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A method of ranking the rate of corrosion of metals in molten fluoride or chloride salts is proposed based on a zero-resistance ammeter (ZRA). The metal of interest for the corrosion study is shorted to a relatively noble metal counter electrode. Stainless steel 316 was tested in FLiNaK (LiF-NaF-KF). Haynes 230, stainless steel 316L, and Hastelloy C-22 were tested in MgCl2-NaCl-KCl. The ZRA oxidation current from SS-316L was reduced by 89% in FLiNaK after the addition of Li metal, which is known to reduce the redox potential. Post-test examination of metal surfaces and salt samples were also consistent with the relative ZRA current response in fluoride salt. Consistency was also observed between the relative ZRA response for the different metal alloys in the chloride salt and post-test analysis of metal and salt samples.

This study addressed the problem of measuring the total mass of molten salt in a nuclear system such as a nuclear fuel electrorefiner or a molten salt reactor. In theory, soluble tracers can be add...

Molten eutectic LiCl-KCl salt is a widely used electrolyte for electrorefining uranium from spent nuclear fuel. Due to the hygroscopic nature of this salt, such operations must be performed under c...

In this study, the stability of Ag|Ag+ molten chloride reference electrodes was studied using mullite and magnesia tubes as reference electrode membrane materials in molten MgCl2-KCl-NaCl for continuous immersion up to 31 d. Two electrochemical methods were used to characterize the long-term performance of the reference electrodes at 500 °C in an inert atmosphere using a Mg rod as the working electrode: open circuit potential (OCP) and onset of Mg(II) reduction as measured by cyclic voltammetry (CV). There was only a 3% difference between the average OCP measured versus the mullite and MgO reference electrodes. Potential drift was higher for mullite (−1.34 mV d−1) than MgO (0.22 mV d−1). But both drift rates were very low compared to the OCP data standard deviation, indicating that no significant drift was measured for us to 31 d.

CaCl2 has applications for electrochemical processing of nuclear materials. Thermal dehydration leads to formation of oxide ions, which are shown to react and cause precipitation of dissolved CeCl3 that was selected as a surrogate for actinide chlorides. Thus, measurement of residual water in CaCl2 is an essential capability. Thermogravimetric analysis (TGA) was shown to underestimate starting water concentration. Subsequent analysis of solid samples via acid–base titration and cyclic voltammetry (CV) of the molten salt yielded consistent values within 5% for residual water. Hydroxides were shown to be unstable, thus oxygen is retained as oxide ions. Thus, total water in a sample of CaCl2 can be quantified by combining TGA with with either CV of molten salt or titration of salt samples. The importance of quantifying residual water in the salt was demonstrated by showing that cerium chloride (surrogate for actinide chlorides) will react with oxide ions in CaCl2 to form insoluble oxides and oxychlorides.

Electrolytic uranium oxide reduction has the potential to be a key process for recycling spent fuel from commercial light water reactors to advanced nuclear reactors—including molten salt reactors and metal fueled reactors. However, several problems with the process have been identified that need to be addressed to support efficient, cost-effective commercial implementation. Process optimization requires attention to metal corrosion, anode stability, cell efficiency, and cathode product purity. Generation of oxygen bubbles at the anode combined with high temperature (650oC) and molten chloride salt (LiCl + 1 wt% Li2O) create a highly oxidizing environment for metals needed for salt containment and shrouding of the anode. The current standard choice for the inert anode is platinum metal, which has fairly good stability in the system. But given the high cost of platinum, alternative anode materials need to be discovered. Efficient removal of oxygen bubbles requires use of a shroud around the anode. The easy fabricability of metals makes them a reasonable choice for the shroud material, but corrosion due to interaction with the salt and oxygen needs to be minimized. Cell efficiency is affected by hydroxide impurity in the salt. Methods for removing water and hydroxides from the salt will be reported that improve cell efficiency. Cell efficiency can also be affected by controlling the reduction mechanism. Uranium oxide can either be reduced chemically by reaction with electrochemically generated lithium atoms or electrolytically with direct reduction of UO2. The reduction mechanism also affects the buildup of entrained lithium oxide in the cathode product. Entrained lithium oxide is problematic as it gets carried on to subsequent processing steps such as electrorefining and molten salt oxidation.

Signature-based safeguards (SBS) is being developed to assist tradition nuclear material accountancy methods in tracking material in pyroprocessing facilities. SBS involves identifying off-normal scenarios that would result in improper movement of material in a pyroprocessing facilities and determining associated sensor response signatures. SBS investigations are undertaken in the computational space utilizing an electrochemical transport code known as enhanced REFIN with anodic dissolution (ERAD) to calculate the affect of off-normal conditions in the electrorefiner (ER) on material movement. Work is undertaken to experimentally validate the predictions and assumptions made by ERAD for off-normal occurrences. These experiments were undertaken on a benchtop scale and involved operating an electrochemical cell at 10 separate current densities for constant current operations to deposit U and Gd at a W cathode. These experiments were then modeled using ERAD to compare calculated predictions versus analytical experimental results it was found. It was discovered both the experimental and calculated results reflect a trend of increased codeposition of U and Gd with increasing current density. ERAD was thus demonstrated to be useful for predicting trends from anomalous operation but will require further optimization to be utilized as a quantitative design tool.

A novel nuclear waste form was synthesized for the disposal of electrorefiner salt from pyrometallurgical reprocessing of used nuclear fuel. Its synthesis constitutes two steps: waste salt dehalogenation via ion exchange with H–Y zeolite, followed by thermal treatment for phase transition and consolidation. Salt cation-loaded zeolite exhibiting greater than 90% dehalogenation was sintered for 12 h at 925 °C and achieved 3 vol% open porosity (determined via Archimedes method). Microstructural imaging and structural characterization revealed a multiphase assemblage of alkali aluminosilicate and mixed oxide phases. Chemical durability experiments were performed using modified ASTM C1308 tests in demineralized water and different silica solutions. Si-containing species appear to exhibit congruent dissolution, while the release behaviors of alkali elements appear to include diffusion-limited contributions. The 4-day cumulative releases for the dehalogenated salt waste form (DSWF) are less than 33% of those measured for the baseline glass-bonded sodalite advanced ceramic waste form (GBS ACWF). Furthermore, the dehalogenation and consolidation processing steps provide a 35% decrease in required storage volume for a given waste salt mass relative to the GBS ACWF.

Molten salt solutions consisting of eutectic LiCl-KCl and concentrations of samarium chloride (0.5 to 3.0 wt%) at 500℃ were analyzed using both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV technique gave the average diffusion coefficient for Sm3+ over the concentration range. Equipped with Sm3+ diffusion coefficient, the Randles-Sevcik equation predicted Sm3+ concentration values that agree with the given experimental values. From CV measurements; the anodic, cathodic, and half-peak potentials were identified and subsequently used as a parameter to acquire EIS spectra. A six-element Voigt model was used to model the EIS data in terms of resistance-time constant pairs. The lowest resistances were observed at the half-peak potential with the associated resistance-time constant pairs characterizing the reversible reaction between Sm3+ and Sm2+. By extrapolation, the Voigt model estimated the polarization resistance and established a polarization resistance-concentration relationship.

Investigation of the kinetics of the ion exchange between protonated ultrastable Y-type (USHY) and surrogate electrorefiner (ER) waste salt was performed to optimize the dechlorination process. The...

4H-SiC alpha detectors were fabricated with a 21-μm thick depletion depth and were packaged into a stainless-steel casing with a mineral insulation cable and a standard BNC connector. The packaged detectors had a resolution of 0.624% FWHM at 5.486 MeV prior to salt immersion. The detectors were then immersed in a LiCl–KCl–UCl3 molten salt at 500 °C, from which a thin layer of depleted uranium was electrodeposited onto the detectors. Alpha particle emission spectra were collected from the electrodeposited source. The energy resolution of the surviving detector was 2.29% FWHM at 4.198 MeV and was sufficient to separate the 234U from 238U alpha emissions (577 keV difference). The 234U/238U activity ratio and the isotopic concentrations of 234U and 238U were determined and are representative of the uranium source used in the electrodeposition.

Dechlorination of eutectic LiCl–KCl based electrorefiner (ER) salt is reported via ion-exchange reaction with protonated ultrastable Y-type (USHY) zeolite bound into mechanically fluidized 45–250 μm diameter particles. Evidence of exchange of cations from the salt (Li+, K+, and fission product cations) into the zeolite lattice replacing H+ ions was found based on a change in unit cell size, ICP-MS, XRD and TEM–EDS in addition to detection of HCl off gas. Ion exchange reaction was carried out at 625 and 650 °C, temperatures above the melting point of eutectic LiCl–KCl. Experiments were carried out to optimize zeolite drying temperature, estimate maximum ion-exchange capacity, and determine the thermal stability of USHY zeolite. The results indicate over 90% dechlorination can be achieved without zeolite structure collapse at 625 °C. This provides a promising route to stabilizing waste from radioactive chloride salts into dechlorinated waste forms for permanent geologic disposal.

Among many mixed ionic electronic conductors (MIECs), lanthanum strontium cobalt iron oxide (LSCF) has been proven as a promising material for use as cathode in SOFCs. The ion and electron conduction in LSCF need to be studied separately. To measure the ionic conductivity of LSCF, YSZ disks were applied to block the electronic current, and multilayered samples were made with YSZ disks in series with an LSCF disk. Both AC and DC techniques were used for the measurements. An LSCF(porous)/LSCF(dense)/LSCF(porous) bar-shaped sample was made to measure the electronic conductivity of LSCF. DC technique was utilized for the measurement. Results show that the ionic conductivity of LSCF is much lower than its electronic conductivity. The ionic conductivity of LSCF increases with increasing temperature (600 °C–900 °C), and the electronic conductivity decreases with increasing temperature (600 °C–900 °C). Measurements were also made on a foil of silver to investigate oxygen transport through it. From this, oxygen ion conductivity through silver was estimated.

Direct electrolytic reduction (DER) of UO 2 utilizes a molten LiCl-Li 2 O electrolyte operating at 650 °C.Productive processes at the cathode are UO 2 and Li 2 O reduction (followed by metallothermic reduction of UO 2 by Li metal). Non-productive reduction current has been observed that could be attributed to impurities produced from interaction of the salt with water. Cyclic voltammetry (CV) scans of molten mixtures of LiCl containing Li 2 O, LiOH, and/or Li 2 O 2 indicate that LiOH is the primary cause of reduction current preceding UO 2 and Li 2 O reduction. LiOH reduction appears as a broad soluble-soluble transition and forms a pre-reduction plateau characteristic of micro-electrode reactions. Electrochemical response to LiOH in the salt is reduced with addition of Li 0 , providing a practical approach to eliminating LiOH from LiCl-Li 2 O salt before the DER process. Generation of H 2 gas was detected while heating Li 0 with LiCl-Li 2 O-LiOH, consistent with a reaction mechanism where LiOH reduction causes formation of Li 2 O and H 2 .

Electrochemical methods have been developed to measure metal ion concentrations in spent nuclear fuel electrorefiner by correlating concentration with current response. Analytes UCl3 and GdCl3 were studied in LiCl-KCl eutectic solvent at 773 K. A mixture matrix, which consisted of varying concentrations of UCl3 and GdCl3 from 1 to 10 wt% and from 1 to 3 wt%, respectively, was tested. Optimized normal pulse voltammetry (NPV) measurements were made on this mixture matrix and used for the concentration correlations. The accuracy of the prediction was improved by including solution resistance compensation and minimizing the working electrode surface area. The presence of GdCl3 showed no effect on the U3+ NPV reduction current, but high U concentrations affected the Gd3+ NPV reduction current. This is speculated to be due to increased migrational current in the molten salt mixture. The average relative measurement errors obtained were 1.6% and 2.7% for UCl3 and GdCl3 respectively.

In a molten salt nuclear reactor system, the redox potential must be controlled for mitigating corrosion of structural materials. The paper presented a critical review on the available knowledge of redox potential control in molten fluoride salt systems. The major phenomena that affect the redox potential and material corrosion are fission, TF production by transmutation, and salt contamination with metal fluorides or other oxidizing impurities. Redox potential control methodologies include gas sparging, contacting the salt with a reducing metal, and adding soluble salt redox buffers to the salt. Redox potential measurement technologies include electrochemical sensors and optical spectroscopy. The paper also analyzed the current technology issues and recommended near future studies.

The alpha emission spectrum of electrodeposited thin film 232Th and depleted uranium sources, including the alpha emitting 232Th decay chain daughters and 238U daughter nuclide 234U, have been measured using a thin film 4H–SiC alpha detector. The energy resolution of this detector was proved suitable for the identification of many of the major characteristic alpha emissions associated with the 232Th daughter isotopes. The identification of the lower energy daughter isotopes made from the 4H–SiC detector measurements was confirmed using a silicon surface barrier detector. A depleted uranium source was fabricated using electrodeposition in a molten salt and the alpha spectrum was acquired with a 4H–SiC detector. The 234U/238U activity ratio and atomic enrichment of 234U in the sample were determined. A method of determining the 235U enrichment in the product stream of the enrichment process used to produce the depleted uranium source was developed. This method makes use of the 234U and 235U waste stream enrichments, as indicated by the depleted uranium source, and a mass balance equation to determine the product 235U enrichment. Since the 235U spectrum was obscured in the electrodeposited source by peak broadening of 238U and 234U, a table of common 235U waste enrichment values was used to compute 235U product enrichments, thereby resulting in a plausible identification of the enrichment process as a Department of Energy HEU enrichment process.

Improvements in the galvanic reduction of UCl 3 from LiCl-KCl- UCl 3 molten salts are reported. This process has potential application for drawdown operations for electrorefiner salt. Short circuiting a gadolinium rod to a stainless steel basket causes a galvanic reaction which results in simultaneous reduction of UCl 3 to U(0) and oxidation of Gd(0) to GdCl 3 . Two galvanic cell configurations were tested: one with the gadolinium metal inserted into the stainless steel basket, and one with the gadolinium metal separated from the stainless steel basket. When using a rotating basket and a physically separated gadolinium metal rod, concentration of uranium decreased from 0.168 to 0.00004 mol % within 105 min, representing over 99.97% removal from salt. Electrochemical potential measurements were recorded for the galvanic couple, and it was found that the potential became more negative during reduction process and leveled off when all of the UCl 3 was reduced. In experiments in which MgCl 2 was added to the salt as a surrogate for PuCl 3 , it was observed to co-deposit with the UCl 3 . Other rare earth chlorides ( LaCl 3 , NdCl 3 , and CeCl 3 ) were not removed from the salt during the reduction process.

In this paper, the thermodynamic activity of two lanthanide chlorides (CeCl3 and NdCl3) in molten LiCl-KCl eutectic salt measured using open circuit potentiometry has been reported. Activity coefficient of CeCl3 was found to be strongly dependent on the concentration of CeCl3 in a concentration window of up to 4.66 mol % CeCl3. The activity coefficient of NdCl3 could not be measured due to the uncertainty in NdCl3/NdCl2 molar ratio in the salt, however the thermodynamic activity was measured relative to a 5 mol% Ag∣AgCl reference electrode. The concurrent analysis of data presented in this paper along with previously published activity data for LaCl3 and GdCl3 demonstrates that the departure from ideal solution behavior shown by the rare earths chlorides correlates with ionic size of underlying rare earth element. The smaller the ionic size of the species under consideration, the greater its departure from ideal solution behavior. Further, using the activity data of all four rare earth chlorides, an ionic size dependent correlation was developed. Using this empirical correlation, it is possible to calculate the activity of all species from La(Z = 57) to Gd (Z = 64) for a concentration of up to 2.5 mol% rare earth chloride in LiCl-KCl molten salt at 773 K.

Reversible cells can be used as solid oxide fuel cells (SOFC) and solid oxide electrolyzer cells (SOEC). The solid electrolytes used for such cells frequently have pure ionic conduction with insignificant electronic conduction. A previous study (Virkar and Tao, 2015) has shown that cells made of ceria doped yttrium stabilized zirconia (YSZ), a mixed ionic electronic conducting (MIEC) material, can be made to operate at the same efficiency level and with superior stability compared to a pure ionic conductor, like pure YSZ. This work is a continuation of that study, examining the use of gadolinium doped ceria (GDC) mixed with YSZ. The MIEC cell, 8mol%GDC+YSZ, will be further tested and designed to consume fuel or water vapor, generate power or hydrogen, and release heat at the same rate as the pure ionic conducting cell, YSZ, when operating in SOFC or SOEC mode. Future testing will also determine if the GDC MIEC cell can match or exceed the durability of the ceria doped YSZ. The electrolyte layer, made of either pure 8YSZ or 8YSZ doped with 8mol%GDC, was die pressed and sintered at 1400oC (2oC/min) for five hours. On one side of the electrolyte, the anode interlayer is mixed with isopropyl alcohol and painted on the electrolyte's surface. The anode interlayer is composed of 50wt% NiO and 50wt% 8YSZ. The cell was heated to 950oC (2oC/min) for one hour. The anode functional layer, 70wt% NiO and 30wt% 8YSZ, was painted on top of the anode interlayer. The sample was then again heated to 950oC (2oC/min) for one hour to burn off any organic compounds. A cathode interlayer was then painted on the other side of the electrolyte layer. The cathode interlayer was also painted on and consists of 50wt% lanthanum strontium manganite (LSM) and 50wt% YSZ. The cell is heated to 1200oC (2oC/min) for two hours. Finally, a pure LSM layer is painted on top as the cathode current collector material and heated to 1100oC (2oC/min) for one hour to ensure good porosity. The cells were then sealed by compression-loading at the edges using glass-mica seals. Results of tests will be reported for both SOEC and SOFC modes at 800oC. Data to be reported include open-circuit voltage, area-specific resistance, corresponding ionic currents based on an applied voltage, and long-term durability of the two cells in both SOFC and SOEC modes.

During normal operations, the only deposition on a spent nuclear fuel electrorefiner cathode consists of uranium. A computer model, ERAD, was used to simulate conditions under which the electrorefiner salt was progressively contaminated from spent nuclear fuel processing without operator intervention. The model was adjusted to reflect three scenarios: one in which salt removed with every cathode deposit was returned but the UCl 3 concentration was never adjusted, one in which the salt was not removed and UCl 3 concentration was never adjusted, and one in which the Pu/U ratio in the salt was allowed to reach a value of one before starting the first scenario. Under the base conditions simulated, uranium initially deposits alone but eventually plutonium begins to co-deposit along with uranium. Up to 350 g of plutonium was calculated to deposit along with 8.3–9.5 kg of uranium. While precise tracking of changes in the salt composition may not be possible, the model was able to identify markers for plutonium deposition by tracking changes in electrode potential. This type of marker should ultimately provide inspectors with more options for situations when they have limited access to electrorefiner data.

The drawdown of actinides is an important unit operation to enable the recycling of electrorefiner salt and minimization of waste. A new method for the drawdown of actinide chlorides from LiCl-KCl molten salt has been demonstrated here. Using the galvanic interaction between the Gd/Gd(III) and U/U(III) redox reactions, it is shown that UCl 3 concentration in eutectic LiCl-KCl can be reduced from 8.06 wt.% (1.39 mol %) to 0.72 wt.% (0.12 mol %) in about an hour via plating U metal onto a steel basket. This is a simple process for returning actinides to the electrorefiner and minimizing their loss to the salt waste stream.

An electrochemical study of manganese chloride in molten salt mixtures of eutectic LiCl-KCl was carried out using a variety of electrochemical methods in a high temperature cell including cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA), and open circuit potentiometry. Single step reduction from Mn2+ to Mn(0) was observed on both W and Mo working electrodes. Using a combination of these methods, measurements were made of activity coefficient and diffusion coefficient for MnCl2 in LiCl-KCl as a function of concentration (3.54 × 10−4 to 3.60 × 10−3 mol fraction of MnCl2) at 773K. From OCP measurements, values for activity coefficient varied from 0.014 to 0.0071. Diffusion coefficients varied with concentration and differed based on measurement method (CV, CA, or CP). Based on cyclic Mn(II) ranged from 1.1 to 2.8 × 10−5 cm2/s depending on concentration.

In this paper, we apply an advanced safeguards approach and associated methods for process monitoring to a hypothetical nuclear material processing system. The assessment regarding the state of the processing facility is conducted at a system-centric level formulated in a hybrid framework. This utilizes architecture for integrating both time- and event-driven data and analysis for decision making. While the time-driven layers of the proposed architecture encompass more traditional process monitoring methods based on time series data and analysis, the event-driven layers encompass operation monitoring methods based on discrete event data and analysis. By integrating process- and operation-related information and methodologies within a unified framework, the task of anomaly detection is greatly improved. This is because decision-making can benefit from not only known time-series relationships among measured signals but also from known event sequence relationships among generated events. This available knowledge at both time series and discrete event layers can then be effectively used to synthesize observation solutions that optimally balance sensor and data processing requirements. The application of the proposed approach is then implemented on an illustrative monitored system based on pyroprocessing and results are discussed.

The application of the rotating cylinder electrode (RCE) to molten LiCl-KCl eutectic mixtures for electroanalytical measurements is presented. This enabled the measurement of the limiting current which was observed to follow a linear trend with the rotational rate raised to 0.64–0.65 power on average, which closely agrees with existing RCE mass-transfer correlations. This is the first publication of electroanalytical RCE measurements in LiCl-KCl eutectic based molten salt mixtures, to our knowledge. These measurements were made in mixtures of molten LiCl-KCl eutectic containing UCl3 and MgCl2. Kinetic parameters were calculated for Mg2+ in LiCl-KCl eutectic. The exchange current density (io) of Mg2+ deposition varied with mole fraction (x) according to io(A cm−2) = 1.64x0.689. The parameters from RCE measurements were also applied in an electrochemical co-deposition model entitled DREP to detect and predict the deposition rate of U and Mg. DREP succeeded in detecting the co-deposition of U and Mg, even when Mg constituted less than 0.5 wt% of the deposit.

The electrochemical behavior of MgCl2 in molten LiCl-KCl eutectic was investigated to evaluate its suitability as a surrogate for PuCl3 in studies related to the eletrorefining of used nuclear fuel. The reduction of Mg2+ was found to be electrochemically reversible up to 300 mV s−1 at 773 K. The diffusion coefficient for Mg2+ was calculated to be 1.74 and 2.17 × 10−5 cm2 s−1 with and without U3+ present, respectively, at 773 K using cyclic voltammetry (CV). Upon comparison to literature data, the diffusion coefficient of Mg2+ differs by only 8.8% (with U3+ present) from that of Pu3+ and the difference in peak potentials was only 79 mV. Binary-analyte mixtures of UCl3 and MgCl2 in eutectic LiCl-KCl were further investigated using CV, normal pulse voltammetry (NPV), chronoamperometry (CA) and open-circuit potential (OCP) measurements for the purpose of comparing each technique's accuracy in measuring U3+ and Mg2+ concentrations. Of all the techniques tested, NPV resulted in the lowest error which was, on average, 11.4% and 9.81% for U3+ and Mg2+, respectively.

Garnet type LLZTO ceramic oxide is a promising solid-state electrolyte for use in Li-ion batteries because it has good chemical stability, adequate mechanical strength. However, lithium dendrite growth still needs to be addressed. The opacity of the solid electrolyte hinders in-situ investigation of dendrite growth. Therefore, semi-transparent LLZTO with high-density is needed. The traditional fabrication process for the garnet type LLZTO is cumbersome, and dense LLZTO disks with high transparency are difficult to fabricate. In this work, Al-LLZTO powder was made by solid-state reaction. A wet ceramic processing method, pressure filtration followed by sintering, was developed to make dense LLZTO with high ionic conductivity (1.47 × 10−4 S/cm) and adequate transmittance (17–23%) to visible light from 500 to 800 nm to observe and monitor dendrite growth.