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At least 145 records · Page 8

Engineered Solutions Group's SMR Containment Cable and Electrical Penetration Assembly System

GAIN Project CRADA Number NFE-21-08839, entitled “SMR Containment Cable and EPA System” was initiated by the partnership of Oak Ridge National Laboratory (ORNL) and Engineered Solutions Group (ESG) to test an ESG-designed Electrical Penetration Assembly and Containment Cabling System Qualified for not only legacy LWR designs, but also Small Modular Reactors designs currently being designed by several different suppliers. This project was undertaken to fill the equipment gap of EPA and Cabling Systems that require much more severe environmental requirements than legacy plant applications present due to their smaller containment volumes that result in high energy densities compared to legacy designs. This high energy density results in severe accident environments and more severe normal operating conditions as well. We developed two approaches to qualify Electrical Penetration Assembly (EPA) and Containment Cabling Systems for SMRs and Advanced Reactors. We take into consideration the more severe environmental parameters found with SMR designs. The system will need to meet a qualification test program addressing wear/cyclic aging, potential radiation exposure, thermal aging, vibration aging, thermal cycling, seismic qualification, electrical fault testing (per IEEE 317) and accident simulation. The equipment must meet the requirements of 10CFR50.49, GDC 50 in 10CFR50 Appendix A, and 10CFR50 Appendix J. NRC Regulatory Guides (RGs) identify an acceptable way of meeting regulatory requirements. RGs frequently endorse a standard for meeting these requirements. Specific to this review, equipment would be qualified in accordance with the following IEEE Standards. • IEEE 317-2013 (Electrical Penetration Assemblies), which is endorsed by RG 1.63, Rev. 3, • IEEE 323-2003 and the more current IEC/IEEE 60780-323 (Environmental Qualification of 1E Equipment) which is endorsed by RG 1.89. IEEE 323-2003 is endorsed by RG 1.209, • IEEE 344-2020 (Seismic Qualification. The 2013 version endorsed by RG 1.100, Rev. 4, with exceptions), • IEEE 383-2015 (Electrical Cables) (which is endorsed by RG 1.189 Rev. 4 and the -2003 version endorsed by RG 1.211 rev. 0), • IEEE 572-2019 (Electrical Connectors and Assemblies), which is endorsed by 1.156 Rev 1, and • [IEEE 1202 (endorsed by RG 1.189) would normally be applicable but the advanced cable designs are impervious to this cable flame test.] The primary goal of such a program is to provide an EPA design that can meet the qualification requirements for all legacy light water reactor plants currently operating as well as new plant designs including light water Small Modular Reactors. Thus, these requirements are applicable to plants licensed under 10CFR50 and 10CFR52. Other reactor designs may be evaluated, and this test system and qualification method applied to those applications if the requirements would satisfy the requirements of the intended plant. A secondary benefit of this work is to document some of the history and background in these requirements as there have been recent delays in an SMR licensing process due to NRC Requests for Additional Information in this subject matter area.

42 ENGINEERING↗

The oxygen stable isotope composition of CRM 125-A UO 2 standard reference material

While there is a clear need for standardized reference materials for analytical calibrations and for inter-laboratory comparisons, there are not currently any for the oxygen stable isotopic composition of uranium oxides. In this paper we summarize the results from four laboratories by seven different methods of oxygen stable isotope analyses using fluorination techniques of CRM 125-A UO 2 Standard Reference Material. We synthesize these data and methods to arrive at a consensus oxygen stable isotope composition for CRM 125-A $δ$ 18 O = -9.63‰ (±0.29‰) VSMOW. We discuss methodological differences between analytical approaches, including furnace vs laser heating, fluorination using BrF 5 or ClF 3 , as well as calibration strategies. We highlight the potential effects of calibration scale compression from single-point calibrations using reference material with $δ$ 18 O values having a large relative difference from the sample being analyzed. We demonstrate how calibration scale compression can yield differences in calibrated $δ$ 18 O values up to ~2‰ for samples with ~20‰ difference from a single reference material, if the calibration slope of different analytical systems differs by 0.1. In conclusion, we suggest the use of liquid water calibration standards sealed in silver capillary tubes for multi-point calibrations of fluorination analysis systems.

07 ISOTOPE AND RADIATION SOURCES↗

Oxygen Isotope Fractionation in U 3 O 8 during Thermal Processing in Humid Atmospheres

The incorporation of oxygen isotopes from water into uranium oxides during industrial processing presents a pathway for determining a material’s geographical origin. This study is founded on the hypothesis that oxygen isotopes from atmospheric water vapor will exchange with isotopes of oxygen in solid uranium oxides during thermal processing or calcination. Using a commonly encountered oxide, U 3 O 8 , the exchange kinetics and equilibrium fractionation with water vapor (in a concentration range of 50–55% relative humidity) were investigated using processing temperatures of 400, 600, and 800 °C. In an atmosphere containing only water vapor diluted in N 2 , oxygen isotope equilibration in U 3 O 8 occurred within 12 h at 400 °C and within 2 h at 600 and 800 °C. Fractionation factors (1000lnα, U 3 O 8 –H 2 O) between the water and oxide were –12.1, –11.0, and –8.0 at 400, 600, and 800 °C, respectively. With both humidity and O 2 present in the calcining atmosphere, isotopic equilibration is attained within 2 h at and above 400 °C. In this mixed atmosphere, which was designed to emulate Earth’s troposphere, isotopes are incorporated preferentially from water vapor at 400 °C and from O 2 at 600 and 800 °C. Rapid and temperature/species-dependent isotope exchange also elucidated the impact of retrograde exchange in humid air, showing a shift from O 2 -dependent to H 2 O-dependent fractionation as U 3 O 8 cooled from 800 °C. These results confirm that uranium oxides inherit oxygen isotopes from humidity during thermal processing, illuminating an important mechanism in the formation of this forensic signature.

07 ISOTOPE AND RADIATION SOURCES↗

Nuclear Forensics

Nuclear forensics is a key part of the nuclear security strategy for the United States and the international community. The NACS Division is central to the leadership role that LLNL has had in nuclear forensics over the past 25 years. Our current nuclear forensic program includes conducting R&D on provenance and attribution signatures, collaborating with international partners, training the next generation of nuclear forensic experts, developing test materials for verification and validation exercises, and providing expert advice to national and international policy makers. Key to our success in these areas has been the strong and continuing involvement in nuclear forensic casework obtained through law enforcement and intelligence channels as well as our outstanding analytical capabilities. NACS must continue to conduct forward-thinking R&D in nuclear forensics that supports operational programs and addresses intelligence gaps. To maintain leadership in nuclear forensics, we must attract, develop, and retain the best talent. The NNSA has a central leadership role in developing educational initiatives for nuclear forensics. In concert with the Glenn T. Seaborg Institute, the NACS Division will continue to participate in all nuclear forensic educational initiatives (undergraduate, graduate, postdoctoral) and incorporate LLNL’s D&I vision into its student and postdoc recruitment efforts. We will continue to build formal relationships with key academic partners and institutions with active and emerging nuclear forensic research interests. We will also strengthen relationships with NNSA DNN and SSAA funded university consortia (e.g. NSSC, ACE, CNEC, CVT, ETI, MTV), helping them conduct research of interest and relevance to nuclear forensics, while at the same time evaluating and recruiting promising talent from these programs.

07 ISOTOPE AND RADIATION SOURCES↗

Active anaerobic methane oxidation and sulfur disproportionation in the deep terrestrial subsurface

Abstract Microbial life is widespread in the terrestrial subsurface and present down to several kilometers depth, but the energy sources that fuel metabolism in deep oligotrophic and anoxic environments remain unclear. In the deep crystalline bedrock of the Fennoscandian Shield at Olkiluoto, Finland, opposing gradients of abiotic methane and ancient seawater-derived sulfate create a terrestrial sulfate-methane transition zone (SMTZ). We used chemical and isotopic data coupled to genome-resolved metaproteogenomics to demonstrate active life and, for the first time, provide direct evidence of active anaerobic oxidation of methane (AOM) in a deep terrestrial bedrock. Proteins from Methanoperedens (formerly ANME-2d) are readily identifiable despite the low abundance (≤1%) of this genus and confirm the occurrence of AOM. This finding is supported by 13C-depleted dissolved inorganic carbon. Proteins from Desulfocapsaceae and Desulfurivibrionaceae, in addition to 34S-enriched sulfate, suggest that these organisms use inorganic sulfur compounds as both electron donor and acceptor. Zerovalent sulfur in the groundwater may derive from abiotic rock interactions, or from a non-obligate syntrophy with Methanoperedens, potentially linking methane and sulfur cycles in Olkiluoto groundwater. Finally, putative episymbionts from the candidate phyla radiation (CPR) and DPANN archaea represented a significant diversity in the groundwater (26/84 genomes) with roles in sulfur and carbon cycling. Our results highlight AOM and sulfur disproportionation as active metabolisms and show that methane and sulfur fuel microbial activity in the deep terrestrial subsurface.

59 BASIC BIOLOGICAL SCIENCES↗

Seasonal delay of Sahelian rainfall driven by an east–west contrast in radiative forcing in idealized CESM experiments

Recent studies suggest the observed seasonal delay of rainfall over the Sahel is mainly driven by anthropogenic aerosol forcing, which features a robust east–west contrasting changes in recent decades, with negative and positive top-of-the-atmosphere shortwave radiative forcing in South and East Asia (SA&EA) and in North America and Europe (NA&EU), respectively. Their individual effects on the Sahel rainfall annual cycle remain unclear. Here, by designing idealized sensitivity experiments based on Community Earth System Model (CESM1.2), we show that both negative radiative forcing over SA&EA and positive radiative forcing over NA&EU contribute to the delayed phase and enhanced amplitude of Sahel rainfall annual cycle. To understand the underlying physical processes, both the convective quasi-equilibrium (CQE) and atmospheric energetic frameworks are utilized. Both frameworks can well explain the seasonal delay in the rainfall annual cycle over the Sahel under the regional radiative forcings, with the CQE framework showing stronger explanatory power. Based on the insights from both frameworks, we conducted a moisture budget analysis and found that the negative radiative forcing over SA&EA causes an anomalous low-level anticyclonic circulation, which transports more moisture to the Sahel. As the anomalous anticyclone is stronger in summer and fall compared to spring, rainfall is delayed in the Sahel. Further, under the influence of the positive radiative forcing over NA&EU, more warming in the northern hemisphere causes northward transport of moisture to the northern tropics associated with the cross-equatorial transport of energy. The moisture transport increases relativehumidity over the Sahel and enhances the effective atmospheric heat capacity that delays the seasonal rainfall.

54 ENVIRONMENTAL SCIENCES↗

Radiation Effects in Used Next Generation Nuclear Fuel Reprocessing Strategies

Given global commitments to significantly increase nuclear energy capacity, it is now more important than ever to develop efficient used nuclear fuel (UNF) management strategies to encourage widespread adoption of closed fuel cycles. To achieve this ambitious goal, a comprehensive understanding of radiation effects is essential for these next generation technologies, as radiolysis often limits longevity and performance. Here, we present new findings on: (i) the radiation robustness and performance of advanced sulfur chloride-based chlorination processes in the presence of nuclear materials (Fig. 1A); and (ii) the impacts of voloxidized uranium and rhenium complexation on monoamide-based UNF direct dissolution strategies (Fig 1B). These studies employed a combination of time-resolved electron pulse and dose accumulation gamma and electron beam irradiation techniques.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Measured Thermal and Fast Neutron Fluence Rates ATR Cycles 171A AFC (Rev. 1)

This report contains the thermal (2200 m/s) and fast (E>1MeV) neutron fluence rate data for ATR Cycle 171A AFC which were measured by the Radiation Measurements Laboratory (RML) as requested by the Power Reactor Programs (ATR Experiments) Radiation Measurements Work Order. This report contains fluence rate values corresponding to the particular elevations (relative to the 80-ft. core elevation) where the measurements were taken. The data in this report consists of (1) a table of the ATR power history and distribution, (2) a listing of the calculated thermal and fast neutron fluence rates, and (3) plots of calculated both the thermal and fast neutron fluence rates.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

In-Situ Liquid Cell Transmission Electron Microscopy of Nanoparticles from Spent Nuclear Fuel

Noble Metal Particles (NMP) that are present in SNF play an important role in the Fuel Matrix Degradation (FMD) Model that is being considered for predicting the release rate of radionuclides from a waste package. Previous characterization of chemically separated NMP from SNF showed that these were well-crystallized nanoparticles containing Mo, Tc, Ru, Rh, and Pd with some evidence of actinides. These same chemically separated particles were re-characterized following 10 years of storage as the separated material in water. Scanning Transmission Electron Microscopy (STEM) analysis revealed that significant alteration had occurred in this material during storage, resulting in the almost complete degradation of the NMP. We hypothesized that radiolytic damaged had occurred in the material. To support these concepts, we synthesized a mixed Ru-Pd nanoparticle and subjected it to irradiation in the electron microscope in an in-situ liquid cell. We demonstrated that intense radiation can lead to the decomposition of these metallic particles.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Generation of high-power few-cycle femtosecond IR pulses by double-chirp parametric amplification

We present an energy scalable configuration for the generation of high-power few-cycle femtosecond IR pulses based on the sequential parametric amplification of chirped radiation pulses at the idler (0.86 μm) and signal (1.39 μm) wavelengths from the multi-terawatt femtosecond laser system made at the Institute of Laser Physics, Siberian Branch of the Russian Academy of Sciences (ILP SB RAS). The configuration under consideration involves the sequential production of radiation pulses with centre wavelengths of 2.24, 3.56, and 7.25 μm. The conditions are determined for the generation of few-cycle pulses with a terawatt peak power in the 3.56 μm (15.8 fs, 1.5 cycles) and 7.25 μm (17.2 fs, shorter than one cycle) domains. The phase transfer between signal and idler waves in the double-chirp parametric amplification is investigated for the first time. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Hybridizing Machine Learning and Physically-based Earth System Models to Improve Prediction of Multivariate Extreme Events (AI Exploration of Wildland Fire Prediction)

Focal Areas: This project responds to two focal areas identified in the DOE Call for AI4ESP White Papers: 1) Predictive modeling through the use of artificial intelligence (AI) techniques, and 2) insights gleaned from complex data using explainable AI and big data analytics. Science Challenge: Large wildland fires (hereafter wildfires) appearing as high-impact compound climate extreme events are closely related to hydroclimate and water cycle extremes that modulate surface fuel supply and combustibility. These compound events have multivariate climatic features (e.g., temperature, precipitation, relative humidity, wind, lightning) and societal drivers (e.g., forest management, land use change, human caused ignitions). Meanwhile, they induce strong feedbacks to the coupled atmosphere, biosphere, and hydrosphere by perturbing regional and global radiation budget as well as ecological, biogeochemical, and water cycles across multiple spatiotemporal scales. The nonlinear interactions between these natural and anthropogenic components of the Earth system are too complex to be completely and adequately represented in today’s Earth system models (ESMs). The inherent stochastic nature of fire activity at all scales further increases the difficulty of its prediction using ESMs that are usually developed from deterministic equations and parameterizations. Besides, concurrence of long-term (decadal to interdecadal) global climate change and fire regime shifts overlapping with short-term (intraseasonal to interannual) variations of regional fire weather and burning activity confound predictability of these compound extreme events. We propose to address the above scientific challenges by using machine learning (ML)-based data-driven modeling techniques to integrate observations and physically-based ESMs’ simulations in a computationally efficient hybrid prediction system. This prediction system is supposed to characterize the wildfire’s sensitivity to climate and exogenous drivers at high resolution (~ 0.25°) on subseasonal to seasonal (S2S) timescales providing improved predictability and explainability. We will use the system to help identify: (1) What are the computational elements of a hybrid system needed to predict compound climate extreme events such as global wildfires? (2) What are the key drivers (either natural or anthropogenic) that modulate short-term variations of multivariate fire weather and burning activity over different regions? How can one take advantage of those driver-response relationships to improve the predictability of large wildfires on S2S time scales? (3) What are the underlying physical mechanisms and sources of improved predictability? Which ML techniques are optimal in revealing and adapting these mechanisms?

54 ENVIRONMENTAL SCIENCES↗

Materials and Fuels Complex (FY22 – FY26 Five-Year Investment Strategy)

The Department of Energy Office of Nuclear Energy (DOE-NE) vision is to “Advance nuclear energy science and technology to meet U.S. energy, environmental, and economic needs.” The Materials and Fuels Complex (MFC) serves as the foundation of a nuclear RD&D enabling test bed at Idaho National Laboratory (INL) and is an integral part of a National Reactor Innovation Center (NRIC) strategy. MFC facilities focus on developing and maintaining RD&D capabilities that can increase research throughput, reduce barriers to deployment, and facilitate commercialization of new ideas and technologies for clean and secure sources of energy.

07 ISOTOPE AND RADIATION SOURCES↗

Analysis of First-Order Gratings in Silicon Photonic Waveguides

A simple thin film effective index analysis for first order gratings in Si photonic waveguides is shown to provide highly accurate results for reflected and transmitted power spectrums as long as the waveguide remains single mode and non-radiating. A cover layer can be added to the grating region of a Si photonic waveguide to increase the strength of the grating, modify transition losses from the input waveguide to the grating waveguide region, and/or modify the width of the reflectivity spectrum. For a given grating period, the peak reflection and spectral width of the reflectivity decrease as the duty cycle is decreased or increased from ~50%. For both radiating and multimode structures, the coupling between all modes, power radiated towards the superstrate (upwards), power radiated downwards (substrate) and transmitted power analyzed by Floquet-Bloch, Eigenmode Expansion and Finite Difference Time Domain methods show excellent agreement. Coupling coefficients calculated using analytic formulas are shown to be accurate only for shallow grating depths.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Eco-friendly passive radiative cooling using recycled packaging plastics

Passive daytime radiative cooling, requiring zero external energy consumption, is a promising cooling strategy achieved by simultaneously reflecting solar irradiance and thermally radiating heat into the cold outer space (~3 K) through the atmospheric transparency window. However, current materials for passive radiative cooling face huge challenges, such as complicated fabrication approaches, expensive raw materials, and environmental requirements for practical applications. In line with the urgent need for plastic recycling to curb global environmental pollution, the recycled plastics are used to fabricate a passive radiative cooling material. Herein, the foam-paper composite (FPC) with excellent self-cooling capability is fabricated by a simple crushing-and-mixing procedure using recycled polystyrene (PS) foam and printer paper. The superhydrophobic PS foam particles not only protect the FPC from water damage for field applications but also reinforce its solar reflectivity via their porous structure. The cellulose fibers in printer paper can efficiently emit infrared thermal radiation into the cold outer space and bond dispersed PS foam particles together, further increasing its mechanical strength. The combination of highly diffusely reflective PS foam particles and fiber-based printer paper results in a reflectivity of 96% in the solar spectrum, a sub-ambient cooling performance of 8.4 degrees C, and a maximum radiative cooling power of 90 W/m2 during a 24-h cycle. Meanwhile, the FPC with high humidity can maintain its high solar reflectivity, which promotes its application in humid subtropical areas. Further, the low material cost and ease of fabrication will provide a path for effective daytime radiative cooling, especially in less developed areas.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Membrane Adsorbents Comprising Self-Assembled Inorganic Nanocages (SINCs) for Super-fast Direct Air Capture Enabled by Passive Cooling

The objectives of the proposed project were to develop highly porous membrane adsorbents comprising CO 2 -philic polymers and self-assembled inorganic nanocages (SINCs) for rapid temperature swing adsorption using electricity-free solar heating and radiative cooling, enabling an economically viable approach for direct air capture (DAC). Our core technical activities combine three key innovations. (1) Highly porous flat-sheet membrane adsorbents contain CO 2 -philic amines that can be easily produced using a phase inversion method. (2) CO 2 -philic SINCs can be easily dispersed in the polymers with great stability (compared with the metal-organic frameworks or MOFs). (3) The adsorption and desorption are integrated with solar heating and radiative cooling for rapid continuous operation, in contrast to traditional long-cycle separate operation. The membrane adsorbents containing amines, polymers, and SINCs were produced using a one-step industrial process. The porous membranes coupled with porous SINCs offer low resistance for gas flow and fast CO 2 sorption/desorption cycles, while the incorporation of the additional amine groups provides high CO 2 sorption capacity. The key achievements are summarized below. (1) Membrane adsorbents with high PEI loading (>40%), high porosity of >80%, and low gasflow resistance were prepared in one step using commercially available, low-cost materials. (2) Membrane adsorbents based on Solupor and PEI show CO 2 sorption capacity of >1.5 mmol/g using air containing 400 ppm at a relative humidity of 15%. (3) Effect of the adsorbent compositions (such as PEI type, PEI content, SINC content, porosity) on the CO 2 sorption was systematically investigated. (4) Effect of the processing conditions (such as CO 2 content, temperature, and relative humidity) on the CO 2 sorption was systematically investigated; (5) The stability of the membrane adsorption against many cycles of sorption and desorption was studied. The higher molecular weight of PEI (PEI25k) shows better stability than PEI800. (6) Advanced materials with radiative cooling were developed, which can decrease the temperature by 5-7 °C compared to the ambient temperature. (7) Preliminary techno-economic analysis shows that our process may achieve a capture cost of $1,343/tonne CO 2 with a total OPEX cost of $1,112/tonne CO 2 . The adsorbent replacement cost accounted for 52% of the total OPEX cost. Membrane adsorbents with lower costs and longer operation life can significantly decrease the cost. The proposed project directly addresses the requirement of DE-FOA-0002188, i.e., novel materials with CO 2 adsorption capacity for direct air capture with integrated solar heating and radiative cooling to reduce the cost of the DAC. Our future work will focus on the development of low-cost adsorbents that can be stable at the sorption and desorption conditions for long term.

14 SOLAR ENERGY↗

Generation and Study of Am(IV) by Temperature-Controlled Electron Pulse Radiolysis

Used nuclear fuel (UNF) separation techniques that strive to separate radiotoxic americium (Am) from trivalent lanthanide fission products through oxidation state control have increased research efforts surrounding Am(V) and Am(VI). However, equivalent knowledge of the tetravalent state, Am(IV), has remained elusive, particularly in conditions more representative of UNF reprocessing, i.e., in concentrated nitric acid (HNO3). With this in mind, we have used electron pulse radiolysis to study the radiation-induced redox reaction of Am(III) with the oxidizing nitrate radical (NO3?) in 6 M HNO3: Am(III) + NO3? ? Am(IV) + NO3? . These experiments enabled us to observe the growth and decay of Am(IV) in a concentrated acidic solution for the first time. The transient Am(IV) species was found to have a lifetime of ~16 µs?sufficiently long-lived to play a critical mechanistic role in UNF reprocessing systems. Additionally, we performed the first-ever temperature-dependent kinetics study of an actinide element, elucidating unprecedented Arrhenius and Eyring activation parameters for the reaction of Am(III) with NO3?. This new knowledge provides much-needed molecular-level insights into the radiation-induced behavior of Am.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Performance and Durability of Heavy-Duty Fuel Cell Systems with an Advanced Ordered Intermetallic ORR Alloy Catalyst and Novel Support

Ordered PtCo intermetallic (OIM) catalyst (L1 0 -PtCo/C) is a promising candidate as the oxygen reduction reaction (ORR) catalyst in hybrid fuel cell systems (FCS) for class-8 heavy duty (HD) trucks. Compared to a baseline annealed Pt on high surface area carbon (a-Pt/HSC) catalyst, its mass activity (MA) is 71% higher initially and 144% higher after 90,000 potential cycles in an accelerated stress test (AST). Analysis of the AST data indicates that the ORR kinetic constants do not change with aging and the degradation in the OIM catalyst activity is linearly proportional to the loss in the electrochemically active surface area (ECSA). Several operational strategies are investigated to mitigate catalyst degradation and achieve 25,000-h electrode lifetime and 2.5 kW g −1 Pt utilization on a HD truck duty cycle including load sharing with the hybrid battery, regulating the radiator fan power to maintain the coolant temperature close to 60 °C, clipping the maximum cell voltage below 850 mV, limiting the ECSA loss to 55%, and oversizing the active area of the membrane electrode assemblies by 20%. Drive cycle simulations indicate that the lifetime average voltage degradation rate is about 1.8 μV h −1 and the integrated stack and FCS drive cycle efficiencies decrease by 3.5 to 3.9%.

25 ENERGY STORAGE↗

Superoxide Radicals in Uranyl Peroxide Solids: Lasting Signatures Identified by Electron Paramagnetic Resonance Spectroscopy

Abstract U(VI) peroxide phases (studtite and meta‐studtite) are found throughout the nuclear fuel cycle and exist as corrosion products in high radiation fields. Peroxides are part of a family of reactive oxygen species (ROS) that include hydroperoxyl and superoxide species and are produced during alpha radiolysis of water. While U(VI) peroxides have been thoroughly investigated, the incorporation and stability of ROS species within studtite have not been validated. In the current study, electron paramagnetic resonance (EPR) spectroscopy was used to identify the presence of free radicals within a series of U(VI) peroxide samples containing depleted, highly enriched, and natural uranium. Density functional theory calculations indicated that the predicted EPR signals matched well with a superoxide (O 2 − ⋅) species incorporated into the studtite structure, confirming the presence of ROS in the material. Further analysis of samples that were synthesized between 1945 and 2023 indicated that there is a correlation between the radical signal and the product of specific activity multiplied by age of the sample.

Scherrer, Sarah K.↗