Revisiting the passivation of stainless steels and other passive CRAs

Abstract

All that was said so far about passivity and passivation was indeed based on electrochemical prejudgments, and all based on unverified postulates. However, due the authors’ fame and for lack of anything better, the great many contradictions were carefully ignored. However, when resuming from raw experimental facts and the present general knowledge, it now appears that passivation always begins by the precipitation of a metallic hydroxide gel. Therefore, all the protectiveness mechanisms already known for porous corrosion layers apply, so that this outstanding protectiveness is indeed governed by the chemistry of transport processes throughout the entrapped water. For Al type passivation, the base metal ions only have deep and complete electronic shells, which precludes any electronic conductivity. Then protectiveness can only arise from gel thickening and densification. For Fe type passivation, an incomplete shell of superficial 3d electrons allows an early metallic or semimetallic conductivity in the gel skeleton, at the onset of the very first perfectly ordered inorganic polymers (- MII-O-MIII-O-)n. Then all depends on the acquisition, maintenance or loss of a sufficient electrical conductivity in this Faraday cage. But for both types of passive layers, all the known features can be explained by the chemistry of transport processes, with neither exception nor contradiction.