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At least 55 records · Page 3

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TPSAS-NF1676L-32099-DND

This talk provides a short overview of the new POWER web site that provides data parameters to energy sector societal benefit areas from NASA research projects. The NASA research projects include the GEWEX Surface Radiation Budget project, the CERES Fast Shortwave and Longwave radiative flux project (FLASHFlux) and NASA Goddard's Global Modeling and Assimilation Office (GMAO) MERRA-2 atmospheric reanalysis. Data products are customized to the energy industry and make products available from the daily time scale to long-term climatological averages. The web services allow uses to choose multiple parameters and obtain the data in multiple file formats. This short talk is designed to be delivered at the NASA booth area at the 2018 Fall American Geophysical Union conference.

Paul W Stackhouse, Jr.↗

A Plausible Prebiotic Path to Nucleosides: Ribosides and Related Aldosides Generated from Ribulose, Fructose, and Similar Abiotic Precursors

The prebiotic origins of ribose, nucleosides, and eventually RNA are enduring questions whose answers are central to the RNA world hypothesis. The abiotic synthesis of sugars was first demonstrated over a century ago, but no known prebiotic reaction produces ribose (an aldose sugar) selectively and in good yield. In contrast, ribulose, and fructose (ketose sugars) and other monosaccharides are formed in high yield by several robust abiotic reactions. It is reported here that ketose sugars - both ketopentoses and ketohexoes - serve as precursors for the formation of ribosides and other aldosides, as demonstrated by glycoside-forming reactions involving barbituric acid, a plausibly prebiotic nucleobase. Moreover, a one-pot reaction of glyceraldehyde and barbituric acid was discovered which under mild conditions, and without special minerals or other catalysts, results in the formation of glycosides. These results reveal that an exclusive or high-yielding generation of free ribose was not required for its incorporation into processes that provided the foundations for life.

Tyler P. Roche↗

Chemistry of Titanium Deposition Precursors for Area-Selective Deposition of Functionalized Silicon [Posters]

Area-selective atomic layer deposition (AS-ALD) is an appealing bottom-up fabrication technique that can produce atomic-scale device features, overcoming challenges in current industrial techniques such as edge alignment errors. TiCI 4 is a common thermal ALD precursor for Ti0 2 thin films, which are appealing candidates for DRAM capacitors due to their excellent dielectric constants. Hydrogen and chlorine termination passivate the Si surface, allowing for selective deposition of TiCI 4 onto HO-terminated areas. However, selectivity loss occurs after several ALD cycles. Ti oxide nucleates onto surface defects on Cl- and H-Si resists. Previously, the use of H-Si as an ALD resist has been studied extensively, but less work has focused on chemical forces driving nucleation, especially for Cl-Si. Here, formation of defect nuclei was investigated with selectivity loss during Ti0 2 ALD with TiCI 4 and water on the (100) and (111) crystal surfaces of hydrogenated, chlorinated, and oxidized Si.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subaru SCExAO First-Light Direct Imaging of a Young Debris Disk around HD 36546

We present H-band scattered light imaging of a bright debris disk around the A0 star HD 36546 obtained from the Subaru Coronagraphic Extreme Adaptive Optics (SCExAO) system with data recorded by the HiCIAO camera using the vector vortex coronagraph. SCExAO traces the disk from r approximately 0 3 to r approximately 0".3 to r approximately 1" (34-114 au). The disk is oriented in a near east west direction (PA approximately 75deg), is inclined by I approximately 70deg-75deg, and is strongly forward-scattering(g greater than 0.5). It is an extended disk rather than a sharp ring; a second, diffuse dust population extends from the disks eastern side. While HD 36546 intrinsic properties are consistent with a wide age range (t approximately 1-250 Myr), its kinematics and analysis of coeval stars suggest a young age (310 Myr) and a possible connection to Taurus-Aurigas star formation history. SCExAOs planet-to-star contrast ratios are comparable to the first-light Gemini Planet Imager contrasts; for an age of 10 Myr, we rule out planets with masses comparable to HR 8799 b beyond a projected separation of 23 au. A massive icy planetesimal disk or an unseen super-Jovian planet at r greater than 20 au may explain the disks visibility. The HD 36546 debris disk may be the youngest debris disk yet imaged, is the first newly identified object from the now-operational SCExAO extreme AO system, is ideally suited for spectroscopic follow-up with SCExAO/CHARIS in 2017, and may be a key probe of icy planet formation and planet disk interactions.

Subaru Coronagraphic Extreme Adaptive Optics (SCEx↗

2022 Cost of Wind Energy Review [Slides]

The 12th annual Cost of Wind Energy Review, now presented in slide deck format, uses representative utility-scale and distributed wind energy projects to estimate the levelized cost of energy (LCOE) for land-based and offshore wind power plants in the United States.

17 WIND ENERGY↗

Characterization of the radial microstructural evolution in LWR UO 2 using electron backscatter diffraction

Studies on high burnup UO 2 subjected to loss-of-coolant accident conditions have shown that restructured regions of the fuel are susceptible to pulverization and eventual dispersal. Due to a lack of pre-test characterization, the distinct microstructural features rendering the fuel prone to fragmentation remain ambiguous. Four samples of commercially irradiated light-water reactor UO 2 have been characterized utilizing electron backscatter diffraction to assess the susceptible microstructure. The microscopy focused on determining the burnup and temperature conditions responsible for the formation of the different microstructural regions where the regions were denoted as the high-burnup structure (HBS), HBS transition, mid-radial, restructured central, and central region. Previous works have outlined the specific conditions required for the restructuring of the microstructure into the HBS, but the conditions responsible for the restructuring in the central region of the fuel are not well understood. The four analyzed samples confirm a burnup threshold of 61 GWd/tU, and an unknown temperature range is needed to facilitate the formation of the restructured central region. In conclusion, additional fuel performance evaluations are needed to quantify the temperature range promoting restructuring in the central region.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Anion-dependent phase behavior of methylimidazolium-based ionic liquids mixed with water: Correlation between local molecular structure and mesoscale behaviors

The mesoscopic phase behavior of decylmethylimidazolium (C 10 mim) ionic liquids (ILs) bearing three monovalent anions—thiocyanate (SCN − ), nitrate (NO 3 − ), and chloride (Cl − )—mixed with water at relatively high IL contents (50–95 wt%) was investigated. Small-angle and wide-angle X-ray scattering (SAXS/WAXS) were employed to follow the evolution of both local and mesoscale structures across this composition range. In the absence of water, C 10 mimSCN and C 10 mimCl behaved as disordered liquids, whereas C 10 mimNO 3 spontaneously formed a hexagonally ordered cylindrical mesophase and displayed a sticky-solid macroscopic appearance. Upon addition of water, C 10 mimSCN remained a viscous liquid and only weakly ordered lamellar domains were observed. This limited ordering is attributed to the lack of hydrogen bonding and weak interaction energy between SCN − anions and C 10 mim + cations. In contrast, the trigonal-planar NO 3 − and point-like Cl − anions promoted the formation of well-defined hexagonal mesophases up to 35–45 wt% water. The formation of hydrogen bonding of the two anions with imidazolium ring protons likely enabled the creation of compact ion clusters that effectively exclude water molecules from the immediate vicinity of the IL aggregates. These findings demonstrate that the interaction energy between ion pairs dictate IL-water interactions and therefore control the transition from disordered liquids to ordered mesophases in IL/water mixtures with high IL contents. In conclusion, the combined SAXS/WAXS analysis reveals a correlation between local intermolecular structure and the emergence of mesoscopic order, providing a systematic framework for tailoring mesoscale structures in alkylimidazolium-based IL/water systems.

36 MATERIALS SCIENCE↗

Atmospheric Characterization and Further Orbital Modeling of κ Andromeda b

We present κ Andromeda b's photometry and astrometry taken with Subaru/SCExAO+HiCIAO and Keck/NIRC2, combined with recently published SCExAO/CHARIS low-resolution spectroscopy and published thermal infrared photometry to further constrain the companion's atmospheric properties and orbit. The Y/Y−K colors of κ And b are redder than field dwarfs, consistent with its youth and lower gravity. Empirical comparisons of its Y-band photometry and CHARIS spectrum to a large spectral library of isolated field dwarfs reaffirm the conclusion from Currie et al. that it likely has a low gravity but admit a wider range of most plausible spectral types (L0–L2). Our gravitational classification also suggests that the best-fit objects for κ And b may have lower gravity than those previously reported. Atmospheric models lacking dust/clouds fail to reproduce its entire 1–4.7 μm spectral energy distribution (SED), and cloudy atmosphere models with temperatures of ~1700–2000 K better match κ And b data. Most well-fitting model comparisons favor 1700–1900 K, a surface gravity of log(g) ~ 4–4.5, and a radius of 1.3–1.6 R (sub Jup); the best-fit model (Drift-Phoenix) yields the coolest and lowest-gravity values: T (sub eff) = 1700 K and log g = 4.0. An update to κ And b's orbit with ExoSOFT using new astrometry spanning 7 yr reaffirms its high eccentricity (0.77 ± 0.08). We consider a scenario where unseen companions are responsible for scattering κ And b to a wide separation and high eccentricity. If three planets, including κ And b, were born with coplanar orbits, and one of them was ejected by gravitational scattering, a potential inner companion with mass ≲10 M (sub Jup) could be located at ≲25 au.

Exoplanet astronomy↗

Photocarrier-induced persistent structural polarization in soft-lattice lead halide perovskites

The success of the lead halide perovskites in diverse optoelectronics has motivated considerable interest in their fundamental photocarrier dynamics. Here, in this work, we report the discovery of photocarrier-induced persistent structural polarization and local ferroelectricity in lead halide perovskites. Photoconductance studies of thin-film single-crystal CsPbBr 3 at 10 K reveal long-lasting persistent photoconductance with an ultralong photocarrier lifetime beyond 10 6 s. X-ray diffraction studies reveal that photocarrier-induced structural polarization is present up to a critical freezing temperature. Photocapacitance studies at cryogenic temperatures further demonstrate a systematic local phase transition from linear dielectric to paraelectric and relaxor ferroelectric under increasing illumination. Our theoretical investigations highlight the critical role of photocarrier–phonon coupling and large polaron formation in driving the local relaxor ferroelectric phase transition. Our findings show that this photocarrier-induced persistent structural polarization enables the formation of ferroelectric nanodomains at low temperature, which suppress carrier recombination and offer the possibility of exploring intriguing carrier–phonon interplay and the rich polaron photophysics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Experimental evaluation of direct current magnetron sputtered and high-power impulse magnetron sputtered Cr coatings on SiC for light water reactor applications

Two types of physical vapor deposition Cr coatings were deposited on chemical vapor deposited SiC coupons using conventional direct current magnetron sputtering (DCMS) and high-power impulse magnetron sputtering (HiPIMS) to mitigate the corrosion of SiC, an advanced fuel and structural material in light water nuclear reactor cores. Coating microstructure was characterized using scanning electron microscopy and scanning transmission election microscopy. X-ray diffraction analysis was conducted for phase identification and qualitative analysis of residual stresses. The mechanical integrity of the coatings was evaluated using scratch testing, micro-indentation, and nano-indentation tests. Additionally, the microstructure of the DCMS coating consisted of fine columnar grains with nanoscale intercolumnar channels, while the HiPIMS microstructure was denser and free of any columnar defects. The DCMS coating showed a small tensile residual stress, while the HiPIMS coating was under compressive stress. Both types of coatings showed good mechanical integrity in terms of ductility and adhesion to the substrate. Corrosion performance of the coatings was assessed with a 30-day high temperature water autoclave test. Both types of coatings formed a protective Cr 2 O 3 surface layer 20-30 nm thick during the autoclave test. In the DCMS coating, the columnar defects provided permeation pathways for water penetration resulting in oxide formation in the intercolumnar regions in the interior of the coating. Overall, both types of Cr coatings offer promise for the mitigation of hydrothermal corrosion of SiC in light water reactor operating environments.

36 MATERIALS SCIENCE↗

Photoluminescence Induced in Mineral Oil by Ionizing Radiation

We have studied photoluminescence (PL) properties of vacuum pump mineral oil as a function of the type and intensity of ionizing radiation exposure. The mineral oil has a simple aliphatic structure, which possesses no chromophore in the traditional sense. Unexpected PL in the mineral oil has characteristic features such as variation of the emission peak wavelength depending on the excitation wavelength and intensity dramatically increasing with radiation dose. The observed behavior can be understood in the framework of a previously suggested model introducing aggregation-induced PL and the formation of conjugated clusters comprising nontraditional chromophores. Our findings can be used for the development of optical sensors for real-time monitoring of oil utilized in vacuum pumps in nuclear fusion reactors.

Bliznyuk, Valery N.↗

Intragroup and Galaxy-linked Diffuse X-ray Emission In Hickson Compact Groups

Isolated compact groups (CGs) of galaxies present a range of dynamical states, group velocity dispersions, and galaxy morphologies with which to study galaxy evolution, particularly the properties of gas both within the galaxies and in the intragroup medium. As part of a large, multiwavelength examination of CGs, we present an archival study of diffuse X-ray emission in a subset of nine Hickson compact groups (HCGs) observed with the Chandra X-Ray Observatory. We find that seven of the groups in our sample exhibit detectable diffuse emission. However, unlike large-scale emission in galaxy clusters, the diffuse features in the majority of the detected groups are linked to the individual galaxies, in the form of both plumes and halos likely as a result of vigourous star formation or activity in the galaxy nucleus, as well as in emission from tidal features. Unlike previous studies from earlier X-ray missions, HCGs 31, 42, 59, and 92 are found to be consistent with the L(sub X-Tau) relationship from clusters within the errors, while HCGs 16 and 31 are consistent with the cluster L(sub X-sigma) relation, though this is likely coincidental given that the hot gas in these two systems is largely due to star formation. We find that L(sub X) increases with decreasing group Hi to dynamical-mass ratio with tentative evidence for a dependence in X-ray luminosity on Hi morphology whereby systems with intragroup Hi indicative of strong interactions are considerably more X-ray luminous than passively evolving groups. We also find a gap in the L(sub X) of groups as a function of the total group specific star formation rate. Our findings suggest that the hot gas in these groups is not in hydrostatic equilibrium and these systems are not low-mass analogs of rich groups or clusters, with the possible exception of HCG 62.

Desjardins, Tyler D.↗

A model for the evolution of CO2 on Mars

We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model. The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures greater than 250 K) and wet (surface pressures greater than 30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, less than 300 mbar in the regolith, and less than 5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (greater than 1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can have a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not form initially, but can form later on, when weathering and escape lower the surface pressure to a point at which polar heating is no longer sufficient to prevent cap formation and the collapse of the climate system. Our modeling suggests this critical initial amount of CO2 is between 1 and 2 bar, but its true value will depend on all factors affecting the polar heat budget.

Haberle, Robert M.↗

Residual stress accumulation in large-scale Ti-6Al-4V wire-arc additive manufacturing

Large-scale additive manufacturing (AM) is of interest in the manufacturing industry to produce components of dimensions on the order of hundreds of millimeters to meters in scale. Wire-arc AM (WAAM) of Ti-6Al-4V (Ti64) is an attractive technique for large-scale AM in the aerospace industry, give the high strength-to-weight ratio of the material and high deposition rate of the process. However, due to the large scale, significant distortion and residual stresses are developed in the material during deposition and cooling, potentially leading to part failure. WAAM of a prototypical large-scale Ti64 machine tool component is studied in this work via finite element analysis (FEA). Element activation/deactivation technique is employed to simulate deposition and the resulting distortion and residual stress (RS) predictions are analyzed to evaluate the possibility of crack formation. Significant distortion (∼10 mm) and RS (>1300 MPa) is predicted, suggesting the formation of cracks and possible crack propagation into the build region. Incorporation of fillets significantly reduces RS concentration regions, thus reducing the possibility of part failure. Material deposition sequence also affects the RS pattern in the build.

Mathews, Ritin↗

Anomalous Anisotropic Nanoparticle Aggregation in Cu 2 (OH) 3 Br Gels

Aerogels are of interest for their ability to uniformly incorporate nanoscale features into macroscopic assemblies, which enabled applications that require low density, high surface area, and/or bicontinuous networks. The structure of the nanoporous network is intrinsically linked to the macroscopic properties of aerogels. Hence, control of this structure is of paramount importance. Small-angle X-ray scattering (SAXS) is used here to monitor nanoparticle aggregation in situ in Cu 2 (OH) 3 Br aerogels formed via epoxide-assisted gelation. Anomalous anisotropic aggregation is observed in the absence of templating agents and is attributed to the molecular structure of the inorganic nanoparticles themselves. This is a fundamental departure from the models currently used to describe traditional inorganic sol–gel chemistry where nanoparticles are believed to undergo isotropic diffusion- and/or kinetically limited aggregation. Time-resolved SAXS indicates that Cu 2 (OH) 3 Br nanoparticles nucleate rapidly from solution to form unbranched chain-like aggregates rather than branched mass-fractal aggregates. Sizes of primary particles (~1.5 nm) and the chain-like structure of their aggregates are independent of particle concentration (gel density), while rates of particle aggregation, gelation time, and aggregate size are strongly dependent upon particle concentration, which implies that the chemistry of particle formation and the physics of particle aggregation are independent processes. Because the conditions necessary for creating anisotropic structures are not unique to Cu 2 (OH) 3 Br, these results could provide insight into the structure and gelation mechanisms of other inorganic aerogels.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural, Spectroscopic, and Kinetic Insight into the Heating Rate Dependence of Studtite and Metastudtite Dehydration

Uranyl peroxide minerals studtite (UO 2 O 2 ·4H 2 O) and metastudtite (UO 2 O 2 ·2H 2 O) are important materials in the nuclear fuel cycle. When heated, they dehydrate and transform to amorphous uranium oxides (UO x ), yet phase stability and heating rate dependence of these transformations are poorly understood. This information is critical to proper management of fuel cycle materials. In this work, we use in situ powder X-ray diffraction (PXRD), Raman spectroscopy, and thermogravimetric analysis (TGA) to monitor the dehydration of studtite and metastudtite. Strong linear correlation between the heating rate and phase transition temperature is observed. Geometric contraction and diffusion-related kinetic models describe studtite dehydration at slow heating rates, whereas Avrami–Erofeev or reaction order models become more accurate for faster thermal treatments. A second order model describes the transition from metastudtite to UO x regardless of the heating rate. Water retention during studtite dehydration is indicated by PXRD, Raman spectroscopy, and TGA. Here, we observe mixed-phase UO x dehydration products of metastudtite with a likely formation mechanism involving conversion of some uranyl centers from hexagonal to pentagonal bipyramidal coordination units via peroxide liberation. Our observations clarify over 100 years of measurements on these materials and represent an advancement in understanding the chemical behavior of nuclear fuel cycle materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A model for the evolution of CO2 on Mars

Our MSATT work has focused on the evolution of CO2 on Mars. We have constructed a model that predicts the evolution of CO2 on Mars from a specified initial amount at the end of the heavy bombardment to the present. The model draws on published estimates of the main process believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures that we calculate using a modified version of the Gierasch and Toon energy balance model. Various aspects of this work are covered.

Haberle, Robert M.↗