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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 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

The Micro-Optical Ring Electrode: A Sensor for Multiple Actinide Ions Monitoring - 17586

We present on the development of the Micro-Optical Ring Electrode (MORE) for the analysis of trans-uranium elements in aqueous mixtures. The MORE is a photo-electrochemical device based on a ring microelectrode that uses the insulator interior to the ring as a light guide. This single device exploits the unique photophysical and electrochemical properties of multiple analytes present in mixtures to quantify them. Our study aims to develop a protocol for the analysis of ions of uranium, neptunium and plutonium, which are most relevant to the nuclear industry, especially in the areas of decommissioning and fuel reprocessing, where speedy and safe identification of radioactive contaminants is essential. The technique offers a number of advantages over traditional methods in the area of radiochemical analysis such as real time monitoring in-situ, reduced radiation dose impact to the analyst as a result of greatly reduced sample handling and preparation, improved analysis times allowing quick decision making, at a much reduced cost (e.g. compared to ICP-MS and Scintillation counting). Here we present results of our study on non-radioactive surrogates for the target elements and discuss the advantages the technique can deliver to the nuclear industry. (authors)

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

Electrochemical Manipulation and Radiolytic Evaluation of Organic Phase Neptunium

Post for LDRD Annual Poster Session Under envisioned used nuclear fuel reprocessing conditions, neptunium (Np) is present in a mixture of extractable Np(IV)/Np(VI) and inextractable Np(V) species, the distribution of which is dependent on several factors that lead to the unintentional partitioning of Np into various phases and product streams, reducing process and cost efficiency. With this in mind, we tested an innovative approach to precisely control the oxidation state distribution of Np using novel, high surface area, optically transparent, ligand modified tin-doped indium oxide electrodes (LMEs). These proof-of-concept experiments employed a variety of radiation and electrochemistry (echem) techniques to determine: electrode radiation stability; aqueous echem behavior of Np at nITO|P3 electrode surfaces; radiation-induced Np-extractant reaction kinetics; and non-aqueous echem of Np in diethylhexyl butyramide (DEHBA) solutions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2023

Solids from Fuel Dissolution, Process Solutions, and Waste Evaporation

Irradiated light water reactor (LWR) fuel contains material which is insoluble in nitric acid, and process solutions are unstable with respect to precipitation of compounds insoluble in nitric acid. Accordingly, solids will be encountered during fuel reprocessing, and operations must be conducted in a way to minimize formation of additional solids and to prevent their interference with reprocessing operations.

Campbell, D. O.↗
DOE OSTI2023

2023 American Society for Mass Spectrometry (ASMS) 71st Annual Conference on Mass Spectrometry and Allied Topics

Introduction (120 words max) Understanding metal-cluster chemistry occuring at solvent boundaries in the aqueous and organic phases has applications in environments from cellular processes to nuclear fuel reprocessing. Transport of metal ions at the boundaries from aqueous to organic phases involves forming a metal-ligand complex, and wherever the initial metal coordination environment is significantly different from the final one, the metal transitions through a series of transient species in passing from one phase to another. Here an investigation of the role of coordination in the chemistry of the transient species using gas-phase measurements that are free of solvent effects to better understand the binding of complexes of metals with triphenylphosphine chalcogenide ligands, examining metal-ligand homo- and hetero-dimers to better understand transient species. Methods (120 word max) Mass spectrometry and collision induced dissociation (CID) experiments were performed with a Bruker (Billerica, MA, USA) micrOTOF-Q II quadrupole time-of-flight mass spectrometer (QTOF) and Bruker amaZon speed ETD (ion trap). High resolution/high mass accuracy spectra were generated using the QTOF. External calibration was performed with Agilent (Santa Clara, CA, USA) ESI-L Low Concentration tuning mix. Both mass spectrometers were equipped with either the electrospray ionization source or nanospray sources. Metal samples were prepared between 40 – 60 uM of the metal-ligand complex in 25% water and 75% acetonitrile. Metal-ion clusters were isolated and subjected to collision induced dissociation. Density functional theory calculations were performed. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters with triphenylphosphine chalcogenide ligands were observed for group I metals with triphenylphosphine chalcogenide samples in the mass spectrum upon electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation spectra were acquired. We observed clusters of group I metal with triphenylphosphine oxide, triphenyl phosphine sulfide, and triphenylphosphine selenide, with homodimers and heterodimer formation. In samples where the ligands were mixed, we observed mixed sodium ligand clusters at varying amounts. These mixed ligand clusters were fragmented. Metal clusters of mixed ligand dimers containing triphenylphosphine oxide showed preferential loss of the other ligand, either triphenylphosphine sulfide or triphenyl selenide. In samples with mixed triphenylphosphine sulfide and triphenylphosphine selenium ligands, sodium bound similarly between the ligands, and losses were more evenly split, showing loss ratio upon CID with losses of triphenylphosphine sulfide:triphenylphosphine selenide 43:57 ratio observed on CID. These results suggest that the oxide binds significantly more strongly than either the selenium or sulfur triphenylphosphine ligand, and the sulfur and selenium ligands are more evenly bound. Calculations were performed using density functional theory to calculate likely structures and bond energies between the group I metal and the ligands. Novel Aspect Novel analysis of sodium bound dimers with chalcogenide triphenylphosphine ligands were investigated using mass spectrometry and theoretical calculations.

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

Investigating Radiation-Induced Actinide Species in Solution

Our fundamental understanding of actinide radiation-induced redox chemistry is crucial to nuclear fuel cycle development, due to the unavoidable exposure of these elements to ionizing radiation fields, both inherent and from in-process applications. Plutonium (Pu) and americium (Am) both possess multiple oxidation states, the careful manipulation of which are essential in the study and utilization of their rich chemistry, developing new nuclear technologies, and securing the long-term sustainability of nuclear power. However, knowledge in this area is far from complete. Consequently, we have studied the radiation-induced chemistry of both Pu and Am through a variety of techniques. Temperature-controlled electron pulse radiolysis has been used to study Am for the first time, determining the feasibility of Am redox reactions under used nuclear fuel reprocessing conditions, (e.g. nitric acid, non-ambient temperature). Additionally, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu redox chemistry due to radiolysis and disproportionation reactions in concentrated nitric acid solutions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Investigating Radiation-Induced Actinide Species in Solution

Our fundamental understanding of actinide radiation-induced redox chemistry is crucial due to their unavoidable exposure to ionizing radiation fields, both inherent and from in-process applications. Plutonium (Pu) and americium (Am) both possess multiple oxidation states, the careful manipulation of which are essential in the study and utilization of their rich chemistry, developing new nuclear technologies, and securing the long-term sustainability of nuclear power. However, knowledge in this area is far from complete. Consequently, we have studied the radiation-induced chemistry of both Pu and Am through a variety of techniques. Temperature-controlled electron pulse radiolysis has been used to study Am for the first time, determining the feasibility of Am redox reactions under used nuclear fuel reprocessing conditions, (e.g. nitric acid, non-ambient temperature). Additionally, we developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu redox chemistry due to radiolysis and disproportionation reactions in concentrated nitric acid solutions.

actinide↗
DOE OSTI2025

R-matrix evaluation of the 15 N Compound System for Criticality Safety Analyses [Abstract]

The evaluation of the 15 N compound system was selected by the Nuclear Criticality Safety Program (NCSP) due to the importance of nitrogen in criticality benchmarks and in actinide chemistry encountered during fuel reprocessing. For improved accuracy in transport calculations, it is recommended to obtain and distribute resonance parameters to describe n + 14 N reactions.

AZURE↗
DOE OSTI2020

Requirements and Conceptual Design of Off-gas Systems for the Reprocessing of Metallic Fuels

An assessment has been conducted to determine how key regulations regarding volatile radionuclide emissions to the atmosphere may apply to the off-gas streams associated with electrochemical reprocessing. The scope of this assessment was based upon a generic electrochemical reprocessing scheme with a throughput rate of 200 MTIHM/y applied to metallic fuel discharged from a sodium fast reactor (SFR), but the findings are able to be translated to other advanced nuclear scenarios as merited. Air dispersion modeling was performed using the EPA CAP-88 model and evaluated the uncontrolled decontamination factors (DFs) that would be required to achieve regulatory compliance with the dose-based limits set forth by EPA regulation 40 CFR 190.10(a). These DFs were compared to those required by fuel cycle–based limits set forth by EPA regulation 40 CFR 190.10(b). Two theoretical sites with disparate climatological conditions were selected for air dispersion modeling (Idaho and Tennessee). The radionuclides modeled included 3 H, 85 Kr, 129 I, and selected alpha-emitting transuranic isotopes (referred to here as 239 Pu-TRU <1y ). It was found that the fuel cycle-based limits in 40 CFR 190.10(b) are most restrictive for 85 Kr and 239 Pu-TRU <1y , with DFs of 3 and 6.1E+09, respectively. The dose-based limit as derived from 40 CFR 190.10(a) could require mitigation of tritium in some scenarios, with an estimated DF of about 3 for the reference scenarios. The fuel cycle-based limit for 129 I resulted in a DF of about 240 for the reference scenario. The need for iodine mitigation based on dose to the public depended upon the physical form of iodine as either particulate or vapor-phase species. Emission of iodine from the facility as a vapor necessitated DFs of about 2 but emission as a particulate would require DFs >6,000 to meet thyroid dose-based limits. Effects of physical form on needed iodine mitigation are significant, but the understanding of speciation of iodine both during electrochemical reprocessing and after release to the atmosphere is limited. The electrochemical processing unit operations were evaluated to identify potential release points for the volatile radionuclides and to assess the potential for retention of the radionuclides within the process (thus decreasing the need for mitigation). Mitigation strategies for 3 H, 85 Kr, 129 I, and 239 Pu-TRU <1y were identified. In all cases, there are reasonably achievable pathways to regulatory compliance, although in some cases additional R&D is merited to verify the chemical speciation of these isotopes and to develop and demonstrate potential treatment technologies for this application. Whether or not additional off-gas controls (beyond common operations such as HEPA filtration and oxygen and moisture control) are needed for any of these regulated or volatile radionuclides depends on the (a) type of facility (NRC-regulated or DOE), (b) used fuel process rate, (c) used fuel burnup and composition, (d) speciation and retention of volatile radionuclides in the process and in the cell gas cleanup system, (e) site-specific parameters such as location, meteorology, stack height, and site boundaries, and (f) levels of conservatism and safety factors used in assessing compliance to air emissions regulations. Performance of this assessment revealed several areas where information is lacking or additional research is required in order to better determine if or what kinds of off-gas control might be needed. First, and most significantly, the understanding of the chemical speciation and physical form and partitioning of iodine during electrochemical processing operations is lacking and prevents the ability to accurately assess the potential iodine mitigation requirements. Future research in this area should be multifaceted and include thermodynamic modeling of iodine speciation in different process steps, experiments to quantify the kinetics of vapor-phase and melt-phase transitions, bench-scale experiments to determine the potential chemical and physical form of iodine emissions from the electrorefining process, and verification of iodine behavior with experiments utilizing operational facilities. Similarly, an improved understanding of iodine behavior in the environment after release from the facility stack will be required to refine dose estimations, as particulate and vapor-phase emissions result in significantly different doses to the MEI.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

The used nuclear fuel problem - can reprocessing and consolidated storage be complementary?

This paper describes our CISF (Consolidated Interim Storage Facilities) and Reprocessing Facility concepts and show how they can be combined with a geologic repository to provide a comprehensive system for dealing with spent fuels in the USA. The performance of the CISF was logistically analyzed under six operational scenarios. A 3-stage plan has been developed to establish the CISF. Stage 1: the construction at the CISF site of only a rail receipt interface and storage pad large enough for the number of casks that will be received. The construction of the CISF Canister Handling Facility, the Storage Cask Fabrication Facility, the Cask Maintenance Facility and supporting infrastructure are performed during stage 2. The construction and placement into operation of a water-filled pool repackaging facility is completed for Stage 3. By using this staged approach, the capital cost of the CISF is spread over a number of years. It also allows more time for a final decision on the geologic repository to be made. A recycling facility will be built, this facility will used the NUEX recycling process that is based on the aqueous-based PUREX solvent extraction process, using a solvent of tri-N-butyl phosphate in a kerosene diluent. It is capable of processing spent fuels at a rate of 5 MT per day, at burn-ups up to 50 GWD per ton of spent fuels and a minimum of 5 years out-of-reactor cooling.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Extending Spent Fuel Storage until Transport for Reprocessing or Disposal

Spent fuel (SF) must be stored until an end point such as reprocessing or geologic disposal is imple-mented. Selection and implementation of an end point for SF depends upon future funding, legisla-tion, licensing and other factors that cannot be predicted with certainty. Past presumptions related to the availability of an end point have often been wrong and resulted in missed opportunities for properly informing spent fuel management policies and strategies. For example, dry cask storage systems were originally conceived to free up needed space in reactor spent fuel pools and also to provide SFS of up to 20 years until reprocessing and/or deep geological disposal became available. Hundreds of dry cask storage systems are now employed throughout the world and will be relied upon well beyond the originally envisioned design life. Given present and projected rates for the use of nuclear power coupled with projections for SF repro-cessing and disposal capacities, one concludes that SF storage will be prolonged, potentially for several decades. The US Nuclear Regulatory Commission has recently considered 300 years of storage to be appropriate for the characterization and prediction of ageing effects and ageing management issues associated with extending SF storage and subsequent transport. This paper encourages addressing the uncertainty associated with the duration of SF storage by de-sign – rather than by default. It suggests ways that this uncertainty may be considered in design, li-censing, policy, and strategy decisions and proposes a framework for safely extending spent fuel storage until SF can be transported for reprocessing or disposal – regardless of how long that may be. The paper however is not intended to either encourage or facilitate needlessly extending spent fuel storage durations. Its intent is to ensure a design and safety basis with sufficient margin to accommodate the full range of potential future scenarios. Although the focus is primarily on storage of SF from commercial operation, the principles described are equally applicable to SF from research and production reactors as well as high-level radioactive waste.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

Exploratory Design of a Reactor/Fuel Cycle Using Spent Nuclear Fuel Without Conventional Reprocessing - 13579

General Atomics has started design of a waste to energy nuclear reactor (EM2) that can use light water reactor (LWR) spent nuclear fuel (SNF). This effort addresses two problems: using an advanced small reactor with long core life to reduce nuclear energy overnight cost and providing a disposal path for LWR SNF. LWR SNF is re-fabricated into new EM2 fuel using a dry voloxidation process modeled on AIROX/ OREOX processes which remove some of the fission products but no heavy metals. By not removing all of the fission products the fuel remains self-protecting. By not separating heavy metals, the process remains proliferation resistant. Implementation of Energy Multiplier Module (EM2) fuel cycle will provide low cost nuclear energy while providing a long term LWR SNF disposition path which is important for LWR waste confidence. With LWR waste confidence recent impacts on reactor licensing, an alternate disposition path is highly relevant. Centered on a reactor operating at 250 MWe, the compact electricity generating system design maximizes site flexibility with truck transport of all system components and available dry cooling features that removes the need to be located near a body of water. A high temperature system using helium coolant, electricity is efficiently produced using an asynchronous high-speed gas turbine while the LWR SNF is converted to fission products. Reactor design features such as vented fuel and silicon carbide cladding support reactor operation for decades between refueling, with improved fuel utilization. Beyond the reactor, the fuel cycle is designed so that subsequent generations of EM2 reactor fuel will use the previous EM2 discharge, providing its own waste confidence plus eliminating the need for enrichment after the first generation. Additional LWR SNF is added at each re-fabrication to replace the removed fission products. The fuel cycle uses a dry voloxidation process for both the initial LWR SNF re-fabrication and later for EM2 discharge reuse. The EM2 waste disposal profile is effectively only fission products, which reduces the mass (about 3% vs LWR), average half life, heat and long term radio-toxicity of the disposal. Widespread implementation of EM2 fuel cycle is highly significant as it would increase world energy reserves; the remaining energy in U.S. LWR SNF alone exceeds that in the U.S. natural gas reserves. Unlike many LWR SNF disposition concepts, the EM2 fuel cycle conversion of SNF produces energy and associated revenue such that the overall project is cost effective. By providing conversion of SNF to fission products the fuel cycle is closed and a non-repository LWR SNF disposition path is created and overall repository requirements are significantly reduced. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

On the possibility of reprocessing spent nuclear fuel and radioactive waste by plasma methods

The concept of plasma separation of spent nuclear fuel and radioactive waste is presented. An approach that is based on using an accelerating potential to overcome the energy and angular spread of plasma ions at the separation region inlet and utilizing a potential well to separate spatially the ions of different masses is proposed. It is demonstrated that such separation may be performed at distances of about 1 m with electrical potentials of about 1 kV and a magnetic field of about 1 kG. The estimates of energy consumption and performance of the plasma separation method are presented. These estimates illustrate its potential for technological application. The results of development and construction of an experimental setup for testing the method of plasma separation are presented.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Application of sensitivity analysis in DYMOND/Dakota to fuel cycle transition scenarios

The ability to perform sensitivity analysis has been enabled for the nuclear fuel cycle simulator DYMOND through its coupling with the design and analysis toolkit Dakota. To test and demonstrate these new capabilities, a transition scenario and multi-parameter study were devised. The transition scenario represents a partial transition from the US nuclear fleet to a closed fuel cycle with small modular LWRs and fast reactors fueled by reprocessed used nuclear fuel. Four uncertain parameters in this transition were studied – start date of reprocessing, total reprocessing capacity, the nuclear energy demand growth, and the rate at which the fast reactors are deployed – with respect to their impact on four response metrics. The responses – total natural uranium consumed, maximum annual enrichment capacity required, total disposed mass, and total cost of the nuclear fuel cycle – were chosen based on measures known to be of interest in transition scenarios and to be significantly impacted by the varying parameters. Furthermore, analysis of this study was performed both from the direct sampling and through surrogate models developed in Dakota to calculate the global sensitivity measures Sobol’ indices. This example application of this new capability showed that the most consequential parameter to most metrics was the share of new build capacity that is fast reactors. However, for the cost metric, the scaling factor of the energy demand growth was significant and had synergistic behavior with the fast reactor new build share.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Novel Glass Formulations for Post Operational Clean Out of Highly Active Storage Tanks - 17596

The UK has a successful history of reprocessing nuclear fuel from both UK nuclear reactors and for overseas customers. Highly Active Liquor (HAL), a waste product from reprocessing, is stored in stainless steel tanks before being incorporated into a stable glass matrix in one of three vitrification lines at Sellafield. Over the next 4 years Sellafield Ltd will cease reprocessing nuclear fuel, and the reprocessing plants and storage tanks will enter a Post Operational Clean Out (POCO) phase to remove the radioactive inventory and prepare for future decommissioning. POCO feeds are expected to differ greatly from current HAL, and will contain high levels of molybdenum solids. This paper, and subsequent poster presentation, introduces the vitrification challenges expected with processing POCO waste-streams. The main challenge is the transfer and processing of high molybdenum containing solids. Details of the application of new glasses onto the active vitrification plant will also be included. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Advanced dismantling techniques applied in an industrial project for the dismantling of highly activated equipment - 15446

Commissioned in 1958 on the CEA nuclear site of Marcoule (France) and shut down in 1997, the former UP1 plant was dedicated to reprocess the spent fuel from G1, G2 and G3 GCR reactors. Since 1998, a wide program for cleaning-up and dismantling the plant has been developed in order to dismantle the process equipment, eliminate any radiological risk in all buildings concerned and remove all the resulting waste. Major technical challenges are related to the wide range of complex components and equipment in the facilities such as chemical dissolvers, extractor batteries, evaporators, tanks; and to a high risk of exposure, due to the presence of fission products. To address these challenges, CEA led R and D programs to develop advanced tools for complex dismantling projects: immersive virtual reality, laser cutting techniques, special remote-controlled arms combining dexterity and high resistance to irradiation The purpose of this paper is to provide an overview of a practical implementation and to show first results of these advanced techniques on a real case: the dismantling of dissolver's equipment from the dissolution workshop of UP1 plant. ONET Technologies has been chosen by CEA to design, build and operate the overall dismantling and waste treatment system for this project. ONET Technologies designed two main subsystems to meet all the requirements for this project: first, the 'Remotely-Operated Handling and Cutting Unit' and second the 'Waste Extraction and Conditioning Unit' and the combining innovative technologies. During the design phase, the 'Immersive Virtual Reality' has been used to qualify the kinematics in the final environment and the preliminary dismantling scenario. Following a first R and D program of CEA regarding the laser cutting technique applied to nuclear decommissioning, ONET Technologies and CEA realized elementary inactive tests based on a 6 kW Nd-Yag laser source to qualify the cutting performance according to material and thickness. Main objective was to meet the safety criteria and to check the physical characteristics of waste resulting from the laser cutting operation. The Remotely-Operated Handling and Cutting Unit was equipped with a MAESTRO manipulator, resulting from ten years of research and development cooperation between CEA and Cybernetix. This manipulator, a 6 axis hydraulic manipulator-arm specifically designed to work in harsh environment, entered in its industrial phase. ONET Technologies was responsible for the overall system integration, confinement and performance. A comprehensive qualification program in real conditions has been driven during 2014. The dismantling scenario was tested with a mockup at a full scale of dissolver equipment and confirmed at this stage the expected level of performance and safety. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Iodine Sorption on AgZ-PAN

The Department of Energy (DOE) Nuclear Fuel Cycle and Supply Chain Program Material Recovery and Waste Form Development (MRWFD) Campaign Off-gas Sigma Team has performed research and development on iodine control and iodine waste forms for the past several years. This research and development has included iodine adsorption tests using a laboratory-scale test system containing multiple-segmented fixed beds of iodine adsorbents. Iodine capture performance has been tested using (a) non-radioactive synthetic gas mixtures blended from air, nitrogen, NO, NO 2 , water, to simulate dissolver off-gas (DOG) and vessel off-gas (VOG) streams from used nuclear fuel aqueous reprocessing, (b) inorganic and organic iodine species, and (c) different sorbents. An initial test of silver-functionalized mordenite in polyacrylonitrile matrix (AgZ-PAN) was conducted to assess if this sorbent, initially designed for selective sorption of Xe that evolves into used fuel reprocessing off-gas streams, could also be a candidate for iodine sorption. This test was conducted using the same deep-bed test system and methodologies used in many prior iodine sorption tests using other sorbents. Diatomic iodine (I2) was used as the target iodide in a gas stream containing air, NO, NO 2 , and moisture designed to simulate an aqueous reprocessing dissolver off-gas (DOG) stream.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Investigation of molybdate melts as an alternative method of reprocessing used nuclear fuel

Here, an investigation of molybdate melts containing sodium molybdate (Na 2 MoO 4 ) and molybdenum trioxide (MoO 3 ) to achieve the separation of uranium from fission products by crystallization has been performed. The separation is based on the difference in solubility of the fission product metal oxides compared to the uranium oxide or molybdate in the molybdate melt. The molybdate melt dissolves uranium dioxide at high temperatures, and upon cooling, uranium precipitates as uranium dioxide or molybdate, whereas the fission product metals remain soluble in the melt. Small-scale experiments using gram quantities of uranium dioxide have been performed to investigate the feasibility of UO 2 purification from the fission products. The composition of the uranium precipitate as well as data for partitioning of several fission product surrogates between the uranium precipitate and molybdate melt for various melt compositions are presented and discussed. The fission products Cs, Sr, Ru and Rh all displayed very large distribution ratios. The fission products Zr, Pd, and the lanthanides also displayed good distribution ratios (D > 10). A melt consisting of 20 wt% MoO 3 -50 wt% Na 2 MoO 4 -30 wt% UO 2 heated to 1313 K and cooled to 1123 K for the physical separation of the UO 2 product from the melt, and washed once with Na 2 MoO 4 displays optimum conditions for separation of the UO 2 from the fission products.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Hydrolysis Reaction Pathways of Thorium Oxide Nanoclusters

Density functional theory benchmarked by correlated molecular orbital theory is used to develop a fundamental and predictive understanding of the interaction of thorium oxide nanoclusters with gas phase water to provide insight into nuclear-waste storage, production of thorium nuclear reactor fuels, and reprocessing of spent fuel. The structures of Th n O 2n (n = 3 – 6) clusters and their interactions with water have been studied at the B3LYP, MP2, and CCSD(T) levels. Hydrolysis is initiated by the formation of Lewis acid-base adducts, with relative H 2 O binding energies (physisorption) ranging from −15 kcal/mol to −22 kcal/mol. The initial H 2 O physisorption energy is ca. −21 kcal/mol regardless of the cluster size and is consistent with the experimentally obtained initial adsorption energy on a thorium dioxide surface. The physisorption enthalpies for additional water molecules can be affected by the presence of terminal groups OH groups generated by proton transfer to a Th-O near the site of adsorption. The hydrolysis products (chemisorption) form either bridging or terminal hydroxides. More exothermic hydrolysis steps were predicted for the formation of terminal hydroxides as compared to the formation of bridging hydroxides. Here, the calculated transition state barriers for transfer of protons from bound water complexes to form the chemisorption products are very low. Overall, water readily reacts with thorium oxide clusters preferring hydroxide products over hydrated complexes. First and second order fits were predicted for the combined physisorption and chemisorption energies for the hydrolysis of thorium oxide clusters. Finally, ionization energies and electron affinities were calculated as were HOMO-LUMO gaps to provide additional insights into the properties of the thorium oxide and hydroxide clusters.

Adsorption↗