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Passivation mechanisms and the effects of controlled pre-oxidation, by exposure to oxygen at ultra-low pressure, on Cr and Mo surface enrichments were investigated on polycrystalline AISI 316L stainless steel surfaces with direct transfer between surface preparation and analysis by X-ray photoelectron spectroscopy and electrochemistry. Exposure to sulfuric acid at open circuit potential causes preferential dissolution of oxidized iron species, which promotes Cr3+ and Mo4+/6+ enrichments. Anodic passivation forces oxide film re-growth and Cr3+ dehydroxylation with no loss of Mo4+/6+ pre-enrichment. Ultra-low pressure preoxidation promotes Mo4+/6+ enrichment in the exchange outer hydroxide layer of the passive film, with no Mo0 depletion in the modified alloy region underneath the oxide film at open circuit potential, and under anodic passivation. Mo4+/6+ enrichment improves protectiveness against transient active dissolution during the active/passive transition [ABSTRACT FROM AUTHOR]

[Display omitted] • 0.5Nb provides the best protection of oxide film in simulated primary coolant. • Corrosion potential does not increase with Nb. • Nb promotes the active dissolution after anodic polarization. • Cr hydroxylation is enhanced by Nb addition. XPS combined with AFM have been used to investigate the surface modifications of nuclear grade FeCrAl- x Nb (x = 0, 0.5, 1.0, 1.5 wt.%) alloys, induced by anodic polarization in a simulated primary coolant. Electrochemical tests were performed to study the role of the minor element Nb on the corrosion potential and composition. The optimal content of Nb, obtained after the comparative analysis of the UHV-sputtered surface, native oxide-covered surface and anodic polarized surface, is 0.5 wt.%. This alloy presents a more compact Al-enriched oxide film consistent with a higher corrosion potential at −89 mV. The protectiveness of oxide film against the active dissolution can be improved by Nb addition, but does not increases linearly with Nb content. High resolution XPS analysis details the changes of Nb oxidized states, and provides the stratification of the oxide film containing the (hydr) oxides of Fe, Al and Cr. [ABSTRACT FROM AUTHOR]

• Formation of bi-layered films with physisorbed outer and chemisorbed inner layers. • 2-MBI bonding by N to metallic and oxidized Cu, S also involved on metallic Cu. • Formation of Cu(I)−2-MBI complex promoted by cathodic conversion of native Cu oxide. • Increased complex formation owing to Cu(I) ions generated by anodic oxidation. • Cu dissolution inhibited depending on pre-treatment used for interface formation. The interfacial bonding and the layered structure of 2-mercaptobenzimidazole (2-MBI) organic films adsorbed on electrochemically controlled copper surfaces and their corrosion inhibition effects in acidic chloride aqueous solution were investigated using an integrated approach of electrochemical methods and advanced surface analyses by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry. It is shown that organic films formed on the copper surfaces are bi-layered with a chemisorbed inner layer and a physisorbed outer layer. In the chemisorbed inner layer, 2-MBI is bonded primarily by its nitrogen atoms with metallic and oxidized copper surfaces. Sulphur atoms are also involved in the bonding mechanism when metallic copper is directly accessible to the 2-MBI molecules. The initial presence of native copper oxides at the interface promotes the formation of Cu(I)-2-MBI metal-organic complexes in the chemisorbed inner layer using cathodic reduction to dissociate the oxide. Metal-organic complexes also form upon anodic polarisation due to Cu(I) ions generated by oxidation of the copper metal. 2-MBI effectively inhibits copper anodic dissolution in varying degrees, between 84% and 93%, depending on the pre-treatment used for the formation of the organic bi-layers. An enhanced protection of the substrate is obtained by adsorbing the 2-MBI inhibitor on an initially oxide-free surface, which is achieved by cathodic pre-treatment in absence of the inhibitor followed by 1 hour exposure to the inhibitor. [ABSTRACT FROM AUTHOR]

Advanced surface analytical techniques were used to study 2-mercaptobenzothiazole (2-MBT) adsorption and interfacial oxide effects on copper, and cyclic voltammetry was used to characterize corrosion inhibition in NaCl solution. 2-MBT adsorbs on metallic copper by its sulphur atoms along with a small fraction of nitrogen atoms. The 2-MBT film formed is thicker when the interfacial oxide is less. Upon anodic polarisation, a direct correlation between the thickness of 2-MBT layer and protection against corrosion initiation is observed. The metal-organic complexes, formed by an interaction between 2-MBT and Cu(I) ions, do not offer additional protection to the substrate. • 2-MBT inhibition of copper initial corrosion in NaCl studied by surface analysis. • 2-MBT adsorption mostly by sulphur atoms and partially by nitrogen atoms. • Thickness of 2-MBT layer dependent on quantity of interfacial oxides present. • Superior protection against corrosion offered by thicker 2-MBT barrier layer. • Metal-organic Cu-2-MBT complexes do not aid in corrosion protection of substrate. [ABSTRACT FROM AUTHOR]