Cathodic driven coating delamination suppressed by inhibition of cation migration along Zn|polymer interface in atmospheric CO2

International audienceThe degradation of the Zn|polymer interface is inhibited by CO 2 gas in a humid environment. The inhibition mechanism varies greatly for different polymer matrices and depends on the affinity of the polymer to CO 2. Coatings based on polymers with high affinity to CO 2 such as polyacrylamide show high delamination rates due to the fast uptake of water. In this case, the cation transport that causes the initial pull down of potential for initiating the oxygen reduction reaction occurs via the polymer. Here CO 2 decreases water uptake due to competitive absorption into the polymer matrix, inhibiting the delamination rate. CO 2 can quickly reach the interface of polymers with functional groups with a low affinity to water and CO 2 , such as polyvinyl butyral and polyvinyl alcohol. In this case, the inhibition of the delamination rate is achieved by a strong decrease in cation migration rate at the Zn| polymer interface accompanied by the formation of mixed hydrozincite/absorbed CO 2 layers on the ZnO surface underneath the polymers. Further experiments showed that the presence of CO 2 accelerates anion migration, suggesting an influence of CO 2 on the surface charge at the Zn|coating interface, thus affecting ion migration. Inhibition of cation migration has never been reported before and should be taken into account into the mechanism of cathodic-driven delamination on Zn under atmospheric conditions

Nanoscale electrochemical mapping

Surfaces and interfaces, of both practical and fundamental interest, have long been recognized to be complex, yet while there are many microscopy and spectroscopy methods for imaging structure, topography and surface chemical composition at high spatial resolution, there are relatively few techniques for mapping associated chemical fluxes in the near-interface region. In this regard, scanning electrochemical probe microscopy (SEPM), which utilizes a small scale electrode probe as an imaging device, has had a unique place in the scanning probe microscopy (SPM) family of techniques, in being able to map chemical fluxes and interfacial reactivity. For a long time, techniques such as scanning electrochemical microscopy (SECM) were largely stuck at the micron –or larger –scale in terms of spatial resolution, but recent years have seen spectacular progress, such that a variety of different types of SEPM technique are now available and 10sof nm spatial resolution is becoming increasingly accessible. This step-change in capability is opening many new opportunities for the characterization of flux processes and interfacial activity in a whole raft of systems, including electrode surfaces, electromaterials, soft matter, living cells and tissues

Nanoscale electrochemical visualization of grain-dependent anodic iron dissolution from low carbon steel

The properties of steels and other alloys are often tailored to suit specific applications through the manipulation of microstructure (e.g., grain structure). Such microscopic heterogeneities are also known to modulate corrosion susceptibility/resistance, but the exact dependency remains unclear, largely due to the challenge of probing and correlating local electrochemistry and structure at complex (alloy) surfaces. Herein, high-resolution scanning electrochemical cell microscopy (SECCM) is employed to perform spatially-resolved potentiodynamic polarisation measurements, which, when correlated to co-located structural information from electron backscatter diffraction (EBSD), analytical scanning electron microscopy (SEM) and scanning transmission electron microscopy (STEM), reveal the relationship between anodic metal (iron) dissolution and the crystallographic orientation of low carbon steel in aqueous sulfuric acid (pH 2.3). Considering hundreds of individual measurements made on each of the low-index planes of body-centred cubic (bcc) low carbon steel, the rate of iron dissolution, and thus overall corrosion susceptibility, increases in the order (101) < (111) < (100). These results are rationalized by complementary density functional theory (DFT) calculations, where the experimental rate of iron dissolution correlates with the energy required to remove (and ionise) one iron atom at the surface of a lattice, calculated for each low index orientation. Overall, this study further demonstrates how nanometre-resolved electrochemical techniques such as SECCM can be effectively utilised to vastly improve the understanding of structure-function in corrosion science, particularly when combined with complementary, co-located structural characterisation (EBSD, STEM etc.) and computational analysis (DFT)

Screening the surface structure-dependent action of a benzotriazole derivative on copper electrochemistry in a triple-phase nanoscale environment

Copper (Cu) corrosion is a compelling problem in the automotive sector and in oil refinery and transport, where it is mainly caused by the action of acidic aqueous droplets dispersed in an oil phase. Corrosion inhibitors, such as benzotriazole (BTAH) and its derivatives, are widely used to limit such corrosion processes. The efficacy of corrosion inhibitors is expected to be dependent on the surface crystallography of metals exposed to the corrosion environment. Yet, studies of the effect of additives at the local level of the surface crystallographic structure of polycrystalline metals are challenging, particularly lacking for the triple-phase corrosion problem (metal/aqueous/oil). To address this issue, scanning electrochemical cell microscopy (SECCM), is used in an acidic nanodroplet meniscus|oil layer|polycrystalline Cu configuration to explore the grain-dependent influence of an oil soluble BTAH derivative (BTA-R) on Cu electrochemistry within the confines of a local aqueous nanoprobe. Electrochemical maps, collected in the voltammetric mode at an array of >1000 points across the Cu surface, reveal both cathodic (mainly the oxygen reduction reaction) and anodic (Cu electrooxidation) processes, of relevance to corrosion, as a function of the local crystallographic structure, deduced with co-located electron backscatter diffraction (EBSD). BTA-R is active on the whole spectrum of crystallographic orientations analyzed, but there is a complex grain-dependent action, distinct for oxygen reduction and Cu oxidation. The methodology pinpoints the surface structural motifs that facilitate corrosion-related processes and where BTA-R works most efficiently. Combined SECCM–EBSD provides a detailed screen of a spectrum of surface sites, and the results should inform future modeling studies, ultimately contributing to a better inhibitor design

L'inhibition de la corrosion d'un galvanisé par des agents encapsulés dans des hydroxydes doubles lamellaires (HDL) : méchanismes de lixiviation et réactions de corrosion

The current work was dedicated to the investigation of the fundamental mechanisms of the action of a layered double hydroxide (LDH) inhibitor hybrid coated systems for the corrosion protection of galvanized steel. The objective of the work was achieved by the realization of three milestones: (1) the identification of the effective water soluble inhibitor on Zn and steel substrates and the understanding the mechanisms of its action, (2) the revealing the factors and mechanisms controlling the release of the selected inhibitor from Zn2Al/-LDH hosts and (3) the understanding the mechanisms of coated system controlled by inhibitor release and its action. MoO42- showed the best inhibition efficiency comparable to CrO42- in alkaline and neutral solutions. The protective properties of MoO42- were assigned to the fast formation of Mo(V) film. The effect of MoO42- on the dissolution of low carbon steel was also verified to exclude the possible accelerating effect of chosen species. The leaching tests showed that MoO42- release from LDH was controlled by the nature of the exchanged ions from the media by ion-exchange mechanism at neutral pH and by the dissolution of the LDH framework at alkaline pH. The presence of only Cl- resulted in less than 40 % of MoO42- release after 24 hours of the immersion while the additions of the carbonates resulted in 100 % release after 1 hour. The immersion tests showed slight inhibiting effect of coated system in Cl and high in CO32- medias coherent with higher level of MoO¬42- released. The ways to control the inhibitor release and hence, the inhibition performance of coated systems were discussed in the vein of environment composition.Le travail présenté essaie de comprendre les mécanismes de l’action d’un inhibiteur de corrosion présent dans un revêtement hybride sous forme de pigments intercalés dans les hydroxydes double lamellaires (HDL) pour la protection de l’acier galvanisé. Trois étapes clés ont été choisies pour ce travail : (1) l’identification d’un inhibiteur de corrosion hydrosoluble pour l’acier galvanisé avec une compréhension de sa réactivité, (2) la détermination des facteurs et des mécanismes contrôlant la libération de l’inhibiteur à partir d’HDL et (3) la compréhension des mécanismes de protection dans un système modèle avec le revêtement hybride contrôlé par la libération de l’inhibiteur et la réactivité d’inhibiteur. MoO42- a montré la meilleure efficacité d'inhibition comparable à CrO42- dans des solutions alcalines et neutres. L’effet inhibiteur de MoO42- a été associé à la formation d’un film riche en Mo(V). L'effet de cet anion sur la dissolution de l'acier à bas carbone a été également vérifié pour exclure la possibilité d'un effet d'accélération des espèces choisies. Les tests de lixiviation ont montré que la libération de MoO42- à partir d’HDL a été contrôlée par la nature des ions échangés à partir du support par un mécanisme d'échange d'ions à un pH neutre et par la dissolution du cadre de la LDH à un pH alcalin. La présence de seulement Cl- conduit à moins de 40% de libération de MoO42- après 24 h d'immersion alors que les additions des carbonates ont abouti à libération de 100% après 1 h. Les tests d'immersion ont montré léger effet d'inhibition du système de revêtement dans Cl- et une augmentation dans CO32- en accords avec le niveau plus élevé de MoO42- libéré

Reflective microscopy for mechanistic insights in corrosion research

Reflective microscopy (RM) is a robust, label free optical imaging technique that allows fast operando measurements of structural changes on metal interfaces at nanoscale in a wide field. Based on the analysis of the reflected light, RM can be simply understood as “video camera” to produce optical photographs of studied interfaces and thus, it has been used for many years as a complementary tool for the visual inspection. However, recent developments in the optical models and refining the experimental design provided means for the quantitative conversion of reflected light intensities into the variations in roughness, thickness of surface films, chemical composition etc., all indispensable for the surface sciences. This review highlights recent advances and contemporary challenges in the methodological developments of RM specifically tailored for the corrosion research

Key Requirements for Advancing Machine Learning Approaches in Single Entity Electrochemistry

Despite the noteworthy progress in Single Entity Electrochemistry (SEE) in the last decade, the field still must undergo further advancements to attain the requisite maturity for facilitating and propelling machine learning (ML)-based discoveries. This mini-review presents an analysis of the required developments in the domain, using the success of AlphaFold in biology as a benchmark for future progress. The first essential requirement is the creation and support of high-quality, centralized, and open-access databases on the electrochemical properties of single entities. This should be facilitated through the automation and standardization of experiments, promoting high-throughput output and facilitating comparison between datasets. Finally, the creation of a new type of interdisciplinary specialist, trained to pinpoint critical issues in SEE and implement solutions from applied informatics, is vital for ML approaches to flourish in the SEE field

Is Unsupervised Dimensionality Reduction Sufficient to Decode the Complexities of Electrochemical Impedance Spectra?

As electrochemical research undergoes rapid technological progression, the acquisition of substantial amounts of electrochemical impedance spectra (EIS) becomes increasingly feasible. Yet, this advancement introduces intricate challenges in data processing, automation, and interpretation. This paper delves into the sufficiency of unsupervised machine learning (ML) and in particular dimensionality reduction methods in decoding EIS complexities, examining its strengths, limitations, and potential pathways for optimization. As we navigated the intricacies of non-linear dimensionality reduction, spotlighting t-distributed stochastic neighbor embedding (t-SNE) and uniform manifold approximation and projection (UMAP) algorithms, a pattern emerged: these techniques excel at categorizing divergent impedance spectra but show limitations when faced with analogous circuit configurations, especially those substituting a capacitor with a constant phase element. This observation not only underscores a limitation but also accentuates that unsupervised ML approaches, alone, may not fully unravel the nuances of EIS spectra. In the concluding section of our manuscript, we discuss the implications of this finding from a practical standpoint, particularly for electrochemists seeking to apply these methods in their work