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DOE OSTI2018

Voltammetric Study of Antitumor Efficient Ethylenediamine-Type of Ligands

The electrochemical behavior of four dialkyl esters (methyl, ethyl, n-propyl and n-butyl) of (S,S)-α,α ′-(1,2-ethanediyldiimino)- bis[cyclohexanepropanoic acid] with moderate antitumor activity has been studied by cyclic voltammetry. I-E curves recorded at boron-doped diamond electrode in -2.00 < Ep < 0.00 V range show a single oxidative peak located in the -0.95 < Ep,a < -0.52 V region in a form of one-electron wave. The electrochemical processes appear to be irreversible for all compounds except for the compound with methyl substituent which demonstrates well-defined reversible electron transfer. Derivatives with bulkier moieties are easier to oxidize. For all investigated compounds an amine-centered redox process is dominant. Further investigation indicates that electrochemical reaction is diffusion controlled, chemically irreversible process. The results are discussed in terms of linking their electrochemical activity to antitumor effect. © 2018 The Electrochemical Society.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Voltammetry Method Evaluation

The purpose of the ANL MPACT Voltammetry project is to evaluate the suitability of previously developed cyclic voltammetry techniques to provide electroanalytical measurements of actinide concentrations in realistic used fuel processing scenarios. The molten salts in these scenarios are very challenging as they include high concentrations of multiple electrochemically active species, thereby creating a variety of complications. Some of the problems that arise therein include issues related to uncompensated resistance, cylindrical diffusion, and alloying of the electrodeposited metals. Improvements to the existing voltammetry technique to account for these issues have been implemented, resulting in good measurements of actinide concentrations across a wide range of adverse conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

Report on Concepts & Approaches for SSBD for eCHEM

The verification of special nuclear material (SNM) in spent fuel pyroprocessing is an important safeguards challenge. The detection of spontaneous fission (SF) neutrons from curium is an accepted, non-destructive technique that has been applied to verify special nuclear material (SNM) content in used fuel and other materials in the fuel cycle. The nuclear material accounting (NMA) technique at the Korea Atomic Energy Research Institute’s Reference Engineering-scale Pyroprocessing Facility (REPF) is based on the Cm balance technique. Several publications have demonstrated the safeguards benefit from using process monitoring (PM) on nuclear facilities as a complementary measure to NMA. More recently, this concept was expanded and preliminarily demonstrated for pyroprocessing. The concept of Signature Based Safeguards (SBS) is part of this expansion, and is built around the interpretation of input from various sensors in a declared facility coupled with complementary NMA methods to increase confidence and lower standard error inventory differences (SEID). The SBS methodology was conceptually developed and relies on near real time analysis of process monitoring data to detect material diversion complemented by robust containment and surveillance (C/S) measures. This work demonstrates one example of how the SBS framework can be used in the electrorefiner. In this SBS application, a combination of cyclic voltammetry (CV) and neutron counting is applied to track and monitor Pu mass balance. The main purpose of this experiment is to determine if meaningful information can be gained from CV measurements with regard to the Mg/Gd ratio. This data will be coupled with ICP-MS to verify Gd concentrations and analyzed for statistical significance. It is expected the CV data will register a significant change under the off-normal operating conditions. Knowing how to identify and interpret those changes may help inform how to target more traditional neutron counting methods, which could support a more efficient safeguards system. The experimental results will be compared with theoretical calculations and the ERAD simulations.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Experiments in anodic film effects during electrorefining of scrap U-10Mo fuels in support of modeling efforts

A monolithic uranium molybdenum alloy clad in zirconium has been proposed as a low enriched uranium (LEU) fuel option for research and test reactors, as part of the Reduced Enrichment for Research and Test Reactors program. Scrap from the fuel's manufacture will contain a significant portion of recoverable LEU. Pyroprocessing has been identified as an option to perform this recovery. A model of a pyroprocessing recovery procedure has been developed to assist in refining the LEU recovery process and designing the facility. Corrosion theory and a two mechanism transport model were implemented on a Mat-Lab platform to perform the modeling. In developing this model, improved anodic behavior prediction became necessary since a dense uranium-rich salt film was observed at the anode surface during electrorefining experiments. Experiments were conducted on uranium metal to determine the film's character and the conditions under which it forms. The electro-refiner salt used in all the experiments was eutectic LiCl/KCl containing UCl{sub 3}. The anodic film material was analyzed with ICP-OES to determine its composition. Both cyclic voltammetry and potentiodynamic scans were conducted at operating temperatures between 475 and 575 C. degrees to interrogate the electrochemical behavior of the uranium. The results show that an anodic film was produced on the uranium electrode. The film initially passivated the surface of the uranium on the working electrode. At high over potentials after a trans-passive region, the current observed was nearly equal to the current observed at the initial active level. Analytical results support the presence of K{sub 2}UCl{sub 6} at the uranium surface, within the error of the analytical method.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2013

Physics-based model for electro-chemical process

Considering the kinetics of electrochemical reactions and mass transfer at the surface and near-surface of the electrode, a physics-based separation model for separating actinides from fission products in an electro-refiner is developed. The model, taking into account the physical, chemical and electrochemical processes at the electrode surface, can be applied to study electrorefining kinetics. One of the methods used for validation has been to apply the developed model to the computation of the cyclic voltammetry process of PuCl{sub 3} and UCl{sub 3} at a solid electrode in molten KCl-LiCl. The computed results appear to be similar to experimental measures. The separation model can be applied to predict materials flows under normal and abnormal operation conditions. Parametric studies can be conducted based on the model to identify the most important factors that affect the electrorefining processes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2018

Electrochemical behavior of Nd and its co-reduction with Bi in molten LiCl-KCl salts - 18360

A molten salt phase is used as the solvent in pyrochemical reprocessing. The molten salt waste generated in pyro-processes contains the residual lanthanides and actinides as various compounds. Various methods have been proposed for recovering and recycling these useful elements. The separation of actinides from lanthanides is performed by electrolysis or reductive extraction. Herein we have studied PyroRedSox-based co-reduction of Nd and Bi via electrolysis in a molten chloride salt. The redox behavior of Nd and the formation potential of intermetallic compounds of Nd and Bi were determined using cyclic voltammetry (CV). Electrorefining was performed under a constant reductive potential at 773 K in LiCl-KCl eutectic mixture; the co-reduction potential was -1.37 V. Lastly, the co-reduction potential of the intermetallic compound was applied to reduce the amount of Nd and Bi. Scanning electron microscopy (SEM) revealed that various kinds of intermetallic compounds were formed in Bi and Nd, and were deposed in the lower part of the molten salt, allowing purification of the contaminated molten salt. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Development and Optimization of Normal Pulse Voltammetry for Real Time Analysis of Electrorefiner Salt with High Concentrations of MgCl{sub 2} and UCl{sub 3}

Electro-refiners can accumulate large holdup of fissile actinides from used nuclear fuel including plutonium and will need to be well safeguarded in a commercial facility. Idaho National Laboratory has operated the Fuel Conditioning Facility, an engineering scale demonstration facility, with two electro-refiners for two decades using mass tracking models supplemented with destructive analysis for the requirements of domestic safeguards. This approach is known to be insufficient of meet international safeguards timeliness requirements. Since there are non-nuclear weapons states that are interested in commercial electro-refiners, there is a need to develop a real time concentration measurement technique. In addition to being useful for safeguards, such a real time measurement would be functional for maintaining optimal process control. Normal pulse voltammetry (NPV) is a powerful electrochemical analysis method that has been identified to have great potential for measuring concentrations of various ions in a given salt mixture. While cyclic voltammetry (CV), chronoamperometry (CA), and chronopotentiometry (CP) result in progressive growth of the working electrode surface area, NPV potentially can circumvent this problem via periodically stripping deposited metals from the electrode (WE) surface. With each successive pulse, the potential is dropped to a more negative level. The corresponding current is a summation of partial currents from each of the reducing species. The ultimate objective of this work is to develop correlations between limiting currents measured via NPV with known concentrations. This is potentially a more accurate method than CV and other methods, because it should keep the WE surface area from growing significantly. Previous work on using NPV for actinide concentration determination in eutectic LiCl-KCl has been reported by M. Iizuka et al. However, only low uranium concentrations were studied in that paper. The maximum concentration of uranium tested was 2.48 wt%. Limiting currents from NPV were found to be proportional to their concentrations up to about 1.7 wt%. They were unable to maintain double plateaus (U and Pu) at uranium concentrations above 1.69 w%. This issue was resolved during our high concentration study. This result represents a significant breakthrough for optimizing voltammetry for analysis of actinides in molten salt.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Investigation on Reaction Probabilities for Cyclic Voltammetry of Zirconium in LiCl-KCl Eutectic Molten Salt via Reverse-Engineering Method

This work focuses on a reverse-engineering program design for the cyclic voltammetry (CV) method to help illustrating, enhancing, and providing robustness in detection probability of the reactions during an electrorefining process. Analyzing the reactions from CV plots for 1.07, 2.49, and 4.98 wt% of zirconium chloride (ZrCl{sub 4}) in a LiCl-KCl molten salt at 773 K under different scan rates from Hoover's study has been accomplished. The results provide the current (Amp) versus potential (V) to investigate the optimum probability of the reactions at each peak. All simulations have been done through the commercial software MATLAB by using various experimental values existing in the literature as a first guess (e.g., the diffusion coefficients, and formal potentials). Preliminary results indicate that the zirconium reactions at each peak from cathodic to anodic side for 1.07 wt% are as followed: combination of Zr{sup +2}/Zr and Zr{sup +4}/ Zr{sup +2} at approximately -1.15 V, Zr{sup +2}/Zr at -1.5 V, Zr{sup +4}/Zr at -1.85 V, 70% Zr/Zr{sup +4} and 30% Zr/Zr{sup +2} at -0.5 V, and Zr{sup +2}/ Zr{sup +4} at - 0.25 V. These mentioned peaks are similar for 2.49 wt% at different voltages. In addition, the highest anodic peak for 4.98 wt% is found to be a combination of 30% Zr/Zr{sup +4} and 70% Zr/Zr{sup +2}. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2016

Metal Oxide Electrolytic Reduction using Glassy Carbon as Anode

Metal oxide electrolytic reduction (OER) is an important electrometallurgical technique, which does not only see its application in pyro-processing of used LWR fuels, but also for high value metal production including aluminum and rare earth critical metals. In this process, metal oxides(e.g. MO{sub 2}) are reduced into metals in the cathode basket while the O{sup 2-} will transfer to the anode to be oxidized into O{sub 2}. The overall reaction is: MO{sub 2} → M + 2O{sub 2}. The sacrificial carbon anode is economical but forms carbides due to the reactions of carbon dioxide in the molten salt. The carbon dioxide dissolves in the salt and can form carbonate ions (CO{sub 3}{sup 2-}). Those can be further reduced to carbon particles on the cathode and react with other metallic particles in the salt to form carbon solid solutions or carbides. It is also worried that the accumulation of carbon dust in the salt can cause short circuits. To facilitate using glassy carbon crucible as anode for metal oxide reduction, a fundamental cyclic voltammetry study was carried out for the glassy carbon materials, which otherwise is a promising candidate for anode material. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Development of Electrochemical Detectors for Elemental Characterization of Actinides - 20563

The characterization of the actinides contained in radioactive waste involves complex and expensive separation processes. Electrochemical methods allow identifying and quantifying quickly and accurately the elementary concentration of actinides such as Th, U, Pu, Am, and Cm in liquid waste. The objective of this research proposal is to build a low-cost portable miniaturized electrochemical detector, which can be an alternative for an initial characterization of actinides in liquid waste. Therefore, this work proposes the use of an electrochemical graphite detector modified with phthalocyanine, to detect and quantify actinides in aqueous media. The electrochemical response of the modified graphite electrodes was performed by cyclic voltammetry, and so the detection and quantification limits for U and Th were determined. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Development of a Smart Signal Detection Method for Cyclic Voltammetry via Artificial Neural Intelligence

The electrorefiner (ER) is the heart of pyroprocessing technology which is a high-temperature method for separating uranium from Used Nuclear Fuel (UNF). It is important to improve this technology with respect to nuclear materials detection and accountability. Artificial Neural Intelligence (ANI) is a novel data analysis and simulation method that can be applied to electrochemical data sets. This computational code, which has been performed using the commercial software MATLAB, can be trained to generalize adequate electrical current and potential simulated data sets for the unseen data with a high accuracy of prediction. For this purpose, a massive collection of cyclic voltammetry (CV) data sets by Hoover (2014), for 0.5, 1, 2.5, and 5 wt% of zirconium chloride in LiCl-KCl molten salt with different scan rates at 773 K has been considered. The computer is trained via ANI to predict the unseen data after providing suitable hidden layers and validation numbers. In addition, this work can trace the CV plot for a blind condition by interpolating between two simulated data set. The different hidden layers with various neurons (from 5 to 30) at several validation numbers (from 5 to 30) has been studied and the average percent error between experimental and theoretical data for 0.5 wt% with 200 and 450 mV/s has been calculated. Preliminary results demonstrate that if the number of hidden layers increases from one to three, the average error falls down from 44% to around 8%. The best condition which gives a minimum average percent error has been discovered and the simulated CV graph has been compared with the experimental data. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Effects of GdCl{sub 3} on U Electrochemical Properties in LiCl-KCl-UCl{sub 3}-GdCl{sub 3} Salt

Studies on pyro-processing technology have been stimulated in several countries including the United State, Russia, France, Japan, South Korea, and India. The main purpose of this technology is to treat the irradiated nuclear fuel, reduce volume of the nuclear waste, recycle actinides, and close the fast reactor fuel cycle. Therefore, ongoing researches and developments are expected. In pyro-processing, the most important process is an electro-refiner (ER) where uranium and minor actinides are separated on electrode surface while rare earth fission products are accumulated in LiCl- KCl eutectic salt. Due to the fact that the recovery of the U and actinide (An) materials are conducted via an electrolysis, many researchers have been investigating fundamental properties of U in LiCl- KCl system by using various electrochemical techniques. The resulting datasets are useful for effective system operation and development of safeguards in ER system. However, these values have been measured in pure UCl{sub 3} system in LiCl- KCl salt, which may not be practical to the real ER system owing to the fact that a variety of other fission products including An and lanthanide (Ln) are coexisting in the ER system. Therefore, in this work, gadolinium (Gd) was selected as a surrogate material for An or Ln materials in ER system. This is because that Gd has similar physical characteristics to Ln and An elements such as ionic size and reduction potential. By conducting electrochemical methods including cyclic voltammetry (CV), open circuit potential (OCP), and electrochemical impedance spectroscopy (EIS), effects of Gd coexistence on the electrochemical, thermodynamic, and kinetic properties of U were observed. It is hoped that this study will help us further understanding fundamental effect of the Ln/An effect on LiCl- KCl-UCl{sub 3}, yielding closer to the practical ER unit operation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Electrochemical Study of BaCl{sub 2} and CsCl on a Liquid Bismuth Cathode in LiCl-KCl Eutectic Salt

Pyro-processing has been proposed and studied for recycling nuclear fuel. In pyro-processing, uranium and other actinides are recovered by electrolytic reduction in molten LiCl-KCl salts within the electro-refiner. However, over time the molten salts experience a buildup of other fission products, mostly alkali/alkaline-earths and rare earths. These products accumulate and degrade the efficiency of the electro-refiner, therefore capture and removal of these products is attractive. However, before a removal system can be designed and studied, fundamental physiochemical and electrochemical knowledge of the behavior of the fission products in the molten salts must be acquired. This project has studied the mass transport and electrochemical properties of BaCl{sub 2} and CsCl within LiCl- KCl eutectic salt on a liquid bismuth electrode. The diffusion coefficient and apparent standard potential of BaCl{sub 2} on the bismuth electrode has been determined from cyclic voltammetry. Charge transfer resistance and exchange current density values have also been obtained from electrochemical impedance spectroscopy (EIS) experiments.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2017

Normal Pulse Voltammetry for Real Time Analysis of Electro-refiner Salt with High Concentrations of Analytes

Spent nuclear fuel pyro-processing could be a preferred alternative for aqueous processing. However, there will be a large hold up of actinides in the molten salt media that must be safeguarded in commercial facilities. A real or near real time monitoring method for electro-refiner salt needs to be developed to meet this requirement. In addition, real time monitoring method can also be applied to optimize process control. Voltammetry would be an ideal method to monitor the ER salt composition because of the low cost and robustness. The equipment required to carry out voltammetry analysis include only a potentiostat and three electrodes, which can be placed in-situ.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

Nuclear Material Monitoring in Molten Salt Systems using Cyclic Voltammetry

As designs for the next generation of nuclear power plants and reprocessing facilities develop, molten salt based systems are receiving increasing attention as fuel containment, cooling and reprocessing media. Traditionally, aqueous systems for power production and fuel reprocessing are associated with well-developed methods for the monitoring and accountancy of nuclear material. Many of these techniques are proving insufficient in providing the same information in molten salt systems. The International Atomic Energy Agency (IAEA) has called for the continued evaluation of advanced measurement techniques in systems such as molten salt as part of the Generation IV International Forum (GIF) and International Project on Innovative Nuclear Reactors and Fuel Cycles (INPRO). Cyclic voltammetry (CV) is an electrochemical technique that offers promising applications in molten salt systems for the in situ monitoring of nuclear material. A technique such as CV offers a method for monitoring nuclear material in a system relying on molten salt for power production, cooling or reprocessing. Cyclic voltammetry has been shown to provide information regarding the diffusion of electroactive species in molten salt. Once a diffusion coefficient data base is assembled, CV can be performed on molten salt systems to determine concentrations of species in situ.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2017

Effect of Concentration, Temperature, and Interelectrode Gap on the Voltage Drop in an Electrochemical System of GdCl{sub 3}-LiCl-KCl

One of the most common conversations for those in the nuclear field and the public when discussing nuclear power is the issue of nuclear waste. When used nuclear fuel (UNF) is removed from a reactor, it contains fission products, some of which are long lived isotopes that will continue to irradiate for hundreds of years. One of several solutions to this issue is reprocessing, a process where minor actinides and other fission products are separated from still fissile and fertile materials. In the United States, there is no reprocessing of UNF at an industrial scale; however, one of the methods that universities and national labs are currently researching is known as pyro-processing. Pyro-processing utilizes electrochemistry in a molten salt environment to treat UNF and remove uranium and plutonium. The heart of the pyro-processing system is an electrorefining process, where most of the U in the UNF is selectively collected on a solid cathode in molten lithium-potassium chloride (LiCl-KCl) at high temperatures (723 K - 773 K). To model the behavior of materials in the electro-refiner, small bench-scale electrochemical experiments are being performed at many research universities and national labs to better understand material behavior. Within the electrochemical cell, there is a small resistance to current between the cathode and anode. This results in a voltage drop, which can affect the results of the experiments. This voltage drop varies based upon concentration of the salt, the temperature, the distance between the anode and cathode, and the scan rate. For this study, cyclic voltammetry will be performed on GdCl{sub 3}-LiCl-KCl at various temperatures (723 K - 798 K), various sample concentrations (1, 5, and 10 wt%), various scan rates (50, 100, 200, and 300 mV/s), and two different electrode spacing configurations. The resulting cyclic voltammograms will be compared for both electrode configurations to see the impact of interelectrode gap on the voltage drop.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗