(General Student Poster Award Winner, 3rd Place) Corrosion Electrochemistry in Molten Flinak Salts
Authors: Chan Ho Lun , Romanovskaia Elena , Hong Minsung , Sur Debashish , Romanovski Valentin , Hosemann Peter , Scully John R. 
Published: February 2024

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).