Abstract
Effects of the precipitation of $\sigma$ phase on the metastable pitting as a precursor of stable pitting corrosion and also on the progress of stale pitting of the 25Cr-7Ni-3Mo-0.25N duplex stainless steel were investigated in chloride solution. Electrochemical potential and current noises of the alloy were measured in 10 % ferric chloride solution ($FeCl_3$) with zero resistance ammeter (ZRA), and then analyzed by power spectral density (PSD) and by corrosion admittance ($A_c$) spectrum. With aging at $850^{\circ}C$, the passive film of the alloy was found to get significantly unstable as represented by power spectral density (PSD) and a transition from metastable pitting state to stable one was observed. In the corrosion admittance spectrum, the number of negative $A_c$ corresponding to the state of localized corrosion increased with aging, suggesting that the precipitation of $\sigma$ phase considerably degraded the passive film by depleting Cr and Mo around it at $\alpha/\sigma$ or $\gamma/\sigma$ phase boundaries, thereby leading to the initiation of the pitting corrosion. However, the Cr and Mo at $\alpha/\sigma$ or $\gamma/\sigma$ phase boundaries which were once depleted due to the precipitation of the $\sigma$ phase were partly replenished by the diffusion of Cr and Mo from the surrounding matrix with aging time longer. The initiation of pitting seems to be associated with the precipitation density of the $\sigma$ phase with an effective size needed to induce the sufficient depletion of Cr and Mo around it.
