The relation between pit morphology and microstructure formed during 850°C isothermal aging of UNS S31803 duplex stainless steel (DSS) could be reached through the explanation of pit nucleation and growth during potentiodynamic polarization in 3.5 wt% sodium chloride (NaCl) aqueous solution. Aging times up to 10 min at 850°C led to sigma formation by direct precipitation from ferrite, resulting in Cr- and Mo-depleted ferrite, or secondary ferrite. Between 30 min and 5 h of aging, the ferrite suffered eutectoid decomposition, resulting in sigma phase and secondary austenite, also impoverished in Cr and Mo. Those Cr- and Mo-depleted zones around the sigma phase were preferential sites for the nucleation of pits. At those sites, the passive film breakdown was easier, as shown by the low pitting potential values found in aged samples. Pit growth occurred as selective corrosion of the metallic matrix surrounding the sigma phase, as a consequence of the lower corrosion resistance of the secondary ferrite and austenite phases found. The low passivation potential values indicated the difficulty in repassivation of the pits formed, probably related to the Cr and Mo depletion of the regions surrounding the sigma phase.

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