Depletion depths of inorganic components from a scribe edge in a polyurethane primer containing Li2CO3, MgO, BaSO4 and TiO2 beneath a topcoat, were determined using a range of techniques including SEM/EDS and proton induced X-ray and γ-ray emission spectroscopies. SEM of sections cut using an ion beam revealed scribe damage penetrating 20–25 μm away from the scribe edge prior to leaching. After neutral salt spray (NSS) exposure a leached zone developing from the scribe edge was observed. For longer NSS exposure times (>96 h) this leached zone of nearly complete Li and Mg depletion did not develop any deeper than the scribe damaged region indicating that the depletion zone was caused by mechanical damage due to scribing. At short times small voids were formed in Li2CO3 particles within the primer well away from the scribe (100–260 μm) whereas a mixture of void and detachment in and around Li2CO3 particles was observed at longer times. The detachment was assumed to be part of a channel network within clusters of particles. Internal stresses within the primer resulting from buildup of inhibitor dissolution product within the voids were modelled using finite element analysis. It was found that strains related to von Mises stresses were concentrated around the inorganic particles and developed preferentially within the plane of the primer beneath the topcoat with some indication of concentration towards the primer/metal interface. These stresses resulted from osmosis and swelling related to the voids. They were also attributed to the observed cracking of the binder at some locations. Leaching experiments showed that Li was released very rapidly from the primer. The leaching data was modelled using a power law where the mass released is proportional to tn where the n is an index that reflects the kinetic behavior dictated by the evolving primer porosity. In this study n values between 0 and 1 were observed for all species, with Li starting at around 0.7 but rapidly decreasing to close to zero.@en

Identifying corrosion initiation events in metals and alloys demands techniques that can provide temporal and spatial resolution simultaneously. Transmission electron microscopy (TEM) enables one to obtain microstructural and chemical descriptors of materials at atomic/nanoscopic level and has been used in corrosion studies of many metal-electrolyte combinations. Conventionally, ex situ and quasi in situ TEM studies of pre- and post-corroded samples were performed, but possible experimental artifacts such as dehydrated surfaces might not fully represent the real interfacial conditions as compared to those when actually immersed in the electrolyte. Recent advances in liquid cell transmission electron microscopy (LC-TEM) allows for in situ monitoring morphological and even compositional evolutions in materials resulting from interaction with gas or liquid environments. Corrosion science, as a challenging field of research, can benefit from this unparalleled opportunity to investigate many complicated corroding systems in aqueous environments at high resolution. However, “real life” corrosion with LC-TEM is still not straightforward in implementation and there are limitations and challenging experimental considerations for conducting reliable examinations. Thus, this study has been devoted to discussing the challenges of in situ LC-TEM wherein state-of-the-art achievements in the field of relevance are reviewed.@en

Studies of Li depletion in sections of a Li 2 CO 3 -primer comprising a polyurethane binder, MgO, TiO 2 , BaSO 4 in addition to Li 2 CO 3, were performed using a combination of particle induced γ-ray and X-ray emission spectroscopies along with SEM/EDS analysis. A mixture of depletion behaviours was observed. At the earliest stages (to around 48 h)initial release was confined to the surface. At longer times (168 h)voids developed deeper into the primer and after 500 h Li 2 CO 3 dissolution was observed at places throughout the thickness of the primer to the metal/primer interface. Microscopic transport pathways formed which involved all large inorganic particles. SEM showed that rupture of the polyurethane matrix contributed to network formation. Finite element analysis indicated that rupture may be due to internal stresses around particles isolated in the polyurethane matrix and associated with water uptake. Thus the transport network seemed to be generated by chemical dissolution at the particle/polymer interface and may be enhanced by mechanical degradation due to internal mechanical stresses. The release kinetics of the Li 2 CO 3 inhibitor from the primer was followed as a function of time and the data analysed according to a release behaviour of t n . There was very rapid initial release of Li followed by a slower release of Mg and to a lesser extent Ba. The value of n varied significant with time, but showed a mixture of Fickian release and direct dissolution for Mg and Ba at intermediate times, but transport through a pore network at longer times. The leaching data was interpreted in terms of local transport networks that developed in the primer with time. @en

In this work, a new finite element modelling (FEM) approach is followed to model spatiotemporally resolved water uptake in organic coatings. To this aim, we start from a physical model, where not only Fickian diffusion of water is taken into account but also the adsorption/desorption reaction of water on the polymer matrix. Starting from a number of important coating properties and crucial model parameters, derived from gravimetric and Fourier transform infrared (FTIR) measurements as the model input, the local water concentration over the coating thickness as a function of time is modelled for a polyethylene glycol diacrylate (PEGDA) coating. The modelled water concentration is then used to calculate virtual capacitance values which are evaluated against experimental capacitance values extracted from impedance measurements. The constraints of the FEM model and ORP-EIS experiments and the discrepancies between them are critically discussed in order to carry out a meaningful model validation, eventually leading to model improvements.@en

For more than six decades, chromic acid anodizing (CAA) has been the central process in the surface pre-treatment of aluminum for adhesively bonded aircraft structures. Unfortunately, this electrolyte contains hexavalent chromium (Cr(VI)), a compound known for its toxicity and carcinogenic properties. To comply with the new strict international regulations, the Cr(VI)-era will soon have to come to an end. Anodizing aluminum in acid electrolytes produces a self-ordered porous oxide layer. Although different acids can be used to create this type of structure, the excellent adhesion and corrosion resistance that is currently achieved by the complete Cr(VI)-based process is not easily matched. This paper provides a critical overview and appraisal of proposed alternatives to CAA, including combinations of multiple anodizing steps, pre- and post anodizing treatments. The work is presented in terms of the modifications to the oxide properties, such as morphological features (e.g., pore size, barrier layer thickness) and surface chemistry, in order to evaluate the link between fundamental principles of adhesion and bond performance.[Figure not available: see fulltext.]@en

The sol–gel process is a chemical surface preparation method based on hydrolysis and polycondensation reactions for enhanced adhesion for metallic substrates in adhesive bonding and coating applications. This paper describes an investigation into the effect of the microstructural complexity of two commonly used aerospace aluminium alloys (AAs) 2024-T3 and 7075-T6, on the response to different surface pre-treatments before deposition of the sol-gel coating and subsequent adhesive bonding. Different surface pre-treatments, including two abrasive treatments and three chemical surface pre-treatments were used, and their effect on surface chemistry, wettability and roughness was assessed. Surfaces were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, profilometry and static contact angles. A hybrid silane sol-gel film was deposited on the differently pre-treated aluminium alloys, an epoxy adhesive was applied and the adhesion properties were evaluated using pull-off testing. The role of the altered physicochemical properties of the pre-treated surfaces was related to the adhesion strength of the sol–gel reinforced epoxy/aluminium interfaces. The microstructural complexity of the aerospace alloys caused non-uniform responses to the pre-treatments, proving the importance of compatibility between material and treatment conditions. Statistical analysis revealed that, despite that overall higher adhesion values were obtained on rougher surfaces, only a strong correlation exists between the surface hydroxyl fraction and adhesion strength. The relation of roughness and water contact angle to interfacial adhesion was found to be non-significant. The findings of this study underscore the critical role of surface pre-treatments and their impact on adhesion strength in aerospace aluminium alloys, providing valuable insights for the effective utilization of sol-gel coatings in adhesive bonding and coating processes.@en

Nanostructured hollow polyaniline (PANI) capsules are good candidates for encapsulation of corrosion inhibitors and pH-responsive release when incorporated into organic coatings. In previous studies, the corrosion protection performance of PANI capsules, containing organic inhibitor 2-Mercaptobenzothiazole (MBT), was demonstrated. The present work studies the influence of capsule concentrations (i.e., 0.3, 1, and 2 wt%) on the corrosion protection properties of the coating system. Anti-corrosion properties of different coatings were compared by means of Electrochemical Impedance Spectroscopy (EIS) and Scanning Vibrating Electrode Technique (SVET). MBT loaded PANI capsules in epoxy ester coating on AA2024-T3 substrate allow for a self-healing effect to be obtained during the corrosion process. The results showed that the concentration of MBT loaded PANI capsules greatly influences the corrosion protection properties of the coatings, and the best corrosion protection performance was observed for the coating system containing 1 wt% PANI capsules. The impedance value of the scratched area of this coating after 7 days of immersion was one order of magnitude higher than that of the control sample.@en

In this work, the correlation between electrolyte transport properties and the variation of pigment volume concentration (PVC) in a series of organic coatings is explored. Using an odd random phase electrochemical impedance spectroscopy (ORP-EIS) approach, the diffusion of ions independent from water take-up is analysed. A higher PVC resulted in a more homogeneous coating morphology, which could be associated with a faster diffusion of ions following a Fickian regime and enhanced water uptake. In the case of lower pigment loading, the obtained heterogenous morphology of the coating introduced new challenges to the physical interpretation of the proposed electrochemical equivalent circuit.@en

Lithium salts are being investigated as leachable corrosion inhibitor and potential replacement for hexavalent chromium in organic coatings. Model coatings loaded with lithium carbonate or lithium oxalate demonstrated active corrosion inhibition and the formation of a protective layer in a damaged area during neutral salt spray exposure. The present paper provides an abridged overview of the initial studies into this novel inhibitor technology for the active corrosion protection of aluminum alloys. Coating defects were investigated by microscopic techniques before and after exposure to corrosive conditions. Scanning electron microscopy analysis of cross-sections of the coating defect area demonstrated that the protective layer comprises a typical three-layered structure, which included a dense layer near the alloy surface, a porous middle layer, and a flake-shaped out layer. Potentiodynamic polarization measurements obtained with a microcapillary cell positioned in the coating defect area and electrochemical impedance spectroscopy confirmed the corrosion protective properties of these protective layers. The long-term corrosion inhibition of the lithium-based coating technology was tested in industrial coating systems.@en

The atmospheric corrosion of carbon steel was monitored by a Fe/Cu type galvanic corrosion sensor for 34 days. Using a random forest (RF)-based machine learning approach, the impacts of relative humidity, temperature and rainfall were identified to be higher than those of airborne particles, sulfur dioxide, nitrogen dioxide, carbon monoxide and ozone on the initial atmospheric corrosion. The RF model demonstrated higher accuracy than artificial neural network (ANN) and support vector regression (SVR) models in predicting instantaneous atmospheric corrosion. The model accuracy can be further improved after taking into consideration of the significant effect of rust formation on the sensor.@en

A global transition towards more sustainable, affordable and reliable energy systems is being stimulated by the Paris Agreement and the United Nation's 2030 Agenda for Sustainable Development. This poses a challenge for the corrosion industry, as building climate-resilient energy systems and infrastructures brings with it a long-term direction, so as a result the long-term behaviour of structural materials (mainly metals and alloys) becomes a major prospect. With this in mind “Corrosion Challenges Towards a Sustainable Society” presents a series of cases showing the importance of corrosion protection of metals and alloys in the development of energy production to further understand the science of corrosion, and bring the need for research and the consequences of corrosion into public and political focus. This includes emphasis on the limitation of greenhouse gas emissions, on the lifetime of infrastructures, implants, cultural heritage artefacts, and a variety of other topics.@en

This work introduces a novel nanocomposite coating with dual-action self-healing corrosion protection activated by the photothermal response of plasmonic titanium nitride nanoparticles (TiN NPs). TiN@mesoporous SiO2 core–shell nanocontainers were developed as reservoirs for benzotriazole (BTA) corrosion inhibitors and incorporated into the shape memory epoxy coating matrix. Under near-infrared (NIR) light irradiation, the thermogenesis effect of TiN could not only promote the release of corrosion inhibitors from nanocontainers into the crevice, but also trigger the shape memory effect of damaged epoxy to merge the coating scratch. As such, the dual-action self-healing mechanisms combining the formation of an inhibitor-based protective layer and the scratch closure efficiently suppressed the corrosion process at the exposed metal surface. Surface characterization and electrochemical measurement results proved that the nanocomposite coating incorporated with 2 wt% of TiN-BTA@SiO2 exhibited the optimal corrosion protection as well as an excellent self-healing performance that can be initiated within 30 s of NIR illumination. This photo-controlled self-healing approach is potentially useful in designing next-generation self-healing coatings with ultrafast response time and high healing efficiency.@en

Lithium leaching coatings have recently been developed as eco-friendly active corrosion protection technology for aerospace aluminium alloys (AAs) by the formation of a conversion layer at coating defects. While general conversion layer formation characteristics were studied and reported before, here we study the local layer formation process with sub-micron resolution at and around intermetallic particles (IMPs) in AA2024-T3. Top- and cross-sectional-view morphological electron micrograph observations along with open circuit potential (OCP) measurements are performed, mimicking coating defect conditions upon lithium carbonate leaching from the coating matrix. The results revealed five stages of the conversion process in which the alloy matrix and different IMPs evolve morphologically, compositionally, and electrochemically. Besides, we found a correlation between the OCP response of the AA2024-T3 system and the morphological and compositional evolutions of the alloy matrix and IMPs at different stages of exposure. Passive layer and alloy matrix dissolution leading to surface Cu-enrichment and S-phase dealloying occur at early stages of exposure. They precede the formation of a columnar layer on the alloy, followed by the establishment of a dense-like layer at the final stage. Dealloying of Al2CuMg can assist the conversion process by providing local supersaturation. Through complementary experiments in a sodium carbonate solution and besides X-ray diffraction analysis, we found out that lithium plays a critical role in stabilising the corrosion product throughout the conversion process.@en

Liquid-phase transmission electron microscopy (LP-TEM) has provided corrosion scientists with a unique opportunity to directly correlate nanoscopic morphological and compositional evolutions to the corresponding electrochemical response of corroding thin TEM specimens. Electrochemical liquid cell designs are key components of a LP-TEM study towards an implementation which is representative for realistic exposure conditions of bulk samples. However, the application of commercially available liquid cells in corrosion studies brings along an important shortcoming of galvanic coupling effects due to the inevitable connection of the TEM specimens with Pt patterned electrodes. Here, we introduce an approach of fabricating electrochemical liquid cells to alleviate the current cell design challenge for corrosion studies. Besides, we present a protocol for preparing thin specimens to be electrochemically investigated with our home-made electrochemical liquid cell. We finally confirm the effectiveness of this methodology by electrochemically evaluating thin specimens of AA2024-T3 in an open-cell configuration through open circuit potential and potentiodynamic polarisation measurements.@en

The long-term strength and durability of an adhesive bond is dependent on the stability of the oxide-adhesive interface. As such, changes in the chemistry of the oxide and/or the adhesive are expected to modify the interfacial properties and affect the joint performance in practice. The upcoming transition to Cr(VI)-free surface pretreatments makes it crucial to evaluate how the incorporation of electrolyte-derived sulfate and phosphate anions from, respectively, phosphoric acid anodizing and sulfuric acid anodizing affect the interfacial chemical properties. Hence, different types of featureless aluminum oxides with well-defined surface chemistries were prepared in this study. The relative amounts of O2−, OH−, , and surface species were quantified using x-ray photoelectron spectroscopy. Next, bonding with two types of commercial aerospace adhesive films was assessed by peel and bondline corrosion tests. The presented results indicate that the durability of the oxide-adhesive interface depends on the interplay between oxide and adhesive chemistries. Epoxy adhesion is highly affected by changes in the oxide surface chemistry, especially the amount of surface hydroxyls. However, the performance of anodic oxides with a lower hydroxyl fraction can be significantly enhanced by the presence of covalent bonds using a silane coupling agent, γ-amino propyl triethoxy. On the contrary, results with Redux 775 adhesive exhibit very low sensitivity to variations in the surface chemistry. Bondline corrosion resistance of the joints is mainly determined by the nature of the adhesive, independent of the varying oxide chemistries.@en

The distribution and chemical composition of inorganic components of a corrosion-inhibiting primer based on polyurethane is determined using a range of characterisation techniques. The primer consists of a Li2CO3 inhibitor phase, along with other inorganic phases including TiO2, BaSO4 and Mg-(hydr)oxide. The characterisation techniques included particle induced X-ray and γ-ray emission spectroscopies (PIXE and PIGE, respectively) on a nuclear microprobe, as well as SEM/EDS hyperspectral mapping. Of the techniques used, only PIGE was able to directly map the Li distribution, although the distribution of Li2CO3 particles could be inferred from SEM through using backscatter contrast and EDS. Characterisation was also performed on a primer coating that had undergone leaching in a neutral salt spray test for 500 h. Overall, it was found that Li2CO3 leaching resulted in a uniform depletion zone near the surface, but also much deeper local depletion, which is thought to be due to the dissolution of clusters of Li2CO3 particles that were connected to the external surface/electrolyte interface@en

This work introduces a new self-healing superhydrophobic coating based on dual actions by the corrosion inhibitor benzotriazole (BTA) and an epoxy-based shape memory polymer (SMP). Damage to the surface morphology (e.g., crushed areas and scratches) and the corresponding superhydrophobicity are shown to be rapidly healed through a simple heat treatment at 60 °C for 20 min. Electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) were used to study the anti-corrosion performance of the scratched and the healed superhydrophobic coatings immersed in a 3.5 wt% NaCl solution. The results revealed that the anti-corrosion performance of the scratched coatings was improved upon the incorporation of BTA. After the heat treatment, the scratched superhydrophobic coatings exhibited excellent recovery of their anti-corrosion performance, which is attributed to the closure of the scratch by the shape memory effect and to the improved inhibition efficiency of BTA. Furthermore, we found that the pre-existing corrosion product inside the coating scratch could hinder the scratch closure by the shape memory effect and reduce the coating adhesion in the scratched region. However, the addition of BTA effectively suppressed the formation of corrosion products and enhanced the self-healing and adhesion performance under these conditions. Importantly, we also demonstrated that these coatings can be autonomously healed within 1 h in an outdoor environment using sunlight as the heat source.@en

The effect of zirconium-based conversion of thermally vaporized zinc, aluminium and magnesium on the chemisorption of dimethylsuccinate was studied using attenuated total reflection – Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) analysis. Two competing chemisorption mechanisms contribute to interfacial bond formation. Hydrogen interactions on one hand were shown to occur between metal hydroxides and non-hydrolysed ester-groups of the molecule. On the other hand, both native and zirconium-treated substrates were shown to form interfacial carboxylate bonds with dimethylsuccinate, evidencing their capability of hydrolysing ester groups towards more reactive acid groups. Both interactions were shown to correlate to the metal oxide acid-base properties.@en

A new approach is proposed to numerically predict and study atmospheric corrosion for ranging droplet size distributions and the influence of the droplet geometry. The proposed methodology allows for a corrosion prediction based on observed droplet size distributions and droplet contact angles. A mechanistic finite element model, including oxygen transport and Butler-Volmer kinetics, is solved in order to obtain the current density as a function of the droplet geometry. This is done for a range of both droplet radii and contact angles. The computed corrosion current densities are then used as input for imposed droplet size distributions. This allows for a calculated material loss estimation for different distributions and electrolyte configurations and shows the extent of the impact of the droplet size distribution on atmospheric corrosion.@en

The adhesion capabilities of sulfuric acid and tartaric-sulfuric-acid anodic oxide films on cladded AA2024-T3 aluminium substrates have been investigated in a quantitative manner. A relatively simple, versatile and industrially applicable test methodology based on DIN EN ISO 29862 has been used. In addition, the effect of anodising process parameters on the oxide film morphology has been studied and correlated with the adhesion results. The process parameters considered are the chemistry of the acidic pickling pre-treatment step, the addition of tartaric acid to the sulfuric acid electrolyte, the formation voltage, and the electrolyte temperature. The suggested tape peel adhesion test is able to differentiate among pre-treatments and anodising conditions showing a good correlation with the morphological features at the ultimate surface. High peel adhesion strengths are measured when topographies such as pore mouth widening and dissolution-driven roughness take place. These morphologies are typically found in anodic layers formed at elevated electrolyte temperatures. The proposed method can be beneficial for a fast assessment of anodising parameters for good adhesion, which is of special interest for the industrial optimisation of anodising processes.@en