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.

The authors regret that an error occurred in the description of equation 3 in the published version of the above-mentioned article, which should be as follows: [Formula presented] The correct equation was implemented for calculating all the results presented in the article, so all results, discussions and conclusions presented in the manuscript remain fully valid > The authors would like to apologise for any inconvenience caused.

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.

Utilizing a dedicated micro-sized three-electrode cell, this study systematically investigates early-stage electrochemical properties and corrosion behavior of pure iron under single droplets. Various volumes and NaCl concentrations were considered during the evaporation-driven shape and concentration evolution of single droplets. The measurements disclosed that reducing the droplet size from 5 µL to 1.5 µL at 0.01 M NaCl concentration, increased noise resistance (R_n) and polarization resistance (R_p) values. However, at 0.1 M and 0.2 M NaCl concentrations, reducing droplet size led to the domination of relatively high chloride ion concentration over oxygen diffusion, resulting in a very low R_n and R_p and hence enhanced localized corrosion.

This paper presents a novel approach to investigate atmospheric corrosion kinetics of carbon steel under multi-droplet conditions. A homemade climate chamber has been developed to accurately control and monitor environmental conditions, including temperature (T) and relative humidity (RH), during exposure. Carbon steel corrosion kinetics are monitored with a custom-designed Electrical Resistance (ER) sensor pair. Savitzky-Golay (S-G) based filtering technique has been used for the corrosion signal processing. In parallel, top-view droplet temporal evolution has been recorded by microscopic imaging and analyzed for both droplet size distribution and the solid-liquid contact angle. The droplet size distribution can typically be described with a power-law form curve. The curve shows a decrease in height and a concurrent expansion in width with progressive drying. The introduction of NaCl into the electrolyte and surface roughness variations have also been identified to substantially influence the carbon steel corrosion rate. A strong correlation between the corrosion rate derived from the ER monitoring method and the RH can be observed. This correlation is further analyzed to incorporate the impact of droplet-based electrolyte conditions. This study offers valuable insights into the development of mechanistic and kinetic prediction models for atmospheric corrosion.

Electrodeposition from an environmentally friendly iron sulfate electrolyte with citric acid as carbon source has gained attention recently, because of excellent mechanical properties of the resulting Fe–C coatings with intentionally codeposited high-carbon concentrations. While being very attractive as protective coatings and sustainable alternatives for hard chrome coatings, comprehensive understanding of the coatings' chemical constitution including the type and location of carbon-containing phases is still lacking. The amount of codeposited carbon of up to about 0.8 wt.% significantly exceeds the solubility of carbon in ferrite, although carbon-free ferrite is the only unambiguously reported phase in as-deposited Fe–C coatings so far. In the present work, time-of-flight secondary ion mass spectrometry, X-ray photoelectron spectroscopy, and soft X-ray emission spectroscopy have been applied to identify the carbon-containing phases, which are present as minor secondary phases in the coatings but are known to have an important influence on the coatings' properties. Three carbon-containing phases could be distinguished, homogeneously distributed in the nanocrystalline ferrite base material. Iron acetates, amorphous carbon, and carbides were found in both as-deposited and annealed Fe–C coatings up to 300°C, but their fraction changes during postdeposition annealing.

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.

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.

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.

The anodising process parameters (voltage, temperature, and electrolyte) control the morphology and the chemical composition of the resulting anodic oxide film by altering the balance between oxide growth and oxide dissolution reactions. The porosity of the oxide film is reduced by the addition of tartaric acid to a sulfuric acid electrolyte, while anodising at elevated temperatures enhances oxide dissolution, leading to wider pores and rougher surfaces. No significant changes in the oxide chemical composition as a function of anodising parameters was found; in particular, no tartrate incorporation took place. The resistance of uncoated anodic oxide films against aggressive media and galvanic stress as a function of anodising parameters has been studied by electrochemical methods. Anodising in a mixed tartaric and sulfuric acid electrolyte improves the resistance of the anodic oxide against galvanic stress and aggressive media in comparison to sulfuric acid ano-dising processes. However, the corrosion protection performance of the anodic oxide films in com-bination with a corrosion-inhibitor loaded organic coating is not governed by the blank oxide properties but by the adhesion-enhancing morphological features formed during anodising at elevated temperatures at the oxide/coating interface.

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.

Herein, we report the development of a self-sensing and active corrosion protection coating which incorporates pH-sensitive multilayer chitosan/alginate-covered CaCO₃ microcontainers containing 1,10-phenanthrolin-5-amine (APhen). The microcontainers can respond to pH variation to release APhen which serves not only as a corrosion indicator but also as an inhibitor. An epoxy coating doped with 5 wt% microcontainers exhibited improved corrosion performance and was capable of inhibiting corrosion spreading from the damaged area in a 3.5 wt% NaCl solution. The salt spray test showed that corrosion damage can be quickly detected by the appearance of a red color within 2 min.

Sr is known to transform the morphology of the eutectic silicon phase as well as the Fe-rich β phase in Al-Si alloys, improving their mechanical properties. However, little is known about the effect Sr has on the (local) corrosion properties of aluminium alloys. This study investigates the effect of Sr addition to a modified AA3003 heat exchanger material on the morphology of the different phases present, especially the Fe-rich phases, as well as on the (local) corrosion properties of this material. This work reports the formation of a Sr-rich phase, which slightly increases the macrohardness of the material. The Fe-rich phases are not shown to be refined/influenced by the addition of Sr Potentiodynamic polarization experiments showed an increase in pitting potential by increasing the amount of Sr in the material up to 0.4 wt.%. Nevertheless, the analysis of the corrosion morphology revealed that the Sr-containing particles did not contribute to the corrosion process despite their cathodic behaviour compared to the Al matrix as measured by Scanning Kelvin Probe Force Microscopy. This behaviour was attributed to the thicker oxide layer found on the Sr-rich particles.

Cerium-based compounds have been studied for decades as non-toxic candidates for the protection of aerospace aluminium alloys (AAs) like AA2024-T3. However, the complex heterogeneous microstructure of these alloys has hindered a thorough understanding of the subsequent stages of corrosion protection provided by this class of inhibitors. Thus, this work is devoted to unravelling the interaction mechanisms of different intermetallic particles (IMPs) in AA2024-T3 with cerium nitrate at the nanoscopic scale. This has been fulfilled through detailed top-view and cross-sectional analytical TEM investigations along with electrochemical evaluations. In line with our recent findings, we here report dealloying of IMPs as the main factor governing the rate of local cerium precipitation in contrast to micro-galvanic corrosion between IMPs and the surrounding matrix. Furthermore, we discuss a connection between the electrochemical response of the AA2024-T3 system and the morphological and compositional evolutions of individual IMPs including Al2CuMg, Al2Cu, Al7Cu2Fe(Mn) and Al76Cu6Fe7Mn5Si6 at different stages of a 96-h exposure.

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.

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.

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.

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.

The sol-gel synthesis process is a versatile method used to produce a wide diversity of materials and is being increasingly used as a surface modification method to alter porosity, wettability, catalytic activity, biocompatibility and corrosion performance of underlying substrates. Silane sol–gel films deposited on aluminium and aluminium alloys have been widely studied as chemical conversion coatings and as coupling agent between the substrate and organic layers. This study set out to investigate the effect of the surface chemical treatment prior to sol-gel application on the interfacial adhesion properties of a hybrid sol-gel film. Different surface pre-treatments, including two abrasive treatments and three chemical surface pre-treatments were used and their effect on surface chemistry and surface roughness was assessed. Surfaces were characterized by scanning electron microscopy, x-ray photoelectron spectroscopy, roughness measurements and static contact angles. Cerium nitrate loaded hybrid sol-gel films were deposited and adhesion on commercially pure aluminium was evaluated using pull-off testing. Statistical analysis revealed that, although highest adhesion values were obtained on rougher surfaces, the strongest correlation exists between the surface hydroxyl fraction and adhesion strength.