The high Si containing X1CrNiSi18-15-4 stainless steel (SS) spontaneously forms a protective oxide film that is mostly composed of mixed chromium and silicon oxides. This film ensures a good durability of the industrial facilities the alloy was designed for, containing very acidic electrolytes such as hot and concentrated nitric acid, HNO 3 , in presence of oxidizing species. In the present work, the chemistry of the oxide formed and the passivation kinetics of the alloy in sulfuric acid, H 2 SO 4 , and for the first time in HNO 3 , were monitored by atomic emission spectroelectrochemistry (AESEC) over successive activation and passivation cycles of the material. X1CrNiSi18-15-4 SS was compared to a low Si containing SS, the X2CrNiN18-10 SS. It was found that a similar quantity and rate of passive film was formed during passivation, and dissolved during activation. Reproducible results were obtained over several active-passive cycles. The excess Cr was correlated with the dissolution rate decay during passivation. The Si/Cr ratio of the passive film was determined by X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy (performed using transmission electron microscopy), and AESEC giving similar results within experimental error. The EDX profile suggest that the passive film consists of a Si rich outer and Cr rich inner layer.

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