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Three-dimensional (3D) time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging is a promising tool in the analysis of surface modifications of alloy matrix and intermetallic particles induced by localized corrosion due to its good spatial resolution and very high sensitivity to chemical identification especially involving light mass elements like Li. In this paper, ToF-SIMS 3D chemical mapping combined with scanning electron microscopy was performed to study the localized corrosion of Al-Cu-Li alloy (AA2050-T8) in a region around an Al-Cu-Fe-Mn intermetallic particles (IMPs) in 0. 1 M NaCl solution. Initiation of corrosion was locally observed on the IMPs and between IMPs and matrix substrate. Moreover, a modified oxide/hydroxide layer was observed over IMPs compared to the matrix. This new corrosion layer was enriched with chlorides and Cu hydroxides. ToF-SIMS 3D imaging revealed that Li was present over the alloy matrix, while no Li was present over the IMPs in regions where localized corrosion occurred. [ABSTRACT FROM AUTHOR]

To elucidate the role of noble metal impurities on corrosion of Mg, 3D time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging in combination with X-ray photoelectron spectroscopy and optical microscopy measurements were carried out on Mg samples (99.9%) before and after Mg polarization at EOCP+0.5 V in 0.1 M NaCl. A significant segregation of Fe (and of Mn and Al) metallic impurities at grain boundaries (GBs) was observed on the Mg surface by 3D ToF-SIMS. A 3-step mechanism of Mg corrosion was proposed, including a catalytic effect of Fe segregated at the GBs on the hydrogen evolution reaction (HER). In the 1st stage, the initiation of Mg corrosion is accompanied by the HER occurring over Fe impurities segregated at GBs leading to formation of small circular defects and propagation with occurrence of dark filiform-like pattern corrosion enriched in Cl-. In the 2nd stage, segregated Fe metallic particles are released by Mg matrix undermining, and are dissolved into Fe2+ ions and in the 3rd stage a redeposition of Fe in the clear areas of Mg surfaces, corresponding to areas with low concentration of Cl-, takes place. [ABSTRACT FROM AUTHOR]

The effects of post-treatment applied on Trivalent Chromium Protection (TCP) coatings deposited on aluminum alloy 2024-T3 was studied by electrochemical and surface analytical techniques: X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The aim of the post-treatment was to improve the corrosion resistance of the TCP coating. To understand the influence of the post-treatment, using a bath containing H2O2 and a lanthanum salt as an inhibitor, our approach was to study the effect of these two components separately. It was found that the improved corrosion protection provided by the post-treated TCP was related to a synergetic effect of the two components. XPS and ToF-SIMS analyses showed that (i) the thickness of the TCP coating is not modified by the post-treatment, (ii) lanthanum is present on the surface and in the bulk of the TCP and (iii) is found in very small amount only on the extreme surface. The total concentration of Cr(VI) (oxide/hydroxide) was estimated to be below 0.1 wt% in the post-treated TCP layer. It was concluded that lanthanum plays a significant role in improving the coating density and homogeneity and has a beneficial effect on the TCP coating cracking as observed by Scanning Electron Microscopy. [ABSTRACT FROM AUTHOR]

Corrosion protection by ultra-thin (< 50 nm) alumina films deposited by atomic layer deposition (ALD) on copper at 250°C was studied in 0.5 M NaCl aqueous solution by combining electrochemical and surface analytical methods. Time-of-Flight Secondary Ion Mass Spectrometry revealed a homogenous in-depth stoichiometry of the alumina coatings and their residual bulk contamination by organic and water precursor fragments. Trace contamination by a spurious Cu oxide was evidenced at the interface with the Cu substrate despite a reducing pre-treatment. Atomic force microscopy images revealed conformal substrate coverage and a granularlike coating morphology at the nanometer scale. Linear Sweep Voltammetry (LSV) and Electrochemical Impedance Spectroscopy (EIS) showed no electrochemical activity of the coating and a corrosion decrease reaching 4 orders of magnitude for coated samples in comparison with bare copper. Uncoated surface fraction was quantified by application of three different methods using the LSV and EIS data which led to results in excellent agreement. The uncoated surface fraction for 50 nm Al2O3 layers was ~0.01%, confirming ALD alumina as an excellent coating for corrosion protection with spectacularly low residual corrosion activity restricted to the bottom of channel defects connecting the substrate to environment through the coating. [ABSTRACT FROM AUTHOR]

Silicate glasses are durable solids, and yet they are chemically unstable in contact with aqueous fluids-this has important implications for numerous industrial applications related to the corrosion resistance of glasses, or the biogeochemical weathering of volcanic glasses in seawater. The aqueous dissolution of synthetic and natural glasses results in the formation of a hydrated, cation-depleted near-surface alteration zone and, depending on alteration conditions, secondary crystalline phases on the surface. The long-standing accepted model of glass corrosion is based on diffusion-coupled hydration and selective cation release, producing a surface-altered zone. However, using a combination of advanced atomic-resolution analytical techniques, our data for the first time reveal that the structural and chemical interface between the pristine glass and altered zone is always extremely sharp, with gradients in the nanometre to sub-nanometre range. These findings support a new corrosion mechanism, interfacial dissolution-reprecipitation. Moreover, they also highlight the importance of using analytical methods with very high spatial and mass resolution for deciphering the nanometre-scale processes controlling corrosion. Our findings provide evidence that interfacial dissolution-reprecipitation may be a universal reaction mechanism that controls both silicate glass corrosion and mineral weathering. [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]

Atomic layer deposited (ALD) aluminum and tantalum oxide (Al2O3 and Ta2O5) and their nanolaminates were applied as corrosion protection coatings on AISI 52100 steel. The aim was to combine the good sealing properties of Al2O3 with the chemical stability of Ta2O5 and to optimize the coating architecture in order to obtain the best possible long-term durability. Coating composition and morphology were studied with time-of-flight elastic recoil detection analysis (ToF-ERDA), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectrometry (EDS). Electrochemical properties were studied with voltammetry and electrochemical impedance spectroscopy (EIS), and corrosion durability with neutral salt spray (NSS) testing. The coatings were observed to be conformal and uniform over rough surfaces, and contained some carbon and hydrogen as impurities. The electrochemical results showed that the Al2O3 coating had superior sealing properties compared to the Ta2O5 coating, and nanolaminates had properties in between those of Al2O3 and Ta2O5. However, in the NSS test the laminate-coated samples survived the best demonstrating long-term durability. Analysis of the laminate structure showed that for 40 and 80 nm laminates the best protection was achieved with 10 and 20 nm layers, respectively. [ABSTRACT FROM AUTHOR]

Abstract: Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) was used to examine the film formed on pure magnesium by immersion for 2min in ultra pure water. The ToF-SIMS data indicates that there is magnesium hydride within the surface film. The presence of MgH2 is a result of the Mg corrosion mechanism. [Copyright &y& Elsevier]

Abstract: The structural modifications of Ni(111) single-crystal surfaces induced by prolonged polarization at the onset of the active/passive transition have been studied at the (sub-)nanometer scale by in situ electrochemical STM (EC-STM) in 0.1M NaOH(aq). The results evidence the effect of the structural order in the passivating monolayer on the corrosion resistance properties and the initiation of localized corrosion. 2D pits are initiated by dissolution on the terraces covered by disordered islands of nickel hydroxide particles and at the boundaries of the crystalline Ni(OH)2(0001) islands. The pits propagate preferentially in the disordered areas. Dissolution is blocked in the well-ordered islands of the passivating monolayer and by the 3D nuclei of the passive film formed at the pre-existing step edges of the nickel substrate. This competitive mechanism of dissolution and passivation, repeated on the terraces newly formed by local dissolution, initiates the growth of 3D pits of nanometer dimensions, i.e. localized corrosion at the nanoscale. A tip effect, promoting the dissolution reaction by a mechanical and/or chemical interaction with the passivating particles, contributed to reveal these local properties. This fundamental understanding of the depassivation/repassivation at the nanoscale opens the way to the search for functional surfaces with self-repair properties. [Copyright &y& Elsevier]

• 5-sulfosalicylate as an inhibitor in 0.6 M NaCl electrolyte is used for Mg-air battery. • Upon the inhibitor application the improved discharge voltage and battery lifetime are observed. • Almost a four-fold reduction of the hydrogen evolution and a reduced Mg corrosion are noticed. • A modified structure and composition of the surface layer is observed. This work aims at employing sodium 5-sulfosalicylate (5-S-Sal) corrosion inhibitor into aqueous NaCl electrolyte to improve the discharge performance of Mg-air battery and decrease the side reactions of Mg anode. The corrosion tests at open circuit potential show a four-fold decrease of hydrogen evolution when 5-S-Sal inhibitor is added. X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry analyses show that due to the presence of 5-S-Sal inhibitor, a corrosion resistant layer has a lower quantity of Mg(OH) 2 (by ∼15%) than that formed in NaCl electrolyte. The surface enrichment in S-like species originating from inhibitor molecule could have an important effect on a decreased corrosion and slow down the H 2 evolution. Within a range of concentrations of 5-S-Sal in NaCl electrolyte (0.05 to 0.15 M), the best discharge performances are achieved with 0.1 M inhibitor. The discharge voltage of full Mg-air battery improves from ∼1.58 to ∼1.82 V at 0.5 mA/cm2 and the discharge lifetime is extended from around 12.5 to around 80 h. Scanning electron microscopy and 3D topography laser microscopy indicate that during the discharge tests much smaller surface degradation occurs and a more uniform surface layer is formed in the presence of inhibitor in the NaCl-based electrolyte. [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]

Electrochemical and surface analyses were applied to study the corrosion mechanisms of aluminium protected by ultra-thin (≤50 nm) alumina coatings grown by atomic layer deposition. Corrosion takes place via residual channel defects connecting the substrate to the electrolyte through the insulating coating. The data evidence the growth of a spurious aluminium oxide film at the substrate/coating interface in the reactor, that is beneficial to the sealing performance of the thinner films (10 nm). The resistance to the initiation of localized corrosion by pitting is increased with thicker films (20 and 50 nm) owing to improved sealing and barrier properties. [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]

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]

Highlights: [•] 40–50nm mixed alumina–tantala coatings were grown by atomic layer deposition. [•] Effects of substrate surface finish and oxide mix were analysed. [•] Nanolaminate stacks are better resistant to breakdown. [•] Localised corrosion occurs at pre-existing coating defects exposing substrate sites. [•] Substrate brushing and H2–Ar plasma pre-treatment hinder pit initiation. [Copyright &y& Elsevier]

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: Combined analysis by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), X-ray Photoelectron Spectroscopy (XPS), polarization curves and Electrochemical Impedance Spectroscopy (EIS) of the relation between chemical architecture of thin (10 and 50nm) chromium and tantalum oxide coatings grown by filtered cathodic arc deposition (FCAD) on carbon steel and their corrosion protection properties is reported. Pre-etching in the deposition process allows reducing the substrate native oxide layer to traces of iron oxide. A carbidic interlayer is then formed by reaction between the first deposited metallic particles and the residual carbon surface contamination of the alloy. The bulk coatings mostly consist of Cr2O3 or Ta2O5 with no in-depth variation of the stoichiometry. Surface and bulk of the coatings are contaminated by hydroxyl and organic groups. The 50nm coating has a relatively large porosity assigned to a columnar growth preventing good sealing at grain boundaries. The duplex structure (Ta/Ta–C) of the carbidic interlayer promotes a less defective growth of tantalum oxide than the single Cr–C interlayer for chromium oxide, thereby improving the sealing properties. The dielectric constants suggest poor insulating properties in line with a defective and porous nanostructure of the coatings. No dissolution was observed for both oxide nanocoatings in neutral 0.2M NaCl. Penetration of the electrolyte and access to the interface with the carbon steel surface cause the dissolution of the Cr–C interlayer, but not that of the Ta/Ta–C interlayer, and a more rapid initiation of localized corrosion. [Copyright &y& Elsevier]

Abstract: Combined analysis by electrochemical impedance spectroscopy (EIS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and field emission scanning electron microscopy (FESEM) of the corrosion protection provided to carbon steel by thin (50nm) Al2O3 coatings grown by atomic layer deposition (ALD) and its failure mechanism is reported. In spite of excellent sealing properties, the results show an average dissolution rate of the alumina coating of ∼7nmh−1 in neutral 0.2M NaCl and increasing porosity of the remaining layers with increasing immersion time. Alumina dissolution is triggered by the penetration of the solution via cracks/pinholes through the coating to the substrate surface where oxygen reduction takes place, raising the pH. At defective substrate surface sites of high aspect ratio and concentrated residual mechanical stress (along scratches) presumably exposing a higher steel surface fraction, localized dissolution of the coating is promoted by a more facile access of the solution to the substrate surface enhancing oxygen reduction. De-adhesion of the coating is also promoted in these sites by the ingress of the anodic dissolution trenching the steel surface. Localized corrosion of the alloy (i.e. pitting) is triggered prior to complete dissolution of the alumina film on the elsewhere still coated surface matrix. [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]