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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 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Asymmetric Lattice Disorder Induced at Oxide Interfaces

Control of order-disorder phase transitions is a fundamental materials science challenge, underpinning the development of energy storage technologies such as solid oxide fuel cells and batteries, ultra-high temperature ceramics, and durable nuclear waste forms. At present, the development of promising complex oxides for these applications is hindered by a poor understanding of how interfaces affect lattice disordering processes and defect transport. Here we explore the evolution of local disorder in ion-irradiated La 2 Ti 2 O 7 /SrTiO 3 thin film heterostructures using a combination of high-resolution scanning transmission electron microscopy (STEM), position-averaged convergent beam electron diffraction (PACBED), electron energy loss spectroscopy (STEM-EELS), and ab initio theory calculations. We observe highly non-uniform lattice disordering driven by asymmetric oxygen vacancy formation across the interface. Our calculations indicate that this asymmetry results from differences in the polyhedral connectivity and vacancy formation energies of the two interface components, suggesting ways to manipulate lattice disorder in functional oxide heterostructures.

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2024

A framework for strategic discovery of credible neural network surrogate models under uncertainty

The widespread integration of deep neural networks in developing data-driven surrogate models for high-fidelity simulations of complex physical systems highlights the critical necessity for robust uncertainty quantification techniques and credibility assessment methodologies, ensuring the reliable deployment of surrogate models in consequential decision-making. Here, this study presents the Occam Plausibility Algorithm for surrogate models (OPAL-surrogate), providing a systematic framework to uncover predictive neural network-based surrogate models within the large space of potential models, including various neural network classes and choices of architecture and hyperparameters. The framework is grounded in hierarchical Bayesian inferences and employs model validation tests to evaluate the credibility and prediction reliability of the surrogate models under uncertainty. Leveraging these principles, OPAL-surrogate introduces a systematic and efficient strategy for balancing the trade-off between model complexity, accuracy, and prediction uncertainty. The effectiveness of OPAL-surrogate is demonstrated through two modeling problems, including the deformation of porous materials for building insulation and turbulent combustion flow for ablation of solid fuels within hybrid rocket motors.

42 ENGINEERING↗
DOE OSTI2023

A first principles analysis of potential-dependent structural evolution of active sites in Fe-N-C catalysts

Fe-N-C (iron–nitrogen–carbon) electrocatalysts have emerged as potential alternatives to precious metal-based materials for the oxygen reduction reaction (ORR). However, the structure of these materials under electrochemical conditions is not well understood, and their poor stability in acidic environments poses a formidable challenge for successful adoption in commercial fuel cells. To provide molecular-level insights into these complex phenomena, we combine periodic density functional theory (DFT) calculations, exhaustive treatment of coadsorption effects for ORR reaction intermediates, including O and OH, and comprehensive analysis of solvation stabilization effects to construct voltage-dependent ab initio thermodynamic phase diagrams that describe the in situ structure of the active sites. These structures are further linked to activity and stability descriptors that can be compared with experimental parameters such as the half-wave potential for ORR and the onset potential for carbon corrosion and CO 2 evolution. The results indicate that pyridinic Fe sites at zigzag carbon edges, as well as other edge sites, exhibit high activity for ORR compared to sites in the bulk. However, edges neighboring the active sites are prone to instability via overoxidation and consequent site loss. The results suggest that it could be beneficial to synthesize Fe-N-C catalysts with small sizes and large perimeter edge lengths to enhance ORR activity, while voltage fluctuations should be limited during fuel cell operation to prevent carbon corrosion of overoxidized edges.

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

Respiration is essential for aerobic growth of Zymomonas mobilis ZM4

ABSTRACT Zymomonas mobilis is an alpha-proteobacterium that is a promising platform for industrial scale production of biofuels due to its efficient ethanol fermentation and low biomass generation. Z. mobilis is aerotolerant and encodes a complete respiratory electron transport chain, but the benefit of respiration for growth in oxic conditions has never been confirmed, despite decades of research. Growth and ethanol production of wild-type Z. mobilis is poor in oxic conditions indicating that it does not benefit from oxidative phosphorylation. Additionally, in previous studies, aerobic growth improved significantly when respiratory genes were disrupted ( ndh ) or acquired point mutations ( cydA and cydB ), even if respiration was significantly reduced by these changes. Here, we obtained clean deletions of respiratory genes ndh and cydAB , individually and in combination, and showed, for the first time, that deletion of cydAB completely inhibited O 2 respiration and dramatically reduced growth in oxic conditions. Both respiration and aerobic growth were restored by expressing a heterologous, water-forming NADH oxidase, noxE . Oxygen can have many negative effects, including formation of reactive oxygen species (ROS) or directly inactivating oxygen sensitive enzymes. Our results suggest that the effect of molecular oxygen on enzymes had a greater negative impact on Z. mobilis than formation of ROS. This result shows that the main role of the electron transport chain in Z. mobilis is reducing the intracellular concentration of molecular oxygen, helping to explain why it is beneficial for Z. mobilis to use electron transport chain complexes that have little capacity to contribute to oxidative phosphorylation. IMPORTANCE A key to producing next-generation biofuels is to engineer microbes that efficiently convert non-food materials into drop-in fuels, and to engineer microbes effectively, we must understand their metabolism thoroughly. Zymomonas mobilis is a bacterium that is a promising candidate biofuel producer, but its metabolism remains poorly understood, especially its metabolism when exposed to oxygen. Although Z. mobilis respires with oxygen, its aerobic growth is poor, and disruption of genes related to respiration counterintuitively improves aerobic growth. This unusual result has sparked decades of research and debate regarding the function of respiration in Z. mobilis . Here, we used a new set of mutants to determine that respiration is essential for aerobic growth and likely protects the cells from damage caused by oxygen. We conclude that the respiratory pathway of Z. mobilis should not be deleted from chassis strains for industrial production because this would yield a strain that is intolerant of oxygen, which is more difficult to manage in industrial settings.

09 BIOMASS FUELS↗
DOE OSTI2020

Systems Theory Principles and Complex Systems Engineering Concepts for Protection and Resilience in Critical Infrastructure: Lessons from the Nuclear Sector

Part of the Presidential Policy Directive 21 (PPD-21) (PPD 2013) mandate includes evaluating safety, security, and safeguards (or nonproliferation) mechanisms traditionally implemented within the nuclear reactors, materials, and waste sector of critical infrastructure—including a complex, dynamic set of risks and threats within an all-hazards approach. In response, research out of Sandia National Laboratories (Sandia) explores the ability of systems theory principles (hierarchy and emergence) and complex systems engineering concepts (multidomain interdependence) to better understand and address these risks and threats. Herein, this Sandia research explores the safety, safeguards, and security risks of three different nuclear sector-related activities—spent nuclear fuel transportation, small modular reactors, and portable nuclear power reactors—to investigate the complex and dynamic risk related to the PPD-21-mandated all-hazards approach. This research showed that a systems-theoretic approach can better identify inter-dependencies, conflicts, gaps, and leverage points across traditional safety, security, and safeguards hazard mitigation strategies in the nuclear reactors, materials, and waste sector. Resulting from this, mitigation strategies from applying systems theoretic principles and complex systems engineering concepts can be (1) designed to better capture interdependencies, (2) implemented to better align with real-world operational uncertainties, and (3) evaluated as a systems-level whole to better identify, characterize, and manage PPD-21's all hazards strategies.

42 ENGINEERING↗
DOE OSTI2022

Tritium Transport Modeling at the Pore Scale in Ceramic Breeder Materials Using TMAP8

Fusion reactors depend on the blanket material to breed and release tritium at the same rate or faster than it is consumed by the fusion reaction. Cellular ceramic breeders (CCBs) are dense materials that can maintain a high tritium breeding ratio while promoting tritium release because of highly connected pores. Assessing the tritium breeding capabilities of these materials requires a combination of extensive experimental and modeling efforts. In this work, we develop and calibrate a multiphysics model of tritium transport. This novel model accounts for ceramic and pore diffusion, trapping and detrapping, and several surface reactions at the pore surface. We perform a sensitivity analysis and calibrate the model by comparing its predictions against experimental measurements of deuterium absorption. The calibrated model is then used to model tritium absorption in samples with different pore microstructures to investigate the effect of pore interconnectivity on tritium absorption. The model is part of the development of the multiscale, multiphysics framework for tritium transport [i.e., the Tritium Migration Analysis Program (TMAP8)], which is itself built on top of the finite-element multiphysics framework multiphysics object-oriented simulation environment (MOOSE). This study demonstrates some of TMAP8’s capabilities and is the first step toward assessing the tritium breeding capabilities of ceramic breeder material designs.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Molten Salt Reactor Signatures and Modeling Study

Molten salt reactor (MSR) technologies, either liquid fueled and cooled or only liquid cooled, pose specific, unique challenges for safeguards of the special nuclear material during the operation, fueling, and maintenance of the reactor. MSRs are one type of Generation IV technologies being invested in and considered for U.S. domestic fabrication primarily for electricity and process heat production. These designs have generated growing commercial interest for several reasons, including high (≈40%) thermal efficiency, ease of fueling, improved use of uranium fuel, potential utilization of thorium fuel, and proposed inherent safety features. U.S. companies have several planned designs that differ in fuel, cooling, and neutron energy spectrum. Driven by commercial interest and the intent of licensing MSRs, the U.S. Nuclear Regulatory Commission (NRC) has developed a vision and strategy to accommodate non-light water reactors (LWR), which include MSRs (U.S. Nuclear Regulatory Commission 2019). In addition, the Department of Energy (DOE) through the Office of Nuclear Energy (NE) Office of Advanced Reactor Technologies (ART), …sponsors research, development and deployment (RD&D) activities through its Next Generation Nuclear Plant (NGNP), Advanced Reactor Concepts (ARC), and Advanced Small Modular Reactor (aSMR) programs to promote safety, technical, economical, and environmental advancements of innovative Generation IV nuclear energy technologies. Reactor types considering the use of salts, liquid metals, or gases for coolant fall under both ARC and aSMR. Therefore, Research Design & Development is being pursued by DOE-NE through national laboratories, universities, and international and industrial collaborations. Additionally, the U.S. is a member of the Gen IV International Forum (GIF). The GIF is a cooperative, multinational organization to guide and carry out research and development needed for the GEN IV reactor systems (Forum 2018). GIF evaluated numerous reactor concepts and down-selected to the six most feasible advanced reactor technologies: gas-cooled fast reactor (GFR), lead-cooled fast reactor (LFR), MSR, supercritical watercooled reactor (SCWR), sodium-cooled fast reactor (SFR), and very high temperature reactor (VHTR). In support of the growing interest domestically and internationally, the Materials Protection, Accounting, and Control Technologies (MPACT) campaign, under the DOE-NE Fuel Cycle Technologies (FCT) program, engages in R&D activities by developing advanced instrumentation and analysis for safeguards and security of modern, advanced nuclear fuel cycle (non-LWR) facilities. Because of the historic experience in the operation of the Aircraft Reactor Experiment (ARE) and the Molten Salt Reactor Experiment (MSRE) (Robertson, MSRE Design and Operations Report Part I 1965), Oak Ridge National Laboratory (ORNL) is heavily engaged in the various R&D activities through the DOE complex related to MSRs including national technical leadership of the DOE-NE MSR campaign. This report discusses and presents the outcomes of the FY19 MPACT MSR Safeguards task. The challenges presented by MSRs for nuclear material accountancy and control (NMAC) and associated safeguards will be investigated. The objective of this research is to explore and compile the safeguards requirements and identify measurement signatures through an initial high-level MSR design and develop complementary advanced simulation and modeling capabilities. A high-level ORNL-developed MSR design called the Molten Salt Demonstration Reactor (MSDR) (Bettis, Alexander and Watts 1972) was used as the target reactor design for this research. The MSDR model incorporates technology from the MSRE and the Molten Salt Breeder Reactor (Robertson, Conceptual Design of a Single-Fluid Molten-Salt Breeder Reactor 1971). But the MSDR is a 750 MWth graphite moderated liquid fueled (low-enriched uranium) MSR compared to the MSRE’s of 7.5 MWth. The focus of this report is to discuss the evaluation of novel signatures, correlations, and indicators to understand the applicability of current safeguards instrumentation to MSRs using the modeling results from the MSDR.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Radiation Effects on Uranyl Tetrachloro Coordination Compounds: Impact of Lattice Water

Nuclear materials, such as uranium-bearing solids, are exposed to high levels of ionizing radiation throughout the nuclear fuel cycle; thus, it is important to develop a molecular-level understanding of how these materials behave and degrade in the presence of gamma (γ) irradiation. In the current study, three U(VI) tetrachloride complexes, M 2 [UO 2 Cl 4 ]·xH 2 O (where M = K + , Rb + , or Cs + and x = 0 or 2), and their respective chloride salts were exposed to 1–50 kGy of γ radiation using a 60 Co source. Irradiated materials were evaluated by using electron paramagnetic resonance (EPR) and Raman spectroscopy and were further explored by using density functional theory (DFT) methods. EPR spectra of the irradiated materials suggest the formation of a Cl-based radical for both the alkali salts and the uranyl tetrachloride compounds, and DFT calculations provide evidence that the Cl 2 –• radical is formed within these materials. The presence of water in the K + and Rb + compounds leads to additional spectroscopic signatures that could be traced back to water radiolysis and the formation of peroxide and superoxide species. DFT results support the formation of HO 2 • in the lattice and potentially the formation of a [UO 2 Cl 3 (O 2 )] 3– species, highlighting the impact of water within the hydrated material to alter U(VI) speciation by radiolysis.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Savannah River Site Composite Analysis (FY2019 Annual Review)

The Savannah River Site (SRS) is a Department of Energy (DOE) site encompassing approximately 310 square miles in South Carolina. It is bounded on the southwest by the Savannah River (SR) and is situated approximately 12 miles south of Aiken, South Carolina, and 15 miles southeast of Augusta, Georgia. Construction of and subsequent operations at the SRS began in 1951 under the direction of the Atomic Energy Commission. The primary mission of the SRS was to produce tritium and plutonium for the national nuclear weapons complex. Between 1953 and 1955, SRS brought five reactors and various support facilities into operation in support of its primary mission. Support facilities included two chemical separations plants, a heavy water extraction plant, a nuclear fuel and target fabrication facility, a tritium extraction facility and waste management facilities. With the declining need for a large nuclear weapons stockpile since the end of the Cold War, many SRS facilities no longer produce or process nuclear materials. All reactors were shut down by 1993. However, the SRS Tritium Extraction Facility continues to supply DOE with tritium. Additionally, operations at the K-Area Complex currently provide interim safe storage for much of DOE’s excess plutonium (Pu) and high enriched uranium, in a building which formerly housed K Reactor. As the SRS mission has changed, many surplus facilities are being dispositioned safely and economically. SRS has completed extensive decommissioning activities in D-Area, M-Area, P-Area, R-Area, and T-Area, with groundwater (GW) remediation ongoing. High-level waste tanks continue to be emptied and closed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

An Anthradithiophene Donor Polymer for Organic Solar Cells with a Good Balance between Efficiency and Synthetic Accessibility

Over the past few years, the organic photovoltaics technology (OPV) has reached remarkable power conversion efficiencies (PCEs), mostly thanks to the advent of nonfullerene acceptors as well as to a high level of materials engineering. Yet, the complex materials syntheses behind these results ultimately limit technological readiness. The quest for scalable organic compounds offering high PCE and reasonably low synthetic complexity is a must to close the gap between laboratory R&D and commercial products. The synthesis and full characterization of a new conjugated polymer called PATTD is reported herein, based on a novel anthradithiophene as an electron–rich building block coupled with a commercially available dithienylbenzodithiophenedione as an electron–withdrawing comonomer. Its photovoltaic properties are studied in blends with IT–4F and IDIC as acceptors. PATTD:IT–4F–based photovoltaic devices exhibit a PCE approaching 10% and over 2300 h shelf–life stability. Finally, the PATTD scalability factor (SF), together with the PATTD–based photovoltaic performances, lead to a PCE/SF value equal to 0.297, placing such devices into the innermost circle of OPV materials, achieving one of the best compromises between efficiency and synthetic complexity and at the same time offering promising industrial perspectives.

14 SOLAR ENERGY↗
DOE OSTI2023

Unleashing the capacity of Rhodococcus for converting lignin into lipids

Bioconversion of bioresources/wastes (e.g., lignin, chemical pulping byproducts) represents a promising approach for developing a bioeconomy to help address growing energy and materials demands. Rhodococcus, a promising microbial strain, utilizes numerous carbon sources to produce lipids, which are precursors for synthesizing biodiesel and aviation fuels. However, compared to chemical conversion, bioconversion involves living cells, which is a more complex system that needs further understanding and upgrading. Various wastes amenable to bioconversion are reviewed herein to highlight the potential of Rhodococci for producing lipid-derived bioproducts. In light of the abundant availability of these substrates, Rhodococcus’ metabolic pathways converting them to lipids are analyzed from a “beginning-to-end” view. Based on an in-depth understanding of microbial metabolic routes, genetic modifications of Rhodococcus by employing emerging tools (e.g., multiplex genome editing, biosensors, and genome-scale metabolic models) are presented for promoting the bioconversion. Co-solvent enhanced lignocellulose fractionation (CELF) strategy facilitates the generation of a lignin-derived aromatic stream suitable for the Rhodococcus’ utilization. Novel alkali sterilization (AS) and elimination of thermal sterilization (ETS) approaches can significantly enhance the bioaccessibility of lignin and its derived aromatics in aqueous fermentation media, which promotes lipid titer significantly. In order to achieve value-added utilization of lignin, biodiesel and aviation fuel synthesis from lignin and lipids are further discussed. In conclusion, the possible directions for unleashing the capacity of Rhodococcus through synergistically modifying microbial strains, substrates, and fermentation processes are proposed toward a sustainable biological lignin valorization.

09 BIOMASS FUELS↗
DOE OSTI2021

Embedded Sensors in Additively Manufactured Silicon Carbide

Silicon carbide (SiC) components are being considered for a wide range of nuclear applications due to their high-temperature strength retention, low neutron absorption, chemical inertness, and dimensional stability under neutron irradiation. However, machining and joining of SiC components have traditionally limited its application to relatively simple geometries. Recent work has demonstrated additive manufacturing of complex, high-purity, crystalline SiC components using a combination of binder jet printing and densification via chemical vapor infiltration (CVI). The process lends itself to embedding of fuel, absorbers, moderators, and sensors at strategic locations within a component. The latter could allow for enhanced in situ performance monitoring of limiting fuel temperatures, self-shielded neutron flux, and potentially spatially distributed strain within complex SiC components if sensors can be successfully embedded during CVI. This work describes (1) methods for embedding sensors; (2) thermodynamic analyses and material compatibility testing for identifying sensors capable of surviving high temperatures and exposure to hydrogen and hydrogen chloride during CVI; and (3) nuclear applications for embedded sensors, including potential failure modes during fabrication and during reactor operation. Molybdenum-sheathed thermocouples were successfully embedded in a complex SiC component, whereas niobium-sheathed high-temperature irradiation-resistant thermocouples started to drift as soon as the reactant gases were introduced and ultimately failed during CVI due to severe constrained expansion, potentially resulting from niobium hydride formation in the low-temperature region of the CVI system. Optical fibers were successfully embedded in SiC, but further work is needed to protect the fragile fiber leads after their protective coatings are removed during CVI.

thermocouples↗
DOE OSTI2020

Characterizing electronic and atomic structures for amorphous and molecular metal oxide catalysts at functional interfaces by combining soft X-ray spectroscopy and high-energy X-ray scattering

Amorphous thin film materials and heterogenized molecular catalysts supported on electrode and other functional interfaces are widely investigated as promising catalyst formats for applications in solar and electrochemical fuels catalysis. However the amorphous character of these catalysts and the complexity of the interfacial architectures that merge charge transport properties of electrode and semiconductor supports with discrete sites for multi-step catalysis poses challenges for probing mechanisms that activate and tune sites for catalysis. This minireview discusses advances in soft X-ray spectroscopy and high-energy X-ray scattering that provide opportunities to resolve interfacial electronic and atomic structures, respectively, that are linked to catalysis. This review discusses how these techniques can be partnered with advances in nanostructured interface synthesis for combined soft X-ray spectroscopy and high-energy X-ray scattering analyses of thin film and heterogenized molecular catalysts. Further, these combined approaches enable opportunities for the characterization of both electronic and atomic structures underlying fundamental catalytic function, and that can be applied under conditions relevant to device applications.

14 SOLAR ENERGY↗
DOE OSTI2024

Thermal Elimination of Pyridine from a Uranium Trichloride Precursor

Renewed interest in advanced nuclear reactors, such as Molten Salt Reactors (MSRs), has spurred studies in actinide halide chemistry and property measurements. Several proposed research-scale and commercial MSR designs incorporate uranium trichloride (UCl 3 ) fuel. There are relatively few preparations for isolated actinide halides reported in the literature, therefore novel methods for the isolation of pure material are desired. This communication describes the thermal elimination of pyridine (py) from the coordination complex UCl 3 py 2 to yield gram-scale quantities of UCl 3 . The purity of the UCl 3 product was determined through powder X-ray Diffractometry (pXRD) and Elemental Analysis (EA).

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

Tailored Fiber Placement for Complex Preforms

Tailored Fiber Placement (TFP) offers a novel approach to optimize fiber architecture for the fabrication of complex, structural parts not traditionally suitable for advanced composites. This technology not only offers new routes for weight reduction via metal substitution, it also offers cost reduction through minimization of material scrap and reduced labor. This reduction in component weight leads to increased fuel efficiency, and reduced production energy consumption, thereby, helping to achieve the stated IACMI technical goals. This technology leverages centuries of manufacturing development in support of the textile and embroidery industry. One major drawback to this technology is the lack of commercial or non- proprietary structural performance data and robust analytical tools used to optimize fiber architecture and predict performance. This project was structured to utilize common sub-element features to validate analytical performance tools, generate performance data, and gather cost and performance data on components of interest. This project was designed to give industry sponsors the confidence and ability to take full advantage of TFP to fabricate primary, highly loaded structure and integrate features such as metallic fasteners. The project focused principally on the use of high strength carbon fiber, such as T700, and the use of aerospace epoxy resin matrix to primarily support development of new composite applications in vehicle, aerospace, and industrial markets. This project applied previously developed analytical tools to predict the performance of TFP produced parts. This work focused on developing the pipeline to characterize material in order to accurately predict component performance when modifying the TFP print paths and stitch density. This focused on experimental characterization via standardized ASTM testing, alongside experimental testing of more representative service components by testing curved beam strength, beam shear performance, a large scale TFP lug, and ultimately designing a fully TFP clip bracket that reduced weight and cost compared to a traditional metallic component. The new knowledge gained from this program included: 1) development and demonstration of novel analytical tools applied to analysis of TFP preforms; 2) development and demonstration of a building block approach using coupons and sub-elements to optimize the design of a more complex component; 3) demonstration that optimized fiber orientation using TFP can exceed performance of conventional textile composite materials and can open new applications currently limited to metallic components; 4) Demonstration of performance and cost benefits of the TFP process as compared to metallic and conventional textile composites. Recommendations for follow-on work include development of design allowables to assess the impact of high temperature/moisture exposure or saturation during loading, tracking the impact of stitching needle wear on the performance of parts and ability to stitch thicker preforms, using TFP preforms as local reinforcement at areas of bearing or complex loading, and topology optimization of components by tow steering. The expertise developed during the course of this project can be leveraged to provide commercial engineering design and fabrication services using TFP. UDRI is in the process of formalizing their partnership with Spintech, who will serve as the commercialization partner for this technology and provide molding services and deliver finished components to the end user. UDRI will continue to produce the preforms until the economics allow Spintech to procure its own TFP equipment or lease UDRI equipment, at which point UDRI will step away from manufacture and serve as the engineering and design lead on product development.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Gas-Phase Stability of Large Lanthanide:Ligand Clusters Evaluated Using Collision-Induced Dissociation

Introduction In the reprocessing of f-elements present in used nuclear fuels, a variety of diglycolamides (DGA’s) are used as extractants for actinide partitioning. In particular, the Actinide-Lanthanide Separation (ALSEP) process typically utilizes either the N,N,N’,N’-tetraoctyl diglycolamide (TODGA) or N,N,N',N'-tetra-2-ethylhexyl diglycolamide (T2EHDGA) extractant ligands following the partitioning of uranium and plutonium from used nuclear fuel. To better understand fundamental interactions in these processes, covalent bonding of several f-elements with diglycolamides, primarily TODGA, is investigated in the gas phase using nanospray ionization and a quadrupole time-of-flight mass spectrometer. Further, analysis of the identity and relative strength of the cluster is enabled by MS2 isolation and collision induced dissociation. Methods Metal ion cluster analysis was completed using a Bruker (Billerica, MA, USA) mircOTOF-Q II quadrupole time-of-flight mass spectrometer with a CaptiveSpray nanospray ion source. Detection was accomplished using positive ionization mode. Metal: ligand solutions were assembled as 30 µM europium nitrate, samarium nitrate, cerium nitrate, or holmium nitrate and 3 µM DGA in acetonitrile or a 50:50 mixture of acetonitrile: isopropanol. Preliminary data The samarium cluster experiments yielded clusters with a samarium:TODGA ratio of up to 1:7 able to be isolated and evidence of greater ratios present in the mass spectrum. This is surprising, as metal clusters are not expected to have a coordination space able to accommodate this many TODGA ligands, due to its size and tridenticity. Collisional activation of [Sm(TODGA)3]3+ suggested loss of a TODGA radical cation, in addition to ligand fragmentation. In contrast, activation of clusters with higher Sm:TODGA ratios resulted in loss of entire ligands, with no evidence of fragmentation. A lower collision energy was required to remove ligands as the number of bound TODGAs increased, suggesting that in larger clusters, ligands are more delicately complexed to the metal. In addition, several clusters were observed with the composition [Sm(NO3)x(TODGA)n x]+3 x. With a single nitrate ion, clusters with up to six TODGAs were able to be isolated. In a similar pattern to the samarium clusters containing only TODGA, less collision energy was required to eliminate one or more TODGAs with increasing size. Clusters with composition [Sm(NO3)(TODGA)n-1]2+ appeared in lower abundance and were more collisionally stable than [Sm(TODGA)n]3+ clusters. With two nitrate ions, only clusters with a single TODGA were able to be isolated. Analogous europium experiments resulted in similar clusters. Ratios of up to 1:7 Eu:TODGA and clusters with one nitrate and up to five TODGAs were isolated. In clusters with two nitrate ions, only one or two TODGAs were observed to be bound. Similar to samarium, MS2 experiments with the Eu clusters suggested that larger clusters required less collision energy to eliminate TODGA. Europium clusters with the composition [Eu(NO3)(TODGA)n-1]2+ were observed in greater abundance and with greater stability than the equivalent cluster with the composition [Eu(TODGA)n]3+. Novel Aspect These are the first reported Ln:TODGA clusters, allowing us to begin to investigate intrinsic complexation of lanthanides with process-relevant ligands.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Versatile TRISO fuel particle modeling in Bison

Tri-structural isotropic (TRISO) fuel particles are a key component in several previous and current reactors as well as in a variety of novel nuclear reactor designs. Interest in TRISO fuel is on the rise, necessitating considerable computer modeling of TRISO fuel behavior in order to support related design and licensing activities. The Bison nuclear fuel performance code, which offers a full set of capabilities for modeling TRISO fuels, makes it easier to explore the various important aspects of TRISO fuel behavior. One key advantage of Bison is its ability to create meshes in 1D, 2D, and 3D. Users can customize these meshes for specific geometries, mesh densities, and use cases. This enables a wide variety of analyses, including thermal, structural, mass diffusion, homogenization, and statistical failure analyses. Furthermore, the meshing capability simplifies analysts’ workflows. The inherent mesh generation capability eliminates the need for separate mesh-generating software and mesh file management. Also, the fact that the meshes are customizable makes it straightforward to automate an investigation over a range of geometric parameters or mesh densities. Here, the present paper highlights the ease with which Bison may be used to create meshes for both simple and relatively complex TRISO fuel particles, and it explores the types of analyses enabled by these meshes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

FFTF HT9 Cladding Microstructure Characterization

The sodium-cooled fast reactor (SFR) is a promising candidate for next generation nuclear reactors, operating at extreme conditions which include high temperatures (>500?C core outlet temperature) and significant neutron damage. High-Cr martensitic HT9 steel is an excellent candidate for SFR cladding and duct material due to its compatibility with liquid sodium, good thermal conductivity, resistance to void swelling, and strong creep rupture strength [1-4].However, the harsh in-core environment of SFRs can cause complex microstructural changes and mechanical property degradation in HT-9. Ensuring the safe use of HT9 cladding for metallic fuel requires both a thorough understanding of its mechanical response to microstructure evolution as well as reliable microstructure-sensitive modeling predictions. Microstructure-sensitive modeling of high temperature creep behavior in HT9 cladding for SFR applications currently lack experimental data to model the phenomena accurately. To fill this need, methods to perform microstructural characterization have been developed and performed on HT9.

36 MATERIALS SCIENCE↗