Rich Basalts at Gusev Crater, Mars

Rocks on the floor of Gusev crater are basalts of uniform composition and mineralogy. Olivine, the only mineral to have been identified or inferred from data by all instruments on the Spirit rover, is especially abundant in these rocks. These picritic basalts are similar in many respects to certain Martian meteorites (olivine-phyric shergottites). The olivine megacrysts in both have intermediate compositions, with modal abundances ranging up to 20-30%. Associated minerals in both include low-calcium and high-calcium pyroxenes, plagioclase of intermediate composition, iron-titanium-chromium oxides, and phosphate. These rocks also share minor element trends, reflected in their nickel-magnesium and chromium-magnesium ratios. Gusev basalts and shergottites appear to have formed from primitive magmas produced by melting an undepleted mantle at depth and erupted without significant fractionation. However, apparent differences between Gusev rocks and shergottites in their ages, plagioclase abundances, and volatile contents preclude direct correlation. Orbital determinations of global olivine distribution and compositions by thermal emission spectroscopy suggest that olivine-rich rocks may be widespread. Because weathering under acidic conditions preferentially attacks olivine and disguises such rocks beneath alteration rinds, picritic basalts formed from primitive magmas may even be a common component of the Martian crust formed during ancient and recent times.

McSween, H. Y.↗