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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 109 records · Page 6

Phosphorus alleviation of nitrogen‐suppressed methane sink in global grasslands

Abstract Grassland ecosystems account for more than 10% of the global CH 4 sink in soils. A 4‐year field experiment found that addition of P alone did not affect CH 4 uptake and experimental addition of N alone significantly suppressed CH 4 uptake, whereas concurrent N and P additions suppressed CH 4 uptake to a lesser degree. A meta‐analysis including 382 data points in global grasslands corroborated these findings. Global extrapolation with an empirical modelling approach estimated that contemporary N addition suppresses CH 4 sink in global grassland by 11.4% and concurrent N and P deposition alleviates this suppression to 5.8%. The P alleviation of N‐suppressed CH 4 sink is primarily attributed to substrate competition, defined as the competition between ammonium and CH 4 for the methane mono‐oxygenase enzyme. The N and P impacts on CH 4 uptake indicate that projected increases in N and P depositions might substantially affect CH 4 uptake and alter the global CH 4 cycle.

Zhang, Lihua↗

The Surprising Occurrence of Non-Steady-State Growth of Divergent Lamellar Decomposition Products in Uranium-Niobium Alloys: A Preliminary Report

Metastable materials are all expected to decompose sooner or later, but sometimes the kinetic paths they travel confound standard textbook explanations. Such is the case for supersaturated uranium-niobium alloy microstructures that transform to lamellar products in the 300-647 ºC temperature range. An experimental study of these isothermal transformation kinetics is reported here for U-5.5Nb and U-7.5Nb alloys. About 85 specimens from each alloy were isothermally aged at eight temperatures for durations spanning five orders of magnitude, up to two years. The volume fractions and growth rates of fine-spacing discontinuous precipitation (DP) and coarse-spacing discontinuous coarsening (DC) lamellar reaction products were directly measured by quantitative metallography. This study was enhanced by explicit consideration of the DP initiation site during measurements: (1) prior matrix grain boundaries (the usual site found in every alloy that produces DP) and (2) carbide inclusions (a rarely-encountered site). This constitutes the first systematic study of inclusion-nucleated DP in any alloy system. The growth rates were measured by the robust method of Cahn and Hagel (1963). The measurements were taken across the entire span of fraction transformed, giving the best opportunity to discriminate between typical vs. anomalous growth behavior. In both alloys the growth rates for DP and DC are constant at the lowest aging temperatures (300-400ºC), in line with standard explanations. The growth rates, however, noticeably diminish with reaction time at the higher aging temperatures (450-625ºC), dropping by an order of magnitude or more. These results corroborate as-yet unpublished data of divergent lamellar spacings (i.e., increase of the spacing with reaction time) observed at the same higher aging temperatures. These surprising results are rationalized in terms of kinetic competition for chemical driving force between the lamellar and precursor nonlamellar reactions on comparable time scales. In previous studies divergent lamellar products occurred only in transformations involving diffusion of both interstitial and substitutional elements. Since the same phenomena are now seen in a purely substitutional system like U-Nb, it is likely that divergent and time-varying lamellar reactions may be more prevalent in other substitutional alloy systems than previously thought.

36 MATERIALS SCIENCE↗

Impact of modifier-rich coatings on the ionic transport of glasses [Poster]

Ionic conduction in silicate glasses is mainly influenced by the nature, concentration, and mobility of the network-modifying (NWM) cations. The electrical conduction in SLS is dominated by the ionic migration of sodium moving from the anode to the cathode. An activation energy for this conduction process was calculated to be 0.82eV and in good agreement with values previously reported. The conduction process associated to the leakage current and relaxation peak in TSDC for HPFS is attributed to conduction between nonbridging oxygen hole centers (NBOHC). It is suggested that ≡Si-OH = ≡Si-O - + H 0 under thermo-electric poling, promoting hole or proton injection from the anode and responsible for the 1.5eV relaxation peak. No previous TSDC data have been found to corroborate this mechanism. The higher activation energy and lower current intensity for the coated HPFS might be attributed to a lower concentration of NBOHC after heat treatment (Si-OH + OH-Si = SiO-Si + H 2 O). This could explain the TSDC signal around room temperature for the coated HPFS. Another possible explanation could be a redox reaction at the anode region dominating the current response.

36 MATERIALS SCIENCE↗

Non-Linear Langevin and Fractional Fokker–Planck Equations for Anomalous Diffusion by Lévy Stable Processes

The numerical solutions to a non-linear Fractional Fokker–Planck (FFP) equation are studied estimating the generalized diffusion coefficients. The aim is to model anomalous diffusion using an FFP description with fractional velocity derivatives and Langevin dynamics where Lévy fluctuations are introduced to model the effect of non-local transport due to fractional diffusion in velocity space. Distribution functions are found using numerical means for varying degrees of fractionality of the stable Lévy distribution as solutions to the FFP equation. The statistical properties of the distribution functions are assessed by a generalized normalized expectation measure and entropy and modified transport coefficient. The transport coefficient significantly increases with decreasing fractality which is corroborated by analysis of experimental data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Elucidating the nature of crystallization kinetics in Zr 46 Cu 46 Al 8 metallic glass through simultaneous WAXS/SAXS measurements

Simultaneous wide- and small-angle X-ray scattering (WAXS/SAXS) measurements were performed to investigate the low-temperature crystallization kinetics of Zr 46 Cu 46 Al 8 bulk metallic glass during isothermal annealing. Quantitative analysis of the WAXS intensity data indicated that the crystallization process was dominated by steady-state homogeneous nucleation and three-dimensional diffusion-controlled growth. This observation was corroborated by quantitative analysis of the SAXS data showing a saturation of the growth of nanoscale crystallites. Comparison of simultaneously measured WAXS and SAXS data showed evidence of composition fluctuation prior to crystallization, suggesting that the crystallization was facilitated by nanoscale phase separation which established regions of favorable compositions catalyzing crystallization. The temperature dependence of crystallization mechanisms and the resulting microstructures in metallic glass are discussed.

36 MATERIALS SCIENCE↗

Evaluation of material heterogeneity dosimetric effects using radiochromic film for COMS eye plaques loaded with {sup 125}I seeds (model I25.S16)

Purpose: (1) To measure absolute dose distributions in eye phantom for COMS eye plaques with {sup 125}I seeds (model I25.S16) using radiochromic EBT film dosimetry. (2) To determine the dose correction function for calculations involving the TG-43 formalism to account for the presence of the COMS eye plaque using Monte Carlo (MC) method specific to this seed model. (3) To test the heterogeneous dose calculation accuracy of the new version of Plaque Simulator (v5.3.9) against the EBT film data for this seed model. Methods: Using EBT film, absolute doses were measured for {sup 125}I seeds (model I25.S16) in COMS eye plaques (1) along the plaque's central axis for (a) uniformly loaded plaques (14-20 mm in diameter) and (b) a 20 mm plaque with single seed, and (2) in off-axis direction at depths of 5 and 12 mm for all four plaque sizes. The EBT film calibration was performed at {sup 125}I photon energy. MC calculations using MCNP5 code for a single seed at the center of a 20 mm plaque in homogeneous water and polystyrene medium were performed. The heterogeneity dose correction function was determined from the MC calculations. These function values at various depths were entered into PS software (v5.3.9) to calculate the heterogeneous dose distributions for the uniformly loaded plaques (of all four sizes). The dose distributions with homogeneous water assumptions were also calculated using PS for comparison. The EBT film measured absolute dose rate values (film) were compared with those calculated using PS with homogeneous assumption (PS Homo) and heterogeneity correction (PS Hetero). The values of dose ratio (film/PS Homo) and (film/PS Hetero) were obtained. Results: The central axis depth dose rate values for a single seed in 20 mm plaque measured using EBT film and calculated with MCNP5 code (both in ploystyrene phantom) were compared, and agreement within 9% was found. The dose ratio (film/PS Homo) values were substantially lower than unity (mostly between 0.8 and 0.9) for all four plaque sizes, indicating dose reduction by COMS plaque compared with homogeneous assumption. The dose ratio (film/PS Hetero) values were close to unity, indicating the PS Hetero calculations agree with those from the film study. Conclusions: Substantial heterogeneity effect on the {sup 125}I dose distributions in an eye phantom for COMS plaques was verified using radiochromic EBT film dosimetry. The calculated doses for uniformly loaded plaques using PS with heterogeneity correction option enabled were corroborated by the EBT film measurement data. Radiochromic EBT film dosimetry is feasible in measuring absolute dose distributions in eye phantom for COMS eye plaques loaded with single or multiple {sup 125}I seeds. Plaque Simulator is a viable tool for the calculation of dose distributions if one understands its limitations and uses the proper heterogeneity correction feature.

60 APPLIED LIFE SCIENCES↗

GlyQ-IQ: Glycomics Quintavariate-Informed Quantification with High-Performance Computing and GlycoGrid 4D Visualization

Dense LC-MS datasets have convoluted extracted ion chromatograms with multiple chromatographic peaks that cloud the differentiation between intact compounds with their overlapping isotopic distributions, peaks due to insource ion fragmentation, and noise. Making this differentiation is critical in glycomics datasets because chromatographic peaks correspond to different intact glycan structural isomers. The GlyQ-IQ software is targeted chromatography centric software designed for chromatogram and mass spectra data processing and subsequent glycan composition annotation. The targeted analysis approach offers several key advantages to LC-MS data processing and annotation over traditional algorithms. A priori information about the individual target’s elemental composition allows for exact isotope profile modeling for improved feature detection and increased sensitivity by focusing chromatogram generation and peak fitting on the isotopic species in the distribution having the highest intensity and data quality. Glycan target annotation is corroborated by glycan family relationships and in source fragmentation detection. The GlyQ-IQ software is developed in this work (Part 1) and was used to profile N-glycan compositions from human serum LC-MS Datasets. The companion manuscript GlyQ-IQ Part 2 discusses developments in human serum N-glycan sample preparation, glycan isomer separation, and glycan electrospray ionization. A case study is presented to demonstrate how GlyQ-IQ identifies and removes confounding chromatographic peaks from high mannose glycan isomers from human blood serum. In addition, GlyQ-IQ was used to generate a broad N-glycan profile from a high resolution (100K/60K) nESI-LS-MS/MS dataset including CID and HCD fragmentation acquired on a Velos Pro Mass spectrometer. 101 glycan compositions and 353 isomer peaks were detected from a single sample. 99% of the GlyQ-IQ glycan-feature assignments passed manual validation and are backed with high resolution mass spectra and mass accuracies less than 7 ppm.

Environmental Molecular Sciences Laboratory↗

Structural Interconversion between Agglomerated Palladium Domains and Mononuclear Pd(II) Cations in Chabazite Zeolites

Palladium-exchanged zeolites are candidate materials for passive NO x adsorption in automotive exhaust aftertreatment, where mononuclear Pd cations behave as precursors to the purported NO x adsorption sites. Yet, the structures of zeolite lattice binding sites capable of stabilizing mononuclear Pd 2+ ions, and the mechanisms that interconvert agglomerated PdO and Pd domains into mononuclear Pd 2+ ions during Pd redispersion treatments, remain incompletely understood. In this work, we use a suite of spectroscopic methods and quantitative site titration techniques to characterize mononuclear and agglomerated Pd species on zeolites with varying material properties and treatment history. Aqueous-phase methods to introduce Pd onto NH 4 -form zeolites initially form mononuclear [Pd(NH 3 ) 4 ] 2+ complexes, but subsequent thermal treatments (573–723 K; air) lead to in situ formation of H 2 that first reduces Pd 2+ to metallic Pd domains, which are then oxidized by air to PdO domains. Progressive treatment of Pd-zeolites in air to higher temperatures (723–1023 K) converts larger fractions of agglomerated PdO to mononuclear Pd 2+ , as quantified by H 2 temperature programmed reduction, because higher temperature treatments facilitate Pd redispersion toward deeper locations within chabazite (CHA) crystallites, which is corroborated by complementary titrimetric and spectroscopic data. Pd-CHA zeolites synthesized with similar bulk Pd and framework Al content, but varying framework Al arrangement, provide evidence that six-membered rings (6-MR) hosting paired Al sites (Al–O–(Si–O) x –Al, x = 1, 2) stabilize Pd 2+ ions and that otherwise isolated Al sites can stabilize [PdOH] + species, identifiable by an IR OH stretch at 3660 cm –1 . These findings clarify the underlying chemical processes and gas environments that cause Pd agglomeration in zeolites and their subsequent redispersion to mononuclear Pd 2+ ions, which prefer binding at 6-MR paired Al sites in CHA, and indicate that higher temperature air treatments lead to more uniform Pd spatial distributions throughout zeolite crystallites.

36 MATERIALS SCIENCE↗

Methyl quantum tunneling in ionic liquid [DMIm][TFSI] facilitated by Bis(trifluoromethane)sulfonimide lithium salt

Here, we probe, for the first time, quantum tunneling in the methyl groups of the ionic liquid [DMIm][TFSI] facilitated by the presence of Bis(trifluoromethane)sulfonimide lithium salt. The observation of tunneling is made possible by crystallization, rather than vitrification, of [DMIm][TFSI] at low temperature. Neutron scattering measurements detect quantum tunneling excitations at ~27 μeV at temperatures below 30 K in the presence of LiTFSI at a concentration of 1 mol/kg, but not in salt-free [DMIm][TFSI]. This indicates that the methyl rotational potential barrier is reduced by the presence of LiTFSI, thus bringing the tunneling excitations into the measurable range. The salt-induced reduction of the rotational barrier is corroborated by quasi-elastic scattering data associated with stochastic re-orientation of methyl groups measured between 40 and 60 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dimensional crossover of electron weak localization in ZnO/TiO{sub x} stacked layers grown by atomic layer deposition

We report on the dimensional crossover of electron weak localization in ZnO/TiO{sub x} stacked layers having well-defined and spatially-localized Ti dopant profiles along film thickness. These films were grown by in situ incorporation of sub-monolayer TiO{sub x} on the growing ZnO film surface and subsequent overgrowth of thin conducting ZnO spacer layer using atomic layer deposition. Film thickness was varied in the range of ∼6–65 nm by vertically stacking different numbers (n = 1–7) of ZnO/TiO{sub x} layers of nearly identical dopant-profiles. The evolution of zero-field sheet resistance (R{sub ◻}) versus temperature with decreasing film thickness showed a metal to insulator transition. On the metallic side of the metal-insulator transition, R{sub ◻}(T) and magnetoresistance data were found to be well corroborated with the theoretical framework of electron weak localization in the diffusive transport regime. The temperature dependence of both R{sub ◻} and inelastic scattering length provided strong evidence for a smooth crossover from 2D to 3D weak localization behaviour. Results of this study provide deeper insight into the electron transport in low-dimensional n-type ZnO/TiO{sub x} stacked layers which have potential applications in the field of transparent oxide electronics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Elevated nocturnal respiratory rates in the mitochondria of CAM plants: current knowledge and unanswered questions

Abstract Crassulacean acid metabolism (CAM) is a metabolic adaptation that has evolved convergently in 38 plant families to aid survival in water-limited niches. Whilst primarily considered a photosynthetic adaptation, CAM also has substantial consequences for nocturnal respiratory metabolism. Here, we outline the history, current state and future of nocturnal respiration research in CAM plants, with a particular focus on the energetics of nocturnal respiratory oxygen consumption. Throughout the 20th century, research interest in nocturnal respiration occurred alongside initial discoveries of CAM, although the energetic and mechanistic implications of nocturnal oxygen consumption and links to the operation of the CAM cycle were not fully understood. Recent flux balance analysis (FBA) models have provided new insights into the role that mitochondria play in the CAM cycle. Several FBA models have predicted that CAM requires elevated nocturnal respiratory rates, compared to C3 species, to power vacuolar malic acid accumulation. We provide physiological data, from the genus Clusia, to corroborate these modelling predictions, thereby reinforcing the importance of elevated nocturnal respiratory rates for CAM. Finally, we outline five unanswered questions pertaining to nocturnal respiration which must be addressed if we are to fully understand and utilize CAM plants in a hotter, drier world.

59 BASIC BIOLOGICAL SCIENCES↗

Fiber-Coupled Multipass NIR Sensor for In Situ, Real-Time Water Vapor Outgassing Monitoring

This work presents the recent development of a fiber-coupled multipass near-infrared (NIR) gas sensor used to monitor water vapor desorption of small material coupons. The gas sensor design employs a White cell topology to maximize the optical path length over a compact, hand-size footprint. Water vapor concentrations are quantified over a large dynamic range by simultaneously applying wavelength modulation and tunable diode laser absorption spectroscopy techniques. A custom headspace optimized for material desorption experiments is assembled using commercially available vacuum chamber components. We provide in situ measurements of water vapor desorption from two geometries of the industrially important silicone elastomer Sylgard-184 as a case study for sensor viability. To corroborate the results, the gas sensor data are compared to numerical simulations based on a triple-mode diffusion–sorption model, consisting of Henry, Langmuir, and Pooling modes.

gas sensor↗

Reactivity of a Carbon-Supported Single-Site Molybdenum Dioxo Catalyst for Biodiesel Synthesis

A single-site molybdenum dioxo catalyst, (O c ) 2 Mo(=O)2@C, was prepared via direct grafting of MoO 2 Cl 2 (dme) (dme = 1,2-dimethoxyethane) on high-surface-area activated carbon. The physicochemical and chemical properties of this catalyst were fully characterized by N 2 physisorption, ICP-AES/OES, PXRD, STEM, XPS, XAS, temperature-programmed reduction with H 2 (TPR-H 2 ), and temperature-programmed NH 3 desorption (TPD-NH 3 ). The single-site nature of the Mo species is corroborated by XPS and TPR-H2 data, and it exhibits the lowest reported MoO x T max of reduction reported to date, suggesting a highly reactive Mo VI center. (O c ) 2 Mo(=O) 2 @C catalyzes the transesterification of a variety of esters and triglycerides with ethanol, exhibiting high activity at moderate temperatures (60–90 °C) and with negligible deactivation. (O c ) 2 Mo(=O) 2 @C is resistant to water and can be recycled at least three times with no loss of activity. The transesterification reaction is determined experimentally to be first order in [ethanol] and first order in [Mo] with ΔH ‡ = 10.5(8) kcal mol –1 and ΔS ‡ = –32(2) eu. Here, the low energy of activation is consistent with the moderate conditions needed to achieve rapid turnover. This highly active carbon-supported single-site molybdenum dioxo species is thus an efficient, robust, and low-cost catalyst with significant potential for transesterification processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revealing Amphiphilic Nanodornains of Anti-Biofouling Polymer Coatings

Undesired bacterial adhesion and biofilm formation on wetted surfaces leads to significant economic and environmental costs in various industries. Amphiphilic coatings with molecular hydrophilic and hydrophobic patches can mitigate such biofouling effectively in an environmentally friendly manner. The coatings are synthesized by copolymerizing (Hydroxyethyl)methacrylate and perfluorodecylacrylate via initiated chemical vapor deposition (iCVD). In previous studies, the size of the patches was estimated to be similar to 1.4-1.75 nm by fitting protein adsorption data to a theoretical model. However, no direct observations of the molecular heterogeneity exist and therefore the origin of the fouling resistance of amphiphilic coatings remains unclear. Here, the amphiphilic nature is investigated by amplitude modulation atomic force microscopy (AM-AFM). High-resolution images obtained by penetrating and oscillating the AFM tip under the naturally present water layer with sub-nanometer amplitudes reveal, for the first time, the existence of amphiphilic nanodomains (1-2 nm(2)). Compositional heterogeneity at the nanoscale is further corroborated by a statistical analysis on the data obtained with dynamic AM-AFM force spectroscopy. Variations in the long range attractive forces, responsible for water affinity, are also identified. These nanoscopic results on the polymers wettability are also confirmed by contact angle measurements (i.e., static and dynamic). The unprecedented ability to visualize the amphiphilic nanodomains as well as sub-nanometer crystalline structures provides strong evidence for the existence of previously postulated nanostructures, and sheds light on the underlying antifouling mechanism of amphiphilic chemistry.

Amadei, CA↗

Historic and modern approaches for discovery of abandoned wells for methane emissions mitigation in Oil Creek State Park, Pennsylvania

Hundreds of oil wells were drilled along Oil Creek in Pennsylvania in the mid-16 1800s, birthing the modern oil industry. No longer in operation, many wells are now classified as abandoned, and, due to their age, their locations are either unknown or inaccurately recorded. These historic well sites present environmental, safety, and economic concerns in the form of possible methane leaks and physical hazards. Airborne magnetic and LiDAR surveys were conducted in the Pioneer Run watershed in Oil Creek State Park to find abandoned wells in a historically significant but physically challenging location. Wells were drilled in this area prior to modern geolocation and legal documentation. Although a large number of old wells were abandoned summarily without remediation of the site, much of the land area within Oil Creek State Park is now covered in trees and dense underbrush, which can obscure wellheads. The thick vegetation and steep terrain limited the possibility of ground-based surveys to easily find well sites for methane emissions studies. The data from remote sensing surveys were used to corroborate potential well locations from historic maps and photographs. Potential well sites were verified in a ground-based field survey and monitored for methane emissions. Two historic photographs documenting oil activity in the late 1800s were georeferenced using a combination of magnetic and LiDAR data. LiDAR data, which were more useful in georeferencing and in field verification, identified 290 field locations in the Pioneer Run watershed, 86% of which were possible well sites. Sixty-two percent of the ground-verified wells remained unplugged and comprised the majority of leaking wells. The mean methane emissions factor for unplugged wells was 0.027 ± 0.099 kg/day, lower than other Appalachian Basin methane emissions estimates. LiDAR was used for the first time, in combination with an airborne magnetic survey, to reveal underground oil industry features and inform well identification and remediation efforts in difficult-to-navigate regions. In the oldest oil fields, where well casing has been removed or wood conductor casing was installed, historic photographs provide additional lines of evidence for oil wells where ground disturbances have concealed surface features. Identification of well sites is necessary for mitigation efforts, as unplugged wells emit methane, a potent greenhouse gas.

02 PETROLEUM↗

Structural, Electronic, Optical, and Magnetic Properties of Fe{sub 3}Al Alloys

We have investigated the structural, optical, and magnetic properties of D0{sub 3} Fe{sub 3}Al alloys along with the electronic structure calculations. X-ray diffraction patterns confirm the single-phase cubic structure with a symmetry for the arc-melted samples. In the field dependence of magnetic data, ferromagnetic behavior is witnessed down to 2 K from room temperature. The electronic structure calculation corroborates the experimental observation of ferromagnetism in this alloy. Further, optical conductivity data in excellent agreement with the electronic structure calculations confirmed that electronic transitions are predominant by the 3d states of Fe.

36 MATERIALS SCIENCE↗

Origin of the lithium metal anode instability in solid-state batteries during discharge

Enabling the lithium metal anode (LMA) in solid-state batteries (SSBs) would increase energy density and specific energy compared with lithium-ion batteries. However, pore formation in LMAs with irregular morphology, even at low current density, during discharge results in an unstable, high-impedance interface. Understanding and addressing this inherent anode instability is essential for increasing the power densities in SSBs. Herein, we suggest that the morphology of the stripped electrode is related to dislocations in the LMA. To investigate the influence of dislocations, symmetric cells, Li|Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO)|X-Li, are studied, where X-Li represents the microstructurally controlled LMA obtained via suitable thermomechanical processing. Operando impedance measurements are corroborated with SEM, confocal microscopy, and AFM data. Based on the experimental observations, a mechanism for pore formation is proposed. Here we show that the stack pressure required to maintain a stable interface is governed by the lithium microstructure and its thermomechanical processing history.

25 ENERGY STORAGE↗