Mullite Membrane Reference Electrode Evaluation and Application for Ni-Cr Corrosion Behavior in High Temperature Chloride Salts

Molten salt reactors (MSRs) using chloride-based salt-matrixes as coolants or fuels are a promising option for advanced nuclear reactors, but the extreme temperatures and corrosivity of molten salts pose a challenge for implementation. Molten MgCl2-NaCl-KCl is a viable candidate for MSRs that is considered in this work. Thermochemical properties are derived from electrochemical tests that aid in characterizing the properties of salts. To study these properties, some work has proposed using a three-electrode system with a reference electrode housed in a ceramic membrane. This research aims to develop a stable high-temperature reference electrode using a ceramic membrane that is then applied to develop an on-line monitoring system of Ni-Cr alloy corrosion in chloride salt. A mullite tube used as the membrane of a Ni(II)/Ni reference electrode in molten MgCl2-NaCl-KCl is studied. The performance of two different membrane thicknesses (1.325mm and 0.255mm) was studied in temperature ranges from 635oC to 835oC and data collected on the calculated formal potential of the Ni(II)/Ni system. Tests indicated that the results were stable and repeatable, and the formal potential for both systems differed from the previous experimental data by 0.12V at most, indicating that the system can be applied as an effective reference electrode. Using the reference electrode, on-line monitoring the corrosion of Ni-15wt.%Cr, Ni-20wt.%Cr, and Ni-30wt.%Cr was studied for 120 hours in MgCl2-NaCl-KCl. The on-line measurements showed the concentration changes of dissolved Cr and Ni by corrosion in the bulk molten salt. This work confirms that Ni(II)/Ni reference electrodes with a mullite tube membrane are stable and effective in molten chloride salt systems, particularly MgCl2-NaCl-KCl. The mullite membrane prepared by the manufacturer may be used directly for electrochemical applications without polishing, simplifying the reference electrode manufacturing process, and making it easier to replicate. The use of a Ni(II)/Ni reference electrode provides an avenue to study a different range of salt systems than previous reference electrodes allowed, particularly alloys in chloride salts at high temperatures. This work also confirms that the mullite tube may be used to perform on-line analysis of alloy corrosion in high temperature molten chloride salts. The study of Ni-Cr alloys in chloride salts better prepares the nuclear industry to select coolant salts and alloy containers with the best set of thermochemical and corrosion resistant characteristics for MSRs.