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Despite extensive research, eliminating hexavalent chromium-based inhibitors from aerospace coatings remains challenging due to a lack of understanding of coating degradation during aircraft service. This study addresses the issue by investigating the protective mechanisms and aging processes of chromate-containing coatings on aircraft components after service for over 35 years. Four aircraft parts underwent visual inspection, disassembly, and analysis using scanning electron microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). While most coating areas remained intact after extended use, three distinct degradation modes were identified: tip erosion, corrosion around rivets, and corrosion around fasteners at the leading edge. These findings reveal the complexity of corrosion protection, emphasizing that hexavalent chromium-containing coatings may not offer comprehensive protection at local design heterogeneities. The study also highlights the need to revisit traditional laboratory analysis protocols based on accelerated corrosion testing of oversimplified sample configurations, given the revealed end-of-service failure mechanisms., Team Arjan Mol

Understanding how late an inhibitor can be released once corrosion initiated without compromising corrosion protection may help in developing more efficient anticorrosion coatings. We explored this idea through time-controlled Ce(NO3)3 availability to AA2024-T3 immersed in 0.05 M NaCl. Ce(NO3)3 was supplied at 0, 30, 60, and 180 s from the start of immersion to get a concentration of 0.001 M. Detailed visualization of surface changes at the intermetallic particle level was obtained using in-situ reflected microscopy. SEM-EDX and confocal laser microscopy confirmed the extent of intermetallic degradation and local inhibitor deposition corresponding to operando changes. When the inhibitor is supplied within 60 s of immersion, the surface changes slowdown earlier and are visually less extensive than in uninhibited systems. Furthermore, our results highlight the potential of reflected microscopy for local corrosion inhibition studies and underscore the importance of understanding the interaction between inhibitor release timing and corrosion protection., Group Garcia Espallargas, Team Arjan Mol

Creating durable, eco-friendly coatings for long-term corrosion protection requires innovative strategies to streamline design and development processes, conserve resources, and decrease maintenance costs. In this pursuit, machine learning emerges as a promising catalyst, despite the challenges presented by the scarcity of high-quality datasets in the field of corrosion inhibition research. To address this obstacle, we have created an extensive electrochemical library of around 80 inhibitor candidates. The electrochemical behaviour of inhibitor-exposed AA2024-T3 substrates was captured using linear polarisation resistance, electrochemical impedance spectroscopy, and potentiodynamic polarisation techniques at different exposure times to obtain the most comprehensive electrochemical picture of the corrosion inhibition over a 24-h period. The experimental results yield target parameters and additional input features that can be combined with computational descriptors to develop quantitative structure–property relationship (QSPR) models augmented by mechanistic input features., Team Arjan Mol, Team Peyman Taheri

This paper for the first time treats the interpretation of electrochemical noise time-frequency spectra as an image classification problem. It investigates the application of a convolutional neural network (CNN) for deep learning image classification of electrochemical noise time-frequency transient information. Representative slices of these spectra were selected by our transient analysis technique and served as input images for the CNN. Corrosion data from two types of pitting corrosion processes serve as test cases: AISI304 and AA2024-T3 immersed in a 0.01M HCl and 0.1M NaCl solution between 0 and 1ks after immersion, respectively. Continuous wavelet transform (CWT) spectra and modulus maxima (MM) are used to train the CNN, either individually or in a combined form. The classification accuracy of the CNN trained with the combined dataset is 0.97 and with the two individual datasets 0.72 (only CWT spectrum) and 0.84 (only MM). The ability to additionally classify a more progressed form of pitting corrosion of AA2024-T3 between 9 and 10ks after immersion indicates that the proposed method is sufficiently robust using combined datasets with CWT spectra and MM. The pitting processes can effectively be detected and classified by the proposed method. The most important contribution of the present work is to introduce a novel procedure that decreases the classical need for large amounts of raw data for training and validation purposes, while still achieving a satisfactory classification robustness. A relatively small number of individual signals thereby generates a multitude of input images that still contain all relevant kinetic information about the underlying chemo-physical process., Team Arjan Mol

The quest for novel alternatives to hexavalent-chromium-based corrosion inhibitors is of utmost significance and urgency. Strict international health and safety regulations, due to growing concerns regarding the impact of hexavalent chromium on human health and the environment, have pushed the commercial introduction of many alternative inhibitor types, but the implementation of alternative active protective primers for structural parts in the aerospace industry is still pending. This endeavour has proven to be remarkably challenging, as the potential replacement coating types must meet numerous functional requirements encompassing cost-effectiveness and exceptional corrosion protection for intrinsically corrosion susceptible aerospace aluminium alloys. In recent years, considerable attention has been drawn to lithium salts as environmentally friendly corrosion inhibitors forming the basis for a novel active protective coating technology. The involvement of lithium ions has been shown to play a pivotal role in the conversion process of aluminium alloy surfaces by stabilizing the reaction products, thereby facilitating the gradual development of a protective layer with a multi-layered configuration, which exhibits considerable variability in morphology, depending on local chemical and electrochemical conditions. The versatility of the lithium-based corrosion protection extends to their application as corrosion inhibiting pigments in organic coatings or as a pre-treatment, directly forming conversion layers, thereby enhancing their practical implementation. However, previous chromate replacement reviews only introduced the promising outcomes provided by the lithium technology, omitting key details of its development and formation mechanism. This paper critically reviews and summarizes the studies conducted to date on lithium-based inhibitor technologies for the corrosion protection of aluminium alloys as well as topics to be investigated in the future., Team Arjan Mol, Team Yaiza Gonzalez Garcia

In this work, the corrosion mechanism of AA2024-T3 covered by a lithium-based conversion layer is studied with high spatial and temporal resolution. Although the aluminium alloy surface is protected by a multi-layered conversion layer, areas around intermetallic phases (IMPs) represent weak spots due to an insufficient generation of a protective inner dense layer. For the freshly formed conversion layer, both the top and the inner layer undergo a gradual dissolution upon exposure to relatively dilute NaCl solution within 2 h due to their chemical instability. For the ambiently-aged conversion layer, most corrosion activity around IMPs is related to the S-phase and large constituent phases, due to their active nature and the lower local conversion layer quality, respectively. Moreover, S-phase-related corrosion activity lasts approximately 8 h due to fast dissolution whereas reactions induced by large constituent particles remain active over the entire re-immersion period of 12 h., Team Arjan Mol, Team Yaiza Gonzalez Garcia