Chromium-based functional coatings (CFCs) are widely recognized for their outstanding wear and corrosion resistance across diverse industrial sectors. However, despite advancements in deposition techniques and microstructural enhancements, many contemporary CFCs remain vulnerable to degradation in highly corrosive environments. For the first time, this research delivers a thorough characterization of the corrosion resistance of advanced CFCs, focusing on the performance of a 5 μm thin dense chromium (TDC) coating. These TDCs exhibit a distinctive, uniform nodular microstructure, characterized by approximately 3.6 μm nodules composed of defect-free near-nanocrystalline grains (227 ± 75 nm) plus enhanced electrochemical nobility. This structure promotes the rapid formation of a stable, dense bilayer oxide, resulting in a remarkably low corrosion susceptibility, effectively impeding both charge transfer and mass transport, particularly the diffusion of Cl^- ions. Furthermore, the coating sustains an exceptionally high polarization resistance over extended exposure times in aqueous NaCl electrolyte. These findings offer critical insights into the design of CFCs optimized for extreme environmental durability.

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The targeted removal of efficient but toxic corrosion inhibitors based on hexavalent chromium has provided an impetus for discovery of new, more benign organic compounds to fill that role. Developments in high-throughput synthesis of organic compounds, the establishment of large libraries of available chemicals, accelerated corrosion inhibition testing technologies, the increased capabilities of machine learning (ML) methods, and a better understanding of mechanisms of inhibition provide the potential to make discovery of new corrosion inhibitors faster and cheaper than ever before. These technical developments in the corrosion inhibition field are summarized herein. We describe how data-driven machine learning methods can generate models linking molecular properties to corrosion inhibition that can be used to predict the performance of materials not yet synthesized or tested. The literature on inhibition mechanisms is briefly summarized along with quantitative structure–property relationships models of small organic molecule corrosion inhibitors. The success of these methods provides a paradigm for the rapid discovery of novel, effective corrosion inhibitors for a range of metals and alloys, in diverse environments. A comprehensive list of corrosion inhibitors tested for various substrates that was curated as part of this review is accessible online https://excorr.web.app/database and available in a machine-readable format.

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Chromium coatings, famed for their superior wear and corrosion resistance, are a critical component in countless industrial processes. However, the longevity of these coatings in aggressive corrosive environments continues to be a significant hurdle, even with recent advances in deposition technology and microstructural improvements. An advanced thin dense chromium (TDC) coating, with a near-nanocrystalline structure and unique morphology, naturally forms a non-conductive nano-bilayer oxide. This passive and protective layer effectively moderates electrical charge transfer, offering superior corrosion resistance. X-ray photoelectron spectroscopy (XPS) shows significant Cr³⁺ oxide layer formation, distinguished by multiplet splitting, after 7 days in a 0.6 M NaCl solution. The unique characteristics of this non-conductive bilayer oxide structure promote its growth and densification, leading to vertical differential charging in the O1s electron energy region. This effect arises from the enhanced resistivity of the oxide layer. Electrochemical impedance spectroscopy (EIS) confirmed these findings, showing a substantial increase in charge transfer resistance at the chromium metal/bilayer oxide interface, reaching 1.01 MΩ. Scanning Kelvin probe force microscopy (SKPFM) analysis shows that both TDC nodules and their boundaries exhibit high surface potential and work function. However, after exposure to NaCl media, these values are moderately reduced, likely due to diminished electrical surface charge distribution.

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The discovery of synergistic strategies effectively improves the corrosion inhibition capability of amino acids. However, the wide variety of amino acid formulations and the time-consuming nature of corrosion tests make combinatorial discovery challenging to achieve. Herein, a library of 70 amino acids was created and tested in a high-throughput manner. Benefiting from a vast amount of labeled data of amino acid formulations, an interpretable machine learning approach was used to reveal the contribution of molecular features to inhibition performance of amino acids and the synergisms in the optimal formulation. The synergism was verified by electrochemical tests and quantum chemical calculations.

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Corrosion-fatigue is considered to be one of the main degradation mechanisms affecting the structural integrity of offshore support structures. This paper presents a feasibility assessment for the detection and monitoring of corrosion-fatigue damage using non-contact acoustic emission (AE). An accelerated corrosion-fatigue experiment was conducted on a S420NL dog-bone specimen. A corrosion-fatigue cell was designed and fabricated to simultaneously apply accelerated corrosion and cyclic loads on the specimen submerged in artificial seawater. A three-electrode electrochemical configuration under potentiostatic control was used to accelerate corrosion. The ultrasound signals were continuously measured using underwater AE transducers (in the frequency range of 50–450 kHz) placed at a fixed distance from the tested coupon. The results of the accelerated corrosion-fatigue experiment suggest that corrosion-fatigue-induced ultrasound signals can be detected with a satisfactory signal-to-noise ratio using non-contact AE sensors. The mean energy of the corrosion-fatigue-induced ultrasound signals was one order of magnitude higher than that of the corrosion-induced signals. The trends of the AE parameters extracted from the AE signals were analysed as functions of the load cycles. The results revealed high potential for the identification and monitoring of corrosion-fatigue damage using the non-contact AE technique.

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Three imidazole-based compounds (imidazole, 2-mercaptobenzimidazole, and 2-mercapto-1-methylbenzimidazole) were studied as corrosion inhibitors of Cu, Zn, and a family of Cu-xZn brass alloys (x = 10−40 wt%) in 3 wt% NaCl solution. The composition of inhibitor layers on the surface was studied using X-ray photoelectron and infrared spectroscopies. The molecular adsorption modes on Cu and Zn were modelled using density-functional theory (DFT) calculations. Mercapto-based inhibitors act as efficient inhibitors on all materials studied due to the formation of inhibitor layer through bonding with nitrogen and sulphur atoms. In contrast, imidazole is a moderate inhibitor for Zn, while it is much less efficient for Cu.

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Microbiologically influenced corrosion (MIC) refers to the deterioration of metal surfaces as a result of the formation of microbial biofilms and metabolic activities at the biofilm/metal interface. Conventional macroscopic electrochemical techniques provide limited spatial resolution to investigate MIC which often occurs at localized environment within micro-/nanoscopic levels. Localized electrochemical techniques have received increasing attention in MIC research as a potential strategy to solve this challenge. This paper provides a focused review of localized electrochemical techniques employed in MIC studies, including their fundamentals and applications. Furthermore, their advantages and challenges as well as topics to be investigated in future are discussed.@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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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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A detailed microstructural and electrochemical analysis of electroless nickel phosphorous (NiP) coatings with P contents of 13.2 ± 1.2 wt%, 12.9 ± 0.7 wt%, and 8.3 ± 0.8 wt% on a copper substrate was performed to study the corrosion behaviour of electroless NiP/Cu systems. The P content of the electroless NiP coatings plays an essential role in the microstructure of the coatings in terms of crystallinity. The crystallinity variations, representing the extent of crystalline and amorphous phases within the material, with P content, affect the local electrochemical characteristics and, hence, the corrosion protection behaviour of electroless NiP coatings. The coatings with the highest P content showed the best corrosion performance in a 3.5 wt-% NaCl solution. In contrast, the surface of the electroless NiP coatings with low P content is more susceptible to corrosion due to the presence of locations with heterogeneous electronic properties that initiate localised corrosion. Microgalvanic interactions with a high cathode-to-anode surface ratio govern the localised corrosion kinetics of the low P-content samples. A high concentration of nodule boundaries and/or other existing structural defects on the surface serve as anodic sites, whereas the remainder of the surface serves as cathodic sites.

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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.@en

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.

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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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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.

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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.

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Machine learning is a powerful means for the rapid development of high-performance functional materials. In this study, we presented a machine learning workflow for predicting the corrosion resistance of a self-healing epoxy coating containing ZIF-8@Ca microfillers. The orthogonal Latin square method was used to investigate the effects of the molecular weight of the polyetheramine curing agent, molar ratio of polyetheramine to epoxy, molar content of the hydrogen bond unit (UPy-D400), and mass content of the solid microfillers (ZIF-8@Ca microfillers) on the low impedance modulus (lg|Z|_0.01Hz) values of the scratched coatings, generating 32 initial datasets. The machine learning workflow was divided into two stages: In stage I, five models were compared and the random forest (RF) model was selected for the active learning. After 5 cycles of active learning, the RF model achieved good prediction accuracy: coefficient of determination (R ²) = 0.709, mean absolute percentage error (MAPE) = 0.081, root mean square error (RMSE) = 0.685 (lg(Ω·cm²)). In stage II, the best coating formulation was identified by Bayesian optimization. Finally, the electrochemical impedance spectroscopy (EIS) results showed that compared with the intact coating ((4.63 ± 2.08) × 10¹¹ Ω·cm²), the |Z|_0.01Hz value of the repaired coating was as high as (4.40 ± 2.04) × 10¹¹ Ω·cm². Besides, the repaired coating showed minimal corrosion and 3.3% of adhesion loss after 60 days of neutral salt spray testing.

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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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Nowadays, Thin Dense Chromium (TDC) coatings are being industrially used in rolling bearings applications due to their claimed advantages such as high hardness, low wear, and good corrosion resistance. However, despite their broad commercial use, very little has been published in the open scientific literature regarding their microstructure, nanomechanical, and tribological properties. In this paper, TDC coatings with a thickness of about 5 µm were deposited by a customized electrochemical process on ASTM 52100 bearing steel substrates. Surface microstructure and chemical composition analysis of the TDC coatings was carried out by scanning electron microscopy and atomic force microscopy. The results revealed a coating with a dense, nodular, and polycrystalline microstructure. Unlike standard electrodeposited “Hard Chromium” coatings, TDC coatings show no presence of micro/nano-cracks, likely contributing to their superior corrosion resistance. The nanomechanical behavior, studied by nanoindentation as a function of penetration depths, exhibits a pronounced size effect near the coating surface that can be linked to the nodular microstructure. A hard surface with hardness HIT 14.9 ± 0.5 GPa and reduced elastic modulus Er = 216.8 ± 3.9 GPa was observed. Tribological characterization under the presence of lubricants was performed by two single-contact tribometers using coated and uncoated steel balls against flat steel substrates. An in-house fretting wear rig was used to measure the lubricated friction coefficient in pure sliding conditions, whilst the friction performance in rolling/sliding lubricated conditions was evaluated using a WAM test rig. In pure sliding, TDC/TDC contacts show ~13% lower friction than for steel. Under rolling/sliding conditions with 5% sliding, the traction coefficient of TDC/TDC coating contact was at least 20% lower than that for steel/steel contact. The tribological results obtained in various contact conditions demonstrate the benefits of applying TDC coatings to reduce bearing friction.@en

The influence of dissolved oxygen (DO) and Shewanella algae on the corrosion behavior of pure titanium were systematically studied in this work. The formation of S. algae biofilms on titanium surface was facilitated by the anaerobic environment, which accelerated titanium corrosion. Upon the breakdown of passive film, S. algae acquired electrons from the titanium base substrate through extracellular electron transfer (EET) processes. Various EET-related genes were overexpressed by the low DO condition, leading to enhanced EET kinetics. High concentration DO increased TiO2 content and the thickness of passive film, which enhanced the protective effect and mitigated microbiologically influenced corrosion.@en