In Operando Analysis of Passive Film Growth on Ni-Cr and Ni-Cr-Mo Alloys in Chloride Solutions
Journal Article - Open Access
University of Virginia Charlottesville United States
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The instantaneous kinetics of oxide formation and growth, in competition with passive film dissolution and breakdown, were investigatedfor Ni-22 Cr and Ni-22 Cr-6 Mo wt during single step passivation at 0.2 VSCE. Experiments were conducted in selected acidic and alkaline chloride-containing environments using simultaneous AC and DC electrochemistry including on-line Inductively Coupled Plasma-Mass Spectrometry ICP-MS. In parallel experiments, in-situ neutron reflectometry NR and ex-situ X-ray photoelectron spectroscopy XPS were utilized to characterize the formation of surface oxide films as a function of time. The specific roles of pH and Mo during passivation and breakdown kinetics are highlighted, providing an insight into the fate of the elements which comprise the alloys, and their effects on passivation behavior. It was observed that early oxidation of both Ni and Cr-species occurred in acidic electrolyte. Preferential dissolution of Ni2 at later times enabled gradual Cr3 enrichment within the surface film. However, greater relative stability of NiO and NiOH2 was observed in the alkaline condition. Upon alloying Ni-Cr with Mo, Cr3 became increasingly enriched in the surface film during anodic polarization. Oxides were interpreted to consist of non-stoichiometric solid solutions formed via solute capture.
- Properties of Metals and Alloys