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At least 811 records · Page 45

A comparative study between real-world and laboratory accelerated aging of Cu/SSZ-13 SCR catalysts

Elucidating aging mechanisms in real-world applications is a critical component for developing and maintaining Cu/SSZ-13 SCR catalysts. To reveal gaps between laboratory accelerated aging and real-world aging, herein we report thorough comparative studies between 6 representative catalysts. Here, we apply a wide range of catalyst characterization methods, including surface area/porosity analysis, X-ray diffraction (XRD), H 2 -temperature programmed reduction, NH3-temperaure programmed desorption, solid-state nuclear magnetic resonance (NMR), in situ X-ray photoelectron (XPS) and electron paramagnetic resonance (EPR) spectroscopies, to gain atomic-level knowledge on Cu transformation under different aging protocols. We then correlate such knowledge to SCR, NH 3 /NO oxidation kinetic behavior of the catalysts. We found that sulfur aging plays the most important role in interpreting catalyst degradation during real-world application, including direct sulfur poisoning of isolated Cu II SCR active species to CuSO 4 -like species, the agglomeration of such species to multinuclear CuSO 4 clusters, and eventually, CuO formation during desulfation treatments. Such chemistries convert SCR active Cu to SCR inert Cu moieties without severely deteriorating catalyst support integrity. These characteristics are partially replicated by hydrothermal aging in the presence of SOx but are poorly mimicked by hydrothermal aging alone.

36 MATERIALS SCIENCE↗

Experimental Evidence and Mechanistic Description of the Phenolic H-Transfer to the Cu 2 O 2 Active Site of oxy-Tyrosinase

Tyrosinase is a ubiquitous coupled binuclear copper enzyme that activates O 2 towards the regioselective monooxygenation of monophenols to catechols via a mechanism that remains only partially defined. Here, we present new mechanistic insights into the initial steps of this monooxygenation reaction by employing a pre-steady state stopped-flow kinetics approach that allows direct measurement of the monooxygenation rates for a series of para-substituted monophenols by oxy-tyrosinase. The biphasic Hammett plot and the associated solvent kinetic isotope effect values provide direct evidence for an initial H-transfer from the protonated phenolic substrate to the Cu 2 O 2 core of oxy-tyrosinase. The correlation of these experimental results to quantum-mechanics/ molecular-mechanics calculations provides a detailed mechanistic description of this H-transfer step. Furthermore, these new mechanistic insights revise and expand our fundamental understanding Cu 2 O 2 active sites in biology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The source and origin of the exotic component and KREEP-rich materials on the moon

The enrichments of trace-element concentrations in lunar soils are attributed to the combined effects of comminution of local rocks and a preferential addition of the exotic component to finer grain sizes. The exotic component appears similar to Fra Mauro materials, and there is a strong correlation between the percentage of exotic component and distance from the Fra Mauro site. Based on trace-element characteristics, it is suggested that the exotic component is finely comminuted KREEP and is dispersed on the lunar surface from the Fra Mauro and other high gamma-ray active regions in the Imbrium-Procellarum regions. The major and trace-element chemistry of these materials is considered to be due to impact melting of trace-element-rich accessory phases followed by variable dilution with partial melts of the bulk solid phases of plagioclase, low-Ca pyroxene, and olivine. The generation of KREEP and the exotic component is an impact-produced local process and need not imply a global occurrence of radioactive crust on the moon.

Murthy, V. R.↗

Static Subspace Approximation for Random Phase Approximation Correlation Energies: Applications to Materials for Catalysis and Electrochemistry

Modeling complex materials using high-fidelity, ab initio methods at low cost is a fundamental goal for quantum chemical software packages. The GW approximation and random phase approximation (RPA) provide a unified description of both electronic structure and total energies using the same physics in a many-body perturbative approach that can be more accurate than generalized-gradient density functional theory (DFT) methods. However, GW/RPA implementations have historically been limited to either specific materials classes or application toward small chemical systems. Here, the static subspace approximation allows for reduced cost full-frequency GW/RPA calculations and has previously been benchmarked thoroughly for GW calculations. Here, we describe our approach to including partial occupations of electronic orbitals in full-frequency GW and RPA calculations for the study of electrocatalysts. We benchmarked RPA total energy calculations using the subspace approximation across a diverse test suite of materials for a variety of computational parameters. The benchmarking quantifies the impact of different extrapolation procedures for representing the static polarizability at infinite screened cutoff, and shows that using screened cutoffs above 20-25 Ryd result in diminishing accuracy returns for predicting RPA total energies. Additionally, for moderately sized electrocatalytic models, 2-3 times fewer computational resources are used to compute RPA total energies by representing the static polarizability with 20-30% of the static subspace basis, with an error of approximately 0.01 eV or better in RPA adsorption energy calculations. Finally, we show that for these electrochemical models RPA can shift DFT adsorption energy shifts by up to 0.5 eV and that GW can frequently shift DFT eigenvalues of surface and adsorbate states by approximately 0.5-1 eV.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Band gap and electronic structure of defects in the ternary nitride BP 3 N 6 : experiment and theory

Recent advances in methods to access nitride systems by a high-pressure high-temperature approach have made possible the one-step synthesis of mixed ternary non-metal nitrides. As a prerequisite to use in a practical device, it is important to understand important bulk electronic properties, such as the band gap, as well as characterizing the presence and effect of defects that are present. In this work, the novel ternary nitride BP 3 N 6 is studied using techniques sensitive to the partial electronic density of states, specifically X-ray absorption spectroscopy and X-ray emission spectroscopy. Complementary full-potential all-electron density functional theory (DFT) calculations allow important bulk electronic parameters, such as the band gap, to be elucidated. The band gap of BP 3 N 6 has been determined to be 3.9 ± 0.2 eV and 4.1 ± 0.4 eV at the B K- and N K-edges, respectively. This is close to a theoretical value of 4.3 eV predicted by the PBEsol exchange–correlation functional and considerably less than a value of 5.8 eV predicted by the modified Becke–Johnson exchange–correlation functional. X-Ray excited optical luminescence (XEOL) measurements are performed to interrogate the presence of point defects in this system. Together with DFT calculations, these measurements reveal the presence of nitrogen vacancies which lead to multiple mid-gap trap states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laser pulse driven control of charge and spin order in the two-dimensional Kondo lattice

Fast and dynamical control of quantum phases is highly desired in the application of quantum phenomena in devices. On the experimental side, ultrafast laser pulses provide an ideal platform to induce femtosecond dynamics in a variety of materials. Here we show that a laser pulse driven heavy fermion system can be tuned to dynamically evolve into a phase, which is not present in equilibrium. Using the state-of-the-art time-dependent variational Monte Carlo method, we perform numerical simulations of realistic laser pulses applied to the Kondo lattice model. By tracking spin and charge degrees of freedom we identify a dynamical phase transition, within the partially Kondo screened phase, from a charge ordered into a metallic state, while preserving the spin order of the system. Furthermore, we propose using high-harmonic generation and nonequilibrium optical conductivity to identify the dynamical phase transition in an ultrafast experiment.

36 MATERIALS SCIENCE↗

Predicting the Value of Adjuvant Therapy in Esophageal Squamous Cell Carcinoma by Combining the Total Number of Examined Lymph Nodes with the Positive Lymph Node Ratio

Background: The value of adjuvant therapy for esophageal squamous cell carcinoma (ESCC) has been controversial, at least partially due to the lack of efficient criteria for selecting suitable patients. This study aimed to explore the existence of parameters related to lymph node (LN) status that can predict the value of adjuvant therapy in ESCC. Methods: The study included 298 patients with ESCC who had undergone radical esophagectomy with lymphadenectomy. Adjuvant therapy was defined as reception of adjuvant chemotherapy, radiotherapy, or chemoradiotherapy. For the study, LN ratio (LNR), total number of resected LNs (TLNs), and pN stage were selected for Cox regression analyses, including their correlations and prognostic values for survival. Log-rank tests were used to compare the survival rates of the patients with and without adjuvant therapy stratified by pN stage, TLNs, LNR, or their combinations. Results: The independent prognostic factors for survival were TLNs, LNR, and pN stage. Whereas pN stage was significantly related to TLNs and LNR, TLNs were not correlated with LNR. The survival rates between the patients with and those without adjuvant therapy stratified by pN stage, TLNs, or LNR did not differ significantly. We used the median values of TLNs and LNR to group the patients into four groups. The patients in the group with fewer TLNs and higher LNR who had undergone adjuvant therapy showed a significantly better survival than those without adjuvant therapy (p = 0.030). Conclusions: In contrast to TLNs, LNR, and pN stage as single factors, the combination of TLNs and LNR can predict the value of adjuvant therapy.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Shock-implanted noble gases - An experimental study with implications for the origin of Martian gases in shergottite meteorites

The shock-implantation of gases is studied by artificially shocking whole rock and power samples of terrestrial basalt to pressures of 2-40 GPa. Ar, Kr, Xe, and Ne were implanted into the silicate. It is observed that the amount of implanted gas is linearly proportional to its partial pressure over a pressure range of 0.0001 to 0.1 atmosphere. The fractionation effect in the implanted gas and the gas diffusion properties are examined. The amounts of gas that would have been implanted with 100 percent efficiency are calculated from the measured porosities of the power samples and are compared to observed abundances. It is determined that the implantation efficiencies are approximately 0.5 percent at 2 GPa, 7 percent at 5 GPa, and greater than 50 percent at both 20 and 35 GPa. The experimental data correlate with the shock implantation of Martian gases without mass fractionation into the shock-melted phase of meteorite EETA 79001.

Bogard, Donald D.↗

Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements

We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCl, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approx.17-47 km) altitude range and over 10 degree latitude bins from 70degS to 70degN. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) 11 data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NO(y)) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and ClONO2; (2) from the N2O-NO(y) correlation, and (3) from the CH4-NO(y) correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NO(x)/NO(y) ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approx. 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45degS and 45degN are also presented. Our analysis indicates that ground-based and HALOE v. 18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45degS suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.

Danilin, M. Y.↗

Quantifying fission gas adsorption onto natural clinoptilolite in the presence of environmental air and water

Adsorption of noble gas fission products onto naturally occurring minerals is of interest for its potential to retain or retard emissions from nuclear fuel reprocessing operations or underground nuclear explosions. However, experimental studies of trace noble gas adsorption in the presence of air and water have largely focused on synthetic materials, such as activated carbon or metal-organic frameworks. Here, in this study, adsorption of Kr and Xe onto the naturally occurring zeolitic mineral clinoptilolite is studied in the presence of nitrogen and water. By varying the composition of the gas phase and monitoring the change in the combined adsorbate mass, the adsorbed concentration of noble gas is calculated gravimetrically. For dry clinoptilolite, the concentration of adsorbed Kr and Xe is linearly correlated with noble gas pressure and Henry's Law appears satisfactory, despite the presence of nitrogen at atmospheric pressures. However, the presence of water significantly reduces the adsorbed concentration of both Kr and Xe, which is typical in nanoporous sorbents. Here, an empirical bivariate model is presented, combining the Henry's Law adsorption model for a dry adsorbent with the exponential reduction in the presence of water, as reported by Lungu and Underhill in 1999. This model provides a means to estimate the adsorbate concentration at the trace partial pressures and higher water contents relevant to field-scale modeling of fission gas transport through the vadose zone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Using Complex Probability Amplitudes to Simulate Solute Transport in Composite Porous Media

Probability amplitudes are fundamental to quantum mechanics and offer robust descriptions of complicated systems, which have allowed physicists to explain behaviors inaccessible to classical physics. This article ponders how some of the same conceptual underpinnings of the mathematics used for modeling quantum systems might be applied to subsurface water resources problems and speculates how these tools could facilitate applications on quantum computers. A probability amplitude-based model for describing advective-dispersive transport in porous media using linear operators is investigated. The proposed complex valued model decomposes spreading into two “sub-continuum partial dispersion” coefficients, and this recovers classical spreading when the sum of these coefficients is the Fickian dispersion coefficient. However, the probability amplitudes have a manyto-one relationship to a probability distribution, so it embeds a level of heterogeneity into seemingly equivalent functions. Two propagators with different sub-continuum coefficients may have the same macroscopic behavior when either is considered in isolation, but when they act on the other the system’s behavior changes. Additionally, differences in the amplitudes cause a reduction in spreading as velocity correlations are disrupted, despite both propagators having identical dispersion coefficients, and this cannot be achieved using classical methods without changing the dispersion coefficient. The main point is that these amplitude-based models offer a way to embed information about the system into the propagators, instead of just “averaging it out” when making an upscaled model.

54 ENVIRONMENTAL SCIENCES↗

Capillary acquisition devices for high-performance vehicles: Executive summary

Technology areas critical to the development of cryogenic capillary devices were studied. Passive cooling of capillary devices was investigated with an analytical and experimental study of wicking flow. Capillary device refilling with settled fluid was studied using an analytical and experimental program that resulted in successful correlation of a versatile computer program with test data. The program was used to predict Centaur D-1S LO2 and LH2 start basket refilling. Comparisons were made between the baseline Centaur D-1S propellant feed system and feed system alternatives including systems using capillary devices. The preferred concepts from the Centaur D-1S study were examined for APOTV and POTV vehicles for delivery and round trip transfer of payloads between LEO and GEO. Mission profiles were determined to provide propellant usage timelines and the payload partials were defined.

Blatt, M. H.↗

Laser-Induced Fluorescence Measurements of Energetic Ions in a 100-A LaB6 Hollow Cathode

Increasingly long-duration space missions require a better understanding of the failure mechanisms of hollow cathodes to enable prediction of lifetime. Energetic ions have been measured in the plume of hollow cathodes but the energies are higher than can be explained classically. One of the mechanisms that appears to be contributing to the ion heating is ion acoustic turbulence (IAT), which has been investigated with plasma probes recently at JPL. In this work the ion velocity distribution has been measured using laser-induced fluorescence (LIF) at several high-current operating conditions on the centerline of a 100 A class hollow cathode at JPL. A retarding potential analyzer was (RPA) was used to measure the ion energy profile in the far plume and a Langmuir probe was used to measure electron temperature and plasma potential fluctuations. RPA energies are shown to correlate with the values measured by LIF. The ion temperature is shown to increase with distance downstream of the cathode. A parametric study of the ion heating as a function of discharge current and cathode flow rate was performed. It was found that for increasing current the ion temperature evolution did not vary even though the wave IAT wave energy increased. The effect of flow rate was more pronounced, with higher values reducing both ion temperature and wave energy linearly. These results indicate that IAT is at least partially responsible for energetic ion production in the hollow cathode plume.

Dodson, Christopher A.↗

A Novel Feature of Valence Quark Distributions in Hadrons

Examining the evolution of the maximum of valence quark distribution, qV, weighted by Bjorken x, h(x,t)≡xqV(x,t), it is observed that h(x,t) at the peak becomes a one-parameter function; h(xp,t)=Φ(xp(t)), where xp is the position of the peak, t=logQ2, and Q2 is the resolution scale. This observation is used to derive a new model-independent relation which connects the partial derivative of the valence parton distribution functions (PDFs) in xp to the quantum chromodynamics (QCD) evolution equation through the xp derivative of the logarithm of the function Φ(xp(t)). A numerical analysis of this relation using empirical PDFs results in an observation of the exponential form of the Φ(xp(t))=h(xp,t)=CeDxp(t) for leading to next-to-next leading order approximations of PDFs for the range of Q2, covering four orders in magnitude. The exponent, D, of the observed “height-position” correlation function converges with the increase in the order of approximation. This result holds for all the PDF sets considered. A similar relation is observed also for the pion valence quark distribution, indicating that the obtained relation may be universal for any non-singlet partonic distribution. The observed “height-position” correlation is used also to indicate that no finite number of exchanges can describe the analytic behavior of the valence quark distribution at the position of the peak at fixed Q2.

Leon, Christopher↗

Thermal system and environmental testing of the Mars Helicopter

The Mars Helicopter will be a technology demonstration conducted during the Mars 2020 mission. The primary mission objective is to achieve several 90-second flights demonstrating the feasibility of heavier than air flight on Mars and capture visible light images via forward and nadir mounted cameras. These flights could possibly provide reconnaissance data for sampling site selection for other Mars surface missions. A solar array and batteries for flight operations, imaging, communications, and survival heating power the Helicopter. The thermal design is driven by minimizing survival heater energy while maintaining compliance with allowable flight temperatures in a variable thermal environment. Due to the small size of the Helicopter and its complex geometries, along with the fact that it operates with very low power and small margins in the extreme Mars environment, additional care had to be paid while planning thermal tests and designing the thermal system. The first section of the paper describes the evolution of the thermal system of the Mars Helicopter. After the first thermal vacuum test of the engineering model, the thermal team has conducted a partial effect analysis on the thermal design components that had a major impact on the system performance. Several design choices derived by analysis and test have been made to meet the energy allocation and the temperature requirements. These changes included increased gas gaps to reduce gas conduction, low emissivity coatings for internal components, blanket implementation, optimization of wire routing and fine-tuning of surface operations to optimize waste heat recovery. The second part of the paper describes the flight model thermal vacuum test and the subsequent thermal model correlation necessary to confirm the fidelity of the analysis results.

Pauken, Michael↗

Experimental Study on the Effect of Localized Blockages on the Friction Factor of a 61-Pin Wire-Wrapped Bundle

Abstract The thermal-hydraulic behavior of the flow in rod bundles has motivated numerous experimental and computational investigations. Previous studies have identified potential for accumulation of debris within the small subchannels of typical wire-wrapped assemblies with subsequent total or partial blockage of subchannel coolant flow. A test campaign was conducted to study the effects of localized blockages on the bundle averaged friction factor of a tightly packed wire-wrapped rod bundle. Blockages were installed within the bundle, and fluid pressure drop was measured across one wire pitch for a Reynolds number range of 500–17,200. The Darcy–Weisbach friction factor of the perturbed rod bundle geometry was compared with that of the unblocked bundle, as well as with the predictions of a well-established friction factor correlation. Differing effects based on blockage size and location for various flow regimes were studied. A number of conclusions can be made about the effects of the blockages on the friction factor, such as an increasing effect of the blockage on friction factor with an increase in Reynolds number, a change in flow behavior in the turbulent transition flow regime near Reynolds number 3000, differences in effect on friction factor for different types of subchannel blockage, and a nonlinear trend in friction factor variation with flow area impeded for edge subchannels. To this end, all data and quantified uncertainty produced in this study are made available for comparison and validation of advanced computational tools.

Engineering↗

Left ventricular endocardial surface detection based on real-time 3D echocardiographic data

OBJECTIVE: A new computerized semi-automatic method for left ventricular (LV) chamber segmentation is presented. METHODS: The LV is imaged by real-time three-dimensional echocardiography (RT3DE). The surface detection model, based on level set techniques, is applied to RT3DE data for image analysis. The modified level set partial differential equation we use is solved by applying numerical methods for conservation laws. The initial conditions are manually established on some slices of the entire volume. The solution obtained for each slice is a contour line corresponding with the boundary between LV cavity and LV endocardium. RESULTS: The mathematical model has been applied to sequences of frames of human hearts (volume range: 34-109 ml) imaged by 2D and reconstructed off-line and RT3DE data. Volume estimation obtained by this new semi-automatic method shows an excellent correlation with those obtained by manual tracing (r = 0.992). Dynamic change of LV volume during the cardiac cycle is also obtained. CONCLUSION: The volume estimation method is accurate; edge based segmentation, image completion and volume reconstruction can be accomplished. The visualization technique also allows to navigate into the reconstructed volume and to display any section of the volume.

Non-NASA Center↗

The Multi-Stage History of Mt. Sharp

The Curiosity rover is exploring Gale crater and Mt. Sharp, Gale's 5‐km high central mound. We are investigating the history of alteration and erosion of Mt. Sharp using orbital imagery, spectroscopy and rover observations. Our results suggest a significant time gap between emplacement of the upper and lower sections of the mound. Crater counts show that the lower mound was formed soon after Gale itself, and that it contains distinct units ranging in altitude from approximately ‐4,500 to ‐1,800 m. Spectral data suggest that many units contain phyllosilicates. We found that these clay‐bearing rocks occur in distinct layers concentrated below ‐2,900 m. Parts of the lower mound exhibit a transition from clays to sulfates with increasing altitude. The lower mound shows evidence of flowing water, including canyons and inverted channels. Wind erosion produced km‐scale yardangs and scalloped cliffs. Our mapping shows that many yardangs in the lower mound are clay‐bearing, with a predominant orientation of around N‐S. Curiosity's ground‐level images show myriad fine‐scale, mainly horizontal layers in the lower mound. The rover has found stream beds and conglomerates, indicating that water once flowed on the crater floor. Drilling near the deepest point in Gale produced abundant clay, providing additional evidence of aqueous alteration. Upper mound units range in altitude from ‐2,100 m to +500 m, and mantle the lower mound above an angular unconformity. Most upper mound units are composed of layers. The formation age of the upper mound is unknown, since few craters are preserved. Clay‐bearing layers are detectable in several locations, mainly at altitudes near ‐2,000 m. There is no evidence of water flow, but wind erosion has scalloped the surfaces and edges of layers, and fine‐scale yardangs are common. Correlations between yardangs and clay spectra are apparent only in the lowermost units of the upper mound. Yardang orientations vary, and include N‐S, NW‐SE, and NE‐SW. Upper mound units resemble the planet‐wide Medusae Fossae formation, dated as Hesperian and argued to be composed of ignimbrites. Medusae Fossae layers are easily eroded by wind, and our mapping demonstrates their resemblance to upper mound fine‐scale yardangs. The history of Mt. Sharp started with deposition and lithification of sediments shortly after crater formation. Some lower mound layers were partially altered to clays and sulfates, and water formed streams and canyons. Wind erosion of the lower mound produced large‐scale yardangs, particularly in clay‐rich layers, oriented generally N‐S. Upper mound units were emplaced following a considerable period of wind erosion. The absence of water flow on the upper mound suggests that these units were emplaced after atmospheric loss rendered water unstable at the surface. The shift in dominant wind direction, as indicated by yardang orientations, also argues for a time gap between erosion of the lower and upper mound. These observations are consistent with upper mound units being related to the Hesperian Medusae Fossae formation. During 2014 Curiosity is expected to reach the foot of Mt. Sharp and ascend through the clay‐rich layers, into the sulfate‐rich layers, and possibly past the interface with the upper mound. This will be a unique opportunity to field check geologic models on the surface of Mars.

Allen, C.↗