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At least 433 records · Page 24

Is phosphorus predictably incompatible in igneous processes?

Siderophile element abundances are central to recent models for core formation in the Earth and Moon and the origin of the Moon. It is important to identify siderophile elements whose behavior in igneous processes is predictable, so that primary mantle abundances can be deduced by subtracting out the effects of igneous processes. Newsom's model for core formation in the Moon requires subchondritic P, and suggests that P was depleted due to volatility. Experiments were conducted to determine P olivine/liquid distribution coefficients. Preliminary results indicate that P can be compatible with olivine during rapid cooling, but is not during isothermal crystallization with long growth times, and tends to be expelled during annealing. It is therefore not likely that P is compatible under any widespread igneous conditions, and the incompatible behavior of P in lunar crustal rocks can be safety assumed. In addition, low fO2 is insufficient to cause P compatibility, so it is unlikely that P-rich silicates formed during the early evolution of the Earth or Moon. These results indicate that P is depleted in the Moon.

Goodrich, C. A.↗

Parameterization of the Vertical Variability of Tropical Cirrus Cloud Microphysical and Optical Properties

Cloud Integrating Nephelometers (CIN) were flown on the U. North Dakota Citation aircraft and the NASA WB-57 aircraft for the purpose of measuring in-situ the optical extinction coefficient and the asymmetry parameter (g) at a wavelength of 635 nm of primarily ice particles encountered during the NASA CRYSTAL-FACE study of large cumulus clouds (Cu) and their anvils found in the southern Florida region. The probes performance was largely successful and produced archived data for vertical profiles of extinction, asymmetry parameter, and effective radius (Re), the latter being obtained by combining CIN and CVI (total water; Oregon State U.) measurements. Composites of the CIN and CVI data describing the average microphysical and optical behavior of the Cu and their anvils showed the following: The extinction increases with height as a result of the size of the particles also decreasing with height as shown by the Re measurements; near the top of anvils the size of the primary ice particles is about 10-um radius; and the value of g does not vary significantly with height and has a mean value of about 0.73 consistent with the idea that ambient ice crystals are primarily of complex shape and reflect solar radiation more efficiently than particles of pristine crystal shape. Other observations include: The g measurements were found to be an indicator of the phase of the cloud permitting identification of the clouds with water droplets, rain, and ice; visual ranges as small as several tens of meters were occasionally found in "extinction cores" that coincided with strong updraft cores; and comparison of the cloud probes on the Citation showed significant disagreement.

Gerber, Hermann E.↗

Majorite-Garnet Partitioning of the Highly Siderophile Elements: New Results and Application to Mars

HSE and Os isotopes are used to constrain processes such as accretion, mantle evolution, crustal recycling, and core-mantle mixing, and to constrain the timing and depth of differentiation of Mars. Although showed that the HSE contents of the martian mantle could have been established by metal-silicate equilibrium in early Mars, the role of a cooling magma ocean and associated crystallization in further fractionating the HSEs is unclear. Garnet is thought to have played an important role in controlling trace element concentrations in the martian mantle reservoirs. However, testing these models, including Os isotopes, has been hindered by a dearth of partitioning data for the HSE in deep mantle phases - majorite, wadsleyite, ringwoodite, akimotoite - that may be present in the martian mantle. We examine the partitioning behavior of HSEs between majorite garnet (gt), olivine (oliv), and silicate liquid (melt).

Danielson, L. R.↗

Tuning Self-Assembly of Gold Nanoparticles Grafted with Charged Polymers by Varying Temperature and Electrolytes

Here, we report on the assembly of gold nanoparticles (AuNPs, 5 and 10 nm core diameters) grafted with poly(ethylene glycol) (PEG) terminated with either positively (–NH 2 ) or negatively charged (–COOH) end groups. We employ synchrotron-based small-angle X-ray scattering (SAXS) techniques to investigate the effect of electrolytes and temperature on the assembly and crystallization behavior of these grafted AuNPs. Our studies reveal that –NH 2 -grafted AuNPs spontaneously assemble into a layered hexagonal structure that deteriorates upon adding K 2 CO 3 to the suspension. The hexagonal structure recovers after heating the same suspension above 60 °C. On the other hand, the COOH-terminated AuNPs remain dispersed in the suspensions and assemble and crystallize into a face-centered cubic structure only in the presence of K 2 CO 3 at temperatures above 60 °C. Varying the pH of the –NH 2 -terminated AuNP suspensions induces short-range order (SRO) structures with a single characteristic length scale that shrinks upon heating. Similarly, SRO for the –COOH-terminated AuNP is realized only by lowering the pH. This study demonstrates the use of electrolytes and temperature on the surface charge of grafted AuNPs as knobs to tune self-assembly and crystallization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dispersive X-ray absorption spectroscopy using independent grazing-incidence focusing and convexly bent Bragg-crystal dispersing optics

We present a modular instrument for dispersive X-ray absorption spectroscopy (DXAS) developed for the Advanced Spectroscopy Beamline at Sector 25 of the Advanced Photon Source. The setup employs a double-multilayer monochromator to provide X-rays with a broad energy bandwidth, Kirkpatrick–Baez mirrors for focusing, a convexly bent Bragg-crystal polychromator for energy dispersion, and a pixel-array detector to resolve all X-ray energies and collect their intensity simultaneously, thereby enabling acquisition of a full X-ray absorption spectrum in a single shot. The use of separate optics for X-ray focusing and energy dispersion provides high spatial resolution and avoids chromatic aberrations inherent in focusing bent-crystal optics, and a modular design makes implementation of the technique at other beamlines possible without requiring modifications to the upstream beamline configurations. Theoretical calculations are performed to determine optimal instrument operating parameters and demonstrate that an energy resolution better than the K-edge core-hole lifetime broadening can be maintained while providing a sufficient bandwidth for X-ray absorption near-edge structure spectroscopy through the full operating range of 5–11 keV. Additionally, instrument design, data analysis methods, and initial DXAS results on lithium–manganese–nickel oxide laminates are presented.

47 OTHER INSTRUMENTATION↗

Phosphates in pallasite meteorites as probes of mantle processes in small planetary bodies

Trace element analyses of the phosphates minerals in stony-iron pallasite meteorites are used here to investigate the magmatic history of the silicate portions of pallasites. In Eagle Station and seven other pallasites, the phosphates have relatively low concentrations of REEs and are strongly enriched in heavy relative to light REE. These patterns are consistent with formation of phosphate by subsolidus reactions between metal and silicate, in which phosphate inherits the REE pattern of olivine. In Springwater and Santa Rosalia, calcium-rich phosphates have higher concentrations of REE, are enriched in light relative to heavy REE, and have negative europium anomalies. These patterns are consistent with crystallization of phosphate from a europium-depleted chondritic liquid. This is unlikely to have happened near the base of the differentiating parent-body mantle; it suggests that some pallasites may come from regions of their parent bodies much nearer the surface than the core-mantle boundary.

Davis, Andrew M.↗

Regional and Localized Deposits on the Moon

Earth-based telescopic remote sensing studies have provided important information concerning lunar pyroclastic deposits. Combined with the returned lunar sample studies and analyses of lunar photography, we have learned a great deal about the nature and origin of these explosive volcanic materials. Lunar pyroclastic deposits are more numerous, extensive, and widely distributed than previously thought. Two generic classes of lunar pyroclastics have been identified, regional and localized. From the former, two separate spectral compositional groups have been identified; one is dominated by Fe(2+)-bearing glasses, the other is composed of ilmenite-rich black spheres. Comparatively, three separate spectral groups have been identified among the localized deposits: highlands-rich, olivine-rich, and mare-rich. Returned sample studies and the recently collected Galileo and Clementine data also corroborate these findings. Albedo data and multispectral imagery suggest that the thicker core deposits of the regional dark mantle deposits (RDMD) are surrounded by pyroclastic debris and subjacent highlands material. The presence of a major component of pyroclastic debris in the regolith surrounding the core regional deposits has important implications for the resource potential of these materials. Both telescopic and orbital spectra indicate that the regional pyroclastic deposits are rich in iron, titanium and oxygen-bearing minerals. Particle shapes vary from simple glass spheres to compound droplets with quench crystallized textures. Their small grain size and friability make them ideal indigenous feedstock. Compared to other resource feedstock sources on the Moon, these pyroclastic materials may be the best oxygen resource on the Moon.

Coombs, Cassandra R.↗

Comparison of PID Shunting in Polycrystalline and Single-Crystal Silicon Modules via Multi-Scale, Multi-Technique Characterization

We used the methods we reported last year to investigate potential-induced degradation (PID). We have now applied these methods to single-crystalline silicon modules that have degraded during field deployment, as well as in minimodules stressed in the laboratory. We will compare these results to the polycrystalline results presented last year. Small cores have been removed from the modules and subjected to analysis. We use a combination of photoluminescence and dark lock-in thermography imaging, laser marking, electron-beam induced current measurements, and subsequent focused ion-beam marking to allow analysis of individual defects via time-of-flight secondary-ion mass spectrometry (TOF-SIMS) to investigate the root-cause mechanism for PID shunting. We see a direct correlation between recombination active shunts and sodium content. The sodium content in shunted areas peaks at the SiN/Si interface and is consistently observed at a concentration of 0.1%-1% in shunted areas. TOF-SIMS data taken on degraded and non-degraded single-crystalline sample areas show a similar trend as in the polycrystalline samples: more sodium is seen in the degraded areas.

14 SOLAR ENERGY↗

Crystal structure of aminopentamide hydrogen sulfate, (C 19 H 25 N 2 O)(HSO 4 )

The crystal structure of aminopentamide hydrogen sulfate has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Aminopentamide hydrogen sulfate crystallizes in space group P2 1 /c (#14) with a = 17.62255(14), b = 6.35534(4), c = 17.82499(10) Å, β = 96.4005(6)°, V = 1983.906(14) Å 3 , and Z = 4. The structure consists of layers parallel to the bc-plane with hydrogen sulfate anions at the core and aminopentamide cations on the outside. There is a strong charge-assisted O49–H53∙∙∙O52 hydrogen bond between the hydrogen sulfate anions. This hydrogen bond links the anions in a chain parallel to the b-axis. The cation forms a discrete N–H∙∙∙O hydrogen bond to the anion. The amide group also forms two weaker discrete hydrogen bonds to the anion. The three N–H∙∙∙O hydrogen bonds link the cations and anions into columns parallel to the b-axis. This commercial material from USP contained an unidentified impurity, the powder pattern of which could be indexed on a monoclinic unit cell. The powder pattern has been submitted to ICDD for inclusion in the Powder Diffraction File™ (PDF®).

36 MATERIALS SCIENCE↗

Emergence of Topologically Nontrivial Spin-Polarized States in a Segmented Linear Chain

The synthesis of new materials with novel or useful properties is one of the most important drivers in the fields of condensed matter physics and materials science. Discoveries of this kind are especially significant when they point to promising future basic research and applications. Van der Waals bonded materials comprised of lower-dimensional building blocks have been shown to exhibit emergent properties when isolated in an atomically thin form. Here, we report the discovery of a transition metal chalcogenide in a heretofore unknown segmented linear chain form, where basic building blocks each consisting of two hafnium atoms and nine tellurium atoms (Hf 2 Te 9 ) are van der Waals bonded end-to-end. First-principle calculations based on density functional theory reveal striking crystal-symmetry-related features in the electronic structure of the segmented chain, including giant spin splitting and nontrivial topological phases of selected energy band states. In this work, atomic-resolution scanning transmission electron microscopy reveals single segmented Hf 2 Te 9 chains isolated within the hollow cores of carbon nanotubes, with a structure consistent with theoretical predictions. Van der Waals-bonded segmented linear chain transition metal chalcogenide materials could open up new opportunities in low-dimensional, gate-tunable, magnetic and topological crystalline systems.

36 MATERIALS SCIENCE↗

Hybrid Ceramic-CMC Vane with EBC for Future Coal Derived Syngas Fired 65% Efficient Turbine Combined Cycle

The efficiency of both simple cycle and combined cycle power generation systems scale with the peak temperature at which the gas exits the combustor to drive the turbine. In conventional systems, a substantial fraction of the total turbine core flow exiting the compressor is diverted downstream to cool metallic turbine hardware rather than power the turbine, much of which is used to cool the first-stage turbine vane. The use of coal derived syngas fuels provides an additional challenge to the lifetime of materials utilized in the turbine, as particulate byproducts created in the coal gasification process melt in the combustion gas, and can subsequently deposit and interact with the turbine hardware. The development of durable hot-section materials capable of operating at temperature well above that of single crystal superalloy airfoil/zirconia based thermal barrier coatings is critical to realizing 65% efficient coal derived syngas fired gas turbine based power systems. To enable higher turbine inlet temperatures while lowering cooling air requirements, United Technologies Research Center (UTRC), the central R&D laboratory supporting UT Pratt & Whitney, led the conceptual design of a new type of ceramic composite turbine hot section materials system. The design focused on a novel hybrid monolithic ceramic-fiber reinforced ceramic matrix composite (CMC) first stage turbine vane having an environmental barrier coating. By utilizing ceramic construction in the turbine hot-section, the core flow normally used to cool metallic components will be substantially reduced, increasing efficiency and reducing emissions. To provide the framework for future demonstration testing, UTRC partnered with University of North Dakota Energy and Environmental Research Center (UNDEERC) to provide a conceptual design for a gasified coal fed high-pressure turbine combustor system designed to mimic the conditions expected in a future 65% fuel to busbar efficient syngas fueled gas turbine based combined cycle. The UNDEERC and UTRC collaborated on characterizing dusts from coal gasifier filtration systems.

10 SYNTHETIC FUELS↗

Metal-olivine associations and Ni-Co contents in two Apollo 12 mare basalts

Olivine crystals in mare basalts 12004,8 and 12022,12 are normally zoned with Cr-poor rims. The Ni content of rare 2- to 10-micron metal inclusions in olivine decreases markedly as Fe/Mg in their immediate olivine hosts increases. Each metal grain appears to have been enclosed by late olivine almost immediately after it crystallized. The fractionation trend for the olivine and metal contrasts with the subsolidus equilibration trend for pallasites. For the basalts, not even local equilibrium of Fe, Ni and Co at metal/olivine interfaces can be detected by microprobe. Ni and Co concentrations range from about 300 ppm in olivine cores to about 70 ppm in rims. The limits of detection, at 95% confidence, are 36 ppm (Ni) and 25 ppm (Co). The distribution of Ni and Co in olivine, like that of Mg and Cr, records the depletion of these elements in the melt.

Hewins, R. H.↗

Enrichment of Phosphates, Lead, and Mixed Soil–Organic Particles in INPs at the Southern Great Plains Site

Ice nucleating particles (INPs) are rare particles that initiate primary ice formation, a critical step required for subsequent important cloud microphysical processes that ultimately govern cloud phase and cloud radiative properties. Laboratory studies have found that organic-rich dusts, such as those found in soils, are more efficient INPs compared to mineral dust. However, the atmospheric relevance of these organic-rich dusts are not well understood, particularly in regions with significant agricultural activity. The Agricultural Ice nuclei at the Southern Great Plains field campaign (AGINSGP) was conducted in rural Oklahoma to investigate how soil dusts contribute to INP populations in the Great Plains. We present chemical characterization of ambient and ice crystal residual particles from a single day of sampling, using single particle mass spectrometry (SPMS) and scanning microscopy. Ambient particles were primarily carbonaceous or secondary aerosol, while the fraction of dust particles was higher in the residual particles. We also observed an unusual particle type consisting of a carbonaceous core mixed with dust fragments on the surface, which was found in higher proportion in residuals. Dust particles measured during residual sampling contained greater proportions of phosphate $(^{63}\text{PO}^-_2$ and $^{79}\text{PO}^-_3)$ and lead ( 206 Pb + ). Strong sulfate signals were not seen in the residual dust particles measured by the SPMS, while nitrate was slightly depleted relative to ambient dust. This study shows that organic-rich soils may be important contributors to the ambient INP population in agricultural regions.

54 ENVIRONMENTAL SCIENCES↗

Spectroscopic characterization of electronic structures of ultra-thin single crystal La0.7Sr0.3MnO3

Abstract We have successfully fabricated high quality single crystalline La 0.7 Sr 0.3 MnO 3 (LSMO) film in the freestanding form that can be transferred onto silicon wafer and copper mesh support. Using soft x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopy in transmission and reflection geometries, we demonstrate that the x-ray emission from Mn 3 s -2 p core-to-core transition (3 s PFY) seen in the RIXS maps can represent the bulk-like absorption signal with minimal self-absorption effect around the Mn L 3 -edge. Similar measurements were also performed on a reference LSMO film grown on the SrTiO 3 substrate and the agreement between measurements substantiates the claim that the bulk electronic structures can be preserved even after the freestanding treatment process. The 3 s PFY spectrum obtained from analyzing the RIXS maps offers a powerful way to probe the bulk electronic structures in thin films and heterostructures when recording the XAS spectra in the transmission mode is not available.

36 MATERIALS SCIENCE↗

Adapting High-Resolution X-Ray Microcalorimeter Spectrometers to Transform MFE Plasma Diagnostics

The aim of this project was to begin the transformation of magnetic fusion energy (MFE) X-ray diagnostics by applying detector technology developed over the past several decades by the astrophysics community. We installed and operated an X-ray microcalorimeter detector system under fusion-relevant plasma conditions at the Madison Symmetric Torus (MST). X-ray microcalorimeter spectrometers combine the best characteristics of instrumentation currently available on fusion devices: the high spectral resolution of crystal spectrometers (2 eV) and broadband coverage provided by pulse-height analysis systems. These spectrometers have small port-access requirements, a key advantage for future MFE experiments. This new plasma diagnostic technique will satisfy the need for multispecies impurity ion data by providing absolute measurements of impurity core accumulation, and it will provide the core impurity ion temperature. This project was a joint effort between Lawrence Livermore National Laboratory (LLNL) and researchers at the Wisconsin Plasma Physics Laboratory (WiPPl) at the University of Wisconsin–Madison (UW–Madison). Megan E. Eckart is the principal investigator at LLNL, which is funded separately from UW–Madison. This final report fulfills the reporting obligation of the UW–Madison effort.

Den Hartog, Daniel J. [Department of Physics, Univ↗

Diogenites: Cumulates from Asteroid 4 Vesta: Insights from Orthopyroxene and Spinel Chemistry

Cumulate rocks are important planetary lithologies, but they can be difficult to interpret. Important clues to the nature of their parental melts may still be present in the interiors of cumulus phases. However, in some cases, even the cores of the cumulus grains may have been modified by postcrystallization reactions with trapped melt and other cumulus phases. We have previously studied the major-, minor-, and trace-element chemistry of orthopyroxene from a suite of diogenites and concluded that their chemical attributes can best be explained by crystallization from parental melts that were derived from a depleted mantle source that had already experienced eucrite removal. However, we and others have had difficulty explaining the great range in concentration of minor elements (Al, Ti) and trace elements (REE, Y, Zr) if all diogenites were derived from a single magmatic system. Therefore, we have investigated the chemistry of diogenitic spinels to see if they still held clues to the diogenite parental melt compositions. Although spinel is low in abundance in diogenites (<5 vol%) it still may hold clues to the maomatic and metamorphic history of these rocks.

Papike, James J.↗