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733 records · Page 41

Machiite, Al2Ti3O9, A New Oxide Mineral from the Murchison Carbonaceous Chondrite: A New Ultra-refractory Phase From the Solar Nebula

Machiite (IMA 2016-067), Al2Ti3O9, is a new mineral that occurs as a single euhedral crystal, 4.4 mm in size, in contact with an euhedral corundum grain, 12 mm in size, in a matrix of the Murchison CM2 carbonaceous chondrite. The mean chemical composition of holotype machiite by electron probe microanalysis is (wt%) TiO2 59.75, Al2O3 15.97, Sc2O3 10.29, ZrO2 9.18, Y2O3 2.86, FeO 1.09, CaO 0.44, SiO2 0.20, MgO 0.10, total 99.87, giving rise to an empirical formula (based on 9 oxygen atoms pfu) of (Al1.17Sc0.56Y0.10Ti4+0.08Fe0.06Ca0.03Mg0.01)(Ti4+2.71Zr0.28Si0.01)O9. The general formula is (Al,Sc)2(Ti4+,Zr)3O9. The end-member formula is Al2Ti3O9. Machiite has the C2/c schreyerite-type structure with a = 17.10 Å, b = 5.03 Å, c = 7.06 Å, b = 107°, V = 581 Å3, and Z = 4, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 4.27 g/cm3. The machiite crystal is highly 16O-depleted relative to the coexisting corundum grain (D17O = –0.2 ± 2.4‰ and –24.1 ± 2.6‰, respectively; where D17O = d17O – 0.52 × d18O). Machiite is a new member of the schreyerite (V2Ti3O9) group and a new Sc,Zr-rich ultrarefractory phase formed in the solar nebula, either by gas-solid condensation or as a result of crystallization from a Ca,Al-rich melt having solar-like oxygen isotopic composition (D17O ~ –25‰) under high-temperature (~1400–1500 °C) and low-pressure (~10-4–10-5 bar) conditions in the CAI-forming region near the protosun. The currently observed disequilibrium oxygen isotopic composition between machiite and corundum may indicate that machiite subsequently experienced oxygen isotopic exchange with a planetary-like 16O-poor gaseous reservoir either in the solar nebula or on the CM chondrite parent body. The name machiite is in honor of Chi Ma, mineralogist at California Institute of Technology, for his contributions to meteorite mineralogy and discovery of many new minerals representing extreme conditions of formation.

Alexander N Krot↗

Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a New Cl-rich Silicate Mineral From the Allende Meteorite: An Alteration Phase in a Ca-Al-rich Inclusion

Adrianite (IMA 2014-028), Ca12(Al4Mg3Si7)O32Cl6, is a new Cl-rich silicate mineral and the Si,Mg analog of wadalite. It occurs with monticellite, grossular, wadalite, and hutcheonite in altered areas along some veins between primary melilite, spinel, and Ti,Al-diopside in a Type B1 FUN (Fractionation and Unidentified Nuclear effects) Ca-Al-rich inclusion (CAI), Egg-3, from the Allende CV3 carbona-ceous chondrite. The mean chemical composition of type adrianite by electron probe microanalysis is (wt%) CaO 41.5, SiO2 27.5, Al2O3 12.4, MgO 7.3, Na2O 0.41, Cl 13.0, O=Cl –2.94, total 99.2, giving rise to an empirical formula of (Ca11.69Na0.21)(Al3.85Mg2.88Si7.23)O32Cl5.80. The end-member formula is Ca12(Mg5Si9)O32Cl6. Adrianite has the I43d wadalite structure with a = 11.981 Å, V = 1719.8 Å3, and Z = 2, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 3.03 g/cm3. Adrianite is a new secondary mineral in Allende, apparently formed by alkali-halogen metasomatic alteration of primary CAI minerals such as melilite, anorthite, perovskite, and Ti,Al-diopside on the CV chondrite parent asteroid. Formation of secondary Cl-rich minerals sodalite, adrianite, and wadalite during metasomatic alteration of the Allende CAIs suggests that the metasomatic fluids had Cl-rich compositions. The mineral name is in honor of Adrian J. Brearley, mineralogist at the University of New Mexico, U.S.A., in recognition of his many contributions to the understanding of secondary mineralization in chondritic meteorites.

Chi Ma↗

Machiite, Al2Ti3O9, a New Oxide Mineral from the Murchison Carbonaceous Chondrite: A New Ultra-refractory Phase from the Solar Nebula

Machiite (IMA 2016-067), Al2Ti3O9, is a new mineral that occurs as a single euhedral crystal, 4.4 mm in size, in contact with an euhedral corundum grain, 12 mm in size, in a matrix of the Murchison CM2 carbonaceous chondrite. The mean chemical composition of holotype machiite by electron probe microanalysis is (wt%) TiO2 59.75, Al2O3 15.97, Sc2O3 10.29, ZrO2 9.18, Y2O3 2.86, FeO 1.09, CaO 0.44, SiO2 0.20, MgO 0.10, total 99.87, giving rise to an empirical formula (based on 9 oxygen atoms pfu) of (Al1.17Sc0.56Y0.10Ti4+0.08Fe0.06Ca0.03Mg0.01)(Ti4+2.71Zr0.28Si0.01)O9. The general formula is (Al,Sc)2(Ti4+,Zr)3O9. The end-member formula is Al2Ti3O9. Machiite has the C2/c schreyerite-type structure with a = 17.10 Å, b = 5.03 Å, c = 7.06 Å, b = 107°, V = 581 Å3, and Z = 4, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 4.27 g/cm3. The machiite crystal is highly 16O-depleted relative to the coexisting corundum grain (D17O = –0.2 ±2.4‰ and –24.1 ± 2.6‰, respectively; where D17O = d17O – 0.52 ×d18O). Machiite is a new member of the schreyerite (V2Ti3O9) group and a new Sc,Zr-rich ultrarefractory phase formed in the solar nebula, either by gas-solid condensation or as a result of crystallization from a Ca, Al-rich melt having solar-like oxygen isotopic composition (D17O ~ –25‰) under high-temperature (~1400–1500 °C) and low-pressure (~10-4–10-5 bar) conditions in the CAI-forming region near the protosun. The currently observed disequilibrium oxygen isotopic composition between machiite and corundum may indicate that machiite subsequently experienced oxygen isotopic exchange with a planetary-like 16O-poor gaseous reservoir either in the solar nebula or on the CM chondrite parent body. The name machiite is in honor of Chi Ma, mineralogist at California Institute of Technology, for his contributions to meteorite mineralogy and discovery of many new minerals representing extreme conditions of formation.

Machiite↗

Adrianite, Ca12(Al4Mg3Si7)O32Cl6, a New Cl-rich Silicate Mineral from the Allende Meteorite: An Alteration Phase in a Ca-Al-rich Inclusion

Adrianite (IMA 2014-028), Ca12 (Al4Mg3Si7)O32Cl6, is a new Cl-rich silicate mineral and the Si, Mg analog of wadalite. It occurs with monticellite, grossular, wadalite, and hutcheonite in altered areas along some veins between primary melilite, spinel, and Ti, Al-diopside in a Type B1 FUN (Fractionation and Unidentified Nuclear effects) Ca-Al-rich inclusion (CAI), Egg-3, from the Allende CV3 carbonaceous chondrite. The mean chemical composition of type adrianite by electron probe microanalysis is (wt%) CaO 41.5, SiO2 27.5, Al2O3 12.4, MgO 7.3, Na2O 0.41, Cl 13.0, O=Cl –2.94, total 99.2, giving rise to an empirical formula of (Ca11.69Na0.21) (Al3.85Mg2.88Si7.23) O32Cl5.80. The end-member formula is Ca12 (Mg5Si9) O32Cl6. Adrianite has the I43d wadalite structure with a = 11.981 Å, V = 1719.8 Å3, and Z = 2, as revealed by electron backscatter diffraction. The calculated density using the measured composition is 3.03 g/cm3. Adrianite is a new secondary mineral in Allende, apparently formed by alkali-halogen metasomatic alteration of primary CAI minerals such as melilite, anorthite, perovskite, and Ti,Al-diopside on the CV chondrite parent asteroid. Formation of secondary Cl-rich minerals sodalite, adrianite, and wadalite during metasomatic alteration of the Allende CAIs suggests that the metasomatic fluids had Cl-rich compositions. The mineral name is in honor of Adrian J. Brearley, mineralogist at the University of New Mexico, U.S.A., in recognition of his many contributions to the understanding of secondary mineralization in chondritic meteorites.

Adrianite↗

Thermochemical/Thermomechanical Synergies in High Temperature Solid Particle Erosion of CMAS-Exposed EBCs

Environmental barrier coatings (EBCs) are an enabling technology for the use of SiC-based ceramic matrix composites in next generation gas turbine engines. In the extreme engine environment, EBCs must be able to withstand a variety of individual damage mechanisms and their interactions with each other. Ingested particulates/debris can cause both thermochemical and thermomechanical degradation of EBCs. Siliceous debris primarily based on calcium magnesium aluminosilicates (CMAS) can melt and infiltrate and/or react with EBCs above >1200°C. Similarly, ingested debris can lead to mechanical damage and recession of coatings due to particulate erosion. Both modes of degradation can occur simultaneously during engine operation, and it is crucial to comprehensively understand the mechanisms of coating failure due to high-temperature particulate interactions. This study assesses the erosion durability of Yb2Si2O7-based EBCs exposed to CMAS of various loads in NASA Glenn’s Erosion Burner Rig Facility. CMAS exposures and erosion testing were carried out at 1316°C. The effects of CMAS loading and exposure time on EBC erosion durability were evaluated using Al2O3 as an erodent material.

EBC↗

High-Temperature Solid Particle Erosion Behavior of an Environmental Barrier Coating

The solid particle erosion (SPE) behavior of a state-of-the-art environmental barrier coating (EBC) was assessed at 2,192 °F (1,200 °C) using alumina (Al2O3) particulate. The effect of particle velocity, particle size, and impingement angle were investigated. Results show that the erosion damage in the EBC is primarily controlled by particle kinetic energy. In addition, the effect of impingement angle demonstrates the contribution of the tangential component of velocity.

Solid Particle Erosion↗

Advanced Al Mirrors Protected with LiF Overcoat to Realize Stable Mirror Coatings for Astronomical Telescopes

Pure Aluminum (Al) exhibits intrinsic high reflectance over the proposed Large UV/Optical/IR (LUVOIR) Surveyor observatory target spectral range (90-2500 nm). However, Al coatings have to be protected from oxygen exposure in order to prevent the formation of the naturally occurring Al2O3 oxide layer, which limit performance for use only above 160 nm. Aluminum protected with fluorides such as LiF or MgF2 have been the most commonly used solutions. But below 102 nm and down to 90 nm, no transparent material is available to protect Al and coating mirror reflectance stays below 40%. But even above 102 nm, the reflectance of protected Al is limited by the residual absorption of the fluoride overcoats. Hence, this paper will report on recent advances in producing enhanced Al-based mirror coatings with the highest possible far-ultraviolet (FUV) reflectance, while exhibiting a more stable LiF protection layer. The process starts with a bare optically smooth glass substrate that is coated with Al in an ultra-high vacuum chamber by using the physical vapor deposition (PVD) process, which has been shown to provide the best aluminum thin-films when compared to other approaches. The next step is done by in-situ exposure of the freshly made Al film to a reactive XeF2 gas that will grant a thin AlF3 overcoat (2-3 nm) to the Al film that prevents further oxidation. This fluorinated Al film is then coated with a final layer of a LiF metal-fluoride overcoat. The coating process is finalized with a second exposure to the XeF2 precursor gas. The preparation of these mirror coatings will be studied and analyzed as a function of the XeF2 exposure time and deposition rate of the LiF layer during the PVD process. This paper will present and discuss characterization of a number of Al+XeLiF witness coupons produced with this reactive PVD (rPVD) process. These studies include characterization of specular reflectance in the 90-2500 nm spectral range, micro-roughness, long-term stability, as well as polarization characteristics in the visible and near-infrared spectral regions. These studies have been performed in order to demonstrate the improved reflectance performance, longer durability, and less hygroscopic nature of protected Al mirrors produced with the rPVD process (through exposure to XeF2) and in comparison with the standard PVD process.

optics↗

Thermochemical/Thermomechanical Synergies in High Temperature Solid Particle Erosion of CMAS Exposed EBCs

Environmental barrier coatings (EBCs) are an enabling technology for the use of SiC-based ceramic matrix composites in next generation gas turbine engines. In the extreme engine environment, EBCs must be able to withstand a variety of individual damage mechanisms and their interactions with each other. Ingested particulates/debris can cause both thermochemical and thermomechanical degradation of EBCs. Siliceous debris primarily based on calcium magnesium aluminosilicates (CMAS) can melt and infiltrate and/or react with EBCs above >1200°C. Similarly, ingested debris can lead to mechanical damage and recession of coatings due to particulate erosion. Both modes of degradation can occur simultaneously during engine operation, and it is crucial to comprehensively understand the mechanisms of coating failure due to high-temperature particulate interactions. This study assesses the erosion durability of Yb 2 Si 2 O 7 -based EBCs exposed to CMAS of various loads in NASA Glenn’s Erosion Burner Rig Facility. CMAS exposures and erosion testing were carried out at 1316°C. The effects of CMAS loading and exposure time on EBC erosion durability were evaluated using Al2O3 as an erodent material.

EBC↗

Thermochemical Interactions of Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced from lunar resources through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar mare and highlands regolith simulants at 1600C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD with an emphasis on elemental and microstructural analysis to assess reactivity and degradation of YSZ. Due to lunar regolith’s similar composition to calcium-magnesium-aluminosilicates (CMAS) and YSZ’s usage as a thermal barrier coating, these interactions can serve to inform YSZ/CMAS behavior by simulating cases of elevated CMAS/YSZ ratios and for higher than intended gas turbine temperatures.

Kevin Yu↗

Thermochemical Interactions Between Yttria-Stabilized Zirconia and Molten Lunar Regolith Simulants

Oxygen produced through in-situ resource utilization (ISRU) is critical to maintaining a permanent human presence on the lunar surface. Molten regolith electrolysis and carbothermal reduction are two promising ISRU techniques for generating oxygen directly from lunar regolith, which is primarily a mixture of oxide minerals; however, both processes require operating temperatures of 1600 C to melt lunar regolith and dissociate the molten oxides. These conditions limit the use of many oxide refractory materials, such as Al2O3 and MgO, due to rapid degradation resulting from reactions between the refractory materials and molten lunar regolith. Yttria-stabilized zirconia (YSZ) is shown here to be a promising refractory oxide to provide containment of molten regolith while demonstrating limited reactivity. This work focuses on corrosion studies of YSZ powders and dense YSZ crucibles in contact with molten lunar maria and highlands regolith simulants at 1600 C. The interactions between YSZ and molten regolith are characterized using SEM/EDS, XRD, and EBSD. A FactSage thermochemical model is created to compare with the experimental results. These combined analyses suggest that lunar maria regolith will degrade YSZ faster than lunar highlands regolith due to the lower viscosity of the maria regolith. The feasibility of long-term molten regolith containment with YSZ is discussed based on the YSZ powder and crucible results.

Kevin Yu↗

Degradation of Yttria-Stabilized Zirconia in Molten Regolith Electrolysis Applications

The generation of oxygen from lunar resources is an enabling technology to support a sustained human presence on the lunar surface. Molten regolith electrolysis is a promising process for directly electrolyzing lunar regolith, which is primarily a mixture of oxide minerals. During electrolysis, metallic products (Fe, Si) are formed at the cathode and oxygen is produced at the anode. In order to perform electrolysis, the regolith must be molten to enable ionic transport of metallic cations and oxygen anions, requiring an operating temperature of 1600C. Common refractory oxide materials, such as Al2O3 and MgO, undergo rapid degradation due to the high operating temperature and contact with the corrosive molten regolith. This work investigates yttria-stabilized zirconia (YSZ) for molten regolith electrolysis applications. Corrosion studies are presented to elucidate the degradation mechanism of YSZ powders and crucibles exposed to lunar regolith simulants at 1600C. Two regolith simulants are used to represent regolith from the lunar maria (JSC-1A) and the lunar highlands (LHS-1). Degradation of YSZ in contact with regolith simulants is evaluated using SEM/EDS, XRD, and EBSD. Furthermore, a modified molten regolith electrolysis reactor is presented utilizing YSZ at the anode to enable facile collection of oxygen produced during electrolysis.

Kevin Yu↗

System Modeling of a Lunar Molten Regolith Electrolysis Plant

Introduction: In-Situ Resource Utilization (ISRU) is the process of extracting local resources to produce commodities for propulsion, life support systems, and off-planet construction rather than transporting consumables from Earth. Molten Regolith Electrolysis (MRE) is a novel ISRU method of extracting oxygen gas and metal alloy from lunar regolith. The MRE process involves placing lunar regolith between two electrodes, through which current is passed, to melt the regolith and reduce the metal oxide constituents by direct electrolysis (e.g. FeO, SiO2, MgO, Al2O3) into oxygen gas and metal alloys. The oxygen is liquefied and used as propellant for landers, while the metals (e.g. Ferro-alloys) are further processed and used in structural building materials and parts manufacturing. A system model was developed that accounted for the major processes of an MRE plant (from excavation of raw materials to storage of products) to assess the feasibility of a lunar MRE plant. The System Engineering and Integration (SE&I) ISRU Modeling and Analysis (SIMA) team utilized its previously documented system sizing model, the Mission Analysis and Integration Tool (MAIT) [1] as framework of the system model. MAIT uses MATLAB/Simulink to integrate subsystem models into a complete system model of the MRE plant. Total mass, volume, and power requirements were computed for numerous iterations of a MRE plant. System Model: Figure 1: MRE Plant Block Diagram The regolith excavation model determines the mass and power needed to excavate sufficient regolith. The preheating auger initiates the regolith heating process before regolith enters the MRE re-actor to reduce the energy required to turn the solid into a molten liquid. The MRE reactor is modeled in COMSOL Multiphysics and based on the research by Dominguez, Sibille, and Schreiner [2, 3, 4]. This preliminary reactor model provides an accurate calculation of thermal equilibrium during electrochemical operation of the reactor system to assess the optimal mass and power required to process the inlet flow of regolith. The model also computes the outlet flowrates of oxygen and molten products. For this analysis, the primary components of the metal alloy considered were iron and silicon. The oxygen is then purified using an Yttrium Stabilized Zirconia (YSZ) electrode, followed by liquefaction using a 90K cryocooler to be stored as liquid oxygen in insulated cylindrical tanks. In future iterations of the system model, the molten metal tapped from the MRE reactor will undergo additional processing or refinement. However, downstream handling of metals is currently a technology gap that is missing a high TRL subsystem model. Therefore, for this analysis, the accumulated metal alloy stream terminates after leaving the MRE reactor. Study Goals: This analysis investigates multiple input variables to the system to determine the sensitivity of a (near) complete plant at full-scale. This preliminary investigation ran parametric sweeps on the MRE reactor geometry, electrical current supply, layers of multi-layer insulation (MLI) on the reactor, size of the electrodes in the oxygen purification model, and regolith composition (based on landing site location). Three production targets of oxygen (1,000, 10,000, and 50,000 kg/yr) were investigated for this analysis. The parametric sweeps conducted in this analysis provide valuable insight into the expected impact of the various model inputs on plant size. This information can be used to identify the most critical components of the plant and guide future decisions on allocating funding for research and development, providing subsystem developers with appropriate interfaces with downstream and upstream processes, and assessing the overall feasibility of MRE when compared to other ISRU plants. References: [1] Carlson, A. et al. (2024) ICES, ICES-2024-53. [2] Dominguez, D.A., and Sibille, L. (2011) AIAA, AIAA-2011-700. [3] Schreiner, S.S. (2015) MIT, Dissertation. [4] Schreiner, S.S. et al. (2016) ASR, 57(7), pp.1585-1603.

ISRU↗

Crystallographic and TEM Features of a TBC/Ti2AlC MAX Phase Interface after 1300°C Burner Rig Oxidation

A FIB/STEM interfacial study was performed on a TBC/Ti 2 AlC MAX phase system, oxidized in an aggressive burner rig test (Mach 0.3 at 1300 °C for 500 h). The 7YSZ TBC, α-Al 2 O 3 TGO, and MAXthal 211 TM Ti 2 AlC base were variously characterized by TEM/STEM, EDS, SADP, and HRTEM. The YSZ was a mix of “clean” featureless and “faulted” high contrast grains. The latter exhibited ferro-elastic domains of high Y content tetragonal t″ variants. No martensite was observed. The TGO was essentially a duplex α-Al 2 O 3 structure of inner columnar plus outer equiaxed grains. It maintained a perfectly intact, clean interface with the Ti 2 AlC substrate. The Ti 2 AlC substrate exhibited no interfacial Al-depletion zone but, rather, numerous faults along the basal plane of the hexagonal structure. These are believed to offer a means of depleting Al by forming crystallographic, low-Al planar defects, proposed as Ti 2.5 AlC 1.5 . These characterizations support and augment prior optical, SEM, and XRD findings that demonstrated remarkable durability for the YSZ/Ti 2 AlC MAX phase system in aggressive burner tests.

TI2AlC↗