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NASA NTRS2015

Quantum Dots Microstructured Optical Fiber for X-Ray Detection

Microstructured optical fibers containing quantum dots scintillation material comprised of zinc sulfide nanocrystals doped with magnesium sulfide are presented. These quantum dots are applied inside the microstructured optical fibers using capillary action. The x-ray photon counts of these fibers are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The results of the fiber light output and associated effects of an acrylate coating and the quantum dot application technique are discussed.

DeHaven, Stan↗

NASA NTRS2016

An Iron-Rain Model for Core Formation on Asteroid 4 Vesta

Asteroid 4 Vesta is differentiated into a crust, mantle, and core, as demonstrated by studies of the eucrite and diogenite meteorites and by data from NASA's Dawn spacecraft. Most models for the differentiation and thermal evolution of Vesta assume that the metal phase completely melts within 20 degrees of the eutectic temperature, well before the onset of silicate melting. In such a model, core formation initially happens by Darcy flow, but this is an inefficient process for liquid metal and solid silicate. However, the likely chemical composition of Vesta, similar to H chondrites with perhaps some CM or CV chondrite, has 13-16 weight percent S. For such compositions, metal-sulfide melting will not be complete until a temperature of at least 1350 degrees Centigrade. The silicate solidus for Vesta's composition is between 1100 and 1150 degrees Centigrade, and thus metal and silicate melting must have substantially overlapped in time on Vesta. In this chemically and physically more likely view of Vesta's evolution, metal sulfide drops will sink by Stokes flow through the partially molten silicate magma ocean in a process that can be envisioned as "iron rain". Measurements of eucrites show that moderately siderophile elements such as Ni, Mo, and W reached chemical equilibrium between the metal and silicate phases, which is an important test for any Vesta differentiation model. The equilibration time is a function of the initial metal grain size, which we take to be 25-45 microns based on recent measurements of H6 chondrites. For these sizes and reasonable silicate magma viscosities, equilibration occurs after a fall distance of just a few meters through the magma ocean. Although metal drops may grow in size by merger with other drops, which increases their settling velocities and decreases the total core formation time, the short equilibration distance ensures that the moderately siderophile elements will reach chemical equilibrium between metal and silicate before metal drop merger becomes important. In this model, there must be at least 30 percent melting of the silicate phase when metal melting is complete, corresponding to a crust thickness of at least 30 kilometers on Vesta, consistent with Dawn gravity observations. Greater degrees of silicate melting and a correspondingly thicker crust are possible if Vesta accreted sufficiently rapidly.

Kiefer, Walter S.↗

NASA NTRS2017

3-D-Observation of Matrix of MIL 090657 Meteorite by Absorption-Phase Tomography

MIL 090657 meteorite (CR2.7) is one of the least altered primitive carbonaceous c hondrites [1]. This meteorite has amorphous silicates like GEMS (glass with embedded metal and sulfide), which are characteristically contained in cometary dust, in matrix [2,3] as with the Paris meteorite [4]. Three lithologies have been recognized; lithology-1 (L 1) dominated by submicron anhydrous silicates, lithology-2 (L2) by GEMS-like amorphous silicates and lithology-3 (L3) by phyllosilicates [2]. Organic materials are abundant in L 1 and L2 [2,3]. L 1 and L2 were further divided into sub-lithology respectively based on their textures and compositions [5]. These studies were performed by 2D SEM and TEM observations of sample surfaces and thin sections that are unable to reveal what constitute each lithology and how these lithologies are distributed and related to each other. This information will provide important insights into alteration and aggregation processes on asteroids and in the early solar nebula. In this study, MIL 090657 matrix was examined in 3D using two types of X-ray tomography; DET (dual-energy tomography) [6] and SIXM (scanning-imaging X-ray microscopy) [7]. Mineral phases can be discriminated based on absorption contrasts at two different X-ray energies in DET. In SIXM, materials composed of light elements such as water or organic materials can be identified based on phase and absorption contrasts. By combining these methods, we can discriminate not only organic materials from voids but also hydrous alteration products, such as hydrated silicates and carbonates, from anhydrous minerals [8]. In this study, we first observed cross sections of MIL 090657 matrix fragments C1 00 mm) in detail using FE-SEM/ EDS. Based on the results, three house-shaped samples (3 0 -50 mm) were extracted from L 1, L2 and their boundary (H1, H3 and H5, respectively) using FIB. 3D imaging of these samples were conducted at BL47XU of SPring-8, a synchrotron radiation facility, with -30-40 nm/ voxel and - 70-80 nm/ voxel at 7keV and 8keV in DET and -100 nm/ voxel at 8keV in SIXM. We found new lithologies that we named L4, L5 and L6 in H1 and H3 in addition to L 1 and L2. L4. L5 and L6 are mainly composed of probably phyllosilicates with different Fe contents. Sulfide and framboidal magnetite were recognized in L4. L5 includes magnetite and carbonate and L6 includes anhydrous silicates having cracks inside. L 1, L2, L4 and L5 are porous while few voids were observed in L6. L4 adjoins to L 1 with boundary, which is not very distinct. L2, L5 and L6 adjoin to each other, and the boundaries of L6 with L2 and L5 are clear. In H5, coarse mineral grains C5-1 0 mm) such as Fe-metal and enstatite are present in L 1 and L2. L 1-L2 boundary is not sharp in 3 D. In conclusion, we found a variety of lithologies by 3D observation for the first time, suggesting that t he MIL 0 90657 meteorite experienced complex alteration and aggregation histories. As L2 is dominated by amorphous silicates, which are extremely susceptible to aqueous alteration, t his is p resumed to be t he most primitive lithology. The contact between L2 and phyllosilicate-bearing lithologies (L5 and L6) with clear boundaries indicates that they were aggregated after aqueous alteration of L5 and L6. The indistinct boundary between L 1 and L2 is suggesting that these two lithologies might originally be the same aggregate composed of amorphous silicates and coarse mineral grains. L 1 might have experienced weak aqueous alteration followed by mild thermal alteration [2], while L2 did not undergo aqueous alteration.

Miyama, Sugimoto↗

NASA NTRS2017

An Overview of Communications Technology and Development Efforts for 2015 SBIR Phase I

This report highlights innovative SBIR 2015 Phase I projects specifically addressing areas in Communications Technology and Development which is one of six core competencies at NASA Glenn Research Center. There are fifteen technologies featured with emphasis on a wide spectrum of applications such as novel solid state lasers for space-based water vapor dial; wide temperature, high voltage and energy density capacitors for aerospace exploration; instrument for airborne measurement of carbonyl sulfide; high-power tunable seed laser for methane Lidar transmitter; ROC-rib deployable ka-band antenna for nanosatellites; a SIC-based microcontroller for high-temperature in-situ instruments and systems; improved yield, performance and reliability of high-actuator-count deformable mirrors; embedded multifunctional optical sensor system; switching electronics for space-based telescopes with advanced AO systems; integrated miniature DBR laser module for Lidar instruments; and much more. Each article in this booklet describes an innovation, technical objective, and highlights NASA commercial and industrial applications. space-based water vapor dial; wide temperature, high voltage and energy density capacitors foraerospace exploration; instrument for airborne measurement of carbonyl sulfide; high-power tunable seed laser formethane Lidar transmitter; ROC-rib deployable ka-band antenna for nanosatellites.

space-based water vapor dial; wide temperature↗

NASA NTRS2017

Highly Reducing Partitioning Experiments Relevant to the Planet Mercury

With the data returned from the MErcury Surface Space ENvironment GEochemistry and Ranging (MESSENGER) mission, there are now numerous constraints on the physical and chemical properties of Mercury, including its surface composition. The high S and low FeO contents observed from MESSENGER on the planet's surface suggests a low oxygen fugacity of the present planetary materials. Estimates of the oxygen fugacity for Mercurian magmas are approximately 3-7 log units below the Iron-Wüstite (Fe-FeO) oxygen buffer, several orders of magnitude more reducing than other terrestrial bodies we have data from such as the Earth, Moon, or Mars. Most of our understanding of elemental partitioning behavior comes from observations made on terrestrial rocks, but Mercury's oxygen fugacity is far outside the conditions of those samples. With limited oxygen available, lithophile elements may instead exhibit chalcophile, halophile, or siderophile behaviors. Furthermore, very few natural samples of rocks that formed under reducing conditions are available in our collections (e.g., enstatite chondrites, achondrites, aubrites). With this limited amount of material, we must perform experiments to determine the elemental partitioning behavior of typically lithophile elements as a function of decreasing oxygen fugacity. Experiments are being conducted at 4 GPa in an 880-ton multi-anvil press, at temperatures up to 1850degC. The composition of starting materials for the experiments were selected for the final run products to contain metal, silicate melt, and sulfide melt phases. Oxygen fugacity is controlled in the experiments by adding silicon metal to the samples, using the Si-SiO2 oxygen buffer, which is approximately 5 log units more reducing than the Fe-FeO oxygen buffer at our temperatures of interest. The target silicate melt compositional is diopside (CaMgSi2O6) because measured surface compositions indicate partial melting of a pyroxene-rich mantle. Elements detected on Mercury's surface by MESSENGER (K, Na, Fe, Ti, Cl, Al, Cr, Mn, U, Th) and other geochemically relevant elements (P, F, H, N, C, Co, Ni, Mo, Ce, Nd, Sm, Eu, Gd, Dy, Yb) are added to the starting composition at trace abundances (approximately 500 ppm) so that they are close enough to infinite dilution to follow Henry's law of trace elements, and their partitioning behavior can be measured between the metal, silicate, and sulfide phases. The results of these experiments will allow us to assess the thermal and magmatic evolution of the planet Mercury from a geochemical standpoint.

Rowland, Rick, II↗

NASA NTRS2015

Quantum Dots Microstructured Optical Fiber for X-Ray Detection

A novel concept for the detection of x-rays with microstructured optical fibers containing quantum dots scintillation material comprised of zinc sulfide nanocrystals doped with magnesium sulfide is presented. These quantum dots are applied inside the microstructured optical fibers using capillary action. The x-ray photon counts of these fibers are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The results of the fiber light output and associated effects of an acrylate coating and the quantum dots application technique are discussed.

DeHaven, S. L.↗

NASA NTRS2017

Chemical and Microstructural Changes in Metallic and Ceramic Materials Exposed to Venusian Surface Conditions

The chemical and microstructural behavior of steels (304, 310, 316, and 1018), nickel-based alloys (beta-NiAl, G30, and 625), gold, coatings (4YSZ, SilcoNert(TradeMark) 1040 (SilcoTek Co.), Dursan(TradeMark) (SilcoTek Co.), and porcelain), and bulk ceramics (alpha-Al2O3, fused quartz, beta-SiC, and alpha-Si3N4) were probed after exposure to supercritical fluid with temperature, pressure, and composition mimicking the Venus lower atmosphere. Exposures were carried out in the Glenn Extreme Environments Rig (GEER) chamber with the Venusian gas mixture (96.5% CO2, 3.5% N2, 30 ppm H2O, 150 ppm SO2, 28 ppm CO, 15 ppm OCS, 3 ppm H2S, 0.5 ppm HCl, and 5 ppb HF) at 92 bar (1330 psi) and 467 C (873 F) for durations of 10 and 42 days. An additional 21-day exposure was done to stainless steel uncoated and coated with SilcoNert(TradeMark) and Dursan(TradeMark). Samples were characterized before and after the experiment by gravimetric analysis, X-ray diffraction, X-ray photoelectron and Auger electron spectroscopies, and cross section electron microscopy analysis. All steels exposed for 10 and 42 days formed double-layered scales consisting mainly of metal (Cr, Fe, Ni) oxides and sulfides showing different chemistry, microstructure, and crystalline phases. The alloys G30 and 625 formed double-layered scales consisting mainly of nickel sulfides. After 10 days, the beta-NiAl exhibited no detectable scale, suggesting only a very thin film was formed. The 304 and 316 stainless steels coated with 4YSZ that were exposed for 10 and 42 days exhibited no significant oxidation. Steel 1018 coated with 4YSZ exhibited a corrosion scale of iron and/or chromium oxide formed at the base of the alloy. The 304 steel coated with porcelain did not exhibit corrosion, although the coating exhibited recession. SilcoNert(TradeMark) exposed for 10 and 42 days exhibited recession, although no oxidation was found to occur at the base of the alloy. Stainless steel 316 coated with Dursan(TradeMark)  exhibited corrosion at the base of the alloy. All ceramics tested showed no clear evidence of reaction. The weight-gain-per-area performance of the materials exposed in the GEER for 10 and 42 days are reported from the lowest to the highest weight gain per area as follows: gold did not exhibit any weight change; nickel-based alloys: beta- NiAl < G30 < 625; steels: 304 < 310 < 316 < 1018; ceramics: considering the experimental uncertainties, no weight change was observed for all ceramics of this work (alpha-Al2O3, Si3N4, SiC, and amorphous SiO2).

Costa, Gustavo C. C.↗

NASA NTRS2015

Sulfur and Metal Fertilization of the Lower Continental Crust

Mantle-derived melts and metasomatic fluids are considered to be important in the transport and distribution of trace elements in the subcontinental lithospheric mantle. However, the mechanisms that facilitate sulfur and metal transfer from the upper mantle into the lower continental crust are poorly constrained. This study addresses this knowledge gap by examining a series of sulfide- and hydrous mineral-rich alkaline mafic-ultramafic pipes that intruded the lower continental crust of the Ivrea-Verbano Zone in the Italian Western Alps. The pipes are relatively small (<300 m diameter) and primarily composed of a matrix of subhedral to anhedral amphibole (pargasite), phlogopite and orthopyroxene that enclose sub-centimeter-sized grains of olivine. The 1 to 5 m wide rim portions of the pipes locally contain significant blebby and disseminated Fe-Ni-Cu-PGE sulfide mineralization.Stratigraphic relationships, mineral chemistry, geochemical modeling and phase equilibria suggest that the pipes represent open-ended conduits within a large magmatic plumbing system. The earliest formed pipe rocks were olivine-rich cumulates that reacted with hydrous melts to produce orthopyroxene, amphibole and phlogopite.Sulfides precipitated as immiscible liquid droplets that were retained within a matrix of silicate crystals and scavenged metals from the percolating hydrous melt. New high-precision chemical abrasion TIMS-UPb dating of zircons from one of the pipes indicates that these pipes were emplaced at 249.1+/-0.2 Ma, following partial melting of lithospheric mantle pods that were metasomatized during the Eo-Variscan oceanic to continental subduction (approx. 420-310 Ma). The thermal energy required to generate partial melting of the metasomatized mantle was most likely derived from crustal extension, lithospheric decompression and subsequent asthenospheric rise during the orogenic collapse of the Variscan belt (<300 Ma). Unlike previous models, outcomes from this study suggest a significant temporal gap between the occurrence of mantle metasomatism, subsequent partial melting and emplacement of the pipes.We argue that this multi-stage process is a very effective mechanism to fertilize the commonly dry and refractory lower continental crust in metals and volatiles. During the four-dimensional evolution of the thermo-tectonic architecture of any given terrain, metals and volatiles stored in the lower continental crust may become available as sources for subsequent ore-forming processes, thus enhancing the prospectivity of continental block margins for a wide range of mineral systems.

Marek Locmelis↗

NASA NTRS2018

Calculating the Modal Mineralogy of Aubrite Meteorites Using X-Ray Computed Tomography

The aubrites are a group of differentiated meteorites that formed in extremely reducing conditions, with oxygen fugacities (ƒO2) ranging from ~2 to ~6 log units below the Iron-Wüstite buffer. At these extreme conditions, elements that are lithophile (silica-loving) on Earth can behave as chalcophiles (sulfur-loving) or siderophiles (metal-loving), and FeO-poor silicates and exotic sulfides can form. Elemental partitioning among minerals at these conditions are still not well understood, thus studying aubrites could help better constrain elemental behavior. Only 30 aubrites exist; however, they display various textures, which can be difficult to identify in small samples. Identifying composite clasts can help in understanding the igneous history of the aubrite parent bodies. In order to distinguish different minerals and textures in larger samples, we use X-ray computed tomography (XCT), which is a useful, non-destructive analysis that can produce a 3D representation of a meteorite's textures, structures, and modal mineralogy. This study investigates the Norton County aubrite using XCT. Norton County is a fragmental impact breccia aubrite, and was an observed fall with a main mass of 1.1 tons. This large amount of material offers an opportunity to investigate a great volume of reduced, aubritic sample and study a more diverse variety of clasts. Here we report XCT results of two samples of Norton County (NC 15417) in order to constrain the 3D modal mineralogy of silicates, sulfides, and metals, and to identify unique clasts within the matrix.

Wilbur, Zoe↗

NASA NTRS2018

Relative Sputtering Rates of FeS, MgS, and Mg Silicates: Implications for ISM Gas Phase Depletions of Rock-Forming Elements

Astronomical measurements of S abundances in the diffuse interstellar medium (ISM) indicate ionized S is a dominant species with little (< 5%) S residing in grains (e.g. Jenkins 2009). This is an enigmatic result, given that abundant Fe-sulfide grains are observed in dust around pre- and post-main sequence stars and are also observed as major components of primitive meteoritic and cometary samples. These disparate observations suggest that the lifetime of sulfide grains in the ISM is short because of destruction processes. Our previous work has shown that FeS and MgS retain their crystallinity and do not amorphize during radiation processing, whereas enstatite and forsterite are readily amorphized. We have extended this study to measure the relative sputtering rates of FeS and MgS compared to enstatite and forsterite. Irradiation of FeS with 4 keV He+ results in preferential sputtering of S and the formation of a thin 2-3 nm, compact Fe metal layer that armors the surface. The zone of S loss extends to a depth of ~8-10 nm below the exposed surface. Despite this S loss, the FeS retains its crystallinity and shows no sign of incipient amorphization. Irradiation of FeS with 5kV Ga+ in a focused ion beam (FIB) instrument resulted in preferential sputtering of S and the formation of a 5-8-nm thick surface layer of nanophase Fe metal. X-ray mapping shows that the zone of S sputtering extends to a depth of nearly 20 nm, but there is no evidence for FeS amorphization, consistent with our previous work. The irradiation experiments show that the relative sputtering rate of FeS and MgS are much higher than olivine or enstatite. Sputtering experiments utilizing 30 kV and 5 kV Ga ions in the FIB produced volume loss in troilite that was ~4X greater than in enstatite or forsterite. The sputter yield under these conditions is such that for every Si atom sputtered from enstatite, ~14 S atoms are sputtered from FeS. We have performed similar sputtering experiments on Fe-bearing niningerite (MgS) and co-existing enstatite from the ALH 84170 EH3 chondrite. MgS also sputters much more rapidly than enstatite with a relative Si:S sputter yield of 1:8. For MgS, sulfur is highly depleted at the surface and the S-depletion zone extends to a depth of ~15 nm (using 5 kV Ga+). There is a corresponding zone of Mg and especially Fe enrichment that extends from 5 to ~10 nm below the surface, respectively. The dominant grain destruction mechanism in the ISM is sputtering from passage of supernova-generated shock waves. This process also results in the amorphization of crystalline silicates in the ISM. Our results indicate that FeS and MgS grains produced in evolved stars and injected into the ISM will be destroyed more rapidly than crystalline silicates. This process may account for the lack of significant depletion of S from the gas phase in the ISM. However, rare nanophase FeS grains occur as inclusions in circumstellar amorphous silicate grains found in comet dust particles analyzed in the laboratory. These results show that a finite amount of S in the ISM is sequestered in solid grains.

SPUTTERING RATES↗

NASA NTRS2019

Space Weathering Maps of (101955) Bennu Using a Radiative Transfer Model

Space weathering is an important process that affects the surfaces of airless bodies, such as (101955) Bennu. The consequences of this process include physical and chemical changes to materials on the surface, which in turn change spectral characteristics, especially in the visible to near infrared wavelengths. These spectral changes are not the same across airless bodies because the changes are dependent on the composition and mineralogy of the surface and even location within the Solar System. The main space weathering products responsible for these spectral changes are submicroscopic particles, which consist of two types, nanophase and microphase particles, and affect visible to near-infrared reflectance spectra differently. Nanophase particles are particles <33 nm in size and occur in agglutinates and within glassy patinas around regolith particles. In contrast, microphase particles are >33 nm in size and are present only within agglutinates. These spectral differences are best illustrated by lunar samples. In lunar soils, the nanophase and microphase particles consist of metallic iron. With increasing abundance of nanophase iron particles in a regolith, its spectrum exhibits a lower overall reflectance in the visible to near infrared, weakened absorption bands, and a reddened continuum slope. In contrast, an increasing abundance of microphase iron only causes decreases in reflectance and not reddening. Because of the spectral differences introduced by these two types of particles, it is possible to model the nanophase and microphase particle abundances of a surface through the radiative transfer technique. Beyond the Moon, the composition of the nanophase and microphase particles can include other phases because the mineralogy of the surfaces of other planetary bodies is different. For example, the nanophase and microphase particles may consist of amorphous carbon (Mercury) and sulfides (Itokawa). The mineralogy of Bennu is consistent with carbonaceous chondrites. From a number of space weathering experiments on CM chondrites, the likely nanophase and microphase mineral phases on Bennu includes iron, magnetite, and sulfides (i.e., pentlandite and troilite). The goal of this work is to input the predicted nanophase and microphase compositions for Bennu into the radiative transfer technique. Next, we use this technique to model the OSIRIS-REx Visible Infrared Spectrometer (OVIRS) so that we can model the nanophase and microphase particle abundances across the surface. This will result in space weathering maps of the surface of Bennu, which are useful for understanding the degree of space weathering across the surface and its relationship to various regions and geological features.

Trang, D.↗

NASA NTRS2020

Chalcophile Element Constraints on the Sulfur Content of the Martian Mantle

The sulfur content of the Martian mantle is critical to understanding volcanic volatiles supplied to the surface of Mars and possibly climate. In the absence of Martian mantle rocks, sulfur content of the mantle has been inferred from S contents of Martian meteorites or from sedimentary sulfate abundances. Estimates of the sulfur content of the Martian mantle vary from 390-2,000 ppm, all of which are higher than that of the terrestrial mantle (~250 ppm;). Residual sulfide in the Martian mantle controls the distribution of chalcophile elements during partial melting. In this study, we report new analyses of Martian meteorites, and use the incompatible behavior of As, Tl and Pb to infer the sulfide mode of the Martian mantle using a different set of assumptions than those of prior studies.

Yang, S.↗

NASA NTRS2021

The Role of Hydrated Minerals and Space Weathering Products in the Bluing of Carbonaceous Asteroids

The surfaces of airless bodies such as lunar and S-type asteroids typically become spectrally redder in visible to near-infrared reflectance with longer exposures to space weathering. However, some carbonaceous asteroids instead become spectrally bluer. Space weathering experiments on carbonaceous meteorites have provided some clues as to the space weathering products that could produce spectral bluing. We applied these experimental results to our Hapke radiative transfer model, with which we modeled spectral data from the OSIRIS-REx mission in order to determine whether these space weathering products—specifically, nanophase and microphase metallic iron, troilite, and magnetite—could explain the globally blue spectrum of the carbonaceous asteroid (101955) Bennu. The model suggests that the surface of Bennu has microphase iron, nanophase magnetite, and nanophase and microphase troilite. Considering previous space weathering experiments together with our spectral modeling of Bennu, we posit that the presence of nanophase magnetite is what causes a carbonaceous asteroid to become spectrally bluer with exposure time. Nanophase magnetite can form on asteroids that have Fe-bearing hydrated minerals (phyllosilicates). On anhydrous carbonaceous asteroids, nanophase iron forms instead of magnetite, leading to spectral reddening. We therefore predict that samples returned by the OSIRIS-REx mission from Bennu will have more nanophase magnetite than nanophase iron with nanophase and microphase sulfides, whereas samples returned by the Hayabusa2 mission from the carbonaceous asteroid (162173) Ryugu, which is spectrally red, will contain nanophase and microphase sulfides as well as more nanophase iron than nanophase magnetite.

David Trang↗

NASA NTRSDate not supplied

Design Considerations for Practical Li-S Batteries for Electric Aviation

The development of high-energy, high-safety, and high-power batteries beyond electric automotive standards is critical for future electric aviation applications. Non-volatile solid-state electrolytes (SSE) offer many promising advantages over traditional flammable liquid electrolytes. Solid-state electrolytes may be an enabling technology for certain battery chemistries by preventing detrimental interactions with liquid electrolytes, for example prevention of the dissolution of intermediates in lithium-sulfur common in traditional liquid organic solvents. However, significant manufacturing challenges must be overcome before the adoption of such technology. This research was conducted to identify processing techniques for producing solid-state battery components with practical dimensions and weights for enabling high specific energy cells. Traditional research has identified a range of very high theoretical ionic conductivities but are impractical due to their instability or inability to be manufactured. Electrolytes explored in this study were produced as sulfide-polymer composites with densified thicknesses below 40 micron using a tape-casting technique and thermoplastic elastomer binder. The combination of high chemical compatibility and flexibility produced robust films that had moderate impact on the ionic conductivity but was capable of dramatically reducing the parasitic mass. Despite minimal conductivity losses, films were produced 10-15 times thinner than comparable bulk powder electrolytes thus leading to overall lower film resistance. Conductivity is maintained above 0.2mS/cm for composite electrolytes. Through the analysis of materials based on their physical properties, such as density, practical cells can be designed. Based on this, low density sulfide-solid-state electrolytes are a promising candidate for achieving the energy and safety metrics for electric aviation, however, further optimization of cathode microstructure and composite processing will be required to achieve the high power metrics and will be the focus of further studies. Additionally, fabrication challenges arise when utilizing metallic lithium foil, due to its soft nature, as overflow and mechanical short circuit can occur on assembly which remains a challenge to overcome before metallic lithium anodes can be fully realized.

batteries↗

NASA NTRSDate not supplied

Heterogeneity of Bulk Oxygen Isotopic Compositions in Anhydrous Interplanetary Dust Particles

Introduction: Anhydrous interplanetary dust particles are one of the least altered ancient solar systemmaterials. Their bulk chemical compositions match those of CI chondrites within a factor of 2-3, except for carbonwhich is enriched in both anhydrous and hydrated IDPs by ~4x CI [1]. Hydrous IDPs often show 16O-poor isotopiccompositions, likely due to the interaction with isotopically heavy H2O [2]. Anhydrous IDPs are interpreted tooriginate from comets from the outer solar system [3]. Oxygen isotopic data for these materials is scarce, but resultspoint to a wider range of compositions [4]. This heterogeneity might be a result of mixing between a 16O-rich and a16O-poor reservoir formed via self-shielding and photodissociation of CO [5]. Here, we report bulk oxygen isotopiccompositions of three anhydrous IDPs in context of their mineralogical composition and discuss possible origins ofisotopic heterogeneity. Experimental: Bulk chemical composition and mineralogy of 70 nm thin ultramicrotomed sections of threeanhydrous IDPs (L2099A7, L2099A8, and L2071AB1) were analyzed using a Thermo Scientific Titan Themis G360-300 TEM equipped with a four-quadrant energy-dispersive X-ray detector (Super-X G2) at University ofMünster. Bulk oxygen isotopic compositions were measured using a NanoSIMS 50 at the Max-Planck-Institut fürChemie in Mainz. A focused Cs+ ion beam (~1 pA, ~100 nm) was rastered over a field of view varying from 5 x 5 to6 x 6 μm2, depending on particle size for 15 layers. Negative secondary ions of 16O, 17O, 18O, 12C14N, and 28Si werecollected on electron multipliers. The 16OH contribution to the 17O peak was 1-2 ‰. As a standard, a matrix regionof meteorite CR2 Queen Alexandra Range (QUE) 99177 was used, whose oxygen isotopic composition wasmeasured by [6]. Results and Discussion: Particles A7 and A8 are both fine-grained, consisting mostly of small, 100 nm-sizedequilibrated aggregates (EA). Both particles exhibit discontinuous magnetite rims with thicknesses up to 50 nm inA7 and 100 nm in A8 on the outsides. In Particle AB1, the upper part of the particle consists of a few EAs, while thelower part contains lots of small GEMS grains with 100-200 nm diameter clustered together. Magnetite rims arenearly absent, the rare rims reaching maximum 20 nm thickness, indicating that AB1 is of more primitive naturethan the other two IDPs [1]. Furthermore, it contains several diffuse GEMS-like areas, identified by an amorphoussilicate groundmass with small nano-inclusions of Fe,Ni-metal and Fe-sulfides. All three particles are subsolar forall major element/Si ratios. Mean S/Si of particles A7 and A8 is 0.046 and 0.048, respectively, while it is an order ofmagnitude higher in AB1 (0.184). This reflects the higher degree of thermal alteration in A7 and A8, resulting in theloss of volatile S and oxidation of Fe-sulfides and FeNi-metal to magnetite as present in particle rims. A8 is rather16O-poor with δ17OSMOW = 7.8 ± 3.4 ‰ and δ18OSMOW = 9.5 ± 3.1 ‰ (1σ), followed by A7 with δ17OSMOW = − 0.8 ±4.6 ‰ and δ18OSMOW = −2.2 ± 3.4 ‰. In contrast to that, AB1 has the most 16O-rich bulk composition with δ17OSMOW= −24.2 ± 5.4 ‰ and δ18OSMOW = −25.3 ± 3.6 ‰. All investigated IDPs plot slightly above the CCAM line aspreviously reported for other anhydrous IDPs [4], maybe due to a contribution from circumstellar dust from AGBstars enriched in 17O [7]. The 16O-rich composition of AB1 is similar to the most 16O-rich anhydrous IDP U2015D21measured by [8] which is dominated by GEMS [9] and the GEMS-rich IDP GM4-2 reported by [10]. Nevertheless,it is unlikely that GEMS are the carrier for the 16O-rich composition of AB1 because most GEMS have O isotopiccompositions indistinguishable from terrestrial values, although errors on these analyses are large [11]. The isotopicheterogeneity is best explained by contribution of grains from different regions in the protoplanetary disk, samplingdifferent O isotope reservoirs, created by self-shielding and photodissociation of CO. This process resulted in 16O-rich CO gas and 16O-poor H2O that froze as ice-mantles onto dust grains [12]. Alternatively, the higher degree ofheating in A7 and A8 could have influenced isotopic fractionation, because higher δ17,18O values are reported fromthe regions of the atmosphere where small particles are heated and oxidized, as observed for the thermal alteration ofcosmic spherules [13]. Acknowledgements: We would like to thank NASA Astromaterials Acquisition & Curation Office for providing IDPsamples and DFG for funding this project (VO1816/5-1)

B Schulz↗

NASA NTRSDate not supplied

Dynamical Considerations of Hypothesized Vertically Stacked Meridional Circulation Cells in the Ice Giant Atmospheres

This study examines the dynamical implications of the vertically stacked meridional circulation structure hypothesized for the atmospheres of Uranus and Neptune. The existence of vertically stacked circulation cells was first hypothesized for Jupiter to explain the puzzling observation during Voyager and Galileo missions that Jupiter’s thunderstorms tend to erupt in regions where the atmosphere is expected to have enhanced static stability rather than reduced static stability. Since then, Juno has added a wealth of data, including the deep ammonia distribution, to add further context to this hypothesis. For the Ice Giant planets, a similar hypothesis for vertically stacked circulation was proposed to explain the meridional distribution of methane in the upper troposphere near the 1-bar level, and further hypothesized that Uranus and Neptune may harbor three layers of cells at depth driven by condensations of methane for the top cell, hydrogen sulfide-methane mixture for the middle cell, and ammonia-hydrogen sulfide-methane mixture for the lowest cell. This study examines the dynamical implications of the existence of such vertically stacked cells. Specifically, using the Eulerian Mean framework in the beta-plane, we derive the constraints for the eddy momentum flux, diabatic heating (i.e. latent heat), and eddy heat flux required to balance the vertically stacked circulation. Using these constraints, observable effects will be identified to guide future observations by the upcoming missions to Uranus and Neptune that may test the hypothesized vertically stacked circulation.

Kunio M Sayanagi↗

NASA NTRSDate not supplied

Mineralogical Analysis of Calcium-Aluminum-Rich Inclusions Provides Insight Into Post-Formation Processes

Introduction: Calcium-aluminum inclusions (CAIs) are cm- to mm-sized intergrowths of refractory phases found in chondritic meteorites [1]. Their mineral compositions closely match the compositions of the solids thought to condense from an extremely hot (>1500K) gas with a bulk solar composition [2-4], suggesting that CAIs were the earliest solids within the Solar System [2-4]. These inclusions provide invaluable insights into the conditions and dynamics of the early Solar System. CAIs must be transported from their formation region near the protosun to the chondrite parent-body accretion region. The nature of their journey could affect how, when, and where the secondary processes recorded in these CAIs occurred [4]. Did these secondary processes occur in the solar nebula or during accretion with the parent body, or both? How were the CAIs affected by varying thermochemical processes? To better answer these questions, we have undertaken an in-depth, textural study of the secondary alteration of select CAI samples. Methods: We chose three CAIs that experienced a range of post-formation processing to gain better understanding of secondary alteration based on previous preliminary examination [5]. Representative CAIs were chosen from NWA 5508 (CV3), NWA 12772 (CV3), and Coolidge (CL4) carbonaceous chondrites. We used scanning electron microscopy (SEM) and electron backscatter diffraction (EBSD) techniques for detailed chemical, mineralogical, and textural analysis of the CAIs. Backscattered electron (BSE) images and X-ray elemental maps were taken of Coolidge and NWA 5508 using the Lunar and Planetary Institute (LPI) Phenom SEM. The JEOL 7900F SEM at NASA Johnson Space Center (JSC) was used to obtain energy dispersive spectroscopy (EDS) chemical maps of all samples. High resolution EBSD analysis identified the mineral phases and textures, providing key information on their nature. Based on the SEM and EBSD data, minerals of interest were selected for quantitative chemical electron probe micro-analysis (EPMA) using the JEOL JXA-8530F at NASA JSC. Results and Discussion: The EDS maps show that the NWA 5508 and NWA 12772 CAIs designated “Saguaro” and “Hoopoe” respectively [5] are enriched in calcium while the Coolidge CAI designated “Cottonwood” is aluminum and magnesium rich. Saguaro. A ~1.5cm diameter igneous Type B CAI with a rounded shape. The dominant phases are melilite, spinel, and Al-Ti pyroxene with minor anorthite. Spinel is subhedral and occurs in clusters. Some of these clusters have a circular geometry which encloses other minerals, known as a palisade structure [6] (Fig. 1). Some palisades form near perfect circles while others are more irregular in shape. Melilite in Saguaro ranges in size from coarse (>250m) to fine-grained (5-7m) and forms intergrown laths. A third of the melilite grains exhibit simple twinning about their <001> axis. The spinel palisades and twinned melilite in Saguaro suggest an igneous history, and the lack of secondary minerals suggests minimal aqueous alteration. At some point in time after the initial condensation of the minerals and formation of the inclusion, the sample was remelted and quickly solidified. The formation of the palisades is still heavily debated. One hypothesis is that the palisades are the rims of smaller CAIs that accreted early on, essentially acting as xenoliths within the larger CAIs [7]. Another hypothesis suggests an igneous origin for palisade structures [6-8] wherein the melt traps gas bubbles, and the spinel nucleates on the surface of this bubble. Based on the WDS spot analyses of 41 melilite grains using EPMA, the data suggest that the composition inside and outside the palisades is nearly identical. This finding indicates that these palisades are likely not exogenous but rather formed from melt-vapor reactions. Our results are consistent with studies by Simon and Grossman,1997 [6] and Zhang et al. (2019) [8]. Hoopoe. A ~0.5cm compact Type A CAI with an irregular shape. The dominant mineral phases are melilite, spinel, and hibonite with minor amounts of anorthite, augite, and perovskite. The melilite ranges in size from ~500 to 50µm. The larger melilite grains have simple twinning along the <001> axis like melilite in Saguaro. Melilite in Hoopoe exhibits crystal-plastic strain with misorientation dominantly about the <010> and <110> axes. Spinel shows subhedral to euhedral morphology and appears in clusters. Hibonite grains are similar to spinel in habit and size but show more plastic strain. The two minerals are often found together with one appearing to replace the other. Perovskite appears in fine grained recrystallized regions alongside fine augite and spinel. The abundant strain and deformation features in the melilite and hibonite suggest that Hoopoe experienced shock. This shock could have occurred in the nebula [9] or from an impact of another body on the parent body asteroid. The appearance of fine-grained (<10m) areas of augite, perovskite, and spinel in the dominantly coarse-grained inclusion suggest recrystallization, possibly due to the sudden increase in pressure and temperature. Cottonwood. This ~0.5cm CAI exhibits distinct mineralogy and textures suggesting a high degree of alteration. It is irregular in shape. The dominant mineral phases are spinel and anorthite with minor amounts of augite and rutile. The two main texture types can be seen in Fig. 2. The first type consists of coarse euhedral to subhedral spinel and anorthite. The second includes fine grained spinel, anorthite, rutile, and iron sulfides. Within these fine-grained regions, the anorthite grains are clustered into domains exhibiting the same crystallographic orientation. Rutile exclusively occurs with fine anorthite indicating a potential relationship between the two. Cottonwood has a clear and unbroken Wark-Lovering [10] rim (Fig. 2) on one side that consists of a sequence of spinel followed by anorthite and an outer layer of augite. The abundance of the fine-grained regions containing iron oxides and iron sulfides, secondary phases such as rutile, and oriented anorthite grains is evidence for recrystallization associated with a high degree of thermal metamorphism. The EPMA analyses on both coarse- and fine-grained spinel show that the fine spinel grains are more enriched in Cr (1-2 wt. %) than their coarse counterparts (0.1-0.5 wt. %). The data suggest thermal metamorphism drove chemical exchange of the previously refractory inclusion, introducing chromium and iron as well as sulfur, which is moderately volatile. Conclusions: The three CAIs analyzed record distinct secondary nebular and parent body processes. Saguaro melted in the nebula as seen by the twinned melilite and spinel palisades. Hoopoe experienced intense shock which deformed its melilite and recrystallized perovskite, augite, and spinel in fine-grained regions. Cottonwood shows evidence of recrystallization and chemical changes consistent with thermal metamorphism occurring after accretion into the parent-body.

V E Burnette↗

DOE OSTI2020

Solid-state laminate electrode assemblies and methods of making

Solid-state laminate electrode assemblies and various methods for making the solid-state laminate electrode assemblies involve a lithium metal layer reactively bonded to a lithium ion conducting sulfide glass layer. During manufacture, highly reactive surfaces of the lithium metal layer and the lithium ion conducting sulfide glass layer are maintained in its substantially unpassivated state until they have been reactively bonded.

25 ENERGY STORAGE↗