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 550 o C and 750 o C 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.% EuF 3 ) 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