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Data recently obtained on model FeCrNi(Mo), 316 L stainless steel, and FeCrNiCo(Mo) passivated surfaces by advanced surface analysis and density functional theory modeling are comprehensively discussed to unravel the multiple effects that molybdenum might have at the nanometer and atomic scales to enhance the stability of passive films. The key role played on corrosion protection by the compositional and structural nanoscale defects of the passive film that originate from the pre-passivation mechanisms of the surface is considered. It is shown how Mo, enriched together with Cr in the nanometer-thick passive film, can combine several effects to enhance the resistance to Cl--induced passivity breakdown. Enriched as Mo(VI) species in the outer exchange layer of the passive film, Mo impedes the deep penetration of Cl- ions and limits their access to the inner barrier layer. Dispersed as Mo(IV) at the interface with the inner layer, Mo protects against the entry of Cl- ions into the defect sites of the Cr(III) oxide barrier. Present as Mo(IV + δ) in the Fe-rich compositional nanoscale defects self-generated by the local failure of Cr supply upon initial formation of the barrier layer, Mo enhances the selective dissolution of iron and its replacement by chromium and molybdenum. By impeding the formation of O vacancies, Mo also increases the resistance against chloride entry in the oxide matrix, thereby curing these the Fe-rich weak sites against Cl--induced passivity breakdown. [ABSTRACT FROM AUTHOR]

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]

A combination of electrochemical measurements, H2 volume measurements and surface analysis using Time-of-Flight SecondaryIon Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS) was used to investigate the role of the metallic Fe impurities (60 ppm) in high purity (99.9 wt%) magnesium and the effect of sulfur on the hydrogen evolution. The Mg corrosion was studied in NaCl solutions containing dissolved hydrogen sulfide. At OCP and under anodic polarization the hydrogen evolution reaction and the growth of dark corroded areas were significantly inhibited in the presence of H2Saq. ToF-SIMS and XPS analyses showed the presence of sulfur adsorbed on Mg and on Fe segregated at grain boundaries. The observed inhibition of hydrogen evolution at OCP and above is assigned to a poisoning effect by adsorbed S of the H adsorption sites on segregated iron which, in the absence of sulfur, provides catalytic sites for excess HER. The equilibrium Pourbaix diagram for the Mg-Fe-S system including the adsorbed species predicts that S is adsorbed on Mg and Fe in the E-pH conditions of this work, which confirms therole assigned to adsorbed sulfur in the inhibition of excess hydrogen evolution at OCP and under anodic polarization in the presence of H2Saq. [ABSTRACT FROM AUTHOR]

The initiation of intergranular corrosion at various types of grain boundaries (GBs) was studied at the nanometer scale on microcrystalline copper in 1 mM HCl aqueous solution. In situ Electrochemical Scanning Tunneling Microscopy (ECSTM) and Electron Back-Scatter Diffraction analysis of the same local microstructural region were combined using an innovative methodology including micro marking performed with the STM tip. The results demonstrate that electrochemically-induced intergranular dissolution, at the surface termination of GBs, is dependent on the grain boundary character. It is found that random high angle boundaries as well as Σ9 coincidence site lattice (CSL) boundaries are susceptible to nanoscale initiation of intergranular corrosion while for Σ3 CSL boundaries the behavior is dependent on the deviation angle of the GB plane from the exact orientation. For the Σ3 twins, a transition from resistance to susceptibility occurs between 1° and 1.7° of deviation as a result of the increase of the density of steps (i.e. misorientation dislocations) in the coincidence boundary plane. The work emphasizes the precision needed in the design of the grain boundary network in applications where intergranular corrosion or its initiation must be controlled at the nanoscale. [ABSTRACT FROM AUTHOR]

Highlights • Current developments of nanoscale insight into passive oxide films. • Cr(III) enrichment and its homogeneity at the nanoscale in passive films. • Corrosion properties of grain boundaries in early intergranular corrosion. • Interaction of organic inhibitor molecules with passivated metallic surfaces. Abstract Oxide passive films are a key for the durability of metals and alloys components as well as a central issue in corrosion science and engineering. Herein, we discuss current developments of the nanometer and sub-nanometer scale knowledge of the barrier properties and adsorption properties of passive oxide films brought by recent model experimental and theoretical investigations. The discussed aspects include (i) the chromium enrichment and its homogeneity at the nanoscale in passive films formed on Cr-bearing alloys such as stainless steel, (ii) the corrosion properties of grain boundaries in early intergranular corrosion before penetration and propagation in the grain boundary network, and (iii) the interaction of organic inhibitor molecules with incompletely passivated metallic surfaces. In all three cases, key issues are highlighted and future developments that we consider as most relevant are identified. [ABSTRACT FROM AUTHOR]

Atomic level characterization brings fundamental insight into the mechanisms of self-protection against corrosion of metals and alloys by oxide passive films and into how localized corrosion is initiated on passivated metal surfaces. This is illustrated in this overview with selected data obtained at the subnanometre, i.e. atomic or molecular, scale and also at the nanometre scale on singlecrystal copper, nickel, chromium and stainless steel surfaces passivated in well-controlled conditions and analysed in situ and/or ex situ by scanning tunnelling microscopy/spectroscopy and atomic force microscopy. A selected example of corrosion modelling by ab initio density functional theory is also presented. The discussed aspects include the surface reconstruction induced by hydroxide adsorption and formation of two-dimensional (hydr)oxide precursors, the atomic structure, orientation and surface hydroxylation of three-dimensional ultrathin oxide passive films, the effect of grain boundaries in polycrystalline passive films acting as preferential sites of passivity breakdown, the differences in local electronic properties measured at grain boundaries of passive films and the role of step edges at the exposed surface of oxide grains on the dissolution of the passive film. This article is part of the themed issue 'The challenges of hydrogen and metals'. [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]

• Surface oxide layers formed on 2304 duplex stainless steel are investigated. • The native surface and the passivated surface are compared. • An innovative coupling of XPS and ToF-SIMS is used. • The oxide layers formed on austenite and ferrite phases are locally characterized. • The effect of passivation on the surface oxide layer is discussed. This work reports an innovative methodology based on the coupling of XPS and ToF-SIMS in order to study the surface oxide layer formed on austenite and ferrite phases of duplex stainless steels. The native oxide film obtained after mechanical polishing and the passive film obtained after electrochemical passivation in 0.05 M H 2 SO 4 were investigated. Chromium and molybdenum contents were found to be higher in the oxide layer formed on ferrite phase. Nickel and nitrogen enrichments were found to be more pronounced under the oxide layer formed on austenite phase. The effect of passivation on the surface oxide layer is discussed. [ABSTRACT FROM AUTHOR]

The role of the SiC substrate surface on the resistance to the local initiation of tarnishing of thin-layered silver stacks for demanding space mirror applications was studied by combined surface and interface analysis on model stack samples deposited by cathodic magnetron sputtering and submitted to accelerated aging in gaseous H 2 S. It is shown that suppressing the surface pores resulting from the bulk SiC material production process by surface pretreatment eliminates the high aspect ratio surface sites that are imperfectly protected by the SiO 2 overcoat after the deposition of silver. The formation of channels connecting the silver layer to its environment through the failing protection layer at the surface pores and locally enabling H 2 S entry and Ag 2 S growth as columns until emergence at the stack surface is suppressed, which markedly delays tarnishing initiation and thereby preserves the optical performance. The results revealed that residual tarnishing initiation proceeds by a mechanism essentially identical in nature but involving different pathways short circuiting the protection layer and enabling H 2 S ingress until the silver layer. These permeation pathways are suggested to be of microstructural origin and could correspond to the incompletely coalesced intergranular boundaries of the SiO 2 layer. [ABSTRACT FROM AUTHOR]

In this work, we addressed the local degradation mechanisms limiting the prelaunch environmental durability of thin-layered silver stacks for demanding space mirror applications. Local initiation and propagation of tarnishing were studied by combined surface and interface analysis on model stack samples consisting of thin silver layers supported on lightweight SiC substrates and protected by thin SiO2 overcoats, deposited by cathodic magnetron sputtering and submitted to accelerated aging in gaseous H2S. The results show that tarnishing is locally initiated by the formation of Ag2S columns erupting above the stack surface. Ag2S growth is promoted at high aspect ratio defects (surface pores) of the SiC substrate as a result of an imperfect protection by the SiO2 overcoat. Channels most likely connect the silver layer to its environment through the protection layer, which enables local H2S entry and Ag2S growth. The silver sulfide columns grow in number and size eventually leading to coalescence with increasing H2S exposure. In more advanced stages, tarnishing slows down owing to saturation of all pre-existing imperfectly protected sites of preferential sulfidation. However, it progresses radially at the basis of the Ag2S columns underneath the protection layer, consuming the metallic silver layer and deteriorating the protecting overcoat. [ABSTRACT FROM AUTHOR]

• Investigation of native and passive surface films formed on Ni-20 at.% Cr alloy surfaces. • Surface analysis by in situ electrochemical measurements combined with advanced ex situ surface analysis. • Mechanistic understanding of the effects of high-temperature hydrogen annealing pretreatment. • Enhanced corrosion resistance of electrochemically passivated surface by high-temperature hydrogen annealing pretreatment. • Increase in Cr enrichment of initially weakly protected sites of the inner barrier layer. The effect of high-temperature annealing under hydrogen gas (H 2) surface preparation on a binary polycrystalline Ni-20 at.% Cr alloy was investigated in comparison with conventional mechanical grinding surface preparation. Duplex surface films with inner Cr(III) oxide and outer Ni(II) and Cr(III) hydroxide layers natively formed before and after H 2 annealing were characterized by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy. A thinner and less homogeneous inner barrier layer formed after H 2 annealing caused an oxidation peak at the active/passive transition in the linear sweep voltammetry measurement in a 0.5 M H 2 SO 4 solution. Despite this high oxidation peak, passivation of the H 2 annealed surface resulted in the formation of a more corrosion resistant inner layer than on the mechanically ground surface, as demonstrated by electrochemical impedance spectroscopy. The corrosion resistant passive film formation of the H 2 annealed surface is attributed to the increased Cr enrichment of the inner layer caused by the selective Ni dissolution providing corrosion resistance to the initially weakly protected sites of the natively formed surface film. [ABSTRACT FROM AUTHOR]

The effect of the interfacial air-formed native copper oxide layer on the corrosion protection of copper with 20 nm Atomic Layer Deposited (ALD) alumina was investigated in 0.5 M NaCl using electrochemical and surface analysis techniques. The results show that dissolution of the interfacial native oxide by a pre-treatment of the copper substrate with phosphoric acid is beneficial to the sealing property of the coating and to the corrosion resistance of the substrate exposed through channel defects. Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) elemental depth profiling evidenced the modifications of the interfacial copper oxide on a pre-treated substrate including cleaning from organic contaminants. The beneficial effects of the pre-treatment include improved ALD nucleation and growth due to interface cleaning and decreased cathodic electrochemical activity (assigned to oxygen reduction) at the end of the channel defects exposing the substrate to the environment. Electrochemical Impedance Spectroscopy (EIS) analysis revealed a remarkably lower porosity of the bulk of the ALD alumina layers as compared to the coating/substrate interface, suggesting interfacial trenching as a major failure mechanism for the corrosion protection. Interfacial trenching can be reduced with a freshly re-grown interfacial oxide on the pre-treated substrate surface. The necessity for better controlling the interface chemistry for improved corrosion protection by ALD alumina is demonstrated. [ABSTRACT FROM AUTHOR]

Copper alloys, often used in cooling circuits of industrial plants using seawater as coolant, can be affected by biocorrosion induced by biofilm formation. Extracellular polymeric substances (EPS) produced by bacteria play a fundamental role in the different stages of biofilm formation, maturation and maintenance. The influence of loosely bound (LB) and tightly bound (TB) EPS, extracted from marine Pseudomonas NCIMB 2021, on the electrochemical behaviour of 70Cu–30Ni (wt.%) alloy in static artificial seawater (ASW) and on the chemical composition of oxide layers was studied by combined electrochemical measurements (polarization curves, EIS) and surface analysis (XPS, ToF-SIMS). Results were compared with those obtained in the presence of bovine serum albumin (BSA), a model protein. Compared to 70Cu–30Ni alloy in static ASW without biomolecules, for which a thick duplex oxide layer (outer redeposited Cu 2 O layer and inner oxidized nickel layer) is shown, the presence of BSA, TB EPS and LB EPS leads to a mixed oxide layer (oxidized copper and nickel) with a lower thickness. In the biomolecules-containing solutions, this oxide layer is covered by an adsorbed organic layer, mainly composed of proteins. A model is proposed to analyse impedance data obtained at the corrosion potential. The fitting procedure of impedance diagrams allows extracting the anodic charge transfer resistance, from which the corrosion current density can be calculated. The results show a slow-down of the anodic reaction in the presence of biomolecules (BSA, TB EPS and LB EPS), and a corrosion inhibition effect by LB EPS and to a lesser extent by BSA. No detrimental effect is evidenced with TB EPS. [ABSTRACT FROM AUTHOR]

Abstract: Copper alloys often used in cooling circuits of industrial plants can be affected by biocorrosion induced by biofilm formation. The objective of this work was to study the influence of protein adsorption, which is the first step in biofilm formation, on the electrochemical behavior of 70Cu–30Ni (wt.%) alloy in static artificial seawater and on the chemical composition of oxide layers. For that purpose, electrochemical measurements performed after 1h of immersion were combined to surface analyses. A model is proposed to analyze impedance data. In the presence of bovine serum albumin (BSA, model protein), the anodic charge transfer resistance deduced from EIS data at Ecorr is slightly higher, corresponding to lower corrosion current. Without BSA, two oxidized layers are shown by XPS and ToF-SIMS: an outer layer mainly composed of copper oxide (Cu2O redeposited layer) and an inner layer mainly composed of oxidized nickel, with a global thickness of ~30nm. The presence of BSA leads to a mixed oxide layer (CuO, Cu2O, Ni(OH)2) with a lower thickness (~10nm). Thus, the protein induces a decrease of the dissolution rate at Ecorr and hence a decrease of the amount of redeposited Cu2O and of the oxide layer thickness. [Copyright &y& Elsevier]

[Display omitted] • Thermal stability of Ni20Cr and Ni20Cr10Mo is investigated by XPS and in situ ToF-SIMS • The chemical modifications are studied during heating of surface oxides in vacuum • The highest thermal stability is observed for the pre-passivated Ni20Cr10Mo alloy. • The findings are useful to improve corrosion protection strategies. Thermal stability of surface oxides on Ni-20Cr and Ni-20Cr-10Mo alloys, including air formed native oxides and passive films formed by electrochemical passivation, was investigated by stepwise heat treatments in ultra-high vacuum up to 300 °C. The modifications of the surface oxides were analyzed by XPS and in situ ToF-SIMS. The analytical surface characterization at the nanoscale revealed modifications of the protective surface oxides that depend on temperature and nature of the alloy. A loss of Ni(OH) 2 in the outer hydroxide layer and a decrease of film thickness are observed on both alloys above 100 °C. At 200 °C, Ni hydroxide in the outer layer is no longer stable while MoO 3 decreases and MoO 2 increases in the oxide film. At 300 °C no native oxide film remains at the surface of Ni-20Cr alloy, whereas a thin Cr oxide film partially covering the surface remains on passivated Ni-20Cr and for both native and passivated surfaces of Ni-20Cr-10Mo alloy. It is shown that the thermal stability of the surface oxide is significantly improved by electrochemical passivation on both alloys and is further enhanced by the presence of Mo in the oxide on the Mo-containing alloy. Such findings are useful for the development of corrosion protection strategies. [ABSTRACT FROM AUTHOR]

• XPS and ToF-SIMS techniques were applied to understand biofilm-surface interaction. • The effect of Escherichia coli on the passive film composition has been explored. • Escherichia coli adhesion leads to a Cr enrichment of the passive film. • A mechanism involving bacterial metabolism explains passive film modifications. Modifications of the passive film on stainless steel (316 L) after Escherichia coli adhesion in the early stage of biofilm formation were investigated by XPS (X-ray Photoelectron Spectroscopy) and ToF-SIMS (Time-of-Flight Secondary Ions Mass Spectrometry). This work evidences an enrichment in Cr(III) in the presence of bacteria, which is known to improve corrosion resistance. The iron depletion is assigned to synthesis by bacteria of organic molecules (siderophore) that specifically chelate Fe3+ ions from the passive layer, followed by the reduction of Fe3+ into Fe2+ ions by the bacterium and finally release of these reduced species into the aqueous solution. [ABSTRACT FROM AUTHOR]

Electrochemical polarization measurements were combined with surface analysis by Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS), X-Ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM) to study the alterations of the passive film on 316 L austenitic stainless steel induced by the presence of chlorides in sulfuric acid electrolyte. The work was performed at a stage of initiation of localized corrosion preceding metastable pitting at the micrometer scale as verified by current transient analysis and AFM. The results show that Cl− ions enter the bilayer structure of the surface oxide already formed in the native oxide-covered initial surface state at concentrations below the detection limit of XPS (<0.5 at%), mostly in the hydroxide outer layer where Fe(III) and Mo(IV,VI) species are concentrated but barely in the oxide inner layer enriched in Cr(III). Their main effect is to produce a less resistive passive state by poisoning dehydroxylation and further Cr(III) and Mo(IV,VI) enrichments obtained in the absence of chlorides. This detrimental effect can be suppressed by pre-passivation in a Cl−-free electrolyte, which blocks the entry of chlorides in the passive film, including in the outer exchange layer, and enables the beneficial aging-induced variations of the composition to take place despite the presence of chlorides in the environment. [ABSTRACT FROM AUTHOR]