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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Carbene Functionalization of Monolayer Tungsten Disulfide for Enhanced Quantum Emission

Semiconducting two-dimensional (2D) transition metal dichalcogenides (TMDs) are promising materials for an array of applications, ranging from conventional field-effect transistors, photodetectors, and light-emitting diodes to their more recent use in quantum photonic technologies. Chemical functionalization of 2D TMDs with organic ligands and adlayers provides an additional means for customizing their electronic and optical properties. While many pathways have been reported for the chemical functionalization of 2D TMDs, their frequent reliance on solution-based methods results in limited control over adlayer thickness and coverage, thus hindering utility in high-performance applications. Here, in this study, we describe the vapor-phase functionalization of a 2D TMD with carbene ligands, specifically tungsten disulfide (WS 2 ) with N-heterocyclic carbenes (NHCs), resulting in molecularly smooth, thin, and uniform adlayers. Reacting NHCs with monolayer WS 2 reduces the broad photoluminescence background observed at cryogenic temperatures by 58%, which facilitates the detection of single-photon emitters from strained monolayer WS 2 , as indicated by second order correlation values ( g (2) ) as low as 0.17 ± 0.07. Chemical characterization coupled with density functional theory calculations suggests that the NHC adlayer has a dual defect-passivation and doping effect on monolayer WS 2 that results in enhanced single-photon emission. Overall, this study establishes vapor-phase carbene functionalization as a homogeneous surface modification scheme for tailoring the quantum emission properties of semiconducting 2D TMDs.

N-heterocyclic carbenes↗
DOE OSTI2021

J-PLUS: Systematic impact of metallicity on photometric calibration with the stellar locus

Here, we present the photometric calibration of the twelve optical passbands for the Javalambre Photometric Local Universe Survey (J-PLUS) second data release (DR2), comprising 1088 pointings of two square degrees, and study the systematic impact of metallicity on the stellar locus technique. The [Fe/H] metallicity from the Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) for 146 184 high-quality calibration stars, defined with signal-to-noise ratio larger than ten in J-PLUS passbands and larger than three in Gaia parallax, was used to compute the metallicity-dependent stellar locus (ZSL). The initial homogenization of J-PLUS photometry, performed with a unique stellar locus, was refined by including the metallicity effect in colors via the ZSL. The variation of the average metallicity along the Milky Way produces a systematic offset in J-PLUS calibration. This effect is well above 1% for the bluer passbands and amounts 0.07, 0.07, 0.05, 0.03, and 0.02 mag in u, J0378, J0395, J0410, and J0430, respectively. We modeled this effect with the Milky Way location of the J-PLUS pointing, also providing an updated calibration for those observations without LAMOST information. The estimated accuracy in the calibration after including the metallicity effect is at 1% for the bluer J-PLUS passbands and below for the rest. Photometric calibration with the stellar locus technique is prone to significant systematic bias in the Milky Way for passbands bluer than λ = 4500 Å. The calibration method for J-PLUS DR2 reaches 1–2% precision and 1% accuracy for 12 optical filters within an area of 2176 square degrees.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Microfluidic Uranium Microspheres Production for TRISO and Advanced Fuel Concepts

The purpose of this project was to expand existing internal gelation sol-gel capabilities at PNNL to explore producing uranium dioxide spheres for potential use as fuel kernels in next generation Tri-isotropic (TRISO) particle fuel. This project expands on previous sol-gel efforts at PNNL by (1) increasing the size regime of sphere production from the micro-fluidic range to the milli-fluidic range, and (2) producing uranium spheres. The approach involved first scaling up the channel size of the fluidic system to the millimeter range, with radiation safety considerations in mind; testing and demonstration on non-radioactive surrogate material, cerium oxide; then transitioning to uranium production and finally optimizing system parameters. Commercially available fluidic chips in the desired size range were could not be found, therefore the project designed and fabricated a T-junction with 1mm channels for droplet production. Because the production process is temperature sensitive, prior efforts have involved performing droplet production in a lab freezer. To reduce radiological waste and footprint, two alternative chilling methods were explored using aluminum thermal beads as a chill bath and a custom aluminum block fit to reagent reservoir sizes. Both were successful in the cerium tests, however the aluminum block design outperformed the thermal bead bath and was further adapted for the radiological test and production run in the Radiochemical Processing Laboratory (RPL). Gelation trials were performed to determine an acceptable range of feed solution parameters for the uranium dioxide gels, characterized by R-values, which is determined by the ratio of uranium nitrate to Hexamethylenetetramine (HMTA)/urea in the feed solution. R-values ranging from 1.6-2 were examined in the gelation trials, with only the 1.8 condition being tested in production. The project was successful in demonstrating a proof of concept design for producing uranium dioxide spheres, however further optimization is needed to dial in production parameters and improve sphere quality and homogeneity.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Emerging contact force heterogeneity in ordered soft granular media

Under external perturbations, inter-particle forces in disordered granular media are well known to form a heterogeneous distribution with filamentary patterns. Better understanding these forces and the distribution is important for predicting the collective behavior of granular media, the media second only to water as the most manipulated material in global industry. However, studies in this regard so far have been largely confined to granular media exhibiting only geometric heterogeneity, leaving the dimension of mechanical heterogeneity a rather uncharted area. In this work, through a FEM contact mechanics model, we show that a heterogeneous inter-particle force distribution can also emerge from the dimension of mechanical heterogeneity alone. Specifically, we numerically study inter-particle forces in packing of mechanically heterogeneous disks arranged over either a square or a hexagonal lattice and under quasi-static isotropic compression. Our results show that, at the system scale, a hexagonal packing exhibit a more heterogeneous inter-particle force distribution than a square packing does; At the particle scale, for both packing lattices, preliminary analysis shows the consistent coexistence of outliers (i.e., softer disks sustaining larger forces while stiffer disks sustaining smaller forces) in comparison to their homogeneous counterparts, which implies the existence of nonlocal effect. Further analysis on the portion of outliers and on spatial contact force correlations suggest that the hexagonal packing shows more pronounced nonlocal effect over the square packing under small mechanical heterogeneity. However, such trend is reversed when assemblies becomes more mechanically heterogeneous. Lastly, we confirm that, in the absence of particle reorganization events, contact friction merely plays the role of packing stabilization while its variation has little effect on inter-particle forces and their distribution.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ionic Dopant-Induced Ordering Enhances the Thermoelectric Properties of a Polythiophene-Based Block Copolymer

Conjugated polymer-based block copolymers (CP-BCPs) are an unexplored class of materials for organic thermoelectrics. In this study, the authors report on the electronic conductivity (σ) and Seebeck coefficient (α) of a newly synthesized CP-BCP, poly(3-hexylthiophene)-block-poly (oligo-oxyethylene methacrylate) (P3HT-b-POEM), upon solution co-processing with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and subsequently vapor-doping with a molecular dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). It is found that the addition of the hydrophilic block POEM greatly enhances the processability of P3HT, enabling homogeneous solution-mixing with LiTFSI. Notably, interactions between P3HT-b-POEM with ionic species significantly improve molecular order and unexpectedly cause electrical oxidizing doping of P3HT block both in solution and solid-states, a phenomenon that has not been previously observed in Li-salt containing P3HT. Vapor doping of P3HT-b-POEM-LiTFSI thin films with F4TCNQ further enhances σ and yields a thermoelectric power factor PF = α 2 σ of 13.0 μW m -1 K -2 , which is more than 20 times higher than salt-free P3HT-b-POEM sample. Through modeling thermoelectric behaviors of P3HT-b-POEM with the Kang-Snyder transport model, the improvement in PF is attributed to higher electronic charge mobility originating from the enhanced molecular ordering of P3HT. The results demonstrate that solution co-processing CP-BCPs with a salt is a powerful method to control structure and performance of organic thermoelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Leak-tight crack repair for 304L stainless steel using friction surfacing

Here, friction surfacing (FS) was investigated as a method for sealing 50 μm wide thru-cracks in 3-mm-thick 304L stainless steel (304L) plate. Friction surfacing was performed using two sizes of 304L consumable rod, with diameters of 9.52 mm and 12.7 mm, on two substrate conditions (clean and oxidized). Friction surfacing was able to deposit a 600 μm thick coating and repair cracks to a depth of 100 μm - 200 μm below the original surface, when using the 12.7-mm-diameter consumable rod for both substrate conditions. Helium leak rates of 10 -10 atm-cc/s were achieved on crack repairs, designating them as leak-tight by the ANSI N14.5 standard. Optical and scanning electron microscopy were used to investigate the coating microstructure and bond interfaces. In this study, the 12.7-mm-diameter rod performed better with disruption of the oxide layer on the oxidized substrate and providing a more homogenous coating. Mechanical properties of the coated samples were evaluated by performing micro-indentation, tensile, bending, and adhesion testing. Higher hardness in the coatings was observed due to the fine equiaxed grains resulting from dynamic recrystallization. Complete consolidation of plastically deformed material on the substrate and a strong diffusion bond across the interface was observed. This was reflected in tensile and bending properties of the FS coatings being comparable to those of uncoated specimen. No delamination of the FS coating was observed during adhesion testing. The results demonstrate that friction surfacing is a viable option to seal cracks in stainless steels.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Development of Mischmetal–Fe–Co–B Permanent Magnet Alloys via High-Throughput Methods

Additive manufacturing synthesis using laser engineered net shaping (LENS) is utilized in this work to rapidly print libraries of mischmetal (MM = La, Ce, Nd, and Pr) containing R 2 TM 14 B alloys (R = MM + separated Nd and TM = Fe and Co) enabling robust evaluation of physical properties over a wide composition range. High-throughput characterization of the magnetic and thermal properties are used to identify compositions for potential high-temperature, high-performance permanent magnets with reduced critical rare-earth elements. Improved Curie temperature ( T c ~ 450 °C) is obtained with substitution of Fe by Co in pseudoternary R 2 TM 14 B alloys. Furthermore, a 4-fold decrease in the Nd content can be achieved through substitution with less critical Ce- and La-rich MM, while retaining high T c . Guided by the properties of the LENS printed samples, selected compositions with and without TiC additions are synthesized via melt-spinning techniques to produce nanostructured ribbons. The maximum room temperature coercivity ( H c ) and energy product ((BH) max ) without TiC are found to be 5.8 kOe, 8.5 MGOe, respectively, while TiC additions as a grain refiner gave H c and (BH) max of 4.9 kOe, 9.8 MGOe, respectively. Structural characterization of the melt-spun ribbons shows homogeneous grain refinement with TiC additions, which leads to an increase in the energy product.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Refining Methods to Determine the Isotopic Composition of Uranium Particles by Laser Ablation MC-ICP-MS

We report on efforts to mitigate the generation of isotopic anomalies during the ablation of micrometer-sized uranium oxide particles and analysis by MC-ICP-MS. The results of testing on particles of U200 indicate that laser fluence and frequency can affect isotopic data produced by laser ablation, but no settings were tested that could eradicate the signal spiking effect and generation of anomalous isotopic data for 234U/238U and 236U/238U. These anomalies are more frequent in samples with higher 235U enrichments, which is expected given their higher abundances of 234U and 236U. Of the standards tested here, only U005-A was anomaly-free. Efforts to compare the laser traces for particles with normal and anomalous isotopic compositions showed subtle differences in the behavior of the 234U/238U and 236U/238U ratios. However, it would be challenging to identify anomalous data points from a population of unknowns using this distinction, i.e., this is unlikely to be diagnostic. Thus, using current analytical hardware, we cannot eradicate the signal spiking phenomenon and cannot unambiguously identify isotopic anomalies from laser ablation traces. Ultimately, laser ablation ICP-MS would either require dramatic improvement to the ablation process and generation of more homogenous aerosols and/or improvements to detector electronics to identify and correct for the spiking phenomenon. Even if the reliability of the technique could be improved, a broader question to address is whether current data quality is of a high enough standard for laser ablation MC-ICP-MS to be used as a complementary technique to LG-SIMS for Safeguards.

organic↗
DOE OSTI2024

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO 2

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO 2 (ECO 2 R) due to their role in the double-layer structure formation and increased CO 2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO 2 R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO 2 mass transport, and ECO 2 R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO 2 R activity of molecular catalysts Ni(cyclam)Cl 2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO 2 capture and conversion technologies for homogeneous and heterogeneous ECO 2 R.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Source scaling comparison and validation in Central Italy: data intensive direct S waves versus the sparse data coda envelope methodology

SUMMARY Robustness of source parameter estimates is a fundamental issue in understanding the relationships between small and large events; however, it is difficult to assess how much of the variability of the source parameters can be attributed to the physical source characteristics or to the uncertainties of the methods and data used to estimate the values. In this study, we apply the coda method by Mayeda et al. using the coda calibration tool (CCT), a freely available Java-based code (https://github.com/LLNL/coda-calibration-tool) to obtain a regional calibration for Central Italy for estimating stable source parameters. We demonstrate the power of the coda technique in this region and show that it provides the same robustness in source parameter estimation as a data-driven methodology [generalized inversion technique (GIT)], but with much fewer calibration events and stations. The Central Italy region is ideal for both GIT and coda approaches as it is characterized by high-quality data, including recent well-recorded seismic sequences such as L'Aquila (2009) and Amatrice–Norcia–Visso (2016–2017). This allows us to apply data-driven methods such as GIT and coda-based methods that require few, but high-quality data. The data set for GIT analysis includes ∼5000 earthquakes and more than 600 stations, while for coda analysis we used a small subset of 39 events spanning 3.5 < Mw < 6.33 and 14 well-distributed broad-band stations. For the common calibration events, as well as an additional 247 events (∼1.7 < Mw < ∼5.0) not used in either calibration, we find excellent agreement between GIT-derived and CCT-derived source spectra. This confirms the ability of the coda approach to obtain stable source parameters even with few calibration events and stations. Even reducing the coda calibration data set by 75 per cent, we found no appreciable degradation in performance. This validation of the coda calibration approach over a broad range of event size demonstrates that this procedure, once extended to other regions, represents a powerful tool for future routine applications to homogeneously evaluate robust source parameters on a national scale. Furthermore, the coda calibration procedure can homogenize the Mw estimates for small and large events without the necessity of introducing any conversion scale between narrow-band measures such as local magnitude (ML) and Mw, which has been shown to introduce significant bias.

Morasca, Paola (ORCID:0000000265254867)↗
DOE OSTI2023

Metaoptics Enabled Multifunctional Imaging

Despite the fact that most microorganisms occupy two- and three-dimensional space in heterogeneous arrangements and in proximity to other microorganisms of different species, much of our current knowledge about their metabolic processes is derived from homogenizing, then analyzing, the chemical content of cultures containing a single microbial species. This project addressed this fundamental dichotomy by developing a set of optical imaging principles combining multiple new technologies. The imaging strategies developed in this project combine metaoptics structures with active in situ nanoscale control of the chemical environment and applied them to a microbial system, Myxococcus xanthus, with particular relevance to the DoE mission. The combination of metaoptical architectures and nanoscale control over the molecular environment enables: (a) precise control over the electromagnetic (EM) field at length scales smaller than the wavelength of light; (b) control of the interaction of the EM field with critical molecular systems in DOE relevant microbes; (c) control over the chemical environment – especially the presence and quantity of reactive oxygen species (ROS) that can affect redox homeostasis; and (d) the ability to ask new kinds of questions not accessible to ‘omics’ approaches or standard methods of biological imaging. These capabilities are applicable to detailed studies of metabolic pathways in microbes and to lignocellulosic biomass deconstruction. To accomplish these objectives, we pursued two over-arching technical goals: (1) the development of new metaoptics-enabled approaches to imaging and spectroscopic characterization; and (2) the development of tools to control the chemical environment of a microbial sample with nanometer-scale precision. Goal 1 was addressed through the design, fabrication, and characterization of new metasurfaces capable of super-resolution imaging through extreme confinement of the optical field. Goal 2 was addressed by controlling the redox potential on the nanoscale in microbial communities and characterizing their effect on intrinsic bacterial fluorophores which act as molecular sentinels and through characterization of soluble factors secreted by Myxococcus xanthus by confocal Raman imaging. The optical imaging/sensing approaches developed here make it possible to use these powerful new imaging and sensing modalities in metabolic studies by making it possible to visualize and track the spatial and temporal expression patterns of natural or engineered pathways in microorganisms.

09 BIOMASS FUELS↗
DOE OSTI2020

Microkinetic Modeling: A Tool for Rational Catalyst Design

The design of heterogeneous catalysts relies on understanding the fundamental surface kinetics that controls catalyst performance, and microkinetic modeling is a tool that can help the researcher in streamlining the process of catalyst design. Microkinetic modeling is used to identify critical reaction intermediates and rate-determining elementary reactions, thereby providing vital information for designing an improved catalyst. In this review, we summarize general procedures for developing microkinetic models using reaction kinetics parameters obtained from experimental data, theoretical correlations, and quantum chemical calculations. We examine the methods required to ensure the thermodynamic consistency of the microkinetic model. We describe procedures required for parameter adjustments to account for the heterogeneity of the catalyst and the inherent errors in parameter estimation. We discuss the analysis of microkinetic models to determine the rate determining reactions using the degree of rate control and reversibility of each elementary reaction. We introduce incorporation of Brønsted–Evans–Polanyi relations and scaling relations in microkinetic models and the effects of these relations on catalytic performance and formation of volcano curves. We review the analysis of reaction schemes in terms of the maximum rate of elementary reactions, and we outline a procedure to identify kinetically significant transition states and adsorbed intermediates. Here, we explore the application of generalized rate expressions for the prediction of optimal binding energies of important surface intermediates and to estimate the extent of potential rate improvement. We also explore the application of microkinetic modeling in homogeneous catalysis, electro-catalysis, and transient reaction kinetics. We conclude by highlighting the challenges and opportunities in the application of microkinetic modeling for catalyst design.

42 ENGINEERING↗
DOE OSTI2020

RELAP-7 Application and Enhancement for FLEX Strategies and ATF Behavior under Extended Loss of AC Power Conditions

This report summarizes the results of a three-year research project sponsored by the U.S. Department of Energy (DOE) Nuclear Energy University Program (NEUP) to enhance and apply the RELAP-7 code by adding and improving several important components (e.g., a mechanistic Reactor Core Isolation Cooling (RCIC) system model) for thermal hydraulic studies of LWRs under ELAP conditions and evaluating the time available for transition to portable FLEX equipment. The project team included University of Massachusetts–Lowell, The Ohio State University, Texas A&M University, Idaho National Laboratory and Oak Ridge National Laboratory. In the Fukushima accident, it was found that the RCIC system played a crucial role in delaying core meltdown by almost three days in Fukushima Daiichi Unit 2, because of self-regulated operation of the steam driven RCIC turbine-pump injection system. Steam flow in the convergent-divergent nozzles of the RCIC Terry turbine is two-phase non-equilibrium transonic flow with homogenous nucleation condensation. To more accurately predict the dynamic process and behavior of the transonic compressible steam flow, a one-dimensional transient two-phase analytical model is presented. A simplified four-fluid model was employed in the present work with the consideration of four separate fluid fields: vapor, liquid film, entrained droplets and condensed droplets. The mass, momentum and energy interactions between the fluids were considered and modeled. An extended seven-equation non-equilibrium critical flow model was developed to obtain the critical pressure and velocities of each phase at the nozzle throat. To predict the wetness in the divergent section, a mechanistic nucleation condensation model was integrated in the nozzle analysis model, considering the generation and consequent growth of droplets. The governing differential equations on a staggered grid were discretized using the second-order Lax-Wendroff scheme with a flux limiter, and the Semi-Implicit Method for Pressure-Linked Equation (SIMPLE) algorithm was employed to solve the discrete linear system. To demonstrate the predictability and reliability of the physical models and the numerical method proposed in the present work, three representative nozzles were modeled and simulated. The results show good agreement with the available experimental data, even for condensation shock. Then, the 1D nozzle model was employed to obtain nozzle flow tables of the Terry turbine nozzle for different working pressures which can cover the operation pressure range of the RCIC system. A mechanistic RCIC turbine-pump system model was developed and implemented in the system code TRACE to simulate dynamic responses of the RCIC system under Beyond Design Basis Accident (BDBA) conditions. The turbine-pump governing equations are based on the control volume approach of the angular momentum balance. The physics based mechanistic RCIC model was developed using the TRACE control system components (i.e., signal variables, control blocks, and tables), and incorporated into a TRACE boiling water reactor (BWR) model. The TRACE model in this report has a detailed nodalization of the reactor pressure vessel (RPV), and all of the major flow paths and system components, including the safety relief valves (SRVs) and the containment suppression pool and drywell. Based on the nozzle flow tables generated from the 1D nozzle model developed, the turbine drive torque can be calculated from table lookup. Since the detailed specifications of the RCIC pump are unavailable, the homologous curves for a Bingham pump were used in the current pump component. A station black-out (SBO) accident test problem was selected to demonstrate the TRACE RCIC model. The short-term SBO simulations were performed for two cladding materials: Zircaloy and FeCrAl, to demonstrate the effect of the accident tolerant fuel cladding on fuel heat-up under BDBA accident conditions. The wetwell plays a vital safety role in SBO and other BWR accident scenarios in that it can reduce containment pressure and supply additional core make-up water. The suppression pool temperature distribution has a very large impact on both RPV and containment pressure. Thus, another novel contribution of the project comes mainly from an improved, systems-level wetwell model which can capture buoyancy-induced thermal stratification effects due to steam injection and condensation. A two-zone stratified wetwell model has been implemented in RELAP-7 and some results from that model are presented. This wetwell model is capable of simulating thermal stratification due to a low steam mass injection rate. With a low mass flow rate, the model assumes that all the steam condenses within the pipe and the resulting plume can be approximated with a purely buoyant, heat-source driven model. The wetwell model developed with these assumptions is adequate to simulate slow transients such as extended SBO transients.

42 ENGINEERING↗
DOE OSTI2023

Effect of Ligand Chemistry on the Electronic Properties and Reactivity of Cobalt Acetate Autoxidation Catalysts

Autoxidation chemistry catalyzed by cobalt(II) acetate is an industrial pathway for converting hydrocarbons into oxygenated compounds and has promising potential applications in plastic waste deconstruction. However, the chemical properties of the Co acetate-based catalysts and their roles in the reaction mechanism are poorly understood, and as a result, attempts to redesign the autoxidation chemical process for novel applications lack clear direction. In this work, we investigate the structure and electronic properties of a series of multinuclear Co(III) compounds that have been proposed as active participants in catalytic autoxidation. Through a combination of X-ray spectroscopic measurements [Co K-edge X-ray absorption spectroscopy (XAS), extended X-ray absorption fine structure (EXAFS), Kβ X-ray emission spectroscopy (XES), and high-energy resolution fluorescence detection (HERFD) XAS] and theoretical methods, we characterize the interactions of Co with acetate and hydroxyl ligands in these compounds. Here we show that the substitution of acetate ligands with hydroxyls in these compounds causes an increase in the electron density on Co, driven by the loss of a π back-bonding interaction between Co and acetate and an increase in electron donation to Co from the hydroxyl ligands. We further classify the bonding between Co and acetate based on the orbital overlap and show that the experimental absorption and emission spectra are well-described by the resulting molecular orbitals. Finally, we predict the impacts of acetate/hydroxyl ligand exchange on autoxidation catalytic properties, showing that the reaction free energies for key Co oxidation and reduction steps are extremely sensitive to metal-ligand bonding interactions and thus have meaningful impacts on overall reactivity. The results of this study constitute an important set of design criteria for developing novel homogeneous autoxidation catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Partially polaron-transformed quantum master equation for exciton and charge transport dynamics

Polaron-transformed quantum master equation (PQME) offers a unified framework to describe the dynamics of quantum systems in both limits of weak and strong couplings to environmental degrees of freedom. Thus, the PQME serves as an efficient method to describe charge and exciton transfer/transport dynamics for a broad range of parameters in condensed or complex environments. However, in some cases, the polaron transformation (PT) being employed in the formulation invokes an over-relaxation of slow modes and results in premature suppression of important coherence terms. A formal framework to address this issue is developed in the present work by employing a partial PT that has smaller weights for low frequency bath modes. In this work, it is shown that a closed form expression of a second order time-local PQME including all the inhomogeneous terms can be derived for a general form of partial PT, although more complicated than that for the full PT. All the expressions needed for numerical calculation are derived in detail. Applications to a model of a two-level system coupled to a bath of harmonic oscillators, with test calculations focused on those due to homogeneous relaxation terms, demonstrate the feasibility and the utility of the present approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Benchmark Solutions for Radiation Transport in Stochastic Media with Inhomogeneous Material Statistics

Accurately solving implicit Monte Carlo (IMC) thermal photon transport problems with mixed material cells is important in realistic applications. The production IMC package at LLNL treats mixed material cells arising from ALE remap and hydrodynamics using the same approximate model. The new Imp IMC thermal photon transport package currently under development has both a material interface reconstruction (MIR) algorithm and a Levermore-Pomraning (LP) stochastic medium algorithm for treating mixed material cells. Existing stochastic medium algorithms for treating mixed material cells in IMC lack a complete theoretical basis. The IMC LP algorithm implementation has been demonstrated to reproduce published deterministic LP solutions for the particular case of spatially homogeneous material statistics. Realistic simulations will include spatially inhomogeneous material statistics (material mean chord lengths). In a previous investigation, the LP-model for transport in binary stochastic media in rod geometry was generalized to accommodate spatially varying material chord lengths, i.e., the mixing statistics were allowed to be nonhomogeneous. Analytical solutions were obtained and used to produce a verifi cation suite for the Imp IMC Levermore-Pomraning implementation for different spatial variations of the chord lengths. However, the accuracy of the LP model when the mixing statistics are nonhomogeneous has not been assessed and leaves open the question of whether local accuracy is improved or further degraded when chord lengths are not uniform. This shortcoming is rectifi ed here by developing benchmark analytic solutions for transport in binary Markovian stochastic mixtures in rod geometry with nonhomogeneous mixing statistics, using spatially varying chord lengths considered in the previous investigation based on the LP model. Methods for sampling a nonhomogeneous Poisson process (NHPP) are first described and used to construct individual realizations of the binary mixtures in rod geometry. Analytic solutions are then obtained for the forward and backward directed fluxes on a given realization, now viewed as a deterministic medium with alternating layers of the two materials with known interface locations. Finally, material averaged scalar fluxes are obtained using these sampling schemes with spatially linear and quadratic chord lengths and used to assess the accuracy of the previously obtained LP-model results.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Beam characterization at NSRL for radiobiological experiments—phase 1

An experimental campaign was carried out at the NASA Space Radiation Laboratory to perform an additional, independent dosimetric characterization of the beams of protons, helium and carbon ions for radiobiological experiments. The campaign was undertaken by the request and with the support from the National Cancer Institute, U.S. In this initial phase, the goals were to obtain a first assessment of the dosimetric reproducibility of the beam control system, including analysis of spatial homogeneity and evaluation of ion beam contamination. They should facilitate the design of further experimental campaigns for beam characterization for radiobiological experiments. Measurements included reference dosimetry with comparison of in-house and external ionization chambers and electrometers, lateral-dose profile measurements in air, depth-dose profile in a water tank, evaluation of water equivalent thickness of a HDPE binary range shifter and estimation of impurities of the investigated helium-ion beam. The experiments and results are presented.

43 PARTICLE ACCELERATORS↗
DOE OSTI2020

Heterogeneity effects on nondestructive assay measurements of enrichment in UF 6 cylinders

A set of measurements were performed using multiple mechanically cooled HPGe detectors at six positions around a cylinder uranium hexafluoride to assess if matrix inhomogeneity is detectible and effects the determined apparent uranium enrichment. These measurements were performed on nine 30B cylinders of uranium hexafluoride. Six of the cylinders appeared to be homogeneous and had similar apparent measured uranium enrichment, as calculated by the FRAM software, at all positions. However, three cylinders appeared to have local inhomogeneity based on the observed results. This was manifested as very low apparent enrichments, often <10% of the declared enrichment, on select positions. The side with a low apparent enrichment shows elevated daughter isotope activity (e.g., elevated 1001 keV and 766 keV peak count rate) and slightly reduced 235 U activity (lower 185.7 keV count rate). We hypothesize that these heterogenous cylinders may have experienced asymmetric solar heating, which caused volatile UF 6 to sublime preferentially away from the warmed side. A similar phenomenon was observed at a second facility where dose rate measurements confirm that the “low-enriched side” of cylinders show elevated gamma ray dose rates, likely from the removal of UF 6 attenuation and concentration of daughter-products. Care should be taken during uranium enrichment verification when applying methods that include gamma-rays associated with daughter nuclides to the determination of uranium enrichment on cylinders that are stored in sunlight and have asymmetric dose readings around the cylinder.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗