For a better understanding of the relationship between the microstructure of UNS S31803 duplex stainless steel (DSS) and the shape of the polarization curves, this study evaluated the influence of the microstructure on the potentiodynamic polarization of the 850°C isothermal-aged UNS S31803 DSS in 0.5 M sulfuric acid (H2SO4). In the transpassive region, selective corrosion of chromium- and molybdenum-rich phases occurred. In the solution-treated sample, ferrite was selectively corroded, and in all aged samples, the sigma phase was the selectively corroded phase. Five current density maxima in the passive region were found during potentiodynamic polarization, and they can be related to the microstructures formed. The current density maximum at 564 mV vs. saturated calomel electrode (SCE) can be related to secondary ferrite, impoverished in chromium and molybdenum, that was formed during direct precipitation of sigma phase from the original ferrite. Secondary austenite, impoverished in chromium and molybdenum and formed together with the sigma phase during eutectoid decomposition of the original ferrite, can be related to the current density maxima at −85 mVSCE and −40 mVSCE. The austenite phase, present in all heat-treatment conditions, can be related to the current density maxima at −155 mVSCE and 111 mVSCE.

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