Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “UF”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Thermoresponsive antifouling ultrafiltration membranes from mesophase templating

Nanostructured polymers synthesized by lyotropic liquid crystal (LLC) templates with normal hexagonal (H 1 ) structure exhibit a 3D-continuous transport path, which makes them ideal for membrane separation application. Incorporating additional functionality, especially stimuli-responsiveness, in such an ordered structure provides even more application opportunities. Here, in this work, we present the first successful synthesis of H 1 -structured thermoresponsive ultrafiltration (UF) membranes via LLC templating. The membrane contains thermoresponsive Pluronic P84 diacrylate (P84DA) which not only acts as the monomer and structure-directing amphiphile, but also enables the pore size change with temperature. Experimental studies reveal that the swelling capacity of H 1 -templated polymer as well as permeability and selectivity of the obtained membrane can be altered by changing the temperature. Increasing the temperature from 25 to 45 °C increases the normalized flux from 28 to 68 L m -2 h -1 μm and molecular weight cut-off (MWCO) from 2200 to 3900 Da. Furthermore, the membrane shows an outstanding fouling resistance against different solutes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Cholesky Decomposition-Based Implementation of Relativistic Two-Component Coupled-Cluster Methods for Medium-Sized Molecules

A Cholesky decomposition (CD)-based implementation of relativistic two-component coupled-cluster (CC) and equation-of-motion CC (EOM-CC) methods using an exact two-component Hamiltonian augmented with atomic-mean-field integrals (the X2CAMF scheme) is reported. Furthermore, the present CD-based implementation of X2CAMF-CC and EOM-CC methods employs atomic-orbital-based algorithms to avoid the construction of two-electron integrals and intermediates involving three and four virtual indices. The CD-based implementation extends the applicability of X2CAMF-CC and EOMCC methods to medium-sized molecules with the correlation of around 1000 spinors. Benchmark calculations for uranium-containing small molecules have been performed to assess the dependence of CC results with respect to the Cholesky threshold. A Cholesky threshold of 10 –4 is shown to maintain chemical accuracy. Example calculations to illustrate the capability of the CD-based relativistic CC methods are reported for the bond dissociation energy of the uranium hexafluoride molecule, UF 6 , with up to quadruple-zeta basis sets and the lowest excitation energy in solvated uranyl ion [UO 2 2+ (H 2 O) 12 ].

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

Theoretical and Experimental Study of the Spectroscopy and Thermochemistry of UC +/0/–

A combination of high-level ab initio calculations and anion photoelectron detachment (PD) measurements is reported for the UC, UC – , and UC + molecules. To better compare the theoretical values with the experimental photoelectron spectrum (PES), a value of 1.493 eV for the adiabatic electron affinity (AEA) of UC was calculated at the Feller–Peterson–Dixon (FPD) level. The lowest vertical detachment energy (VDE) is predicted to be 1.500 eV compared to the experimental value of 1.487 ± 0.035 eV. A shoulder to lower energy in the experimental PD spectrum with the 355 nm laser can be assigned to a combination of low-lying excited states of UC – and excited vibrational states. The VDEs calculated for the low-lying excited electronic states of UC at the SO-CASPT2 level are consistent with the observed additional electron binding energies at 1.990, 2.112, 2.316, and 3.760 eV. Potential energy curves for the Ω states and the associated spectroscopic properties are also reported. Compared to UN and UN + , the bond dissociation energy (BDE) of UC (411.3 kJ/mol) is predicted to be considerably lower. The natural bond orbitals (NBO) calculations show that the UC 0/+/– molecules have a bond order of 2.5 with their ground-state configuration arising from changes in the oxidation state of the U atom in terms of the 7s orbital occupation: UC (5f 2 7s 1 ), UC – (5f 2 7s 2 ), and UC + (5f 2 7s 0 ). Furthermore, the behavior of the UN and UC sequence of molecules and anions differs from the corresponding sequences for UO and UF.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAu n – , n = 3–7

A collaborative effort between experiment and theory towards elucidating the electronic and molecular structures of uranium-gold clusters is presented. Anion photoelectron spectra of UAu n – (n=3-7) were taken at third (355 nm) and fourth (266 nm) harmonics of a Nd:YAG laser, as well as excimer (ArF 193nm) photon energies, where the experimental adiabatic electron affinities (AEA) and vertical detachment energies (VDE) values were measured. Complementary first principles calculations were subsequently carried out to corroborate experimentally determined electron detachment energies and to determine the geometry and electronic structure for each cluster. Except for the ring-like neutral isomer of UAu 6 where one unpaired electron is spread over the Au atoms, all other neutral and anionic UAu n clusters (n = 3 - 7) were calculated to possess open-shell electrons with the unpaired electrons localized on the central U atom. The smaller clusters closely resemble the analogous UF n species, but significant deviations are seen starting with UAu 5 where a competition between U-Au and Au-Au bonding begins to become apparent. The UAu 6 system appears to mark a transition where Au-Au interactions begin to dominate, where both a ring-like and two heavily distorted octahedral structures around the central U atom are to be nearly isoenergetic. With UAu 7 , only ring-like structures are calculated. Altogether, the calculated electron detachment energies are in good agreement with the experimental values

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Bond Dissociation Energies and Electronic Calculations on the Actinide Halides ThX and UX (X = Cl, Br, I)

Resonant two-photon ionization spectroscopy has been used to locate predissociation thresholds in the spectra of the actinide halides ThX and UX, where X = Cl, Br, and I. These predissociation thresholds are identified as the bond dissociation energies (BDEs) of the molecules. The resulting values show very similar BDEs for the corresponding ThX and UX species, with the thorium molecules being slightly more strongly bound: D 0 (ThCl) = 5.077(6) eV, D 0 (ThBr) = 4.391(4) eV, D 0 (ThI) = 3.537(8) eV, D 0 (UCl) = 4.989(3) eV, D 0 (UBr) = 4.313(3) eV, and D 0 (UI) = 3.449(8) eV. Here, the estimated error limit is given in parentheses in units of the last reported digit. Spinor-based coupled cluster calculations have also been carried out on the halides of this work, including also ThF and UF. Here, the final D 0 values after including contributions due to basis set incompleteness, outer-core-correlation, picture-change, and QED effects are within 0.04 eV of the present experimental values in each case.

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

Decoding the Pair Distribution Function of Uranium in Molten Fluoride Salts from X-Ray Absorption Spectroscopy Data by Machine Learning

Thermal properties of actinides in molten salts are linked to the strongly disordered local environment of actinide ions. Here, we illustrate both the limitations of the commonly used fitting method for analysis of extended X-ray absorption fine structure (EXAFS) spectra in molten UF 4 and a possible solution using an "objective neural network - EXAFS" (ONNE) method. ONNE provides both extraction of the pair distribution function, as validated by its application to the EXAFS spectra calculated on molecular dynamics trajectory, and the EXAFS data reconstruction. The ONNE analysis of the molten UF4 has revealed reduction of the first nearest neighbor U-F coordination number, expansion of the U-F bond length and smaller contribution to the second shell compared to its crystalline counterpart. This method is therefore an attractive alternative to conventional EXAFS analysis and molecular dynamics simulations for studies of disordered environment of actinides in molten salts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Chemical and spectroscopic characterization of plutonium tetrafluoride

Anhydrous plutonium tetrafluoride is an important intermediate in the production of metallic Pu. This historically important compound is also known to exist in at least two distinct, yet understudied hydrate forms, PuF 4 ·xH 2 O(s) (0.5 ≤ x ≤ 2) and PuF 4 ·2.5H 2 O(s). X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) are the most common tools used to characterize these materials, often in a context for studying structural and morphological changes that arise from aging or calcination. However, fundamental electronic and vibrational spectroscopic information is rather scarce. Here, in this study, we measured the visible and shortwave infrared (SWIR) diffuse reflectance, Fourier transform infrared (FTIR), fluorescence and Raman spectra of PuF 4 (s) and PuF 4 ·xH 2 O(s) to obtain a better electronic and vibrational fingerprint. Our work provides clear indication of the polymeric structure of anhydrous PuF 4 , consistent with the Raman spectrum of UF 4 (s) and its hydrates. This is supplemented with XRD, TGA and SEM analysis. Findings in this study indicate that the spectra are modified by particle size, which in turn is influenced by synthetic technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A High-Assay Low-Enriched Uranium Fuel Transportation Concept

The uranium 235U enrichment commonly used in fuel production for U.S. light water nuclear reactors typically does not exceed 5 wt%. In contrast, many of the currently investigated advanced reactor concepts demand fuel with higher enrichments. This includes high-assay low-enriched uranium (HALEU), characterized by a 235U enrichment of 5 to 20 wt%. The necessity of HALEU transportation in the fuel production cycle leads to new challenges caused by various technical and regulatory hurdles. Current U.S. Nuclear Regulatory Commission–approved transportation package designs for UF6 with enrichments above 5 wt% provide relatively small payloads [=116 kg (250 lb)]. Furthermore, in accordance with 10 CFR 71.55, package design activities for fissile material enriched above 5 wt% need to consider water infiltration in the containment as part of the criticality safety evaluations. This study presents a transportation package concept for HALEU advanced nuclear reactor fuel with a significantly higher payload of up to 376 kg (830 lb) of fissile material per package and up to 1881 kg (4149 lb) of HALEU per legal weight truck. The anticipated chemical form of the transported material is UO2 downblended from available highly enriched uranium. The concept utilizes a combination of existing transportation packaging, 18 inner canisters, and a novel basket design that includes a borated aluminum flux trap. Criticality and shielding evaluations; fundamental structural, confinement, and thermal assessments; and studies on package operations are presented. The results of this study build significant confidence in the technical feasibility of a high-capacity HALEU transportation package concept while demonstrating the concept’s potential to meet U.S. regulatory requirements.

Eidelpes, Elmar↗
DOE OSTI2022

5f covalency from x-ray resonant Raman spectroscopy

Here, X-ray resonant Raman spectroscopy (XRRS), a variant of resonant inelastic x-ray scattering, has been used to investigate the two prototype systems, UF 4 and UO 2 . Both are U5f 2 and each is an example of 5f localized, ionic behavior and 5f localized, covalent behavior, respectively. From the M 5 XRRS measurements, the 5f band gap in each can be directly determined and, moreover, a clear and powerful sensitivity to 5f covalency emerges.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Proactive Frequency Stability Scheme via Bayesian Filters and Synchrophasors

Underfrequency (UF) load shedding schemes are traditionally implemented in two ways: One approach is based on manual load shedding, with system operators requesting loads to be shed ahead of anticipated stressful operating conditions. Manual load shedding is usually done through phone calls. The second method is automatic load shedding via underfrequency relays. Using static static settings, these schemes can be designed to operate in stages and drop previously identified loads. The main limitation of traditional load shedding schemes is that they are reactive and leave little room for optimized corrective actions. This work presents a proactive and automatic underfrequency load shedding solution for power systems. Measurements are captured via phasor measurement units (PMUs) at relatively low sampling rates of 30 Hz. These measurements are then processed by particle filters who predict the future state of the system's frequency. Based on these predictions excess load is determined and shed. Comparative case studies are performed in simulated environments. Easy-to-implement models, without hard-to-derive parameters, highlight potential aspects for real-life implementation.

Paramo, Gian↗
DOE OSTI2021

Underlying simplicity of 5f unoccupied electronic structure

Using a simple empirical model based upon the bremsstrahlung isochromat spectroscopy of elemental Th, it is possible to explain the recent high energy resolution fluorescence detection measurements of UF 4 (n = 2) and UCd 11 (n = 3) as well as the new inverse photoelectron spectroscopy of Pu 2 O 3 (n = 5), where n is the 5f occupation number. Furthermore, a critical issue in this analysis is the assumption that the Th 5f states are essentially empty, which will be confirmed both experimentally and computationally. Thus, for 5f systems, this simple model provides a unified and consistent picture of 5f unoccupied density of states in simple, localized systems, as the 5f occupation varies in the early part of the series, for n = 0, 2, 3, and 5.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Kinetic Parameters and Diffusivity of Uranium in FLiNaK and ClLiK

Anodic stripping voltammetry (ASV) and cyclic voltammetry (CV) measurements at 773, 823, and 873 K were made of uranium trifluoride (UF 3 ) in lithium fluoride-sodium fluoride-potassium fluoride eutectic (FLiNaK) and uranium trichloride (UCl 3 ) in lithium chloride-potassium chloride eutectic (ClLiK). ASV data were used to estimate the charge transfer coefficients, exchange current densities, and activation energies of the uranium reactions. Charge transfer coefficients of both salt systems were within the range of 0.17 to 0.38. Exchange current densities in the fluoride and chloride salts were estimated within the range of 0.060 to 0.12 A cm -2 . Activation energy of uranium exchange current was 16.0 kJ mol -1 in the fluoride salt and 28.9 kJ mol -1 in the chloride salt. Kinetics of charge transfer were found to be faster in FLiNaK. Analyses of the CV data suggest the electrochemical system was diffusion controlled and irreversible in the chloride and fluoride salt mixtures. Diffusion coefficients of uranium in the range of temperatures were on the order of 10-5 cm 2 s -1 in both systems. Greater values of diffusivity in ClLiK are attributed to its lower density compared with FLiNaK. Activation energy of uranium diffusion in the fluoride and chloride salt mixtures were 53.4 and 89.4 kJ mol -1 , respectively.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

iClick Synthesis of Metallopolymers and Highly Emissive Materials

This project involves the exploitation of iClick (Inorganic Click) to link two or more metal ions. The novel cycloaddition between a metal-azide and a metal-acetylide developed at UF provides an opportunity to prepare materials that were previously unimaginable. Further developing the synthetic methodology of iClick will open new frontiers for materials synthesis. Three specific goals are outlined in the project: 1) investigate the chemistry of iClick and its application to linking metal ions, 2) develop a method to dynamically tune the emission color of soluble gold-oligomers, and 3) exploit iClick synthesis to develop new conjugated Pt- and Ru-metallopolymers. Metallopolymers are on the cusp of revolutionizing the energy sector, information storage, and materials synthesis. Uniquely, transition metal chemistry marries polymer science in these hybrid materials wherein the metal ion imparts new properties unimaginable for organic polymers alone.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Assessment of Existing Transportation Packages for Use with HALEU

Commercial light water reactor operators and fuel vendors in the United States are pursuing changes to fuel that include increased 235 U enrichment. Economic studies generally anticipate maximum near-term fuel assembly designs with up to 8 wt.% 235 U. Many next-generation nuclear reactor designs require high-assay low-enriched uranium (HALEU) (19.75 wt.% > 235 U > 5 wt.%) fuel. One necessary element for the commercial-scale use of HALEU is the ability to safely transport large quantities of enriched fuel material in multiple forms. However, there is uncertainty as to whether subcriticality requirements can be satisfied with existing package designs and whether existing critical benchmark experiment data are sufficient to support criticality safety code validation for HALEU transportation applications. This study assesses the potential to use currently licensed transportation packages for the transportation of increased enrichment unirradiated U fuel forms. The assessment uses selected package designs that represent the five categories of fuel form-boiling water reactor pins and assemblies, pressurized water reactor pins and assemblies, UF 6 , U-metal and tristructural isotropic (TRISO) particles, and UO 2 pellets or powder-and focuses on demonstrating subcriticality and identifying benchmark critical experiments appropriate for use in criticality computer code validation. Key quantities of interest that relate to subcriticality are limiting conditions (e.g., optimum moderation), package or package array k eff , package capacity, and package transportation array size. The SCALE TSUNAMI-3D and TSUNAMI Indices and Parameters codes are used for sensitivity and uncertainty calculations and for identification of candidate critical benchmark experiments for code validation. The primary metric for identifying candidate benchmarks is the similarity coefficient, c k . For each fuel form category, a representative package is evaluated. Results provided for each package evaluation include enrichment and packaging limits (e.g., maximum transportation array size as a function of enrichment) and benchmark critical experiment similarity coefficients. Results indicate that there are viable means for increasing enrichments into the HALEU range across the spectrum of fuel forms with differing increase amounts available for different packages. Sources of subcriticality margin to offset increased enrichment reactivity include reduced transportation array size, reduced fissile mass, burnable absorber credit, and safety analysis margin harvesting. For all packages except the DN-30, numerous critical benchmark experiment candidates for validation were identified.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Analysis of ISOCS Measurements to Establish Methodology Uncertainty

Qualification measurements were performed at the US Department of Energy’s (DOE’s) Oak Ridge National Laboratory (ORNL) on a variety of measurement standards. These measurements will be used to qualify the In-Situ Object Counting System (ISOCS) measurement method with a high-purity germanium (HPGe) detector for use at ORNL. Measured items include uranium isotopic standards, filter papers coated with uranium oxide (U 3 O 8 ), U 3 O 8 line sources, and a uranium tetrafluoride (UF 4 ) source. The 235 U mass was estimated using the ISOCS calibration software for each source and compared with the declared isotope mass value.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Criticality Safety and Fuel Performance Considerations for Enrichment Above 5 Weight Percent in the Uranium Dioxide Fuel Cycle

The U.S. Nuclear Regulatory Commission (NRC) is preparing for anticipated licensing applications requesting fuel enrichments of UO 2 ceramic fuels enriched in excess of 5 weight percent (w/o) 235 U for commercial light-water reactors (LWRs). PNNL has been tasked with providing technical assistance to the NRC related to the review and approval of requests for enrichment increases above the current 5 w/o 235 U enrichment limit. This report will provide the agency with technical assistance to enhance the staff’s knowledge base and to identify developmental needs required to support the licensing of greater than 5 w/o UO 2 ceramic fuels. This report provides a background on increasing enrichment of UO 2 LWR fuel beyond 5 w/o 235 U. The primary concern of increasing enrichment is the impacts to criticality safety. This report will focus on criticality safety as it relates to enrichment, conversion of uranium hexafluoride to UO 2 , fuel assembly fabrication, transportation of fresh/spent fuel assemblies, reactor operations, and storage of fresh/spent fuel assemblies. The report provides a general summary of each of the steps in the UO 2 fuel cycle starting from transportation of enriched UF 6 through dry cask storage of spent fuel assemblies. This report also discusses other impacts of increased enrichment during reactor operation and the surrounding fuel cycle activities. Current needs regarding both data and analytical codes to support the increase above 5 w/o 235 U are identified and discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗