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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Pore-scale observations of natural hydrate-bearing sediments via pressure core sub-coring and micro-CT scanning

Abstract Both intra-pore hydrate morphology and inter-pore hydrate distribution influence the physical properties of hydrate-bearing sediments, yet there has been no pore-scale observations of hydrate habit under pressure in preserved pressure core samples so far. We present for the first time a pore-scale micro-CT study of natural hydrate-bearing cores that were acquired from Green Canyon Block 955 in UT-GOM2-1 Expedition and preserved within hydrate pressure–temperature stability conditions throughout sub-sampling and imaging processes. Measured hydrate saturation in the sub-samples, taken from units expected to have in-situ saturation of 80% or more, ranges from 3 ± 1% to 56 ± 11% as interpreted from micro-CT images. Pore-scale observations of gas hydrate in the sub-samples suggest that hydrate in silty sediments at the Gulf of Mexico is pore-invasive rather than particle displacive, and hydrate particles in these natural water-saturated samples are pore-filling with no evidence of grain-coating. Hydrate can form a connected 3D network and provide mechanical support for the sediments even without cementation. The technical breakthrough to directly visualize particle-level hydrate pore habits in natural sediments reported here sheds light on future investigations of pressure- and temperature-sensitive processes including hydrate-bearing sediments, dissolved gases, and other biochemical processes in the deep-sea environment.

58 GEOSCIENCES↗
DOE OSTI2024

Imaging of dark line defect growth in high-power diode laser cavities using broadband near infrared light emission from the laser cavity

An in situ and nondestructive technique is developed to image the formation and evolution of dark line defects in the cavity of a high-power diode laser. Here, the technique uses broadband near infrared emission that originates in the laser's core layers and enables defects to be imaged with high spatial resolution through the substrate. In particular, it enables defect imaging through the substrate of shorter wavelength lasers, even when the substrate is opaque near the lasing wavelength. The evolution of dark line defects during aging is studied in several devices, with correlations established between the observed characteristics of defect growth and changes in device parameters such as optical power, operating wavelength, threshold current, and slope efficiency. Gradual degradation is found to be associated with dark line defects that slowly propagate from dark spots that are present in the device interior in its fresh (unaged) condition, rather than propagating from spots that are formed during aging, suggesting a strategy to screen fresh devices for expected reliability. This defect growth phenomenon is found to be particularly evident in the dark spots near the output facet.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Implementation of a Drift Flux Model into SAM with Development of a Verification and Validation Test Suite for Modeling of Noncondensable Gas Mixtures

The advanced thermal-hydraulic system code, System Analysis Module (SAM), was originally developed for the modeling of single-phase flow in advanced reactors. It has since been expanded to include a four-equation drift flux model for the modeling of two-phase flows containing a noncondensable gas. The model was expanded to support the modeling of molten salt reactor (MSR) designs in which the fuel is directly dissolved in the circulating coolant. These designs have shown that circulating gas bubbles can play an important role in the management of fission products and the operational behavior of the reactor. A drift flux model was implemented to more accurately capture the localized behavior of the void in the core and its impact on the mass transfer of fission products. A thorough assessment of the new model was performed by developing a verification and validation test suite. Verification problems were designed to test all major terms in the new governing equations. The new model converged to the correct solution at the expected order of accuracy for all verification cases. The validation cases included a wide range of flow and void conditions in different pipe geometries. Although higher void experiments show a slight underprediction of void by the drift flux model, experiments that aim to reproduce Molten Salt Reactor Experiment (MSRE) experimental conditions show good agreement with the model. The gas transport model was activated for a SAM model of the MSRE to demonstrate that it can be used in a more complex model. Finally, this gas transport model will be used along with an interfacial area transport equation being implemented in SAM for the prediction of mass transport behavior in MSR conditions.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Effect of surface oxides on tritium entrance and permeation in FeCrAl alloys for nuclear fuel cladding: a review

Abstract Iron-chromium-aluminum (FeCrAl) alloys are being considered for the cladding of uranium dioxide fuel in light water reactors (LWRs). FeCrAl alloys have good mechanical properties at temperatures of 300 °C and higher, and have superlative resistance to attack by steam at temperatures of up to 1000 °C and higher. A concern has been raised that the use of FeCrAl for cladding would result in a higher content of tritium in the reactor coolant as compared with the current system where the cladding is a zirconium based alloy. This review shows that the flux of tritium from the fuel rod cavities to the coolant across the fuel cladding wall will be greatly reduced by the presence of oxides on the surface of the cladding. The review of current literature and permeation data show that (a) protective oxides are expected to be present on both sides of the FeCrAl cladding, and (b) depending on the characteristics of these oxide layers it is reasonable to expect about two–three orders of magnitude reduction in tritium permeation, relative to the permeation response in clean, unoxidized condition for FeCrAl steels of interest, around 277 °C–377 °C temperatures.

Electrochemistry↗
DOE OSTI2020

Comparison of Extended and Accelerated VOG Tests

The reprocessing of used nuclear fuel would release volatile radionuclides into the off-gas streams of a processing plant, including ¹²⁹I. The dissolver off-gas and more dilute vessel off-gas streams (VOG) must both be targeted when mitigating ¹²⁹I environmental release because each contains some amount of iodine. Iodine-129 will likely be found as elemental iodine (I₂) and methyl iodide (CH₃I) in these off-gas streams. Reduced silver-exchanged mordenite (AgZ or Ag⁰Z) has been investigated as a potential sorbent for iodine abatement and is studied here under prototypic VOG conditions. Because of the relatively low iodine abundance and high flow rates of the VOG, total iodine concentrations are expected to be in the parts per billion range. Thus, VOG experiments need to run for extended durations at low concentrations to reach sorbent saturation. Because the sorbent will be exposed to oxidizing gas streams for extended periods of time, aging effects and sorbent degradation need to be considered when designing a sorbent-based abatement system. Three sets of experiments were performed with the aim of determining how the adsorption of iodine by AgZ is affected by differing test durations and gas compositions. The first tested the capacity of sorbent aged for 8 months under a humid air stream. The second tested differences in sorbent capacity and mass transfer zone (MTZ) length during high-concentration (1200 ppb v ) CH₃I loading in a humid nitrogen gas (N₂) stream and a humid air gas stream over 28 days. The third tested sorbent capacity and MTZ length during low concentration (< 200 ppb v ) CH₃I and I₂ loading in a humid air stream over 9 months. The results of these tests suggest that AgZ capacity drops by ~50% after 1 month of aging, by ~60% after 2 months of aging, and then does not continue to decrease significantly at up to 8 months of aging. One-month aging tests that compared N₂ and air as the gas stream diluent resulted in similar maximum loading capacities and overall loading curves, indicating that the effects of aging cannot be mitigated by avoiding air as the balance gas. The 9-month extended VOG tests did not result in clear sorbent saturation at the inlet, but it can be inferred using an assumption of a maximum capacity of 45 mg I/g AgZ. Applying this assumption, then the MTZ of CH₃I is 12.8 cm, and the MTZ of I₂ is 12.4 cm. These results are similar to previous tests. Comparisons to tests completed at Idaho National Laboratory suggest that the CH₃I MTZ may be dependent on concentration. Future work should re-evaluate the design of the VOG iodine capture system with this updated data and should seek to understand fundamental characteristics of CH₃I adsorption by AgZ, such as the effect of concentration, gas velocity, and gas composition.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Modeling Molten Salt Spreading and Heat Transfer using MELTSPREAD – Model Development Updates

This report summarizes spreading and heat transfer results calculated using MELTSPREAD for a scenario of molten FLiNaK spilling onto a flat stainless steel substrate that was inspired by the “maximum credible accident” scenario of the Molten Salt Reactor Experiment (MSRE). MELTSPREAD was developed at Argonne to model the one-dimensional flowing and freezing of molten corium and was applied to model molten salts for the first time during FY21. The molten salt MELTSPREAD model that was developed during FY21 was updated as part of this work using a corrected heat of fusion value of FLiNaK and to accommodate a larger salt spill volume. The model was run with and without the inclusion of contributions from decay heat and a sensitivity analysis of initial spill conditions was performed to determine the importance of those factors on model outcome. The results provide insight into the expected spreading and heat transfer behavior of simulated and irradiated fuel salt that has been spilled and indicate aspects of the model to be revised in future versions of the MELTSPREAD model for applications to molten salt.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Lower Snake River Dams Contribution to Grid Services

Hydroelectric generation and water storage have long been components of the clean energy mix, providing both reliable steady output and operational flexibility. As variable renewable energy sources such as wind and solar increasingly replace traditional generation, the role of all flexible resources—including hydropower—in balancing supply and demand continues to evolve. This study examined the contribution of the Lower Snake River (LSR) Dam plants to Bonneville Power Administration grid services in maintaining power system reliability within the Western Interconnection. By analyzing publicly available data, the study evaluated various reliability services through performance metrics including energy capacity, balancing and ramping, voltage and reactive power support, frequency response, and transmission impact. Results indicated that the LSR plants deliver services as expected based on their size, contributing to the balancing process, ramping capabilities, and operational reserves, particularly during peak load conditions and weather events, while also providing measurable frequency and voltage support to the grid.

13 HYDRO ENERGY↗
DOE OSTI2025

Preliminary modeling of triply periodic minimal surface (TPMS) structures using RELAP5-3D

With the United States Department of Energy (DOE)’s goal of quadrupling the nation’s nuclear energy supply by 2050, and with the Advanced Fuels Campaign pushing for new types of advanced reactor fuels and geometries, the need has arisen for new nuclear fuel designs. One such design is to swap out current nuclear fuel geometries in exchange for another type of geometry, called a Triply Periodic Minimal Surface (TPMS). TPMSs are self-supporting, infinitely repeating lattices—attributes that lend themselves well to additive manufacturing. These surfaces also possess enhanced heat transfer properties thanks to their internal area changes and large surface-area-to-volume ratios. Their drawback, however, is an increased pressure drop. Given the small amount of correlations and data (Reynolds numbers in the 2,000–8,000 range), and the minimal amount of experience so far obtained by modeling TPMS structures using 1D systems codes such as the Reactor Excursion and Leak Analysis Program (RELAP5-3D), further research into this topic was needed. Using data from the University of Wisconsin - Madison (UW), curve fits were created for both a Heat Transfer Coefficient (HTC) correlation and a Darcy friction factor empirical coefficient correlation. The curves’ coefficients and multipliers were then output and utilized in RELAP5-3D models of two upcoming experiments—Flow Loop for INFLUX Pressure drop (FLIP) and Microreactor Agile Non-nuclear Experimental Test (MAGNET)—aimed at increasing the available data for Reynolds numbers to the 16,000–36,000 range for TPMS structures. The models were run under the conditions utilized by a Computational Fluid Dynamics (CFD) analysis performed by another group at Idaho National Laboratory. Only CFD pressure drop values were obtained from the FLIP test, and those values showed that the RELAP5-3D models had a lower rate of pressure increase in comparison to the CFD values. In addition, there seemed to be a vertical shift upward in the pressure drop for both models whenever the TPMS porosity decreased, and the RELAP5-3D models showed a higher vertical shift in comparison to the CFD values. The MAGNET results did not correspond to any CFD or experimental results against which they could be compared, so they were instead compared against the proposed CFD input conditions. These values were then compared with each other to make sure the model seemed to be performing as expected, paving the way for future tests that can be run for the purpose of further analyses and comparisons. The pressure drop increased with temperature and mass flow rate independently. The temperature change would decrease with increasing mass flow rate and temperature, which was just as we expected based on the fact that the lower viscosity and decreased density would result in higher friction and churning losses. The last metric that was assessed was the enthalpy flow change, which increased with increasing mass flow rate and decreasing temperature.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2026

Aircraft-derived particle fluxes distinguish entrainment zone and decoupled layer nucleation in marine boundary layers

The vertical distribution of freshly nucleated aerosol particles in the marine boundary layer remains poorly constrained, limiting our ability to represent new particle formation in climate models. Here we characterize 3–10 nm particle events, termed small particle events (SPEs), by deriving their vertical turbulent fluxes from aircraft measurements during the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) campaign. To overcome stationarity limitations of traditional eddy covariance methods, we applied continuous wavelet transform analysis to data collected during June–July 2017 and January–February 2018 flights over the Azores. Our flux-based analysis revealed two distinct SPE scenarios with different vertical structures and spatial extents. The first featured nucleation in the entrainment zone, where free tropospheric air entrains into the boundary layer. The second showed nucleation in the decoupled layer, a stratified region between the well-mixed surface layer and cloud-topped upper boundary layer. In both cases, convergence of air masses from different layers diluted preexisting aerosol surface area to very low levels, creating conditions favorable for nucleation and generating strong downward particle fluxes. SPEs occurred in 15 % of flights, challenging prevailing theoretical expectations that new particle formation should rarely occur in marine boundary layers due to high condensation and coagulation sink capacity of sea spray aerosols. Aircraft-derived particle fluxes provide first observational constraints on the vertical location and source strength of likely nucleation regions in the remote marine boundary layer, improving aerosol source representations in climate models and reducing uncertainties in aerosol-cloud interactions.

Rasheeda Satheesh, Ajmal [North Carolina State Uni↗
DOE OSTI2021

Evaluating Cell Temperature Models and the Effect of Wind Speed in PV System Capacity Testing: Preprint

Capacity testing is a routine procedure for assessing a photovoltaic system's performance relative to expectations. The most common test method involves fitting a regression model that predicts system output power using operating weather conditions including wind speed. Structural modifications to the regression model to incorporate wind in different ways improved the model's ability to fit measured system performance, but the observed improvements were small and unlikely to change the result of a capacity test. However, the results showed that the choice of reporting wind speed and inclusion or exclusion of wind speed in the performance model used as the test benchmark can significantly change the test result.

41 EE - Solar Energy Technologies Office (EE-4S)↗
DOE OSTI2023

Wind Turbine Noise Code Benchmark: A Comparison and Verification Exercise: Preprint

In a number of institutions and companies, researchers and engineers are developing modeling numerical frameworks that are used to predict the aerodynamic noise emission from a wind turbine rotor. The simulation codes vary from empirically-tuned engineering models to high-fidelity computational ones. Their common feature is the fact that they all specifically model the main aerodynamic noise mechanisms occurring at the rotating blades, namely trailing edge noise and turbulent inflow noise. Nevertheless, it can be expected that these different modeling frameworks will produce different results for a same given rotor design, and identical operating conditions. Trailing edge noise is put at the forefront of the study as it is recognized as the main audible source of noise from wind turbines. The present benchmark aims at comparing the results from the different modeling approaches, and drawing some conclusions from these comparisons. This effort, denoted as Wind Turbine Noise Code benchmark, was initiated in 2019 as a joint-activity between the IEA Wind Task 39 (Quiet Wind Turbine Technology) and Task 29 (Detailed Aerodynamics of Wind Turbines, now Task 47). In addition to the investigation of the noise emissions themselves, the rotor aerodynamic characteristics are investigated as they have a significant impact on the noise generation mechanisms. A number of test cases are defined and the aerodynamic and aeroacoustic predictions from the various models are compared. There exist some discrepancies between the different methods, but it is difficult to conclude if one methodology is better than another in order to design a wind turbine with noise as a constraint.

aeroacoustics↗
DOE OSTI2025

Considerations for Thermal Annealing of Zr-Alloy Cladding During Dry Storage

In January 2025, the U.S. Department of Energy (DOE) sponsored a technical workshop with fuel vendors that provided a forum for increased collaboration on backend fuel cycle research. The workshop reviewed observations of thermal annealing of irradiated zirconium alloys in simulated dry storage conditions and discussed implications to the industry’s interest in reducing wet storage to optimize operational flexibility and the expected trend of increasing discharge burnup (and decay heats), which could lead to an increase in dry storage temperatures. One approach to accommodate increased decay heats in dry storage is to increase the regulatory temperature limit during dry storage, which is now 400°C. However, this could lead to thermal annealing of the cladding, which will tend to increase creep rates, creep strains, and ductility while decreasing yield strength. These considerations are compounded by bonding between the pellet and cladding at high burnup, which results in the pellet carrying more load during fuel rod deformations, especially in bending, which is the dominant deformation phenomenon in canister drop analyses. Because the U.S. Nuclear Regulatory Commission (NRC) recommends yield strength as a primary failure criterion for accident analyses in storage and transportation, particularly for canister drop scenarios, the purpose of the workshop was to develop options for alternative failure criterion that could replace yield strength in canister drop analyses. Topics discussed were (1) the regulatory framework, (2) the effect of thermal annealing on microhardness and tensile properties of cladding materials, (3) the effect of thermal annealing on fuel rod failure during bending, bending fatigue, and pinch loading, and (4) an alternative failure criterion for canister drop analyses. This paper provides a summary of the key discussions and outcomes of the workshop

Cantonwine, Paul [ORNL] (ORCID:0009000522247033)↗
DOE OSTI2024

Solidification of SRPPF Aqueous Recovery Liquid: Process Disruptions

Savannah River National Laboratory has identified a magnesium oxysulfate grout formulation to solidify the liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery System (ARS). The formulation uses reactive, light burnt MgO, anhydrous MgSO 4 , and dead burnt MgO and provides good mixability, similar density to the original Portland Cement-based mix, and a leachate pH of 9.39, within the assumed Waste Isolation Pilot Plant (WIPP) brine pH range. The formulation will solidify the effluent using a solid first, lost paddle design, within a 55-gallon drum. A series of seven different process disruptions, or irregular processing during the expected ARS liquid effluent solidification process, were completed to assess the severity of the impact of the process disruption and how the formulation behaves under these conditions. Seven process disruptions were investigated including: No Mixing, Partial Mixing, Compacted/Stratified, Sealed, Overfilled, Underfilled, and Undermixed. The impact on solidification, leachate pH, Er (a Pu/Am surrogate) distribution, and density of the resulting grout were established. Overall, four of the process disruptions, No Mixing, Partial Mixing, Compacted/Stratified, and Overfilled, resulted in basic, unabsorbed liquid that would require additional solidification to be acceptable for WIPP. Most solids generated in this testing met the expected WIPP leachate pH requirements. Solids from the Compacted/Stratified process disruption test, however, produced a leachate pH slightly above the assumed range in the WIPP performance assessment. The distribution of Er for most of the tests was relatively consistent. The No Mixing process disruption test, however, resulted in non-homogeneous Er distribution, indicating that radioactive material would not be evenly distributed throughout this solid’s matrix. The Overfilled test is the only mix with a density slightly below the acceptable value. The Sealed and Overmixed tests produced a solid closest to the standard mix with no unabsorbed liquid, expected leachate pH levels, consistent Er concentrations, and expected density, indicating these process disruptions do not have a negative impact on the final grout form. Based on the other process disruptions, it is critical to have premixed dry materials and a well-defined mixing process to produce a solid, homogeneous magnesium oxysulfate cement, with no unabsorbed liquid. These process disruption tests show that the lack of adequate mixing is fundamental to creating an improperly solidified material that may require remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Neutron source reconstruction using a generalized expectation–maximization algorithm on one-dimensional neutron images from the Z facility

Magnetized Liner Inertial Fusion experiments have been performed at the Z facility at Sandia National Laboratories. These experiments use deuterium fuel, which produces 2.45 MeV neutrons on reaching thermonuclear conditions. To study the spatial structure of neutron production, the one-dimensional imager of neutrons diagnostic was fielded to record axial resolved neutron images. In this diagnostic, neutrons passing through a rolled edge aperture form an image on a CR-39-based solid state nuclear track detector. In this report we present a modified generalized expectation–maximization algorithm to reconstruct an axial neutron emission profile of the stagnated fusion plasma. We validate the approach by comparing the reconstructed neutron emission profile to an x-ray emission profile provided by a time-integrated pinhole camera.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Vacancy-mediated transport and segregation tendencies of solutes in fcc nickel under diffusional creep: A density functional theory study

The Nabarro-Herring (NH) diffusional creep theory postulates the vacancy-mediated transport of atoms under a stress gradient as the creep mechanism under low-stress and high-temperature conditions. In multicomponent alloys, we premise that this stress-assisted flow of vacancies to and from grain boundaries will produce elemental segregation. An observation of such segregation, validated with theoretical predictions, can provide the necessary experimental evidence for the occurrence of NH creep. Theoretical calculations of the segregation tendencies via analyzing the dominant solute diffusion mechanisms and the difference in diffusivities of the elements are therefore essential. To this end, this study applies density functional theory calculations of migration barriers and solute-vacancy binding energies as input to the self-consistent mean-field theory to assess the vacancy-mediated diffusion mechanisms, transport coefficients, and segregation tendencies of Co, Cr, Mo, Re, Ta, and W solutes in face-centered-cubic Ni. We find Co, Re, and W to be slow diffusers at high temperatures and Cr, Mo, and Ta to be fast diffusers. Further analysis shows that the slow diffusers tend to always enrich at vacancy sinks over a wide range of temperatures. In contrast, the fast diffusers show a transition from depletion to enrichment as the temperature lowers. Furthermore, our analysis of the segregation tendencies under tensile hydrostatic strains shows that slow diffusers are largely unaffected by the strain and favor enrichment. On the other hand, the fast diffusers exhibit high sensitivity to strain and their segregation tendency can transition from depletion to enrichment at a given temperature. Finally, the transport coefficients calculated in this work are expected to serve as input to mesoscale microstructure models to provide a more rigorous assessment of solute segregation under NH creep conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Hanford Reach Fall Chinook Salmon Productivity Analysis, Brood Years 1975–2016

Updating the Hanford Reach fall Chinook salmon productivity analysis to include seven additional years of data (BY 2010–2016), including three years of record escapements (>150,000 adults), reaffirmed the highly productive nature of this population and the positive effect of flow fluctuation constraints as implemented at Priest Rapids Dam by the VBSA and HRFCPP. The addition of several years of high escapements also revealed that competition among juveniles (and not spawning habitat limitations) is likely the mechanism driving density dependence in the Hanford Reach. The addition of the high escapement brood years also provided evidence for the high recruitment capacity of the population. As such, the WDFW may consider increasing the maximum escapement goal from 42,000 adults to 49,000 adults, which would be more in-line with SMSY as estimated from this update. Given the in-river protections that are in place as part of the HRFCPP, ocean conditions appear to be the primary factor controlling adult production. Therefore, the success of any additional management actions taken in freshwater are likely to be dependent on survival in the ocean. As such, the most effective management actions may be those that limit juvenile competition and density dependent growth effects in the Hanford Reach. Limiting competition would be expected to increase growth, resulting in larger smolts that would be less likely to suffer size-dependent mortality in the marine environment, even during years of poor ocean conditions. Increasing terminal harvest rates when high escapements are anticipated (from downstream dam counts) is one management option that could help to curtail juvenile competition.

Harnish, Ryan A.↗
DOE OSTI2025

Colloidal Behavior of Plutonium Oxide in Concentrated Electrolyte Solutions

The Hanford Site in Washington State manages legacy high-level radioactive waste streams that display major chemistry and engineering challenges, including the high salt levels and pH values that correspond to conditions under which many classical concepts describing chemical reactivity cannot be applied. One particular challenge that needs to be tackled at Hanford is that Pu concentrations, [Pu], in the soluble phases of the tank wastes are higher than expected based on the solubility of crystalline PuO2, which is widely accepted to be caused by the formation of PuO2 colloid, consisting of nano- to submicron-sized particles (PuO2 NPs). Fundamental research underpinning the behavior of PuO2 NPs under conditions not only relevant to the Hanford tank waste but at high ionic strength in general is needed to reliably predict the chemical reactivity of PuO2 NPs and develop engineering solutions to safely and efficiently process high-level radioactive waste into forms suitable for long-term storage. In this work, we study the behavior of PuO2 NPs (particle size ~100 nm) under high ionic strength conditions by reacting it with highly concentrated (up to 5 M) salt solutions. We explore different electrolyte compositions to elucidate the impact of different anions (NO3-, Cl-, ClO4-, SO42-, C2O42-, CO32-) on the stability of PuO2 NP in the acidic and alkaline pH regime. PuO2 NP aggregation and precipitation as function electrolyte concentration is tracked by a combination of liquid scintillation counting, dynamic light scattering for determination of particle size distributions, and zeta potentials as a proxy for particle charge. At acidic pH, electrolytes containing non-coordinating anions, such as NaNO3, NaCl, and NaClO4 mostly stabilize PuO2 NPs over a large electrolyte concentration range, showing only subtle differences in their reactivity. Other electrolyte anions show a more pronounced effect on the PuO2 NP stability: SO42-, binds directly to the particles’ surface, reverses the particle charge, and precipitates the PuO2 NPs efficiently even at intermediate sulfate concentrations (>0.1 M). In contrast, C2O42- is found to lead to high [Pu] in solution, in the milli-molar range, even at mildly acidic pH (~4). Thermodynamic modeling of the dissolved Pu concentrations using PHREEQC is unable to predict the observed [Pu] in the acidic pH regime, supporting the influence of colloids in maintaining elevated [Pu]. It is noteworthy that the current thermodynamic databases do not include constants for colloidal Pu phases and cannot accurately predict many of the high ionic strength solutions relevant to this work. The mechanisms and models responsible for these observations will need further investigation in the future. At high pH values (~12), PuO2 NPs exhibits classical sol-gel chemistry, meaning that upon destabilization of the colloidal sol, for example by addition of concentrated NaOH, highly porous and viscid PuO2 coagulates are formed that consist of a three-dimensional network likely held together by physical interactions. The PuO2 NP coagulate shows no significant reversibility of the aggregation when contacted with concentrated brines; however, PuO2 NPs can be efficiently resuspended in solution by addition of diluted electrolytes, alkaline solutions containing high amounts of carbonate, or simple addition of water. Especially carbonate is shown to stabilize PuO2 NPs in solution at high pH, characterized by stable colloidal suspensions that are resistant against sedimentation during centrifugation. Thermodynamic modeling of the carbonate system was able to predict an increasing dissolved Pu concentration with increasing carbonate concentration. However, the model was profoundly sensitive to the fixed redox potential and does not include any thermodynamic constants for colloidal Pu species.

Neumann, Julia↗
DOE OSTI2024

Review and Summary of Corrosion Behavior for Aluminum-Clad Spent Nuclear Fuel in Dry Storage

A description of the corrosion behavior of aluminum alloys used for cladding on aluminum-based, aluminum-clad nuclear fuel used in research reactors under potential dry storage conditions has been compiled. An evaluation is made of potential additional corrosion with water postulated to not be removed during drying. The relative humidity (RH) produced by typical dryness criteria for industrial spent nuclear fuel drying is expected to be low, particularly at high temperatures (17% RH at 20°C and lower at higher temperatures). Existing corrosion data suggests that negligible vapor-phase corrosion of aluminum is expected at such low humidity, even for nominally bare aluminum surfaces. That is, the predicted relative humidity from free water (e.g., 17% RH) is below the “critical” relative humidity (~40% RH at room temperature), below which no significant corrosion is observed for bare aluminum. Furthermore, reported room-temperature corrosion rates are very low even under saturated (100% RH) water vapor. Existing results showing significant vapor-phase corrosion corresponded specifically to conditions of high temper ed with high relative humidity. A relatively large reservoir of (chemically bound) water exists in the aluminum (oxy)hydroxide films on the SNF cladding surface. The estimated total could saturate the gas even at relatively high temperature if fully released; however, its release as molecular water is expected to only be plausible if the temperature during storage exceeds both the drying temperature and the threshold for thermal decomposition of the trihydroxides (~220°C). Therefore, the combination of high temperature and high relative humidity that could drive significant corrosion is considered implausible during sealed dry storage following an appropriate drying process, to include >220°C drying for canisters that may approach or exceed this temperature during storage. Vapor-phase testing of aluminum samples with an adherent (oxy)hydroxide layer, prepared in liquid water to resemble those on actual aluminum-clad spent nuclear fuel (ASNF), did not observe evidence of additional corrosion even at combined high-temperature (up to 180°C) and high-humidity (up to 100% RH) conditions. Instead, small net mass losses were observed for most specimens and attributed to dehydration of the samples, which had been air-dried only prior to testing. ASNF being moved to dry storage is expected to have an existing (oxy)hydroxide film, suggesting that the cladding will be less prone to additional corrosion than bare aluminum metal. If significant corrosion did occur during sealed storage, the overall extent and impact is expected to be small. Corrosion post-closure of a canister would not alter the total amount of hydrogen in the canister, so it would have no effect on the maximum H 2 release already assessed in existing bounding calculations. In addition, the total amount of water in a 25-µm dense bayerite film would consume a only ~8 µm additional aluminum metal on average, if fully consumed by oxidizing aluminum metal to Al 2 O 3 . These conclusions are consistent with ASNF-in-canister simulations to date, which included a reaction pathway for corrosion using kinetics from previous literature and believed to be conservative and predicted very low rates of corrosion.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗