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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Alpha-Quartz Plastic Strength Investigation Via Diffraction Experiments on Novaculite Using A D-Dia and Elastic Plastic Self- Consistent Interpretation [Thesis}

X-Ray Tomography. Porosity is commonly measured using mercury injection (MI) or water immersion porosimeter (WIP). Both MI and WIP utilize pressure to fill open voids with mercury or water respectively. A measure of the volume change of the sample is then used to estimate the percentage of open voids. However, for the purpose of rheological study it is important to get an accurate measure of open and closed voids. X-ray tomography has been selected as it offers a three-dimensional view into the sample that can quantify all pores limited only by the voxel size which is in the micron range for this study. Radiographs for tomography were collected at the Material Science and Technology Division at Los Alamos National Lab using the Carl Zeiss Xradio 520 instrument and Scout-and-Scan version 16.1 operating software. Two samples were imaged, the starting material and the deformed sample SiO2_65. 3001 radiographs were taken of the starting material with a 6 second exposure time using a 4x objective lens. The x-ray beam was set to 60 kilovoltage peak (kVp) and 5 watts. 1901 radiographs were taken of SiO2_65 with a 25 second exposure time using a 10x objective lens. The x-ray beam was set to 80 kVp and 7 watts. Radiograph files were analyzed by Brian Patterson using Avizo. Void and inclusion volumes were output by voxel sized (1.03 μm) slices, used to calculate a total percentage volume for the starting material.

36 MATERIALS SCIENCE↗
DOE OSTI2024

DECOVALEX-2023: Task C Final Report

The Full-scale Emplacement (FE) heater experiment at the Mont Terri Underground Rock Laboratory (URL) was designed and conducted by Nagra to replicate an emplacement tunnel of Nagra’s reference repository design at 1:1 scale. Alongside testing the technical feasibility of constructing disposal tunnels, emplacing waste containers in the tunnels and then backfilling them, the main goals of the FE experiment are (1) to obtain a better understanding of the coupled effects of induced thermo-hydro-mechanical (THM) processes that may occur and (2) to validate existing coupled THM models (Müller et al., 2017). A key aspect of ensuring safety for repositories located in low-permeability rock involves minimizing any damage to the rock itself, thereby preserving its integrity and promoting a stable environment Amongst a number of processes that could damage the rock is the increase in pore pressure due to thermal loading caused by heat emitted from the waste. To reduce the potential damage of the rock, it is important to analyse the evolution of heat over time due to the heat load of the containers and assess possible consequences by coupled THM models. The aim of Task C of DECOVALEX-2023 was to build 3D numerical models of the FE experiment, focussing in particular on the heating induced pore pressure change in the Opalinus Clay. Data from a large number of sensors were available from the FE experiment for model comparison. These sensors measured temperature and relative humidity in the bentonite around the heaters, and temperature, pressure and displacement/strain in the surrounding Opalinus clay. Data were available from the start of excavation (April 2012) up to August 2020 for most sensors (more than 5 years from the start of heating in December 2014). To fulfil the overall aim of the task, the work was broken down into a number of steps, starting with simpler models to build confidence in each team’s approach and then moving to more complex models that better represent the FE experiment. Step 0 consisted of 2D benchmark models, gradually increasing the number of processes that are represented from thermal (T) only models in Step 0a, to coupled thermal hydraulic (TH) models in Step 0b with a representation of changing porosity, to coupled thermo-hydro-mechanical (THM) models in Step 0c, where porosity changes are calculated by the mechanical model. A detailed specification of processes, parameters, initial and boundary conditions was provided for this step, with the ambition that all teams would work towards close agreement in their model results, thus building confidence in the model implementations. vi It was not straightforward to achieve agreement between the teams, so additional steps (Step 0b2, 0b3, 0c2, 0c3) were added along with derivation of some analytical solutions against which the models could be compared. The reasons for the differences between teams were investigated and found to be caused primarily by different conceptual model assumptions (including temperature dependence of the thermal expansion of water), different model formulations (including porosity evolution) and differences in modelled domain sizes, boundary conditions and grid discretisation. This demonstrates that comparisons between multiple modelling teams and/or comparison with analytical results and experimental data are highly beneficial in providing an indication of uncertainty in model predictions. At the conclusion of Step 0, almost all teams had achieved a close agreement in model results and those that had not achieved an agreement knew the reason for this. Step 1 moved from 2D models to 3D models of the FE experiment without adding technical features like shotcrete or EDZ, and only considering the heating phase. Initially the 3D model was tightly specified to continue to build confidence in the model implementations (Step 1a). The results of Step 1a were compared to the data from the FE-experiment without the teams seeing the data. The teams were then provided with a sub-set of the data from the FE-experiment and invited to consider how best to use the large dataset for model comparison (Step 1b). Teams were then asked to use the data provided to calibrate their models, only changing material property values rather than adding features or processes to their models (Step 1c). In Step 1, teams were asked to only model the heating phase of the experiment, so pressure in the Opalinus Clay was reported as change in pressure since the initial conditions were specified rather than modelled. The change from 2D to 3D models was accompanied by an increase in the dispersion of results between the teams. Some of this was resolved during the task, but some remained and is potentially due to model discretisation. Calibration of parameters was useful in improving the fit of the models to the data but the remaining differences indicated that the models were missing features or processes. In Step 2, the teams were asked to update their models with additional features and processes as well as calibrating parameters to try and improve the fit of the models to the data. Teams were encouraged to represent ventilation of the open FE tunnel prior to backfilling with heaters and bentonite and in Step 2, the absolute pressure in the Opalinus Clay was compared between the teams. Teams took different approaches, but there was consideration of adding shotcrete and an EDZ into the model, representing stress change during excavation and different approaches to modelling ventilation of the FE tunnel. Overall, the documented results showed a very good agreement for temperature. The results for porewater pressure evolution showed a significant improvement for most teams compared to Step 1c with a good agreement to the measurements for several teams whereas some teams overpredicted the pressure increase and others overpredicted the drainage effect especially for the sensors close to the heater. Step 3 was an opportunity for teams to use the models developed in Step 1 and Step 2 to make predictions about the temperature and pressure changes that will be expected at the FE experiment over the next few years in light of the planned changes in thermal output of the heaters.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

An Exploration into Elemental Additions to Tungsten Electrodes

The scope of this study is to evaluate the arc start capabilities of various tungsten electrode alloys—2% Thoriated, 2% Ceriated, 2% Lanthanated, and a proprietary Tri-Mix WS2 on Stainless Steel 304 and Molybdenum. Each electrode maintained consistent geometry: 0.040" diameter, 2.000" length, and a 0.0010" flat tip with a 40° tip angle. The testing procedure aimed to determine the minimum starting amperage required to achieve 10 consecutive successful arc starts per electrode type.

36 MATERIALS SCIENCE↗
DOE OSTI2024

MICROREACTOR APPLICATIONS, RESEARCH, VALIDATION, AND EVALUATION (MARVEL) REACTOR ? STATUS, CONSTRUCTION, AND TESTING

The paper presents the current status of the Microreactor Applications, Research, Validation, and Evaluation (MARVEL) microreactor design, qualification testing, fabrication, and high-level construction schedule. An overview of initial criticality, low power physics testing, and start-up testing is included, as well as an overview of the envisioned processes in which end-users can engage the project for access to operational data or specific demonstrations. Designed by the Idaho National Laboratory (INL) under the auspices of the US Department of Energy’s Microreactor Program for construction and operation at the INL, MARVEL is a small, fully functional advanced reactor with UZrH fuel and thermal output of 85 kW. It offers a unique opportunity for scaled demonstrations that can dramatically accelerate the design, licensing, and deployment of commercial microreactors for power production or process heat applications. MARVEL’s objective is to build a small liquid-metal thermal reactor at the INL to demonstrate design and operating processes for microreactors, microgrid integration, and process heat applications. MARVEL finished 90%-final-design in September 2023 and completed an independent project assessment in early 2024. Fabrication of long-lead components and fuel, safety analysis review, and procurement for construction are underway. MARVEL assembly and construction will start in 2025 and fuel loading is expected in mid- 2027. Initial criticality will be performed in a dry condition in late 2027, followed by loading of NaK coolant and start-up testing. Approximately six months later, release for unrestricted operations will enable subsequent testing of microreactor characteristics, microgrid integration and select heat extraction applications.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2026

ZEUS: An Efficient GPU Optimization Method Integrating PSO, BFGS, and Automatic Differentiation

We introduce a novel, efficient computational method, ZEUS, for numerical optimization, and provide an open-source implementation. It has four key ingredients: (1) particle swarm optimization (PSO), (2) the use of the Broyden-Fletcher-Goldfarb-Shanno (BFGS) method, (3) automatic differentiation (AD), and (4) GPUs. Our approach addresses the computational challenges inherent in high-dimensional, non-convex optimization problems. In the first phase of the algorithm, we get a potentially good set of starting points using PSO. Thereafter, we run BFGS independently in parallel from these starting points. BFGS is one of the best-performing algorithms for numerical optimization. However, it requires the gradient of the function being optimized. ZEUS integrates automatic differentiation into BFGS thus avoiding the need for the user to calculate derivatives explicitly. The use of GPUs allows ZEUS to speed up the calculations substantially. We carry out systematic studies to explore the trade-offs between the number of PSO iterations taken, starting points, and BFGS iteration depth. We show that a handful of iterations of PSO can improve global convergence when combined with BFGS. We also present performance studies using common test functions. The source code can be found at https://github.com/fnal-numerics/global-optimizer-gpu.

Soos, Dominik [Old Dominion U.]↗
DOE OSTI2026

Expanding the genetic toolkit: adenine and cytosine base editors for gene disruption in Aspergillus niger

Despite revolutionizing fungal genetic engineering, conventional CRISPR/Cas9-mediated knockouts rely on DNA double-strand breaks (DSBs), which can cause unwanted insertions and deletions, chromosomal abnormalities, and cytotoxicity. Base editors such as adenine base editors (ABEs), which convert A‧T to G‧C, and cytosine base editors (CBEs), which convert C‧G to T‧A, offer a safer alternative by enabling predictable, target-specific single-nucleotide changes without introducing DSBs. To overcome the limitations of traditional genome editing in filamentous fungi, we developed efficient base-editing systems in Aspergillus niger . For the first time, we constructed an ABE in A. niger , achieving up to 80% editing efficiency and inducing predictable A-to-G mutations at the intended intron sites, disrupting gene function through mRNA mis-splicing. We also developed a highly efficient CBE system, capable of introducing premature stop codons with 50–100% efficiency. To broaden the editing scope, we implemented a Cas9-NG variant recognizing a relaxed PAM sequence requiring only a single guanine (G), enabling editing at start codons and splice sites. Leveraging this expanded scope, we established gene disruption approaches by targeting start codons via ABE-mediated A-to-G conversions (ATG-to-GTG and ATG-to-ACG) and CBE-mediated C-to-T conversion (ATG-to-ATA). Additionally, our base-editing systems enable multiplex gRNA delivery and marker-free editing of multiple genes. Collectively, the scope-expanding strategies increase the number of genes targetable for disruption by base-editing in A. niger by 26.3% and enable near-complete coverage of 96% of the coding genes. Overall, this work demonstrates the potential of ABE and CBE systems as versatile, efficient, and safer alternatives to DSBs-based gene disruption in filamentous fungi.

Aspergillus↗
DOE OSTI2025

ChatPORT: Fine-Tuned LLM for Easy Code {PORT}ing

Fine-tuning existing LLMs for specialized tasks has become a very attractive alternative due to its low cost and quick development cycle. With many pre-trained LLMs available, it is an increasingly complex task to choose the correct model as the starting point or base model. In this work we discuss ChatPORT - a specialized fine-tuned LLM geared towards providing correctly translated codes from one programming model to another. We evaluate a number of base models and compare and contrast their features and characteristics that make them a viable starting point. In this paper, we focus on the OpenMP offload porting capabilities of ChatPORT. We build our training data using kernels from the Heterogeneous Computing Benchmarks (HeCBench) [12] and the OpenMP Validation and Verification suite [5] to fine-tune the base models. We then test the model using unseen kernels extracted from the HeCBench benchmark suite. Our results show that: (1) not all open LLMs geared towards HPC are aware of programming models like OpenMP, (2) although all base models benefit from fine-tuning they learn differently and produce different correctness rates, (3) depending on the memory size and compute resource available, different base models can be used for fine-tuning without significantly affecting the quality of transpiled code they generate, (4) fine-tuning improved the correctness rate of the LLM by an average of 43.2%, and (5) feedback-based training data further increased the correctness rate by an average of 6% over the LLMs tested.

Pophale, Swaroop [ORNL] (ORCID:0000000185446367)↗
DOE OSTI2025

Effect of bisphosphonate treatment on the oim mouse middle ear ossicles' structure, composition and hearing

Hearing loss is common in people with osteogenesis imperfecta (OI or brittle bone disease). Bisphosphonates are commonly used to treat long bone fragility in children with OI. However, its impact on the bone quality of the middle ear ossicles and hearing remains unknown. This study determines whether bisphosphonates treatment itself may contribute to hearing loss in OI by evaluating its effects in the oim/oim mouse model of severe OI having normal auditory function. Specifically, this study reports the effects of alendronate (ALN), a nitrogen-containing bisphosphonate, on ossicle morphology, porosity, and elemental composition in 14-week-old oim/oim mice treated weekly, starting at 2 weeks of age. The ossicles were examined using synchrotron microtomography and X-ray fluorescence microscopy (XFM). Hearing was assessed longitudinally until 26 weeks of age by determining auditory brainstem response (ABR) thresholds in another group of mice also treated weekly starting at 2 weeks of age. ALN treatment further reduces in size the already small oim/oim ossicles, specifically in female mice. Porosity, bone composition, and hearing function, however, were generally not affected by the ALN treatment. Furthermore, ALN does not prevent joint fusions, excessive bone formations, or enlarged joint spaces in WT or oim/oim experimental groups. One ALN-treated oim/oim mouse with a bone formation in the interior of the footplate, and one ALN-treated WT mouse with a fixed footplate had frequency-specific hearing loss. Since footplate abnormalities are not observed in PBS-treated mice in this study, it remains unclear whether ALN fails to prevent these changes or contributes to their development. Future studies should investigate the mechanisms of ossicular abnormalities and bisphosphonates modulatory role in the ossicles.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Toward more-robust, AI-enabled subsurface seismic imaging for geotechnical applications

Non-invasive seismic imaging has the potential to cost-effectively evaluate large volumes of subsurface material to inform geotechnical site investigation. However, seismic imaging using full waveform inversion (FWI) requires significant computational time and is dependent on an initial starting model. As a result, FWI has not yet been widely adopted into geotechnical practice. Previous efforts, on relatively simple two-layered models, indicate that data-driven artificial intelligence (AI) models may be as effective as FWI at predicting 2D images of shear wave velocity (V s ). Furthermore, the AI model predictions can be made almost instantaneously after data acquisition and do not require an initial starting model. We examine the generality of these findings by developing a new AI model for subsurface seismic imaging, whereby we make several notable contributions. First, we architect a multimodal AI model that combines time- and frequency-domain representations of the seismic wavefield to predict a 50 m by 20 m subsurface image of V s . Second, we developed a new diverse dataset of 100,000 images with their corresponding seismic wavefields to train the AI model. Third, we propose four physics-informed data augmentations for data-driven seismic imaging. Fourth, we develop two prediction consistency tests to evaluate the model’s performance when the true subsurface is unknown. Our final model, which has been made publicly available, is capable of predicting a subsurface V s image from a single seismic wavefield with an average, mean absolute percent error (MAPE) of 24 %. The predictive model is applied to a field dataset and shown to be consistent with local geology and shear-wave refraction measurements from the same location.

Artificial intelligence↗
DOE OSTI2024

Reactive Fe anode for electrolytic reduction of solid metal oxide in molten LiCl-Li 2 O

Iron metal was investigated for use as a consumable anode for electrolytic reduction of solid metal oxides in molten LiCl-Li 2 O (2.0 - 2.4 wt%). Tests were performed where the potential of Fe anodes was increased incrementally from 0.1 to 1.0 V (vs Ni/NiO). Oxide formation on the anode started at a potential of 0.4 V and was identified as FeO via X-ray diffraction. In the absence of a pre-formed oxide layer, severe attack of the anode started at a potential of 0.7 V and was accompanied by an increase in Fe concentration in the salt. When an oxide layer was allowed to form on the anode, the Fe concentration did not increase in the salt. O 2 was detected in the headspace gas at an anode potential of 1.0 V only when an oxide layer was present on the anode. Finally, the results of this study support the idea that an inexpensive sacrificial anode could be an ideal replacement for expensive Pt that is currently widely used for this process.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A comprehensive numerical investigation on spray models for Direct-Injection Spark-Ignition engines

Gasoline direct-injection spark-ignition (DISI) engines generate a large portion of their unburned hydrocarbon (UHC) and soot emissions during the cold-start phase. A predictive computational fluid dynamics (CFD) modeling framework can be used to understand the physical processes that characterize fuel spray evolution and fuel-film formation at cold start conditions, which can help to reduce engine-out particulate emissions. This study systematically evaluated spray submodels and developed a set of simulation best practices for physical-numerical submodels with the goal of enabling accurate simulations of liquid spray behavior in a DISI engine. Three comprehensive experimental datasets containing free-spray projected liquid volume (PLV), liquid volume fraction (LVF), and near-field X-ray radiography data were used to validate the simulation results and evaluate the spray submodels. Systematic analysis delved into injected parcel distribution, droplet collision, spray breakup, and evaporation via a detailed assessment of the relevant spray submodels. Moreover, the effects of turbulence models and the initial turbulent flow properties on the liquid spray evolution were examined. Based on extensive calibration efforts, a set of simulation best practices for the free spray was developed and validated against the PLV/LVF data. Simulation results indicated that the uniform distribution for parcel initialization, coupled with appropriate droplet collision submodels, provides an improved spray morphology compared to the cluster distribution. The findings also underscored the importance of calibrating the Kelvin-Helmholtz Rayleigh-Taylor (KH-RT) breakup model constants and droplet heat transfer coefficient scaling factor to achieve favorable agreement regarding measured liquid penetration and spray widths. In conclusion, this study marks a substantial stride towards accurately predicting fuel film evolution and soot formation within DISI engine performance.

ECN Spray G↗
DOE OSTI2025

A new synthetic method of [Ru(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)Cl] + complexes using cis -[Ru(2,2′:6′,2″-terpyridine)(NCCH 3 ) 2 Cl] + as an intermediate and comparison to a method using [Ru(benzene)(2,2′-bipyridine)Cl] + intermediates

A new method of synthesizing [Ru(terpy)(bpy)Cl] + (terpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine) complexes using the starting material cis-[Ru(terpy)(NCCH 3 ) 2 Cl](PF 6 ) is reported. The yields of four derivatives ([Ru(terpy)(NN)Cl](PF 6 ): NN = bpy, 1; 4,4′-(MeO) 2 bpy, 2; 4,4′-(CF 3 ) 2 bpy, 3; 2,2′-biquinoline, 4) with this method range from 58 to 94 % and are similar to or greater than a known reaction in which the starting material is [Ru(benzene)(NN)Cl](PF 6 ). However, the use of cis-[Ru(terpy)(NCCH 3 ) 2 Cl](PF 6 ) results in lower levels of homoleptic Ru byproducts in the synthesis of 1 as compared to the use of [Ru(benzene)(bpy)Cl](PF 6 ) as determined by 1 H NMR spectroscopy. In addition, a high-purity and gram-scale synthesis of cis-[Ru(terpy)(NCCH 3 ) 2 Cl](PF 6 ) that does not use column chromatography is reported, in contrast to the original synthesis disclosed in the literature.

Bipyridine↗
DOE OSTI2025

Free-spray characteristics and spray-wall interactions of methanol on a gasoline direct injector under flash-boiling and non-flash-boiling conditions

Methanol is considered a promising alternative fuel for internal combustion engines (ICEs) due to its high-octane number, fast laminar flame speed, and elevated latent heat of vaporization, all of which support higher compression ratios and improved thermal efficiency. However, its substantial latent heat of vaporization also poses cold-start challenges, such as misfire and fuel film deposition. This study aims to investigate methanol spray morphology and spray-wall interaction using the Spray M injector from the Engine Combustion Network within a constant-pressure flow vessel. A recently developed unified numerical framework capable of modeling both flash and non-flash boiling sprays is validated against experimental liquid volume fraction data acquired via 3-D computed tomography. Here, the results reveal that flash boiling significantly alters the spray morphology, leading to smaller droplets and spray collapse due to enhanced air-entrainment-induced turbulence. Quantitative agreement between experiments and simulations confirms this behavior. Coupled 0-D equilibrium and 3-D computational fluid dynamics analyses show that flash boiling accelerates evaporation and reduces fuel residence time, while non-flash conditions maintain a persistent liquid core more susceptible to wall wetting. Wall temperature diagnostics reveal that spray collapse alters heat transfer patterns by shifting cooling effects. Mixture fraction analysis indicates that evaporation is primarily governed by shear-layer turbulence, though deviations from adiabatic equilibrium mixing emerge under low-turbulence conditions. Finally, increasing fuel, ambient, and wall temperatures reduces wall wetting and film thickness, mitigating cold-start risks. These findings enhance the understanding of methanol sprays’ behavior and support its adoption as a viable, alternative fuel for ICEs.

Engine Combustion Network↗
DOE OSTI2025

Modeling supercritical CO2 injection induced rupture of a minor fault embedded in a poroelastic layered reservoir-caprock system

CO2 injection for geologic carbon sequestration involves hydromechanical processes that lead to changes in fluid pressure and stresses that can activate existing faults. This paper presents a new method and workflow of modeling fault activation considering more complex three-dimensional geometry of natural faults using the TOUGH-FLAC multiphase fluid flow and geomechanical simulator. In this method and workflow, FLAC3D mechanical interfaces and TOUGH3 finite volume elements are discretized using computer aided design and gridding software along with a tailored mesh translation routine. The method and workflow are demonstrated with a model of a curved minor fault embedded in a poro-elastic layered reservoir-caprock system. The model is used for a comprehensive sensitivity analysis of fault responses to fault length, injection mass rate, injection schedule, well-fault distance, and well locations versus fault location. Four metrics (CO2 plume, shear state of fault, pressure and stress path at fault monitoring points) are selected to assess CO2 migration, pressure change, and the reactivation of faults. The results reveal that CO2 can bypass around the tip of the minor impermeable fault, building up pressure and poro-elastic stress on both sides that tends to impede fault rupture. Our study shows the benefit of carefully designing the injection to achieve the targeted final storage volume, starting at a relatively low rate for considerable time, and then ramping up the injection rate to the full rate of injection. The initial low injection has two distinct benefits: (1) it allows for the formation of an extensive CO2 plume with a much higher mobility through a low viscosity that will result in a lower pressure for a given injection rate, and (2) it allows for gradual build-up of horizontal poro-elastic stress within the reservoir that will tend to impede activation of steeply dipping faults. The injection scenario starting at a low injection rate, denoted here as conservative injection, can significantly reduce the risk of fault activation as high fluid mobility and reservoir strengthening poro-elastic stress has been established long before reaching the peak injection rates. Moreover, simultaneous injection in two injection wells on both sides of fault can provide further reservoir strengthening through poro-elastic stress buildup acting on a fault under normal faulting stress regime. The findings presented in the paper can provide practical and effective guidance on long-term, safe, and reliable geological CO2 storage.

Cao, Meng↗
DOE OSTI2025

Autonomous alloy composition optimization using molecular dynamics guided by a large language model

Here, we present an autonomous materials discovery framework that couples a large language model (LLM) with molecular dynamics (MD) simulations to optimize Fe–Cr–Mn alloy compositions for tensile strength. Starting from six distinct compositions, the LLM operated as an intelligent agent, iteratively proposing changes based on prior simulation results and constraints. Over 50 iterations per case, the LLM adaptively explored the composition space, identifying high-strength regions, not easily accessible by conventional methods. The highest strength, 18.7 GPa, was achieved with Fe 71 Cr 25 Mn 4 composition, identified from a Fe 75 Cr 20 Mn 5 starting point. The LLM autonomously adjusted its strategy in real time, demonstrating closed-loop decision-making using commodity hardware. This approach showcases the potential of LLMs as scientific co-pilots, capable of accelerating materials discovery and generalizable to other domains like biology and drug design.

Autonomy↗
DOE OSTI2024

Thoughts on the past, present and future of UHV surface chemistry and the birth of Single-Atom Alloys

Throughout its relatively short lifetime, ultra-high vacuum (UHV) surface chemistry has progressed quickly. In the 1960's, pioneers like Ertl and Somorjai started the field using single crystals and gained significant insight into catalytic processes by relating surface structure to reactivity. The more recent proliferation of scanning probes has significantly increased the power of the single crystal approach by enabling the atomic-scale structure of active sites to be correlated with their reactivity. In this perspective we briefly discuss how the field developed, identify some challenges, and highlight Single-Atom Alloys (SAAs), a new class of heterogeneous catalyst that was developed from a fundamental surface science approach. However, despite recent successes, funding for fundamental surface science has declined. Academic hires in the discipline are also declining in part due to the start-up costs. We make the case that fundamental UHV surface chemistry is still too young a field to be in recession.

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

Synthesis and characterization of isotopically barcoded nickel, molybdenum, and tungsten taggants for intentional nuclear forensics

Intentional nuclear forensics is a concept wherein the deliberate addition of benign and persistent material signatures to nuclear material can be used to reduce the time between the discovery of material outside of regulatory control and determination of its original provenance. One concept within intentional nuclear forensics involves the use of perturbed stable isotopes to generate unique isotope ratio “barcodes” to encode information (e.g., production batch, location, etc.) and track material throughout the nuclear fuel cycle. Synthesis of taggant species of nickel (Ni), molybdenum (Mo), and tungsten (W) was undertaken via a double-spike mechanism, wherein two highly enriched isotopes of interest per elemental taggant were mixed to form an enriched “double-spike” which was subsequently isotopically diluted with bulk material having a natural isotopic composition. Two taggant species perturbing isotopic ratios, alpha (α) and beta (β), for each of Ni, Mo, and W were synthesized. Independent measurements of double spikes and alpha and beta taggant species agreed within uncertainty and are clearly resolvable from natural compositions. High-precision analyses were independently performed by MC-ICP-MS at two U.S. National Laboratories, with consensus values and uncertainties calculated for all samples. Observed isotopic perturbations in the final taggant species measured on the order of hundreds to thousands of permille (‰) with respect to natural for isotope ratios of interest (e.g., 60 Ni/ 58 Ni, 100 Mo/ 98 Mo, 186 W/ 183 W). Discrepancies between modeled and measured isotopic compositions were observed and are largely attributed to imprecise vendor assay values for starting materials. Using measured starting material compositions as inputs for the mixing model improved the level of agreement between predicted and measured α and β taggant isotope ratios. Overall, characterization of all taggant species demonstrates that this “barcode” concept could have viability for use in nuclear forensics. Finally, it is expected that for any two-isotope mixing array dozens of isotopic barcodes could be encoded into a material system and subsequently resolved utilizing modern mass spectrometric methods.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2026

Reactions of U(DMSO) 8 (ClO 4 ) 4 with Terpyridine Yield Dimeric Hydrolysis Products and Induce C–C Coupling

Reactions have been carried out using UIV(DMSO) 8 (ClO 4 ) 4 with 2,2′:6′,2″-terpyridine (terpy) under nonaqueous conditions. At room temperature in acetonitrile, the combination of the U(IV) starting material with terpy resulted in a mixture containing [UO 2 (DMSO) 2 terpy][ClO 4 ] 2 ·MeCN, while increasing the water content led to the hydrolysis products [(UO 2 (DMSO)terpy) 2 (μ 2 –O)][ClO 4 ] 2 and [(UO 2 terpy) 2 (μ 2 –OH) 2 ][ClO 4 ] 2 ·MeCN·H 2 O. Performing the reaction at slightly elevated temperature with no added water led to the formation of [UO 2 sexipyridine][ClO 4 ] 2 ·MeCN. This new uranyl complex contains the hexadentate ligand 2,2′:6′,2″:6″,2″:6‴,2⁗:6⁗,2⁗′-sexipyridine, which formed in situ from the tetravalent uranium starting material, where photoexcited uranyl or in situ generated peroxide could have induced C–C coupling. Analysis of bonding in the dimeric uranyl species via quantum chemical methods revealed a small increase in covalency of the bridging oxo unit and a slightly greater stability compared to the bridging hydroxo compound, which causes a significant shift in the uranyl symmetric stretch in the Raman spectrum. Structural, spectroscopic, and computational comparisons are made across the series of compounds, providing insight into the bonding and reactivity of uranium in nonaqueous media.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗