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.@en

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.

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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.@en

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.

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The substitution of chromate-containing structural coating systems in aviation with alternatives complying with nowadays strict environmental, health and safety regulations remains a formidable challenge. This complexity is partly due to the absence of a standardized from-test-to-market methodology, including a performance comparison between chromate-containing and alternative coating systems. To address this gap, the present study delves into the identification of crucial degradation factors that merit inclusion in such a methodology. Concurrently, it investigates the protective mechanisms inherent in chromate-containing coating systems and proposes improvements that can be applied to alternative coating systems. This study entails a comprehensive post-service examination of the degradation of paint applied to an aircraft component with over 35 years of service, employing electrochemical, microscopic and spectroscopic techniques. The findings underscore the role of thermo-oxidation as a significant degradation factor in the aging process of such coatings. Furthermore, the investigation elucidates a notable phenomenon in which aluminium ions within the coating pores form an aluminium hydroxide gel onto which chromate adsorbs. This process contributes to an increase in pore resistance upon exposure to electrolyte, leading to a self-healing barrier effect within the coating. Remarkably, this self-healing mechanism continues to offer long-term protection even when the coating matrix is sub-optimally cured due to application errors. Furthermore, this study reveals that the significant changes in capacitance during immersion testing result primarily from inhibitor leaching, emphasizing the effectiveness of combining Electrochemical Impedance Spectroscopy (EIS) with Scanning Electron Microscopy (SEM) analysis for studying coating degradation.

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Stochastic electrochemical measurement has come of age as a powerful analytical tool in corrosion science, electrophysiology, and single-entity electrochemistry. It relies on the fundamental trait that most electrochemical processes are stochastic and discrete in nature. Stochastic measurement of a single entity probes the charge transfer from a few or even one electroactive species. In corrosion, the stochastic measurements capture either the average amplitude/frequency of many events taking place spontaneously or probe discrete transients, signifying localized dissolution. The measurement principles vary in corrosion, single-entity, and electrophysiology, yet the main quantifiable values are commonly the frequency and amplitude of events. This perspective delves into the methodologies for the analysis and deconvolution of stochastic signals in electrochemistry. Ranging from visual assessment of transients to time/frequency analyses of the data and state-of-the-art machine learning, these methodologies mainly aim at identifying patterns, singular events, and rates of electrochemical processes from stochastic signals.

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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.

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The influence of ageing under ambient conditions on the corrosion protective behaviour of a lithium-based conversion layer on AA2024-T3 is studied in this work. Conversion layers aged at ambient conditions for relatively short times (0 h and 4 h), show an initial high degree of corrosion inhibition but a much lower protectiveness after the inhibition stage terminates. Conversion layers with relatively long ageing times (24 h and 72 h) show a rather stable corrosion resistance which is higher than that of short-time aged samples. It is hypothesized that the freshly-formed conversion layer has trapped a certain amount of lithium ions and water molecules, leading to ongoing and heterogeneous growth of the conversion layer with time under ambient indoor conditions. Moreover, conversion layers with short ageing times show early-stage active corrosion protection by lithium-ion release.

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Scanning electrochemical microscopy (SECM) is employed to characterize the evolution of local electrochemical surface activity during lithium-based conversion layer formation on legacy aerospace aluminium alloy AA2024-T3. Initially, three types of studied intermetallic particles - S-, θ- and constituent phases - act as active cathodic areas. Subsequently, θ- and constituent phases show passivation preceding that of S-phase particles during the later conversion layer formation stages. The entire surface, including the matrix region, shows a higher reactivity at the beginning and then gradually shows decreasing reactivity. Hydrogen evolution-generated bubbles attach to the alloy surface and locally hinder the conversion layer formation, weakening the corrosion protection the conversion layer provides at those locations.

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In this work a diffusion-driven inhibitor transport model is used to help in the design of inhibitor-loaded carriers for anticorrosive primers. The work focuses on inhibitor release at damaged locations of different dimensions exposed to electrolyte and is validated experimentally. The damage dimensions are first simulated to determine the minimal inhibitor release rate necessary to reach the required inhibitor concentrations for corrosion protection of the exposed metal. Kinematic and mass conservation laws are then used as first-order approximations to study the effect of different characteristics of nano- and micro-particles loaded with inhibitors embedded in an organic coating during the first 100 s of immersion. The simulated results are validated experimentally using epoxy coatings containing cerium-loaded zeolites and diatomaceous earth as nano- and micro-carriers respectively. These experiments confirmed the simulated predictions, showing that under the used exposure conditions nano-particles are only able to protect relatively small damages of micron size dimensions. Micron-sized carriers on the other hand allow sufficient release to protect larger damages, even at lower pigment volume concentrations. Additional simulations on rapid electrolyte diffusion pathways inside the coating are also in good agreement with the experiments, indicating the presence of diffusion pathways might play an important role in sustained inhibitor release and corrosion protection at local damages.

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This work investigates an integrated analysis of in-situ optical data and time-frequency information from electrochemical potential noise (EPN) data to study the effectiveness and durability of an anodic and cathodic corrosion inhibitor. Two different corrosion inhibiting species, cerium(III) (Ce(III)) and phytic acid (PHA), are tested on aluminum alloy AA2024-T3. Corrosion of AA2024-T3 serves as a negative reference. Time-frequency analysis of EPN data provides a direct insight in the kinetics of the electrochemical processes related to different types of corrosion and/or inhibitor activity over time. The simultaneous, in-situ optical technique allows visualizing and quantifying the surface changes associated with the electrochemical signals. Both Ce(III) and PHA were not capable to inhibit corrosion to a large extent, as re-immersion led to electrochemical (corrosion) activity for both inhibitors. Time-variant changes between corrosion, inhibitor activity, inhibited state and re-activation can effectively be discriminated from each other.

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The formation process of a lithium-based conversion layer on AA2024-T3 and its corrosion protective behavior are studied using electrochemical noise (EN). Wavelet transform, as well as noise resistance analysis, have been employed to interpret the EN data. The EN data confirmed five different stages during the conversion layer growth, accompanied by anodic dissolution, increasing corrosion protection of the conversion layer, and adsorption, growth and desorption of hydrogen bubbles simultaneously. The detachment of hydrogen bubbles, localized and uniform corrosion generate different features in the EN signals with energy maxima in high, intermediate and low frequency bands, respectively. In addition, EN results show that the lithium-based conversion layer still provides efficient protection after re-immersion in a corrosive environment, even though localized damage occurs. Moreover, the EN data corresponds well with the morphological layer formation and breakdown observed with microscopy techniques. The results demonstrate that EN is a powerful tool to provide continuous time- and frequency-resolved information about inhibition efficiency.

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Shewanella oneidensis MR-1 is an attractive model microbe for elucidating the biofilm-metal interactions that contribute to the billions of dollars in corrosion damage to industrial applications each year. Multiple mechanisms for S. oneidensis-enhanced corrosion have been proposed, but none of these mechanisms have previously been rigorously investigated with methods that rule out alternative routes for electron transfer. We found that S. oneidensis grown under aerobic conditions formed thick biofilms (∼50 µm) on stainless steel coupons, accelerating corrosion over sterile controls. H₂ and flavins were ruled out as intermediary electron carriers because stainless steel did not reduce riboflavin and previous studies have demonstrated stainless does not generate H₂. Strain ∆mtrCBA, in which the genes for the most abundant porin-cytochrome conduit in S. oneidensis were deleted, corroded stainless steel substantially less than wild-type in aerobic cultures. Wild-type biofilms readily reduced nitrate with stainless steel as the sole electron donor under anaerobic conditions, but strain ∆mtrCBA did not. These results demonstrate that S. oneidensis can directly consume electrons from iron-containing metals and illustrate how direct metal-to-microbe electron transfer can be an important route for corrosion, even in aerobic environments.

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In previous work, the importance of taking the time-domain into account when studying corrosion inhibitor-containing electrochemical systems was highlighted. In this work, odd random phase electrochemical impedance spectroscopy (ORP-EIS) is applied as the electrochemical tool to study the time-effect by the evaluation of the non-stationarities per frequency decade over time for the screening of different silica- and phosphate- based corrosion inhibitors for hot-dip galvanized steel and possible corrosion inhibitor synergism. This serves as the basis for the interpretation of the results obtained from different macroscopic electrochemical techniques such as potentiodynamic polarization (PP), open circuit potential (OCP) with superimposed linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) measurements. The analysis of the time-domain shows that all systems have a system-specific ‘stabilization’ time which affects the interpretation of the results obtained from the macroscopic electrochemical techniques. Furthermore, these results indicate that all corrosion inhibitors tested exhibit corrosion protective action and that the combination of both silica-based corrosion inhibitors show synergistic action on hot-dip galvanized steel.

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Real-time optical analysis is used to improve the interpretation of electrochemical noise signals (EN). The concept is presented for the case of AA2024-T3 under immersion in various NaCl concentrations. An in-house developed optical-electrochemical technique allowed for high spatiotemporal resolution and was used to visualize and quantify surface changes in parallel with monitoring EN signals. EN analysis was performed in the time-frequency domain using continuous wavelet transform (CWT). Correlations between the two procedures enabled the identification of corrosion processes in time, such as de-alloying, etching, pitting and subsurface corrosion. Besides this, optical measurements at higher magnification were used to analyse a smaller section of the exposed metal with a spatial resolution below 1 μm. This enabled the quantification on the size, number and nearest neighbor distance of local corrosion events, such as pits and corrosion rings. The set-up and optical protocol allowed for the first time (i) to establish a direct relationship between EN signals and the occurrence of specific localized corrosion phenomena and (ii) an in-situ highly-resolved monitoring of local corrosion processes. As a final result of the optical analysis we introduce a straightforward illustration that allows the direct identification of EN features to macroscopic local corrosion phenomena.

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In this paper, different macroscopic electrochemical techniques are applied to study the corrosion inhibitor efficiency, protection mechanism and stability of a calcium aluminum polyphosphate silicate hydrate inhibitor on hot-dip galvanized steel in the time-domain. Potentiodynamic polarization (PP) measurements are applied to study the anodic and cathodic mechanistic behavior as well as inhibitor efficiencies at discrete and single times of exposure. Open circuit potential (OCP) with superimposed linear polarization resistance (LPR) measurements are applied as a faster, non-invasive alternative to PP, characterizing the overall performance of the system in terms of the polarization resistance. Electrochemical impedance spectroscopy (EIS) measurements are applied to detail both the overall performance of the system as well as the corrosion inhibition mechanism related to the electrochemical system’s physicochemical representation over time. Electrochemical noise (EN) measurement are used to evaluate the inhibition efficiency as a function of exposure time, represented by the electrochemical noise resistance. Odd random phase electrochemical impedance spectroscopy (ORP-EIS) is selected as the electrochemical tool to study the system’s instability, by evaluation of the non-linearities and non-stationarities over time. The non-stationarities present in the inhibitor-containing electrochemical system are shown to cause the overall instability of the system and should be taken into account when interpreting results from the different techniques over time.

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A potentially powerful tool to detect and classify corrosion mechanisms is the analysis of electrochemical noise (EN). Data analysis in the time-frequency domain using, e.g., continuous wavelet transform (CWT) allows the extraction of localized frequency information, providing information on the type of corrosion, i.e., uniform or localized corrosion, from the EN signal. The CWT provides the opportunity to analyze changes in frequency behavior of EN signals over time. In the presence of transients generated by pitting corrosion that occur only during short instants of time, this is an important property. This paper introduces the combination of automated transient detection with wavelet transform modulus maxima (WTMM) and the Holder exponent. WTMM enhances the determination of transient frequencies by indicating the ridges of a CWT spectrum. The Holder exponent, a measure of singularity of an EN signal, provides a single parameter discrimination tool based on WTMM and serves to differentiate between general corrosion and two types of pitting corrosion of stainless steel Type 304 exposed to aqueous HCl solutions of different concentrations and as such at different pH values.

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Different techniques have been employed for the investigation of under deposit corrosion (UDC). However, most of these methods suffer from complications regarding the mechanistic analysis of UDC in terms of localized electrochemical factors that influence the corrosion process. The present work investigates a novel methodology based on complementary evaluation of UDC in marine environments by electrochemical impedance spectroscopy (EIS) and electrochemical noise (EN) analysis using Hilbert spectra. Two different electrodes (AISI 316L and mild steel) covered by calcareous deposit and exposed in 3 wt.% NaCl solution were studied, employing the proposed measurement approach coupled with microscopic observations. It was found that the combined investigation of the instantaneous frequency decomposition of transients in the electrochemical potential noise (EPN) signals and damage indices calculated from EIS measurements led to a more detailed mechanistic understanding of UDC evolution. Changes in the corrosion process over time were observed for both electrodes, including two different stages: the onset of pit formation followed by a large timescale process in terms of active-passive behavior of the substrates. Low-frequency variations of the impedance magnitude, as well as the corresponding damage indices, indicated a transition stage of UDC. Finally, these stages were identified by the analysis of the EN signals, together with investigation of the micrographs of the damaged surface.

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