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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 1,693 records · Page 94
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Revealing structural evolution of PbS nanocrystal catalysts in electrochemical CO 2 reduction using in situ synchrotron radiation X-ray diffraction

We investigated the structural evolution of PbS catalysts under electrochemical CO 2 reduction reaction (eCO 2 RR) conditions using an in situ synchrotron radiation X-ray diffraction (SR-XRD) technique. The PbS catalyst with an initial form of size-tunable nanocrystals (NCs) performed efficiently in the electrochemical conversion of CO 2 to formate with a record-high mass activity (MA) of 52.2 ± 5.2 mA mg Pb -1 at -1.2 V and 74.9 ± 4.7 mA mg Pb -1 at -1.4 V vs. the reversible hydrogen electrode (RHE). In situ SR-XRD analyses revealed that PbS NCs underwent rapid structural transformation to Pb thin films during the eCO 2 RR, providing the real catalytic surface for the eCO 2 RR. Such a structural change is complex, with PbS first being converted to PbCO 3 and the latter species being further reduced to Pb. This work highlights the importance of understanding environmental impacts on the instability of nanocatalysts under eCO 2 RR conditions and the need for designing more robust electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reaction dynamics of S( 3 P) with 1,3-butadiene and isoprene: crossed-beam scattering, low-temperature flow experiments, and high-level electronic structure calculations

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S( 3 P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H 2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C 3 H 4 S (loss of ethene or H 2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles.

Lang, Jinxin↗
DOE OSTI2023

A giant umbrella-like stellar stream around the tidal ring galaxy NGC 922

Tidal ring galaxies (TRGs) are rarely observed in the local universe due to their intrinsically transient nature. The tidal ring structures are the result of strong interactions between gas-rich stellar disks and smaller galactic systems, and do not last longer than ~500 Myr. Therefore, these are perfect scenarios in which to look for the debris of recently accreted dwarf galactic systems. Our goal is to study the low surface brightness stellar structures around the TRG NGC 922 and to revise the hypothesis of its formation in light of these new data. We present new deep images of the TRG NGC 922 and its surroundings from the DESI Legacy survey data and from our observations with an amateur telescope. These observations are compared with results from high-resolution N-body simulations that were designed to reproduce an alternative formation scenario for this peculiar galaxy. Our new observations unveil that the low surface brightness stellar tidal structures around NGC 922 are much more complex than reported in previous works. In particular, the formerly detected tidal spike-like structure at the north-east of the central galaxy disk is not connected with the dwarf companion galaxy PGC 3080368, which has been suggested as the intruder triggering the ring formation of NGC 922. The deep images reveal that this tidal structure mainly has a fainter giant umbrella-like shape, and thus it was formed from the tidal disruption of a different satellite. Using the broad-band g, r, and z DESI LS images, we measured the photometric properties of this stellar stream, estimating a total absolute magnitude in the r band of M r = -17.0 ± 0.03 mag and a total stellar mass for the stream of between 6.9 and 8.5×10 8 M ⊙ . We performed a set of N-body simulations to reproduce the observed NGC922-intruder interaction, suggesting a new scenario for the formation of its tidal ring from the infall of a gas-rich satellite around 150 Myr ago. Finally, our deep images also reveal a tidal shell around the dwarf galaxy PGC 3080368, a possible fossil of a recent merger with a smaller satellite, which may suggest it is in its first infall towards NGC 922.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2014

Methanol synthesis on ZnO(0001{sup ¯}). IV. Reaction mechanisms and electronic structure

Methanol synthesis from CO and H{sub 2} over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partially hydroxylated and defective ZnO(0001{sup ¯}) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving “near-surface” molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H{sub 2} stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Communication: Analytical optimal pulse shapes obtained with the aid of genetic algorithms: Controlling the photoisomerization yield of retinal

We recently proposed a Quantum Optimal Control (QOC) method constrained to build pulses from analytical pulse shapes [R. D. Guerrero et al., J. Chem. Phys. 143(12), 124108 (2015)]. This approach was applied to control the dissociation channel yields of the diatomic molecule KH, considering three potential energy curves and one degree of freedom. In this work, we utilized this methodology to study the strong field control of the cis-trans photoisomerization of 11-cis retinal. This more complex system was modeled with a Hamiltonian comprising two potential energy surfaces and two degrees of freedom. The resulting optimal pulse, made of 6 linearly chirped pulses, was capable of controlling the population of the trans isomer on the ground electronic surface for nearly 200 fs. The simplicity of the pulse generated with our QOC approach offers two clear advantages: a direct analysis of the sequence of events occurring during the driven dynamics, and its reproducibility in the laboratory with current laser technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A variational method for the sheath potential of hypersonic leading edges with space-charge limitations

Electron transpiration cooling for the leading edges (LE) of hypersonic aircraft utilizes thermionic emission; however, space-charge effects limit the electron emission rate, potentially diminishing the efficiency of this cooling mechanism. We develop a variational weak form of the Poisson equation that describes the sheath potential and then numerically solve it using the finite element method. This formulation has two main benefits: (1) the space-charge limit condition can be incorporated as a constraint and (2) it allows for the analysis of three-dimensional geometries with complex boundary conditions. We demonstrate that the current emitted from the surface of an LE is generally a small fraction of the Child–Langmuir limit due to space charge. We then propose several methods to enhance the emitted current from the surface and to boost the cooling effect of thermionic emission. These include increasing the plasma density, applying a negative surface potential, and using fringe fields under suitable geometric conditions. For a LaB6 emitting LE, the total emitted current is shown to be minimal and independent of the temperature of a surface with floating potential. However, when a negative potential is applied and the surface is heated, the emitted current follows the Richardson–Dushman relationship up to a critical temperature, beyond which it remains constant. At an applied surface potential of −5 V, the critical temperature is around 1700 K.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Functional analysis of human cytochrome P450 21A2 variants involved in congenital adrenal hyperplasia

Cytochrome P450 (P450, CYP) 21A2 is the major steroid 21-hydroxylase, converting progesterone to 11-deoxycorticosterone and 17α-hydroxyprogesterone (17α-OH-progesterone) to 11-deoxycortisol. More than 100 CYP21A2 variants give rise to congenital adrenal hyperplasia (CAH). We previously reported a structure of WT human P450 21A2 with bound progesterone and now present a structure bound to the other substrate (17α-OH-progesterone). We found that the 17α-OH-progesterone- and progesterone-bound complex structures are highly similar, with only some minor differences in surface loop regions. Twelve P450 21A2 variants associated with either salt-wasting or nonclassical forms of CAH were expressed, purified, and analyzed. The catalytic activities of these 12 variants ranged from 0.00009% to 30% of WT P450 21A2 and the extent of heme incorporation from 10% to 95% of the WT. Substrate dissociation constants (K s ) for four variants were 37–13,000-fold higher than for WT P450 21A2. Cytochrome b 5 , which augments several P450 activities, inhibited P450 21A2 activity. Similar to the WT enzyme, high noncompetitive intermolecular kinetic deuterium isotope effects (≥ 5.5) were observed for all six P450 21A2 variants examined for 21-hydroxylation of 21-d3-progesterone, indicating that C–H bond breaking is a rate-limiting step over a 104-fold range of catalytic efficiency. Using UV-visible and CD spectroscopy, we found that P450 21A2 thermal stability assessed in bacterial cells and with purified enzymes differed among salt-wasting- and nonclassical-associated variants, but these differences did not correlate with catalytic activity. Our in-depth investigation of CAH-associated P450 21A2 variants reveals critical insight into the effects of disease-causing mutations on this important enzyme.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2017

Pressure evolution equation for the particulate phase in inhomogeneous compressible disperse multiphase flows

An analytical expression describing the unsteady pressure evolution of the dispersed phase driven by variations in the carrier phase is presented. In this article, the term “dispersed phase” represents rigid particles, droplets, or bubbles. Letting both the dispersed and continuous phases be inhomogeneous, unsteady, and compressible, the developed pressure equation describes the particle response and its eventual equilibration with that of the carrier fluid. The study involves impingement of a plane traveling wave of a given frequency and subsequent volume-averaged particle pressure calculation due to a single wave. The ambient or continuous fluid's pressure and density-weighted normal velocity are identified as the source terms governing the particle pressure. Analogous to the generalized Faxén theorem, which is applicable to the particle equation of motion, the pressure expression is also written in terms of the surface average of time-varying incoming flow properties. The surface average allows the current formulation to be generalized for any complex incident flow, including situations where the particle size is comparable to that of the incoming flow. Further, the particle pressure is also found to depend on the dispersed-to-continuous fluid density ratio and speed of sound ratio in addition to dynamic viscosities of both fluids. The model is applied to predict the unsteady pressure variation inside an aluminum particle subjected to normal shock waves. The results are compared against numerical simulations and found to be in good agreement. Furthermore, it is shown that, although the analysis is conducted in the limit of negligible flow Reynolds and Mach numbers, it can be used to compute the density and volume of the dispersed phase to reasonable accuracy. Finally, analogous to the pressure evolution expression, an equation describing the time-dependent particle radius is deduced and is shown to reduce to the Rayleigh-Plesset equation in the linear limit.

42 ENGINEERING↗
DOE OSTI2017

Resonances in the Field-Angle-Resolved Thermal Conductivity of CeCoIn 5

Here, the thermal conductivity measurement in a rotating magnetic field is a powerful probe of the structure of the superconducting energy gap. We present high-precision measurements of the low-temperature thermal conductivity in the unconventional heavy-fermion superconductor CeCoIn 5 , with the heat current J along the nodal [110] direction of its d x 2 –y 2 order parameter and the magnetic field up to 7 T rotating in the ab plane. In contrast to the smooth oscillations found previously for J∥[100], we observe a sharp resonancelike peak in the thermal conductivity when the magnetic field is also in the [110] direction, parallel to the heat current. We explain this peak qualitatively via a model of the heat transport in a d-wave superconductor. In addition, we observe two smaller but also very sharp peaks in the thermal conductivity for the field directions at angles Θ≈±33° with respect to J. The origin of the observed resonances at Θ≈±33° at present defies theoretical explanation. The challenge of uncovering their source will dictate exploring theoretically more complex models, which might include, e.g., fine details of the Fermi surface, Andreev bound vortex core states, a secondary superconducting order parameter, and the existence of gaps in spin and charge excitations.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Intertwined charge and spin density waves in a topological kagome material

Using neutrons and x rays we show the topological kagome antiferromagnet Mn 3 Sn for T < 285 K forms a homogeneous spin and charge ordered state comprising a longitudinally polarized spin density wave with wave vector k β = k β c ̂ , a helical modulated version of the room temperature antichiral magnetic order with k χ = k χ c ̂ , and charge density waves with wave vectors 2 k β , 2 k χ , and k β + k χ . Though k χ and k β coincide for 200 K < T < 230 K , they exhibit distinct continuous T dependencies before locking to commensurate values of k β = 1 12 c * and k χ = 5 48 c * at low T . Density functional theory indicates this complex modulated state may be associated with the nesting of Fermi surfaces from correlated flat kagome bands, which host Weyl nodes that are annihilated as it forms. Published by the American Physical Society 2024

Chen, Y. (ORCID:0000000177169179)↗
DOE OSTI2014

Emerging Techniques for Field Device Security

Critical infrastructure, such as electrical power plants and oil refineries, rely on embedded devices to control essential processes. State of the art security is unable to detect attacks on these devices at the hardware or firmware level. We provide an overview of the hardware used in industrial control system field devices, look at how these devices have been attacked, and discuss techniques and new technologies that may be used to secure them. We follow three themes: (1) Inspectability, the capability for an external arbiter to monitor the internal state of a device. (2) Trustworthiness, the degree to which a system will continue to function correctly despite disruption, error, or attack. (3) Diversity, the use of adaptive systems and complexity to make attacks more difficult by reducing the feasible attack surface.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2015

SU-E-T-632: Preliminary Study On Treating Nose Skin Using Energy and Intensity Modulated Electron Beams with Monte Carlo Based Dose Calculations

Purpose: Uneven nose surfaces and air cavities underneath and the use of bolus present complexity and dose uncertainty when using a single electron energy beam to plan treatments of nose skin with a pencil beam-based planning system. This work demonstrates more accurate dose calculation and more optimal planning using energy and intensity modulated electron radiotherapy (MERT) delivered with a pMLC. Methods: An in-house developed Monte Carlo (MC)-based dose calculation/optimization planning system was employed for treatment planning. Phase space data (6, 9, 12 and 15 MeV) were used as an input source for MC dose calculations for the linac. To reduce the scatter-caused penumbra, a short SSD (61 cm) was used. Our previous work demonstrates good agreement in percentage depth dose and off-axis dose between calculations and film measurement for various field sizes. A MERT plan was generated for treating the nose skin using a patient geometry and a dose volume histogram (DVH) was obtained. The work also shows the comparison of 2D dose distributions between a clinically used conventional single electron energy plan and the MERT plan. Results: The MERT plan resulted in improved target dose coverage as compared to the conventional plan, which demonstrated a target dose deficit at the field edge. The conventional plan showed higher dose normal tissue irradiation underneath the nose skin while the MERT plan resulted in improved conformity and thus reduces normal tissue dose. Conclusion: This preliminary work illustrates that MC-based MERT planning is a promising technique in treating nose skin, not only providing more accurate dose calculation, but also offering an improved target dose coverage and conformity. In addition, this technique may eliminate the necessity of bolus, which often produces dose delivery uncertainty due to the air gaps that may exist between the bolus and skin.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2018

Laser-Induced Modification of the Surface of Ge{sub 2}Sb{sub 2}Te{sub 5} Thin Films: Phase Changes and Periodic-Structure Formation

Submicron periodic lattices are formed at the surface of phase-change-memory film materials based on the complex chalcogenide Ge{sub 2}Sb{sub 2}Te{sub 5} when exposed to nanosecond laser pulses. The geometric characteristics and structural properties of laser-induced lattices are studied by optical and atomic-force microscopies and Raman spectroscopy. It is shown that, at appropriately chosen parameters of exposure to laser radiation, it is possible to implement periodic modulation of the refractive index in the structures formed. Modulation is due to the postexposure solidification of grating ridges and valleys in different phase states, whose dielectric constants widely differ from each other. In the vicinity of the maxima of the wavy structure, the amorphous state is mainly formed, whereas in the region of minima, the Ge{sub 2}Sb{sub 2}Te{sub 5} structure corresponds mainly to the crystalline phase.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Electricity Generation from Geothermal Resources on the Fort Peck Reservation in Northeast Montana

Tribal lands owned by Assiniboine and Sioux Tribes on the Fort Peck Indian Reservation, located in Northeastern Montana, overlie large volumes of deep, hot, saline water. Our study area included all the Fort Peck Reservation occupying roughly 1,456 sq miles. The geothermal water present in the Fort Peck Reservation is located in the western part of the Williston Basin in the Madison Group complex ranging in depths of 5500 to 7500 feet. Although no surface hot springs exist on the Reservation, water temperatures within oil wells that intercept these geothermal resources in the Madison Formation range from 150 to 278 degrees F.

15 GEOTHERMAL ENERGY↗
DOE OSTI2016

Feasibility Study for Electrical Discharge Machining of Large DU-Mo Castings

U-10 wt. % Mo (U-10Mo) alloys are being developed as low enrichment monolithic fuel for the CONVERT program. Optimization of processing for the monolithic fuel is being pursued with the use of electrical discharge machining (EDM) under CONVERT HPRR WBS 1.2.4.5 Optimization of Coupon Preparation. The process is applicable to manufacturing experimental fuel plate specimens for the Mini-Plate-1 (MP-1) irradiation campaign. The benefits of EDM are reduced machining costs, ability to achieve higher tolerances, stress-free, burr-free surfaces eliminating the need for milling, and the ability to machine complex shapes. Kerf losses are much smaller with EDM (tenths of mm) compared to conventional machining (mm). Reliable repeatability is achievable with EDM due to its computer-generated machining programs.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

ER-20-12: A Case Study of Corrective Action Investigation in a Challenging Environment - 17236

Low-level tritium was unexpectedly detected in 2010 in a monitoring well located more than three kilometers (km) down-gradient of an area formerly used for underground nuclear testing. The approach used by the U.S. Department of Energy (DOE) to investigate potential sources for the tritium is an exemplary case study of corrective action investigation at the Nevada National Security Site (NNSS). Multiple challenges presented themselves during the course of the investigation, ranging from difficulties associated with confirming the presence tritium within the well to a field site characterized by remote, rugged terrain, high elevation, inclement weather, great depths to groundwater, complex geology, and residual surficial contamination originating from the near-surface detonations of two large-scale nuclear plowshare tests. Limited resources required a judicious process for evaluating competing conceptual models. Timely communication of monitoring results to stakeholders and early involvement of regulatory authorities in the planning process were critical components of the overall investigation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Utilization of GIS technology to support development of flow and contaminant fate and transport models at US DOE sites - 15457

U.S. Department of Energy (DOE) sites have accumulated years of data and millions of spatial and temporal records related to the hydrological cycle, contaminant transport, and parameters of remediation technologies. In addition, numerical models which use field monitoring data to help understand flow and transport produce gigabytes of computed spatial and temporal data for each computation node. There is a need therefore for an advanced spatial data structure that can be used to address the management, processing, and analysis of spatial and temporal numerical modeling data derived from multiple sources. This can be accomplished using a geo-database. The development of an ArcSDE geo-database facilitates the centralized storage, backup, accessibility, organization, and management of model configuration and computed simulation data, putting it into a structured, coherent, and logical computer-supported system. GIS data processing and automation would enable faster and hence more complex analyses of field test data. The Applied Research Center (ARC) at Florida International University (FIU) has provided analysis of flow and transport for several watersheds at DOE's Oak Ridge Reservation (ORR), including East Fork Poplar Creek (EFPC), Upper EFPC in the Y-12 National Security Complex area (Y-12 NSC) and White Oak Creek (WOC). Integrated surface and subsurface flow, fate and transport models were developed to provide analysis of contaminant patterns within each watershed. In addition, digital monitoring data available from the Oak Ridge Environmental Information System (OREIS) related to mercury (Hg) contamination and remediation within these watersheds was used for calibration and verification of the model. Experimental studies were also carried out which provided kinetic and equilibrium data about important parameters related to Hg transport, speciation and methylation/demethylation kinetics within the watershed. Geographic Information Systems (GIS) technology was employed to support the modeling work through storage and geo-processing of spatial and temporal data required by the models and to produce hydrogeological maps for visualization. An ArcGIS geo-database was developed for centralized storage and management of experimental and computed model data and its capabilities were extended over the years using tools such as ModelBuilder combined with Python scripting to automate repetitive tasks, perform statistical analyses and generate maps and reports. The hydrologic geo-database model developed possesses a structure that enables linkage with scalable hydrologic modeling tools/applications to model hydrologic systems, and in this case, enables the testing of the potential impacts of various remediation scenarios on the ORR watersheds. The ArcSDE geo-database can also be used to automate and simplify the process of calling stored GIS and time series data. This geo-database can serve as a tool for contaminant flow and transport analyses which require large amounts of high-quality spatial and temporal data in order to ensure reliability and validity of modeling results. The existing geo-database structure developed for the hydrological modeling at ORR was designed to be replicable for application at other DOE sites. An investigation of downloadable free/open source GIS software along with required security protocols to facilitate online querying of the database was also conducted to determine methods by which project-derived data can be more easily shared with other project stakeholders such as DOE personnel and site contractors. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Role of macrocyclic effect in complex formation of palladium(II) with ligands anchored on a solid support

The method for grafting dithiacrown ether and its linear analogue to the silica surface using preliminary prepared organosilicon derivative is developed. The importance of the acylation step in the process of grafting is underlined. The acylation is required to prevent sorption of platinum metals complex anions by the anion exchange mechanism, the probability of which increases due to protonation of the spacer in an acidic medium. The interaction of palladium(II) with anchored ligands in hydrochloric acid media was studied in details. The comparative study of two sorbents revealed that the macrocyclic effect plays a negligible role in binding of palladi um(II) ions. Therefore, linear ligands are preferred for the development of sorbents for molecular recognition of platinum metals ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗