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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., (© 2013.)

Contemporary aspects of corrosion science are reviewed to show how insightful a surface science approach is to understand the mechanisms of corrosion initiation at the atomic and nanometric scales. The review covers experimental approaches using advanced surface analytical techniques applied to single-crystal surfaces of metal and alloys exposed to corrosive aqueous environments in well-controlled conditions and analysed in situ under electrochemical control and/or ex situ by scanning tunneling microscopy/spectroscopy, atomic force microscopy and X-ray diffraction. Complementary theoretical approaches based on atomistic modeling are also covered. The discussed aspects include the metal-water interfacial structure and the surface reconstruction induced by hydroxide adsorption and formation of 2D (hyd)oxide precursors, the structure alterations accompanying anodic dissolution processes of metals without or with 2D protective layers and selective dissolution (i.e. dealloying) of alloys, the atomic structure, orientation and surface hydroxylation of ultrathin passive films, the role of step edges at the exposed surface of oxide grains on the dissolution of passive films and the effect of grain boundaries in polycrystalline passive films acting as preferential sites of passivity breakdown, the differences in local electronic properties measured at passive films grain boundaries, and the structure of adlayers of organic inhibitor molecules. [ABSTRACT FROM AUTHOR]

We modelled with Density Functional Theory (DFT) an Al-Cu alloy covered with a passive film, with several Cu concentrations (from the limit of the isolated atom to the monolayer) at the interface with the oxide, as well as Guinier-Preston 1 (GP1) zones. At low (respectively high) concentration, Cu segregates in the first (respectively second) metal layer underneath the passive film. The Cu monolayer is the most stable configuration (-0.37 eV/Cu atom). GP1 zones were modelled, with a three-copper atom cluster in the alloy. The GP1 zone is slightly favoured with respect to the Cu monolayer under the oxide film. A low (respectively high) Cu concentration induces an electronic workfunction increase (respectively decrease) by 0.3 eV (respectively -0.4 to -0.6 eV) as compared to pure Al. In contrast, without oxide, Cu segregation at the Al surface induces no workfunction change at low concentration and an increase of 0.3 eV of the workfunction at high concentration. Thus, the presence of oxide modifies the expected tendency of workfunction increase by adding a more noble metal. For the studied models, no spontaneous electron transfer occurs to the O2 molecule. [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]

Atomic layer deposited (ALD) 50 nm Al xTa yO z mixture coatings are grown on steel for corrosion protection. In morphological and compositional analyses the coatings are found to be uniform, conformal, well-adhered, and low in defect density. Corrosion protection properties are evaluated with polarization measurements and neutral salt spray (NSS) testing. The sealing properties of the mixtures improve with increasing aluminum oxide content, whereas the protection durability improves with increasing tantalum oxide content. In comparison to single-layer and nano-laminate ALD Al2O3 and Ta2O5 coatings, all mixtures are found to have better protective properties. [ABSTRACT FROM AUTHOR]

Abstract: The nanometer scale chemical and structural aspects of ultrathin oxide passive films providing self-protection against corrosion to metals and alloys in aqueous environments are reviewed. Data on the nucleation and growth of 2D anodic oxide films, details on the atomic structure and nanostructure of 3D passive films, the preferential role of surface step edges in dissolution in the passive state and the preferential role of grain boundaries of the passive films in passivity breakdown are presented. Future perspectives are discussed, and exemplified by new data obtained on the relationship between the nanostructure of oxide passive films and their local electronic properties. Atomistic corrosion modeling by ab initio density functional theory (DFT) is illustrated by the example of interactions of chloride ions with hydroxylated oxide surfaces, including the role of surface step edges. Data obtained on well-defined substrate surfaces with surface analytical techniques are emphasized. [Copyright &y& Elsevier]

Low corrosion protection performances of Trivalent Chromium Process (TCP) coatings with reference to Chromium Conversion Coatings (CCC) deposited on aluminium alloys can be overcome by application of post-treatment processes. This work shows the effect of post-treatment bath (containing hydrogen peroxide and lanthanum salt) on the chemical composition, structure and the corrosion performances of TCP coating deposited on AA 2024-T3 aluminium alloy. Different times of post-treatment bath were applied on the TCP coating and the samples were analyzed by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), X-ray Photoelectron Spectroscopy (XPS) and Glow Discharge-Optical Emission Spectrometry (GD-OES). The ToF-SIMS and GD-OES depth profiles show that the post-treatment time has no influence on the thickness of the TCP coating and on its bi-layered structure. It is composed of an outer layer, rich in zirconium and chromium oxides and an inner layer rich in aluminium oxides and oxy-fluorides. 3D ToF-SIMS images reveal an enrichment of Cr and Zr-like species over the surface of intermetallic particles with reference to alloy matrix, whereas a homogenous distribution of La is observed. The analysis of in-depth distribution shows that La is present principally in the outer part of the TCP coating. The La concentration increases with increasing post-treatment time. The effect of post-treatment time on protection was evaluated by Electrochemical Impedance Spectroscopy (EIS) and Linear Sweep Voltammetry (LSV) in a 0.001 M NaCl + 0.1 M Na 2 SO 4 electrolyte. The increased post-treatment time enhances the cathodic inhibition against oxygen reduction. The post-treatment provides improved coating homogeneity and sealing properties. • No thickness and structure modification of TCP coating induced by post-treatment • Significant inhibition of the cathodic oxygen reduction induced by post-treatment • Increase of La and decrease of Cr in TCP with higher post-treatment time • Homogenous surface distribution of La responsible for sealing coating defects [ABSTRACT FROM AUTHOR]

The effects of surface pretreatments (degreasing and pickling) on the characteristics of the Trivalent Chromium Process (TCP) coating on pure aluminum and on AA2024-T351 aluminum alloy were investigated here by means of surface sensitive techniques: X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The XPS and ToF-SIMS results evidence that the TCP coating homogeneity is strongly dependent on the pretreatment process used. The TCP coverage factor, calculated from XPS results, is significantly lower, on both pure aluminum and AA2024-T351 alloy surface, when a pickling step is applied. One of the main effects of pickling pretreatment is strong metallic copper enrichment at the surface of the 2024 alloy, associated with chemical dissolution of Al-Cu intermetallic particles. However, it is evidenced here, that the copper enrichment is not detrimental for the quality of the TCP coating. The coating failure, observed when the pickling step is applied, can be assigned to a faster kinetics of the coating growth leading to formation of thicker conversion coating more susceptible to cracking or to the localized presence of aluminum fluoride species leading to the appearance of coating defects or detachment. [ABSTRACT FROM AUTHOR]

Surface smoothening by substrate annealing was studied as a pre-treatment for improving the corrosion protection provided to copper by 10, 20 and 50 nm thick alumina coatings deposited by atomic layer deposition. The interplay between substrate surface state and deposited film thickness for controlling the corrosion protection provided by ultrathin barrier films is demonstrated. Pre-annealing at 750 °C heals out the dispersed surface heterogeneities left by electropolishing and reduces the surface roughness to less than 2 nm independently of the deposited film thickness. For 10 nm coatings, substrate surface smoothening promotes the corrosion resistance. However, for 20 and 50 nm coatings, it is detrimental to the corrosion protection due to local detachment of the deposited films. The weaker adherence of the thicker coatings is assigned to the stresses accumulated in the films with increasing deposited thickness. Healing out the local heterogeneities on the substrate surface diminishes the interfacial strength that is bearing the stresses of the deposited films, thereby increasing adhesion failure for the thicker films. Pitting corrosion occurs at the local sites of adhesion failure. Intergranular corrosion occurs at the initially well coated substrate grain boundaries because of the growth of a more defective and permeable coating at grain boundaries. [ABSTRACT FROM AUTHOR]

Sublayers grown with filtered cathodic arc deposition (FCAD) were added under atomic layer deposited (ALD) oxide coatings for interface control and improved corrosion protection of low alloy steel. The FCAD sublayer was either Ta:O or Cr:O-Ta:O nanolaminate, and the ALD layer was Al2O3-Ta2O5 nanolaminate, AlxTayOz mixture or graded mixture. The total thicknesses of the FCAD/ALD duplex coatings were between 65 and 120 nm. Thorough analysis of the coatings was conducted to gain insight into the influence of the FCAD sublayer on the overall coating performance. Similar characteristics as with single FCAD and ALD coatings on steel were found in the morphology and composition of the duplex coatings. However, the FCAD process allowed better control of the interface with the steel by reducing the native oxide and preventing its regrowth during the initial stages of the ALD process. Residual hydrocarbon impurities were buried in the interface between the FCAD layer and steel. This enabled growth of ALD layers with improved electrochemical sealing properties, inhibiting the development of localized corrosion by pitting during immersion in acidic NaCl and enhancing durability in neutral salt spray testing. [ABSTRACT FROM AUTHOR]

[Display omitted] • Copolymerization of MAPTMS and acrylate monomer (length 1–12 C atoms) depends on alkyl and perfluoroalkyl chain length. • The presence of the siloxane network increases the thermal conductivity of acrylic coatings. • The coating porosity increases with the increasing length of the acrylate monomer. • Short-chain siloxane-polyacrylic coatings on AA7075-T6 show excellent corrosion resistance in 5 wt% NaCl. • No degradation of coatings was detected by ToF-SIMS and GDOES upon immersion in chloride solution. Siloxane-polyacrylic coatings were synthesized from 3-(trimethoxysilyl)propyl methacrylate, different acrylate derivatives and tetraethyl orthosilicate. Derivatives of different lengths of alkyl and perfluoroalkyl chains were characterized in terms of kinetics of copolymerization during sol synthesis, and of the coatings composition, structure, wettability, thermal properties and porosity using real-time Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, glow discharge optical emission spectroscopy and photothermal beam deflection spectrometry. The siloxane backbones are surrounded by the organic network identified by characteristic fragments. Coatings are homogeneous. The surface water contact angle is between 70° and 85° for the acrylic chains and 90° for the perfluoroalkyl chain. The coatings thermal conductivity is ca. 0.3 W/m⋅K. The porosity of the coatings increases with the length of the acrylate derivative. Long-term corrosion protection of the coatings deposited on aluminium alloy AA7075-T6 was analysed using electrochemical impedance spectroscopy in 5 wt% NaCl and salt spray chamber test. The coatings containing ethyl and butyl derivatives have superior corrosion resistance accompanied by low porosity compared to long-chain derivatives. A special emphasis was given to the possibility to follow the degradation of these sol–gel coatings upon immersion in chloride solution by surface analytical tools. [ABSTRACT FROM AUTHOR]

Abstract: The effect of H2–Ar plasma pre-treatment prior to thermal atomic layer deposition (ALD) and plasma-enhanced atomic layer deposition (PEALD) of Al2O3 films on steel for corrosion protection was investigated. Time-of-flight secondary ion mass spectrometry and transmission electron microscopy were used to observe the changes in the interface. The electrochemical properties of the samples were studied with polarization measurements, and the coating porosities were calculated from the polarization results for easier comparison of the coatings. Prior to thermal ALD the plasma pre-treatment was observed to reduce the amount of impurities at the interface and coating porosity by 1–3 orders of magnitude. The anti-corrosion properties of the PEALD coatings could also be improved by the pre-treatment. However, exposure of the pre-treatment plasma activated steel surface to oxygen plasma species in PEALD led to facile oxide layer formation in the interface. The oxide layer formed this way was thicker than the native oxide layer and appeared to be detrimental to the protective properties of the coating. The best performance for PEALD Al2O3 coatings was achieved when, after the plasma pre-treatment, the surface was given time to regrow a thin protective interfacial oxide prior to exposure to the oxygen plasma. The different effects that thermal and plasma-enhanced ALD have on the substrate-coating interface were compared. The reactivity of the oxygen precursor was shown to have a significant influence on substrate surface in the early stages of film growth and thereafter also on the overall quality of the protective film. [Copyright &y& Elsevier]

Abstract: A comparative study by Time-of-Flight Secondary Ions Mass Spectrometry and X-ray Photoelectron Spectroscopy, i–E polarization curves and Electrochemical Impedance Spectroscopy of the corrosion protection of low alloy steel by 50nm thick tantalum oxide coatings prepared by low temperature Atomic Layer Deposition (ALD) and Filtered Cathodic Arc Deposition (FCAD) is reported. The data evidence the presence of a spurious oxide layer mostly consisting of iron grown by transient thermal oxidation at the ALD film/substrate interface in the initial stages of deposition and its suppression by pre-treatment in the FCAD process. Carbonaceous contamination (organic and carbidic) resulting from incomplete removal of the organic precursor is the major cause of the poorer sealing properties of the ALD film. No coating dissolution is demonstrated in neutral or acid 0.2M NaCl solutions. In acid solution localized corrosion by pitting proceeds faster with the ALD than with the FCAD coating. The roles of the pre-existing channel defects exposing the substrate surface and of the spurious interfacial oxide promoting coating breakdown and/or delamination are emphasized. [Copyright &y& Elsevier]

Besides their noteworthy tribological and corrosion protection properties, Plasma Electrolytic Oxidation (PEO) coatings feature a porous microstructure that is able to host corrosion inhibitors. This study reveals that although 2,5pyridindicarboxylate (2,5PDC) shows a remarkable corrosion inhibition effect for bare AZ21 Mg alloy, it can extensively deteriorate a PEO coating on the same Mg substrate, resulting in an overall accelerated failure of the PEO-coated AZ21 alloy. The deteriorative behavior of 2,5PDC towards PEO-coated AZ21 is explained based on the characterization of the bare and PEO-coated AZ21 exposed to the NaCl electrolyte with and without inhibitor using EIS, SEM, STEM and ToF-SIMS. • 2,5PDC could effectively inhibit the corrosion of AZ21 in 3.5 wt% NaCl. • 2,5PDC could accelerate the degradation of AZ21 coated with the phosphate-based PEO. • The inhibition/adverse effect of 2,5PDC on bare/coated AZ21 is intensified with its concentration. • Formation of a soluble complex between Mg2+ and 2,5PDC destabilizes the PEO layer. • Formation of a relatively thick corrosion layer on AZ21 accelerates the failure of PEO coating. [ABSTRACT FROM AUTHOR]

• Adsorption of MBT corrosion inhibitor studied at atomic scale on oxidized copper. • DFT modelling performed on Cu(111) covered by ultrathin Cu 2 O(111) film. • Strong covalent bonding between exo cyclic sulfur atom and under coordinated Cu site. • Saturation monolayer coverage favored over single molecular low coverage adsorption. • Protective layer formed by substituting surface H 2 O and OH in aqueous environment. 2-mercaptobenzothiazole (MBT) is known as an efficient corrosion inhibitor for copper. In the present work, we performed quantum chemical DFT calculations of the interaction of MBT on Cu(111) surfaces covered by an ultrathin Cu 2 O(111) film, in order to bring atomic scale insight on the corrosion inhibition properties of MBT on oxidized copper surfaces. Thione and thiolate forms of MBT are found to interact strongly with the oxidized surfaces. The formation of a monolayer at full coverage is favored over single molecular adsorption at low coverage with the molecules adopting a perpendicular orientation. Thione binds strongly via covalent bonding between the exocyclic sulfur atom and the under coordinated Cu site, and additional H-bonding between the NH group and surface oxygen atoms (NH...O H-bond). Thiolate binds more strongly via a second covalent bond between the N atom and saturated Cu site. Bonding interaction is confirmed by the electronic structure analysis and charge transfer. The adsorption process leads to the reconstruction of the topmost oxide surface. The calculations suggest that both forms of MBT may substitute H 2 O and OH at the Cu 2 O film surface, and thus may form a protective layer on oxidized copper surfaces in aqueous environment. [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]