One of the promising candidates for heat transfer fluid is molten chloride salts. They have been studied in various fields such as the electrolyte of pyroprocessing, the molten salt reactor coolant, and the energy storage system media. Main considerations for utilizing molten chloride salts are the compatibility of salts with structural materials. The corrosion behavior of structural materials in molten chloride salts must be understood to identify suitable materials against the corrosive environment. In this study, the corrosion behavior of a candidate structural material, Hastelloy N, in molten LiCl- KCl salt at 500°C were investigated by the electrochemical impedance spectroscopy (EIS) method. The sheet type of Hastelloy N was utilized as the working electrode in LiCl-KCl to measure the EIS data for 100 hours with 5 hours of time intervals. The EIS data were measured in the frequency range from 104 Hz to 10-2 Hz with the AC signal (amplitude = 20 mV) at open circuit potential. The capacitance semicircle observed in Nyquist plots for all periods indicates that charge-transfer controlled reactions occur. As the immersion time progresses, the radius of the semicircle in Nyquist plots and the impedance and phase angle in Bode plots decrease. These behaviors suggest a decreasing reaction resistance and the corrosion reactions are accelerated with the immersion time. The EIS data were fitted using the equivalent circuit to achieve quantitative results. Two capacitor-resistor components were considered due to the overlapped shape of two valleys in phase angle. The depressed shape of the semicircle in Nyquist plots led to the use of the constant phase element(Q) instead of the capacitor. Therefore, R(Q(R(QR))) circuit was selected to fit the EIS data. Fitting results show that the charge transfer resistance decreases dramatically within 1 day and then converges. The film resistance shows no clear trends, but the increase of the film admittance value indicates the decreased film thickness. Consequently, the film appears to exist like the oxide layer but it does not act as a protective layer. The real-time EIS data were measured in molten salt and provides the corrosion behavior over time. The corrosion mitigation strategy should consider that the corrosion of Hastelloy N accelerates over time and its intrinsic film cannot act as the protective layer. The next steps of this study are to evaluate other candidate structural materials and to demonstrate the presence of the film.

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.

NaCl과 LiNO2의 첨가량에 따른 콘크리트에 매립된 철근의 부식거동을 전기화학적 임피던스 분광법을 이용하여 고찰하였다. 부식 가속 방법중 하나인 건습반복법을 이용하여 단기간 내에 부식현상을 촉진하였으며, 측정된 임피던스 값을 통해 등가회로를 제안할 수 있었다. NaCl 1.2 kg/m3이 첨가된 콘크리트에 매립된 철근의 부동태 피막이 빠르게 파괴되는 것을 확인할 수 있었으며, 염화물 첨가량 대비 0.6M의 LiNO2를 첨가한 경우 부식진행속도가 크게 저하하는 것을 확인할 수 있었다. 또한 염화물 첨가량 대비 1.2M의 LiNO2를 첨가한 경우 부동태 피 막이 부식가속시간이 지나도 파괴되지 않고 성능이 유지되는 것을 확인할 수 있었다.