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.

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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.

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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

It has been demonstrated previously that lithium salts containing organic coatings offer effective active corrosion protection on AA2024-T3 alloys when exposed to neutral salt spray test for 168 hours [1, 2]. In the presence of a coating defect the lithium salts leach from the organic coating to the exposed metal substrate increasing the local pH to moderate alkaline conditions followed by the formation of a protective layer within the defect site [2, 3]. The lithium accumulation at the defect site and hence the formation of the protective layer is influenced by the inhibitor loading and solubility in the coating as well as the coating defect size. Three different surface compositions of the lithium protective layer have been recently identified as lithium-based layered double hydroxide (Li-LDH), lithium mixed pseudo-boehmite (Li-PB) and pseudo-boehmite (PB) each depending on the lithium leaching rate and the coating defect size [4]. For small defect sizes a high lithium concentration is hypothesized to result in the generation of Li-LDH. Furthermore, Li-PB is identified within moderate defect sizes and moderate inhibitor concentration and PB is generated within large defect sizes where low lithium concentrations are expected. On this basis, this paper describes the lithium active corrosion protection on aerospace aluminium alloys as a function of the inhibitor concentration. In doing so, commercial AA2198-T8 and AA2024-T3 aluminium alloys are immersed for 24 hours in lithium salt containing aqueous solutions at systematically varied lithium salts concentration from 10-6 M to 10-1 M. The alloys are then transferred to 10-1 M aqueous NaCl solution at near neutral pH conditions and either LPR measurements are performed as a function of time over 100 hours or anodic polarization is performed. The surface composition of the alloys after 24 hours immersion in lithium containing aqueous solution is also characterized. The surface composition and the electrochemical characteristics of each lithium passive layer generated is determined as a function of the lithium concentration. The surface composition of the passive layer ranges from PB to Li-PB and Li-LDH with increasing inhibitor concentration. The polarization resistance obtained as a function of time is correlated to the corrosion rate of each generated passive layer thus demonstrating the corrosion protection performance of Li-LDH, Li-PB and PB. The generation and corrosion protection performance of each passive layer is also demonstrated under relatively thin electrolyte layers mimicking the exposure of a coating defect and the leaching of lithium salt from the coating matrix under atmospheric conditions. @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.

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This study presents the active protective properties of lithium-leaching coatings for a range of aluminium alloys. Coatings with and without lithium carbonate as leachable inhibitor were applied on the aluminium alloys, artificially damaged and exposed to the neutral salt spray. A combined approach of scanning electron microscopy and electrochemical measurements revealed that the lithium carbonate leaching coating provided effective corrosion inhibition on AA2024, AA7075, AA5083, and AA6014 by the formation of a protective layer in the defect area and preventing local corrosion processes despite the different intrinsic electrochemical activity of the alloys.

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Chemical throwing power, being the distance over which an inhibitor is able to protect a defect effectively, is an important parameter for active protective coatings. This study investigates the chemical throwing power of lithium-based leachable corrosion inhibitors exhibiting different leaching kinetics, from coatings at different inhibitor loading concentrations. The results demonstrate that Li-salt loaded coatings provide corrosion protection of defect areas up to a width of 6 mm. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to detect the lateral spread of Li in the defect areas and provide the chemical speciation of corrosion protective layers in the defect areas.

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For decades, scientists and engineers are searching for a safe and environmentally friendly alternative for the toxic chromate corrosion inhibitors in active protective coatings for the protection of aerospace aluminium alloys. In this search many different compounds have been investigated as leachable corrosion inhibitor, but no alternative with equal or better performance compared to chromates has been found yet. In 2010 it was discovered that organic coatings loaded with lithium-salts (Li) as leachable corrosion inhibitor provided very effective and promising corrosion inhibition on aluminium alloys when exposed to industrial accelerated corrosion tests. Initial investigations showed the formation of a corrosion protective layer on the aluminium alloy in a defect area, which appears to be a key feature of these Li-leaching coatings.@en

Inhibitor leaching, fast, effective and irreversible passivation are essential for active protective coatings to protect aluminium alloys. This study presents the comparison of the active protective properties of lithium carbonate and two organic corrosion inhibitors, benzotriazole and 2-mercaptobenzothiazole, on aluminium alloy 2024-T3 with a special focus on the irreversibility of the inhibition. A combined approach of electrochemical measurements, optical observations, surface roughness and weight-loss measurements revealed the reversible inhibition behaviour of benzotriazole and 2-mercaptobenzothiazole on AA2024-T3. On the contrary, lithium carbonate demonstrated fast, effective and irreversible corrosion inhibition, providing the essential characteristics needed for effective active corrosion protection from coatings.@en

This study focuses on the elucidation of the formation mechanism of passive layers on AA2024-T3 during the exposure to alkaline lithium carbonate solutions in the presence of sodium chloride. Under controlled conditions, in an electrochemical cell, a protective layer was generated comprising an amorphous inner layer and a crystalline outer-layer. In order to resolve the formation mechanism, the layers were characterized using surface analytical techniques to characterize the surface morphology, thickness and elemental composition of the layers at different stages of the formation process. In addition, electrochemical techniques were applied to link the electrochemical properties of the layers with the different stages of formation. The results demonstrate that the formation mechanism of these layers comprises three different stages: (I) oxide thinning, (II) anodic dissolution and film formation, followed by (III) film growth through a competitive growth-dissolution process. The passive properties of the layers are generated in the third stage through the densification of the amorphous layer. The combined results provide an enhanced insight in the formation mechanism and the development of the passive properties of these layers when lithium salts are used as leaching corrosion inhibitor for coated AA2024-T3.

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In this work, the study of the time-dependent behaviour of lithium carbonate based inhibitor technology for the active corrosion protection of aluminium alloy 2024-T3 is presented. Odd random phase electrochemical impedance spectroscopy (ORP-EIS) is selected as the electrochemical tool to study the corrosion protective properties of a model organic coating with and without lithium carbonate as a function of immersion time, by examination of the non-linearities and non-stationarities in the system. A dedicated qualitative and quantitative analysis allows linking the presence of non-stationarities in a certain frequency range with the (un)stable behaviour of different electrochemical processes. Monitoring of the system with and without lithium corrosion inhibitors during the first 12 h after immersion in a 0.05 M NaCl aqueous solution and modelling the ORP-EIS data with equivalent electrical circuit (EEC) models revealed a relation between the trends in the parameter evolution and the (un)stable behaviour of the morphological changes taking place. This paper shows that the ORP-EIS based methodology allows us to study the behaviour of corrosion inhibitors in an alternative way; the time-dependent behaviour of corrosion inhibitor containing electrochemical systems is highlighted, proving that this a useful approach for further corrosion inhibitor and active protective coating research.

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This work presents the electrochemical evaluation of protective layers generated in a coating defect from lithium-leaching organic coatings on AA2024-T3 aluminum alloys as a function of neutral salt spray exposure time. Electrochemical impedance spectroscopy was used to study the electrochemical properties on a macroscopic scale. An electrochemical model allowed to quantitatively link the electrochemical behavior with the physical model of the layer in the damaged area as studied by scanning electron microscopy. Local potentiodynamic polarization curves obtained from micro-cell measurements showed an increase of the passive range in the defect area due to the formation of a robust protective layer. Scanning vibrating electrode technique measurements confirmed the non-reversible long-term corrosion protection of these generated layers in the coating defect. @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

The protective film formed in a defect by leaching of lithium oxalate from model organic coatings during neutral salt spray exposure has been investigated. A scribed area of about 1 mm width was introduced on the coated AA2024‐T3 aluminium alloy. The scribed area was examined before and after exposure in neutral salt spray environment for 4, 8, 24 and 168 h by scanning and transmission electron microscopies. It was found that the lithium oxalate was able to leach from the organic coating during neutral salt spray exposure and it promoted the formation of a film that provided effective corrosion protection to the alloy. The typical film morphology consists of three different layers, including a relatively compact layer near the alloy substrate, a porous middle layer and a columnar outer layer. Variation of the film morphology was also observed at different locations of the scribed alloy surface, which may be related to the difference of local concentration of lithium species. Electron energy loss spectroscopy detected lithium, aluminium and oxygen in the film. Although the film showed the varied morphologies in different regions of the scribed area, the alloy substrate was protected from corrosion when the film was formed@en

Lithium salts were investigated as leachable corrosion inhibitor and potential replacement for hexavalent chromium in organic coatings. Coatings loaded with lithium carbonate or lithium oxalate demonstrated active corrosion inhibition by the formation of a protective layer in a damaged area. The present paper provides more insight into the formation and composition of the protective layer in a damaged area generated from the lithium salt loaded coatings when exposed to neutral salt spray testing conditions (ASTM B-117). Lithium-ion leaching from the coating matrix was demonstrated with atomic absorption spectroscopy and the pH conditions in the damaged area were determined with a scanning ion-selective electrode technique. Additionally, the formation of the protective layer was studied with microscopic and surface analytical techniques. Scanning electron micrographs and Auger electron spectroscopy depth profiles revealed the process of coverage and growth of the protective layer in the damaged area. Furthermore, X-ray photoelectron spectroscopy analysis indicated that the protective layer likely consists of a hydrated oxide in the form of a (pseudo) boehmite with lithium distributed in its matrix.

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Aircraft are complex multi-material structures that are optimized for strength to weight ratio, fatigue properties and operational performance. Corrosion control is an important aspect in the aerospace industry. Therefore, active protective coatings are an important part of the corrosion protection scheme within the aircraft design. This chapter provides an overview of the field of aerospace coatings, the different types of coatings and their role in the corrosion protection scheme. Active corrosion protection is a key feature of these coatings. For decades, the aerospace industry has been relying on hexavalent chromate as the active corrosion inhibiting species. The industry is facing an enormous challenge because this toxic material needs to be replaced by environmentally-friendly alternatives. This chapter provides a review of the challenges and developments towards hexavalent chromium free coating systems and it provides insight in the current status and trends in the industry of aerospace coatings and discusses the new approaches and corrosion inhibiting strategies towards chromate-free active protective coating systems.@en