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At least 37 records · Page 2

Electrochemical Investigation of Moisture Byproducts in Molten Calcium Chloride

Residual water in molten CaCl 2 reacts to form different byproducts, such as HCl, which can impact the corrosivity of the salt and efficiency of electrochemical operations, such as electrolytic oxide reduction and electrorefining. The ability to detect and quantify these byproducts electrochemically can provide feedback on the efficacy of vacuum drying and other purification methods, as well as the impact of these byproducts on process operations. An electrochemical signal’s association with the production of H 2 is verified and characterized using cyclic voltammetry (CV) and residual gas analysis. CV estimated a 2-electron exchange process associated with H 2 production. CV detected trace quantities of an oxidized species containing hydrogen in the salt on the order of 10 ppm. Different salt handling methods were compared for their impact on the hydrogen electrochemical signal. It was found that 30 min of exposure of CaCl 2 in a beaker to low-humidity air (<20%) had minimal impact on the H 2 production signal.

Electrochemistry

TEX-Cl: Integral Experiment Execution of Thermal/Epithermal eXperiments using Highly Enriched Uranium with Polyethylene and Chloride Absorbers

This report documents the experimental configurations and measurements performed for IER-499, TEX with chlorine (TEX-Cl). TEX-Cl is a variant of the TEX-HEU campaign and utilizes highly enriched uranium fuel, high-density polyethylene (HDPE) moderators and reflectors, and interstitial NaCl salt absorbers. These experiments probe the chlorine (from the sodium chloride) absorption cross section in the thermal and intermediate neutron energy regimes, with a small portion in the fast neutron energy regime. Three configurations were selected by maximizing the sensitivity in k eff to the needs of Y-12 for their electrorefining operations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Application of Partial Least Squares Approaches to Pyroprocessing ER Data

Multivariate approaches show promise for application to process monitoring for safeguards of pyroprocessing. Past MPACT work explored the application of Principal Component Analysis (PCA) to detect off-normal conditions in pyroprocessing electrorefiner (ER) data from in the Hot Fuel Examination Facility (HFEF) at Idaho National Laboratory (INL) known as the Scalable Pyrochemical Recycling testbed (SPyRe) ER. PCA, however, does not consider the output variables. In FY24, multivariate analysis was extended from PCA to Partial Least Squares (PLS) analysis. PLS maximizes the variance between both the input signals and output variables. In the case of this work, PLS was applied in two different manners: Predictive PLS and Discriminant PLS. Predictive PLS maximizes the covariance between the process variables of the ER and the measured U concentration from in-situ voltammetry. Discriminant PLS maximizes the covariance between the process variables and a set of training process “states” such as known off-normal conditions. By projecting into the latent variable space in PLS, the process variables can be regressed onto the outputs and predictions can be made for new data sets. In this work, by applying predictive PLS, a penalized non-linear PLS approach was able to make predictions of concentration based on test and training data and detect when operations were off-normal. However, the predictive PLS does not classify the signals to which off-normal operations are attributable. Discriminant PLS can be used to classify off-normal operations but is inadequate to properly classify specific off-normal classes like power supply faults when the Discriminant PLS model is only specifically trained to detect that off-normal class. When all faults are trained against the observation data, all three operational classes are accurately classified and distinguished. Thus, future application of latent variable techniques should not select any given method, but should use a mixture of PCA, Predictive PLS, and Discriminant PLS.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Solubility and Dissolution Rate of LiCl-KCl-NaCl

This work aims to determine the potential risk of directly storing waste salt from the electrorefining process of used nuclear fuel in a geologic repository. To accomplish this, the solubility limit and dissolution rate of four representative chloride salt mixtures (solutes) in water and two brine solutions (solvents) are observed and documented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Assessment of Active Metal Removal from Pyroprocessing Salt by Electrodeposition

Active metals present in used nuclear fuel dissolve into the salt during pyroprocessing, but are not recovered during electrorefining or drawdown operations due to their chemical stability in the salt. The accumulation of 137 Cs and 90 Sr in process salt over time increases the heat load and ionizing radiation level of the salt such that it must be replaced frequently, resulting in a significant amount of salt waste. An effective means of removing active metals from the molten salt to enable recycle of the electrolyte (e.g., LiCl/KCl) would increase the efficiency of pyroprocessing and decrease the volume of salt waste requiring disposal.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Operation of Argonne's Liquid Salt-Liquid Metal Separation Testbed for U/TRU Product Processing

Argonne National Laboratory has constructed a liquid salt-liquid metal separation testbed for use in the development and advancement of cathode processing of U/TRU co‑deposits generated by pyroprocessing of used nuclear fuel. The U/TRU product recovered from the electrorefiner contains adhered and entrained salt that must be removed prior to consolidation of the U/TRU alloy for use in advanced reactor fuel fabrication. The bottom pour operation utilizes the low melting points of U/TRU co‑deposits and higher densities of molten metals compared to molten salts to separate and consolidate the U/TRU product. Argonne’s testbed is designed to support the development and optimization of bottom-pouring configurations for batch and semi-continuous operations, integration of process monitoring and control technologies, and determination of operational requirements for implementing in an industrial setting. Scoping tests were performed to demonstrate operational aspects of the testbed, including operation using single-pour spout and dual-pour spout configurations, effectiveness of salt containment and extent of salt vaporization, and the use of sensor probes to detect the location of the interface between the metal and salt phases during pouring. Recommendations for process optimization testing for further development of bottom pour processing to separate U/TRU alloys from adhered salt were made based on the results of scoping tests. Completing the recommended activities will increase the technical readiness level (TRL) of the liquid salt-liquid metal separation operation and consolidation of U/TRU alloys to support industrialization of pyroprocessing.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

TEX-Chlorine Assemblies: Highly Enriched Uranium Plates with Sodium Chloride Absorbers Using Polyethylene Moderator and Polyethylene Reflector

This evaluation documents highly enriched uranium (HEU) experimental critical configurations with polyethylene moderators and sodium chloride absorbers conducted as part of the United States Nuclear Criticality Safety Program’s Thermal/Epithermal eXperiments (TEX) program. HEU-MET-MIXED-021 provides the benchmark evaluation of five TEX experiments designed to establish baseline configurations with HEU Jemima plates moderated by high density polyethylene (HDPE). The TEX-HEU experiments were designed to cover five different fission energy regimes by varying the thickness of the interstitial HDPE moderator, with varying fractions of thermal, intermediate, and fast fissions, and to be easily modified to accommodate test materials of interest. HEU-MET-INTER-013 documents the first TEX-HEU variation, incorporating hafnium in seven different experimental configurations. This evaluation covers an additional variant that incorporates absorber plates of compacted high-purity sodium chloride salt. These experiments were motivated by a criticality safety need for validation data for uranium purification by means of electrorefining with chloride salts, especially thermal and intermediate energy configurations resulting from moderator upset conditions, and their design was optimized by matching sensitivity profiles from application cases. All three experimental configurations are judged to be acceptable as benchmark cases. The main parameter varied between the configurations is the thickness of the polyethylene moderators and the sodium chloride absorbers between the HEU plates. Varying the thickness of the polyethylene tunes the neutron energy spectrum between majority thermal (Case 1 and 2) and intermediate (Case 3). The fission fractions, presented in Table 1, are determined calculationally. Case 3 is cross listed as HEU-MET-INTER-014.

42 ENGINEERING

Finding ways to reduce nuclear waste: searching for the unknown one step at a time

In my home country, Venezuela, research has been stagnant. Due to the political turmoil and the crisis, many educated people have left the country in search for a better life. This has caused a deficit in any technological and scientific advances, making Venezuela one of the first South American countries to have its rate of publications decline by 29% in 2013. Currently, Venezuela lacks the infrastructure and the means to keep up with the research progress as compared to other countries in South America, such as Brazil. Since coming to the United States (US), and currently working for a national laboratory, the active research environment endorses a wide range of careers and engineering programs that allow researchers to thrive at any given field. Researchers have access to funds and tools to succeed in developing materials for the future. There are 17 national laboratories in the US, and all of these have a different research focus/objective. As examples, Los Alamos National Laboratory and Sandia National Laboratory focus is on national homeland security, weapon science, radiation effects, among others. Argonne National Laboratory focuses on nuclear energy, energy storage, high performance computing, etc. At Idaho National Laboratory (INL) the research focuses on innovating nuclear energy and clean energy resources, critical infrastructure materials, along with fuel cycle solutions to manage, dispose and find ways to recycle current and future radiological waste. Compared to other national laboratories, INL focuses slightly more on applied processes and how nuclear energy can be innovated to next reactor design and technologies. The research being conducted at INL made me apply for a Seaborg distinguished postdoctoral position. For the position itself, the researcher must submit a proposal related to actinide chemistry on a research field area. In this position, 50% of my time will be focused on my own proposal. The proposal that I am working on is focused on the innovation of nuclear energy and fuel cycle recycling, which is why I was mainly interested on working at this national laboratory. To give a bit more context of what my proposal is about, a little bit of background is necessary: After the nuclear fuel (UO2) is used in a reactor, the fuel matrix is then characterized by various fission products (FP). Among these FP (including rare earth elements, alkali/alkaline earths, and actinides), many can potentially be recovered through nuclear reprocessing technologies. In pyroprocessing, the used nuclear fuel undergoes electrochemical dissolution into a molten chloride salt mixture in an electrorefiner. Initially, uranium is reduced onto an inert cathode by applied potentials. However, numerous remaining FPs accumulate in the melt and pose challenges for recovery by an inert electrode, particularly the rare earth elements (e.g., Nd, Gd, Pr, Sm) due to their multivalent oxidation states and tendencies toward side reactions, leading to their dissolution in the electrolyte. These recovery challenges result in inefficiencies and necessitate the continual discarding of the molten chloride salt, thereby generating additional waste. Furthermore, the presence of rare earth elements and other fission products in the molten salt electrolyte alters its physical and chemical properties, affecting both uranium recovery efficiency and the longevity of the molten chloride salt. To improve the recovery efficiency of the FP, specifically rare earth elements, I am investigating the fundamental interactions between rare earth elements in the molten chloride salt and their metallic form. The kinetic pathways and the chemical reactions of these elements will give insights on how the recovery efficiency can be improved. The interactions and speciation of these elements are being studied by spectro-electrochemistry at high temperature environments in quartz and other ceramic materials (e.g., alumina crucibles). Some of the challenges I am facing specifically relates the reactivity of some of these elements with different glass and crucible materials. Although my research focuses on fundamental science, it will benefit the applied process by generating new scientific knowledge and closing the gap for an efficient recycling of the waste: one step at a time.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

High-Temperature Reference Electrode for Chloride Salts

The unique properties of molten salts enable their use in a wide range of applications, including metal electrodeposition, electrorefining, and as electrolytes in high-temperature batteries. Moreover, molten salts will be used as a coolant in molten salt reactors and as working media in pyrorocessing for nuclear energy applications. As a result, predicting the behavior and properties of the elements involved in the technological processes that employ molten salts is important. The activity of chloride ions in chloride molten salts has a large influence on the behavior of the salts in these applications and one of the key components in measuring the chloride activity is a stable reference electrode. This project aims to develop a reliable and convenient method for measuring chloride ion activity over a wide range of temperatures and salt compositions in chloride salt mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Criteria for Retention of 3013 S1 Containers Based on Relative Risk and Expert Judgment

An evaluation was performed to assess the suitability of thirty-three 3013 containers proposed for retention. These containers have moisture levels greater than 0.08 wt.% – the S1 population. The remainder of the S1 population stored at SRS will be down blended and disposed of by the end of 2028. Based on field surveillance and shelf-life data available to date as well as informed technical judgment, no container is currently expected to fail in its 50-year storage period. However, corrosion risk varies across the S1 population. Relative risks were evaluated using predicted Consensus Scores and their 95% Upper Prediction Limits (UPLs). The predicted values are based on a statistical model of Consensus Score as a function of moisture, chloride, and whether the packaged material was electrorefining scrap packaged at Hanford. Consensus Score has been shown to be a useful indicator of corrosion potential, and the UPL captures uncertainty in the model predictions, providing a conservative indicator of corrosion potential. Using UPLs to determine relative risks, together with expert review, three containers were identified as not suitable for retention, and the remainder were determined to be suitable.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Fabrication and Evaluation of Large Alumina Crucibles by Vat Photopolymerization Additive Manufacturing for High-Temperature Actinide Chemistry

Additive manufacturing (AM) offers opportunities to advance the design and function of ceramic tooling in high temperature actinide pyrochemistry. In technical ceramics such as alumina, conventional forming techniques often restrict design flexibility and can limit experimental progress. In this study, we investigate the use of vat photopolymerization (VP) with commercial resins to fabricate large-scale alumina crucibles, reaching dimensions up to 125 mm, which is significantly larger than typically reported for dense VP ceramics. Notably, these additively manufactured components are produced using consumer-grade hardware, which limits process control, but offers significant upside in scalability and accessibility. Using microscopy and X-ray computed tomography, the VP alumina parts have high bulk densities above 95%, but also the prevalence of AM-induced artifacts and surface defects. Mechanical testing showed these defects to significantly reduce flexural strength and compromise part reliability. Electrorefining trials under sustained exposure to molten salts and metals reveal mixed results, with the AM material exhibiting high chemical compatibility, but mechanical failures due to the reduced strength were prevalent. Our findings illustrate both the promise and current limitations of AM ceramics for actinide chemistry, and point toward future improvements in process optimization, design strategies, and part screening to enhance performance and reliability.

Materials science

Extraterrestrial materials processing and construction

Three different chemical processing schemes were identified for separating lunar soils into the major oxides and elements. Feedstock production for space industry; an HF acid leach process; electrorefining processes for lunar free metal and metal derived from chemical processing of lunar soils; production and use of silanes and spectrally selective materials; glass, ceramics, and electrochemistry workshops; and an econometric model of bootstrapping space industry are discussed.

Criswell, D. R.

MARIE: A Python-Based Framework for Comprehensive Fuel Recycling Modeling

One of the most pressing challenges to the continued deployment of nuclear energy systems is in the ultimate management and disposition of discharged fuel assemblies. While reprocessing and recovery of valuable materials from UNF assemblies has been considered as part of an overall strategy for minimization of the volume of reactor-based wastes to be managed, the deployment of commercial-scale reprocessing facilities presents an enormous economic challenge. The MARIE software package has been developed as a means of confronting this challenge. Representing components of a generic fuel reprocessing operation as individual physical processes, MARIE is designed as a modular framework intended to allow for analysis and cost-optimization for a hypothetical reprocessing facility while realistically accounting for the physical characteristics of the used fuel source term, such as decay heat, activity, and radiation dose (informing corresponding shielding requirements). Capabilities supported by MARIE include head-end operations such as fuel shearing, voloxidation, and dissolution; generic solvent extraction operations informed by available open-literature data; a suite of unit operations intended to represent electrochemical processing of used fuel assemblies (i.e., oxide reduction, electrorefining, and electrowinning); and finally, accounting for both costs and physical features of discharged waste streams, which can be used to inform follow-on analyses such as the feasibility of deep-borehole disposal of HLW. This paper presents an overview of the MARIE software capabilities, including how individual unit operations are implemented to enable a larger-scale optimization of a hypothetical reprocessing operation on aspects such as cost and recovery of valuable materials.

Skutnik, Steve [ORNL] (ORCID:000000016441135X)

Traveling Molten Zone Refining Process Development for Innovative Fuel Cycle Solutions

This ARPA-E ONWARDS project successfully developed and demonstrated an innovative immiscibility zone refining process for separating actinides from active fission products in metallic nuclear fuel applications. The technology addresses a critical challenge in advanced nuclear fuel cycles by providing a high-throughput, low-waste alternative to conventional electrorefining.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Field Testing of Safeguards Technologies in the Hot Fuel Examination Facility

Recent developments in nuclear fuel reprocessing techniques have yielded more efficient processes and fuel cycle options that strengthen the nuclear industry and production of clean energy. One such area of interest is pyroprocessing of used oxide fuel. However, with these advances in the back end of the nuclear fuel cycle, advances in safeguards instrumentation, measurements, and approaches are needed to ensure special nuclear material (SNM) is accounted for according to regulatory requirements. As a high-level overview of a nominal pyroprocessing approach, used oxide fuel from commercial light water reactors (LWR) is mechanically removed from the metallic cladding. Then the fuel is crushed and randomized representative samples are taken and sent to an analytical lab for analysis. The analytical results of the feed material are used for input accountancy into the rest of the process. The crushed oxide fuel is then moved to the oxide reduction (OR) furnace where it is reduced from an oxide to metallic form. The OR product is distilled to remove salt and then moved to an electrorefiner (ER), where it is immersed in a eutectic mixture of lithium chloride potassium chloride (LiCl-KCl) that typically ranges between 450-550 ?. Within the ER, the usable uranium is electrochemically transported through the molten salt from the anode to the cathode, and then subsequently removed as a relatively pure U product.. A simplified model of pyroprocessing techniques with added emphasis on the safeguards can be seen below in Fig. 1

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS

Multi-species electrolyte migration kinetics with directed flow

Here, this paper investigates an electrochemical process designed to control mixing kinetics in liquid electrolytes. The process utilizes an electrochemical cell with anode and cathode chambers connected by a channel without a membrane. This configuration depletes multiple electroactive species in the cathode chamber while selectively replenishing them in the anode chamber. A key application is the removal of impurity species from the cathode chamber electrolyte and the selective replenishment of primary electroactive species in the anode chamber. Aqueous cell experiments were conducted to validate the theoretical model, and simulations were performed for molten salt electrolytes. This approach minimizes waste by reducing the need for additional electrolyte supplies and extends the utilization of anion species, contributing to environmentally sustainable electrochemical materials processing.

Electrochemical Process

Phosphate-Based Approaches for Dechlorination and Treatment of Salt Waste from Electrochemical Processing of Used Nuclear Fuel: A Perspective on Recent Work

Phosphate-based reagents are being considered by the U.S. Department of Energy (DOE) Office of Nuclear Energy to process halide salt-based nuclear wastes for stabilization prior to disposal. As evidenced by the Experimental Breeder Reactor-II (EBR-II) project, electrochemical processing (pyroprocessing) can be employed to recover uranium and other actinides for reintegration into the nuclear fuel cycle from metallic fuels. The resultant salt-based wastes generated from electrochemical processing of EBR-II fuel contains fission products within a LiCl–KCl eutectic salt that necessitate appropriate disposal. This paper provides an overview of recent efforts to support halide-based salt waste treatment for disposition, as well as a basis for comparison with other related efforts in salt waste treatment through salt partitioning initiatives. The U.S. DOE has selected a phosphate waste form reference material for further investigation and longer-term studies.

electrorefiner