Molten FLiNaK Research Articles

Effect of cryogenic milling on the mechanical and corrosion properties of ODS Hastelloy-N

This study entails the fabrication of two oxide-dispersion strengthened (ODS) Hastelloy-N (HN) alloys utilizing divergent methods. The first alloy was synthesized using cryogenic attritor milling coupled with spark plasma sintering (SPS), while the second was produced via room temperature attritor milling and SPS. The ODS HN alloy derived from cryogenic milling demonstrated superior strength relative to its commercial-grade counterpart. Conversely, the alloy produced through room temperature milling exhibited lower ultimate tensile strength (UTS), attributed to manufacturing defects and the precipitation of Zr at grain boundaries. Corrosion resistance in molten FLiNaK for both ODS samples was found to be inferior compared to commercial HN. Particularly, in the room temperature-milled ODS HN, Zr present at grain boundaries appeared to dissolve more readily than in cryogenic or commercial samples, facilitating enhanced penetration by molten salt. The cryogenically-milled ODS HN contained Zr, yet it was not segregated to grain boundaries. Although the homogeneously dispersed Mo-based compound in the cryogenically-milled ODS HN augmented mechanical properties, it also accelerated corrosion propagation beyond that of the commercial-grade alloy.

Thermophysical properties of Molten FLiNaK: A moment tensor potential approach

Fluoride salts demonstrate significant potential for applications in next-generation nuclear reactors, necessitating a comprehensive understanding of their thermophysical properties for technological advancements. Experimental measurement of these properties poses challenges, due to factors such as high temperatures, impurity control, and corrosion. Consequently, precise computational modeling methods become essential for predicting the thermophysical properties of molten salts. In this work, we performed molecular dynamics (MD) simulations of several thermophysical properties of the eutectic salt mixture LiF-NaF-KF (FLiNaK) melt, including density, self-diffusion coefficients, viscosity, and thermal conductivity. We demonstrated the successful application of moment tensor potentials (MTP) as an accurate model for interatomic interactions in FLiNaK. Our results on thermophysical properties calculations exhibit strong agreement with experimental data. An important aspect of our methodology is the incorporation of an active learning scheme, which enables the generation of a robust and accurate potential, while maintaining a moderate-sized training dataset.

Stability of a Ni/NiF2 Reference Electrode with a Metallic Membrane for Use in Molten Fluoride Salts

In this study, an experimental high-temperature fluoride salt reference electrode (RE) developed by HiFunda LLC was tested in molten FLiNaK at 550 °C. The high-temperature reference electrode (HTRE), based on the Ni/NiF2 redox couple, was tested over a period of 13 d for short-term stability, long-term stability, and electrochemical analysis capabilities. The HTRE was tested using open circuit potentiometry (OCP), cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The HTRE reference potential was measured against changes in salt composition by increasing FeF2 concentrations in the melt across six additions from 0 to 0.1 mol% FeF2. The long-term stability of the electrode was then tested over ten days at a constant composition of 0.1 mol% FeF2. OCP, SWV, and CV were used to calculate an average potential drift between 7–10 mV per day. Using CV and SWV, the number of electrons transferred for iron reduction and the diffusion coefficient of Fe2+ were measured.

Thermodynamic modeling of CsF with LiF-NaF-KF for molten fluoride-fueled reactors

Gibbs energy models were developed to describe the thermochemical behavior of CsF in molten FLiNaK (46.5LiF-11.5NaF-42KF mol%), a proposed molten salt reactor (MSR) fuel solvent and coolant, as cesium is of concern due to its high radiotoxicity and volatility. Initially, it was necessary to obtain a more accurate Gibbs energy function for CsF which required fitting parameters to reported vapor pressures over condensed phase CsF. The pseudo-binary systems CsF-LiF, CsF-NaF and CsF-KF were then evaluated utilizing phase equilibria and enthalpy of mixing (ΔmixH) values, together with original differential scanning calorimetry (DSC) measurements performed for the CsF-LiF and CsF-KF systems. The CsF-LiF-NaF, CsF-LiF-KF and CsF-NaF-KF pseudo-ternary system representations were obtained by interpolation of the constituent pseudo-binary systems, with DSC measurements performed for the CsF-LiF-NaF system to corroborate the calculated liquidus temperature. Ultimately, the pseudo-ternary systems were interpolated to obtain Gibbs energy models for the pseudo-quaternary CsF-LiF-NaF-KF system, supported by DSC measurements at low CsF compositions (1–10 mol%), yielding computed equilibria and cesium-containing vapor pressures that compare favorably with reported values. The Molten Salt Thermal Properties Database – Thermochemical (MSTDB-TC) was subsequently expanded to include these Gibbs energy models allowing description of the thermochemical behavior of the CsF-LiF-NaF-KF system.

Effects of Impurities and Additives on Interactions of Nuclear-Grade Graphite with Molten LiF-NaF-KF

It has been widely acknowledged that the presence of impurities in molten fluoride salt can alter the salt/material interactions. However, the effects of various impurities such as oxides, metal fluorides, reducing impurities, etc., on the behavior of nuclear-grade graphite in molten fluoride salts have not been reported. This study focuses on understanding the effects of various oxidizing and reducing impurities on the wetting and infiltration behavior of molten FLiNaK salt for nuclear-grade IG-110 graphite. Our results suggest that different impurities can cause different effects on nuclear graphite–molten salt interactions, with some impurities leading to significant degradation of the graphite. Our results demonstrate that certain impurities, such as Cr2O3 and CrF3, lead to a limited increase in wetting and infiltration of molten salt into nuclear graphite, while impurities such as Li2O lead to significantly increased wetting and infiltration throughout the cross section of the graphite specimen. Certain impurities, such as Li, can also lead to significant degradation of the graphite in the salt, with the extent of degradation increasing with the increase in the quantity of Li added. Our results also demonstrate that firing of IG-110 graphite at 900°C under a reducing atmosphere made the graphite surface resistant to wetting by molten FLiNaK salt, as compared to the nonfired sample.

Environmentally-assisted cracking of electropolished 316L stainless steel in molten FLiNaK salt

Environmentally-assisted cracking is a well-known and extensively studied phenomenon in light water reactor environments but remains relatively unexplored in proposed molten salt reactor systems where the mechanisms at play are expected to be quite different. Here, slow strain rate testing has been performed on 316L stainless steel tensile specimens during simultaneous exposure to a molten LiF-KF-NaF eutectic salt environment at 600°C with a strain rate between 1E-5 to 1E-7 s-1. Sample ductility and ultimate tensile strength were both observed to decrease for slower strain rates/longer salt exposures. Post-mortem characterization of fractured specimens revealed Fe deposits and Cr- and O-rich precipitates decorating surface grain boundaries and crack surfaces, suggesting a cracking mechanism driven by embrittlement of the crack tip due to oxide formation. Unlike previous studies, intergranular Cr corrosion into the bulk was not observed, and distinct differences in surface morphology between electropolished and non-electropolished sample surfaces are reported. Trace metal salt chemistry measurements showed accumulation of 316L alloying elements over the course of the tests. It appears likely that the surface oxide layer induced by electropolishing, in addition to oxygen and moisture impurities in the salt, led to the formation of LiCrO2 which had a net passivating effect that prevented significant bulk corrosion, though some interplay between mechanical and environmental stressors is still observed.

Corrosion mechanism of cold forged 316 stainless steel in molten FLiNaK salt

This study examined how cold forging (CF) affects the corrosion of 316 stainless steel (SS) in molten FLiNaK salt at 700 °C for 48 h. CF samples had two corrosion areas: one near the top and another displaying intergranular corrosion (IGC). Samples with lower CF (5–30 %) showed more IGC, while the 50 % CF sample had less IGC but the shallowest corrosion depth. This was due to the increased number of grain boundaries, which raised the potential corrosion initiation sites, and certain grain boundaries promoting chromium dissolution, thus enhancing IGC.

Influence of SiC content in B4C–nSiC composites corrosion in molten FLiNaK salt at 800°C

AbstractThe present study investigates the influences of SiC incorporation on the microstructure and corrosion behavior of B4C–nSiC composites in molten FLiNaK salt at 800°C. The corrosion characteristics and mechanisms of B4C–nSiC composites in molten FLiNaK salt were thoroughly characterized and extensively discussed. The B4C–nSiC composites exhibited a more refined grain size and lowered apparent porosity as the SiC content increased. Additionally, the concentration of high‐angle grain boundaries (HAGBs) in B4C–nSiC composites increased as the SiC content increased. The incorporation of 10 wt.% SiC improved the corrosion resistance of B4C–nSiC composites against molten FLiNaK salt. However, the incorporation of excessive SiC (≥20 wt.%) did not improve the corrosion resistance. The best corrosion resistance of B4C–10% SiC ceramic composite was attributed, on the one hand, to its relatively low apparent porosity and the low concentration of HAGBs with high structural disorder. On the other hand, the selective corrosion of B4C in B4C–10% SiC ceramic composite rapidly formed a sufficiently thick and highly graphitized C‐rich layer on its surface during the initial stages of the corrosion test. The C‐rich layer maintained the integral structure of the ceramic and prevented subsequent corrosive medium from penetrating into the ceramic.

A reactive force field approach to modeling corrosion of NiCr alloys in molten FLiNaK salts

The interface between NiCr alloys and FLiNaK molten salt exhibits complex corrosion behavior, mainly driven by intricate chemical interactions involving Cr and F−ions. Understanding these dynamic reactions is crucial for developing effective corrosion mitigation strategies to ensure the long-term durability of Ni-based alloy components in molten salt technologies. However, obtaining molecular-level understanding through experiments is challenging. To address this, we utilize reactive molecular dynamics simulations enabled by a reactive force field, ReaxFF, to investigate detailed reaction dynamics at the atomic level. We first present the development of the ReaxFF parameter set for Ni/Cr/F/Li/Na/K based on extensive first-principles calculations. With this force field, we achieve a strong agreement for the structure of FLiNaK molten salt by comparing the pair distribution functions with experimental and simulation results. Furthermore, our simulations successfully reproduce the experimental phenomenon of Cr dissolution in fluoride salt, with the corrosion rate depending on the alloy and salt compositions. Particularly, our simulations reveal that increasing the concentration of Li can enhance the formation of a compact double layer, mitigating Cr dissolution. This work enables a fundamental understanding of the interfacial behavior between fluoride salt and NiCr alloys.

(General Student Poster Award Winner, 3rd Place) Corrosion Electrochemistry in Molten Flinak Salts

An existing knowledge gap in the field of molten salt (MS) corrosion is the lack of in situ, diagnostical and instantaneous measurements of the underlying corrosion system. Numerous investigations comparing the corrosion behavior of commercial alloys with complex microstructures and compositions in molten fluoride salts have been conducted during the past five years. A few of these have been expanded from exposure studies to those using electrochemical methods[1,2]. In essence, electrochemical techniques offer an in situ and diagnostical way to analyze the corrosion behavior of potential materials in real-time, either in open-circuit (static immersion) or polarized conditions. Investigations on MS corrosion have found few mechanistic insights that elucidate the fundamentals of electrode reactions and characteristics of the electrode-salt interface. However, fate of elements oxidized are not tracked. Nonetheless can be difficult to understand the electrochemical corrosion behavior of structural alloys in non-aqueous, aggressive media, such as molten LiF-NaF-KF (FLiNaK) salts, as they may be influenced by a wide range of parameters (such as microstructure, impurity, and potential).Understanding the mechanism of an alloy's most susceptible alloying constituent's dissolution and describing the rate-determining steps (RDS) of this process using the principles of thermodynamics, kinetics, and electrochemistry are fundamental initial steps in understanding the complexities of alloy corrosion. Chromium (Cr) is frequently referred to in molten fluorides research as an essential yet harmful alloying element in candidate molten salt reactor structural alloys (i.e.Ni-based superalloys and stainless steels) due to its high thermodynamic driving force to dissolve relative to other alloying elements. Because of that Cr is a crucial material for research because it serves as the basis for work on Fe-Cr, Ni-Cr, and Fe-Ni-Cr alloys as well as other alloys. However, published research does not consistently describe the mechanism relating to Cr corrosion in FLiNaK.The objective of this work was to explore the electrochemical corrosion behavior of pure Cr in molten FLiNaK salts at 600oC using electrochemical methods. In this study, we describe and clarify the regimes of Cr corrosion in FLiNaK at 600 oC that are potential-dependent, rate-limiting charge-transfer and mass-transport regulated.A range of measurements based on electrochemistry and material characterization, such as linear, cyclic, and potentiostatic polarization techniques, is presented. A key finding in this work was the attempt to establish a connection between the reactivity of Cr in an aggressive, non-aqueous electrolyte such as molten FLiNaK to electrochemical potentials and corrosion morphology predicted thermodynamically. It was found, that the corrosion mechanism of Cr in FLiNaK was dependent upon mixed potentials established by the anodic Cr/Cr(II) and/or Cr(II) /Cr(III) oxidations coupled with cathodic reactions by multiple oxidizer candidates whose predominance is a function of salt impurity level and Cr exposure times. Results suggest that the early stage of Cr dissolution is regulated by charge-transfer (or activation-controlled) in FLiNaK at 600oC. This type of mechanism can occur at low overpotential (i.e. lower driving force) and can be interrupted by the oversaturation of Cr at the surface. Its presence may be eliminated if the salt film is present. The electrochemical potential in which mass transport regime is rate-limiting falls within the phase stability field where CrF6 3- species dominates, and leading to the formation of a K3CrF6 salt film. The post-exposure SEM analysis revealed that Cr dissolution in this regime involves volume transport within each grain, resulting in the revelation of surface facets containing crystallographic features of cubic crystals.The application of electrochemistry enables a more straightforward way to identify potential RDS that control the rate of Cr corrosion and offers a temporal description of the corrosion mechanism. Such fundamental understanding, especially on the nature of cathodic and anodic reactions of Cr, can provide a baseline to understand the corrosion mechanism of complex alloys. The post-corrosion microstructure investigation, the XRD of the solidified salt combination, and the thermodynamic analysis of the stable phases present in each corrosion regime all corroborated these conclusions. Acknowledgments Research is primarily supported as part of the fundamental understanding of transport under reactor extremes (FUTURE), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Wang, Y. L., et al. Corrosion Science 109, 43–49 (2016).Chan, H.L., et al. NPJ Materials Degradation 6(1), 46 (2022).

Corrosion Behavior of Binary Ni-Cr Alloys in Molten FLiNaK Salts at Different Electrochemical Potentials

The development of molten salt reactors (MSRs) is a collaborative effort among academia, government laboratories, and industry, with the aim of realizing the potential of clean nuclear energy. However, the corrosion of structural alloys presents a significant engineering challenge in this application. Addressing this issue requires investment not only in testing and characterizing candidate alloys, but also in developing a scientific framework to understand the fundamental mechanisms governing the corrosion of metallic materials in molten fluorides which can then guide alloy design [1].In this work, the corrosion behavior of binary Ni-Cr alloys (5-20 wt.% Cr) in molten LiF-NaF-KF (or FLiNaK) salts between 550oC and 750oC was interrogated using electrochemical methods coupled with thermo-kinetic analysis. Electrochemical techniques, including linear sweep voltammetry, electrochemical impedance spectroscopy (EIS) and chronoamperometry, were utilized to elucidate the rate-limiting kinetic factors and to identify the dependence of corrosion morphology on applied potential. Additionally, Ni-Cr alloys were also immersed 99.9% pure FLiNaK salts with a known oxidizer concentration (e.g., 0.1-5 wt.% EuF3) coupled with open-circuit potential measurement to provide a time-based description of morphological evolution in the case of a dynamically changing electrode potential. These results are corroborated by examination of the post-corrosion morphology using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron backscatter diffraction (EBSD) techniques as well as salt composition analysis using inductively coupled plasma mass spectrometry (ICP-MS), X-ray diffraction (XRD) and in situ cyclic voltammetry.The systematic choice of potential revealed multiple potential regimes in which Ni-Cr alloys exhibit distinctly different corrosion morphologies. At intermediate potentials, a porous bicontinuous structure is formed by dealloying of the less noble element (Cr) and percolation into the Ni-rich alloy within grains and along grain boundaries. At other potentials, charge transfer control dissolution of both Cr and Ni leads to the formation of a crystallographic faceted structure. The morphological differences suggest the presence of multiple corrosion processes in Ni-Cr in FLiNaK controlled by either transport or interfacial reaction. These findings can be explained through electrochemical processes at the alloy-salt interface, as well as the roles of surface, grain boundary and bulk diffusion kinetics involving the alloying constituents. Furthermore, the effect of radiation damage on Ni20Cr alloys on these rate-limiting corrosion regimes will be investigated. Acknowledgment Research is primarily supported as part of the fundamental understanding of transport under reactor extremes (FUTURE), an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES).[1] Chan, H.L., et al. Npj Materials Degradation 6(1), 46 (2022).

Revisiting Open Circuit Corrosion of Cr in Unpurified Molten FLiNaK Salts with a Multi-Modal Approach

Corrosion and mitigation of environmental degradation of structural materials in high-temperature Gen IV molten salt reactors, are critical issues. However, any corrosion studies have historically been forensic post-test examinations and materials development has occurred mainly by trial and error until recently. Meanwhile, a fundamental understanding can only be achieved by recognizing how the corrosion system of model materials in molten fluoride salts evolves as a function of time. A number of in-situ spectroscopy techniques to identify corrosion product compositions in molten salts have been suggested in recent years. Raman, high-temperature UV-Vis absorption spectroscopy, and X-ray absorption spectroscopy are a few of them [1,2]. These techniques' major limitations include the fact that they are mainly qualitative, and complex hardware requiring a beam focusing inside the glove box is needed. At the same time, electrochemical techniques have been presented which can provide the information on behavior of both metal and its corrosion product in the continuously evolving corrosion system in molten salts. However, use of single isolated methods renders it difficult to obtain mechanistic information on instantaneous, time-dependent processes and phenomena during corrosion. These are needs gaps opportunities. In this work we present a detailed electrochemical analysis of the corrosion of polycrystalline chromium at 600°C in FLiNaK over 50 h including an electrochemical analysis of in-situ near-instantaneous corrosion rates corroborated with other methods.A variety of corroborating methods including (1) in-situ electrochemical diagnostic techniques, (2) static immersion exposure with gravimetric and SEM analysis, (3) electrochemical impedance spectroscopy, (4) XRD, (5) ICP-OES, was utilized to study the corrosion behavior in unpurified FLiNaK at 600°C. The focus was to evaluate the viability of using an external non-reactive electrode to measure the concentration of corrosion products via redox process analysis in order to determine the corrosion rate during the process of OCP corrosion of Cr in FLiNaK. This work reports the possibility of using of electrochemical techniques such as CV for the instantaneous determination of Cr corrosion rates when Cr is exposed to a 600oC FLiNaK salts for 50 h. It was found that the concentration of dissolved corrosion products, in the more likely possible forms of CrF3 - and CrF6 3- , might be calculated by established analytical approaches to CV analysis such as Berzins-Delahay (soluble/insoluble) and Randles-Ševcik equations (soluble/soluble). The calculated values showed the definite concentration of Cr(II)/Cr(III) corrosion products at the distance of the external electrode (due to the static corrosion conditions). These finding supported by XRD and ICP-OES. A semi-infinite diffusion model was employed in this study to adjust the calculated concentrations assuming a stagnant solution and diffusion based one-dimensional concentration diffusion profile in order to calculated the Cr(III) concentration at a fixed position in the Cr(III) concentration gradient. It was shown that the semi-infinite diffusion model helps correctly describe this profile between 10 and 50 h, based on the geometry of the working electrode and corrosion cell. Based on these results the OCP corrosion rate was interpreted to switch over 50 h from initially charge transfer control Cr(II) oxidation at early times with likely HF and Cr(III) reduction, followed by mass transport control regulated by a salt film and then possible stifling due to depletion of HF and Cr(III) solubility limits.The results of half-cell redox potentials and peak currents pertaining to oxidation/reduction of Cr corrosion products were correlated to the concentrations of particular Cr species and compared with the results of mass loss experiment and ex-situ ICP-OES of post-exposed FLiNaK. The mass loss of the Cr(II)/Cr(III) metal that was approximated by spatially integrating the concentration profiles at a selected time, and the result of Cr mass loss separately obtained from gravimetric measurements showed a reasonable agreement. Furthermore, the rate of accumulation of Cr ions in the residual FLiNaK salt after 50 h of exposure determined by ICP-OES, correlated with the electrochemical CV and EIS analysis. In addition to this, the oxidation and reduction peak potentials pertaining to Cr/CrF3 - and CrF3 -/CrF6 3- redox reactions (measured on Pt wire) were compared with the OCP (measured on Cr) to provide insights on the predominant anodic and cathodic reactions. Acknowledgments This research was supported as part of the fundamental understanding of transport under reactor extremes (FUTURE), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Utilization of the Malvern-Panalytical Empyrean diffractometer was supported by Nanoscale Materials Characterization Facility with National Science Foundation under award CHE-2102156. References Y. Liu et al., (2020) Corrosion Science. 169 108636. https://doi.org/10.1016/j.corsci.2020.108636.S. Fayfar, et al., (2022). https://doi.org/10.26434/chemrxiv-2022-3nspm.

ELECTROCONDUCTIVITY OF MOLTEN FLiNaK AND FLiNaK–CeF<sub>3</sub>

The eutectic mixture LiF–NaF–KF (FLiNaK) is promising as a carrier salt for molten-salt reactors. Cerium fluoride CeF3 can be considered as a simulant of plutonium fluoride PuF3. In this work, the temperature dependence of the electrical conductivity of the molten ternary eutectic LiF–KF–NaF containing from 0 to 25 mol % cerium fluoride in the temperature range 480–777°C. FliNaK–CeF3 mixtures containing up to 25 mol. % of cerium fluoride were prepared directly in the experimental cell, dropping the required amount of CeF3 into the melt and keeping mixtures of a given composition for 12 h at temperatures exceeding the liquidus temperatures of the studied compositions. The electrolyte resistance was determined from impedance hodographs, which were taken using the Z-1500J impedance meter. A two-electrode cell with Pt electrodes was used. Analysis of the experimental values of the electrical conductivity of double and triple fluoride melts KF–LiF available in the literature; KF–NaF; LiF–NaF–KF shows that our data on the electrical conductivity of the LiF–NaF–KF (FLiNaK) eutectic mixture are consistent with the general trend in electrical conductivity with increasing KF concentration in the melt. A significant decrease in the specific electrical conductivity of the molten system and a slight increase in the activation energy of electrical conductivity with an increase in the concentration of cerium fluoride are shown. The temperature dependences of the electrical conductivity of the molten system were approximated by second-order polynomials. The formation of the \({\text{CeF}}_{6}^{{3 - }}\) complex ion in the melt was confirmed by spectral studies. The Raman spectra of molten FLiNaK and FliNaK–CeF3 mixtures containing 8 and 15 mol. % of cerium fluoride were recorded. With an increase in the concentration of CeF3 in the melt, the amount of \({\text{CeF}}_{6}^{{3 - }}\) complex ions increases, which leads to an increase in the intensity of the observed vibrational bands.

Effect of irradiation damage defects on the impurity containing molten salt corrosion behavior in GH3535 alloy

This study explores the corrosion response of irradiated nickel-based GH3535 alloy in impurity-enriched molten FLiNaK salt at 650 °C. Displacement damage resulting from Au ion irradiation formats dislocation loops, whose distribution is influenced by subsequent He ion irradiation and He bubble formation. Samples irradiated with Au ions exhibit a shallow corrosion layer with big-size and dense distributed Cr2O3 particles, while a contrasting trend is observed in samples irradiated with He ions. Displacement damage decelerates Cr outward diffusion by promoting protective Cr2O3 formation with SO42- impurities, thereby inhibiting impurity-accelerated corrosion. However, the accelerating effect of He bubbles subsequently counteracts this inhibitory impact on corrosion.

Corrosion Electrochemistry of Chromium in Molten FLiNaK Salt at 600 °C

The manuscript revisits the corrosion behavior of pure Cr in molten FLiNaK salt at 600 °C from the perspective of corrosion electrochemistry. In this work, the potential-dependent, rate-limiting charge-transfer, and salt film-mediated mass-transport controlled regimes of Cr corrosion in FLiNaK at 600 °C are investigated. The kinetic and thermodynamic parameters that limit electrodissolution and the consideration of grain orientation on these regimes are elucidated. At low Cr(III) concentrations, the corrosion process is governed by charge transfer control at low overpotentials and is crystal orientation dependent. However, when Cr(III) concentrations are high or when there is a high overpotential, the formation of a metal fluoride salt film on the Cr surface shifts the kinetic behavior to be governed by mass transport control at all anodic potentials with a surface morphology controlled by salt film deposition location and identity. Evan’s diagrams were developed to consolidate and elucidate these observations. These findings were supported by an examination of the post-corrosion microstructure, X-ray diffraction of solidified salts, and thermo-kinetics analysis in each corrosion regime.

An In Situ, multi-electrode electrochemical method to assess the open circuit potential corrosion of Cr in unpurified molten FLiNaK

An in situ electrochemical method to investigate the time-dependent spontaneous corrosion of pure Cr in an unpurified LiF-NaF-KF eutectic salt at 600 °C was developed. A multi-electrode electrochemical cell and a dual-electrode method were utilized to detect Cr(II) and Cr(III) ions on a platinum working electrode using cyclic voltammetry as a function of exposure time and compensating for the distance from the Cr electrode. XRD was performed to characterize the crystalline composition of the exposed FLiNaK and the salt films formed on the working electrodes. The fate of all electro-oxidized Cr must be accounted for to quantify corrosion rates. The concentrations of Cr(II) and Cr(III) species obtained were compared with the gravimetric mass change and ICP-OES analysis of the residual salt. Outcomes, difficulties, and limitations are discussed.

In-Situ Analysis of Corrosion Products in Molten Salt: X-ray Absorption Reveals Both Ionic and Metallic Species.

Understanding and controlling the chemical processes between molten salts and alloys is vital for the safe operation of molten-salt nuclear reactors. Corrosion processes in molten salts are highly dependent on the redox potential of the solution that changes with the presence of fission and corrosion processes, and as such, reactor designers develop electrochemical methods to monitor the salt. However, electrochemical techniques rely on the deconvolution of broad peaks, a process that may be imprecise in the presence of multiple species that emerge during reactor operation. Here, we describe in situ measurements of the concentration and chemical state of corrosion products in molten FLiNaK (eutectic mixture of LiF-NaK-KF) by high-resolution X-ray absorption spectroscopy. We placed a NiCr foil in molten FLiNaK and found the presence of both Ni2+ ions and metallic Ni in the melt, which we attribute to the foil disintegration due to Cr dealloying.

Application of the Solute-Solvent EMF Cell to Measure Activity of NiF2 in Molten FLiNaK

Electromotive force (emf) measurements made using a combination of solute- and solvent-based electrodes were used to determine the activity of NiF2 in molten FLiNaK eutectic at 823 K across a concentration range of x NiF2 = 5.2 × 10–4–1.0 × 10–2. The solute emf values were measured using electrodes consisting of Ni wires immersed in FLiNaK with dissolved NiF2 contained in graphite crucibles. The measured emf values were then converted to the FLiNaK Eutectic Potassium Electrode (FEKE) potential and used to quantify the activity of dissolved NiF2. This quantification was based upon comparative measurements of a reference solvent electrode consisting of a K-Bi alloy immersed in pure FLiNaK contained in a boron nitride crucible and a solute electrode. Short cell lives were characteristic of the measurements due to the corrosive nature of the fluoride salts. Quantifying the activity of NiF2 will improve the utility of Ni2+/Ni reference electrodes in molten fluoride salts, which are notoriously difficult electrolytes to work with because of their reactivity. This work demonstrates the general nature of the solute-solvent approach as a repeatable, easily employed method for measuring the activity values of electroactive species in a variety of molten salts to improve understanding of the electroactive species behavior in these systems.

Corrosion property of Alloy 625 in Molten FLiNaK salt according to the Tellurium Concentrations

The corrosion properties of Alloy 625 have been studied in molten FLiNaK salt for 48 h at 700 °C as a function of tellurium (Te) concentrations using immersion tests and electrochemical methods. Under specific Te concentrations, we found that Te-induced corrosion can be suppressed and help protect the alloy against corrosion. The sample after the immersion test containing 0.1 wt.% Te (0.1 wt.% Te sample) had the lowest corrosion depth and mass loss, coupled with the highest charge transfer resistance, obtained using electrochemical impedance spectroscopy (EIS). On the other hand, the alloy with Te content above 0.1 wt.% exhibited severe corrosion penetration and lower charge transfer resistance in FLiNaK. Based on thermodynamical and electrochemical analyses, a corrosion mechanism of Alloy 625 in the molten salt containing Te was theorized involving the formation of stable corrosion products such as Ni/Fe rich layer depleted in Cr, nickel telluride, and chromium oxide.

Tritium release behavior from neutron-irradiated FLiNaK mixed with Ti powder

• FLiNaK mixed with Ti powder was irradiated by mainly thermal neutrons. • Amounts of TF, T2 and T2O released from the FLiNaK by heating were investigated. • Chemical form ratio of released tritium was approximately TF:T2:T2O = 5:70:25. • Approximately 70% of tritium was released as T2O from the FLiNaK exposed to air. • Ti powder mixed to the FLiNaK contributed to the suppression of tritium release. FLiNaK is used as a simulant of FLiBe and FLiNaBe which are promising candidates of liquid blanket material in fusion reactors. In this study, to obtain useful knowledge for tritium release behavior from molten salts such as FLiBe and FLiNaBe, tritium release experiments were carried out for neutron-irradiated FLiNaK containing Ti powder. The solid-state samples were irradiated by mainly thermal neutrons at Kyoto University Research Reactor, and tritium release behavior as TF and T 2 by heating in Ar gas flow was observed and additionally total amount of released T 2 O was obtained. Most of the tritium generated inside the FLiNaK was released to the gas phase even when the FLiNaK was in a solid state at a temperature below its melting point. From the molten FLiNaK unintentionally exposed to air, approximately 70% of tritium was released as tritiated water vapor. The amount of TF released from the molten FLiNaK was considerably less than that of T 2 . This result is consistent with the tendency of tritium release from neutron-irradiated FLiNaBe in our previous study. The ratio of chemical form was approximately TF:T 2 :T 2 O = 5:70:25. It was experimentally confirmed that the Ti powder added to the salt contributes to the suppression of tritium release from the molten salt.