Peter Visser

Model samples of active protective coatings were investigated by synchrotron radiation-based X-ray computed tomography. The resulting 3D images reveal the complex microstructure of the coatings and the progress of the leaching induced by controlled exposure to water between scans. Quantitative analysis of the image data capturing several time steps of the leaching process yields a new experimental validation of the power law commonly used to describe the leaching. Thanks to the 3D imaging, local deviations can be explained by microstructural features. Moreover, clusters of interconnected pores are identified and visualized.

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.

Corrosion protection systems based on hexavalent chromium are traditionally perceived to be a panacea for many engineering metals including magnesium alloys. However, bans and strict application regulations attributed to environmental concerns and the carcinogenic nature of hexavalent chromium have driven a considerable amount of effort into developing safer and more environmentally friendly alternative techniques that provide the desired corrosion protection performance for magnesium and its alloys. Part I of this review series considers the various pre-treatment methods as the earliest step involved in the preparation of Mg surfaces for the purpose of further anti-corrosion treatments. The decisive effect of pre-treatment on the corrosion properties of both bare and coated magnesium is discussed. The second section of this review covers the fundamentals and performance of conventional and state-of-the-art conversion coating formulations including phosphate-based, rare-earth-based, vanadate, fluoride-based, and LDH. In addition, the advantages and challenges of each conversion coating formulation are discussed to accommodate the perspectives on their application and future development. Several auspicious corrosion protection performances have been reported as the outcome of extensive ongoing research dedicated to the development of conversion coatings, which can potentially replace hazardous chromium(VI)-based technologies in industries.

Although hexavalent chromium-based protection systems are effective and their long-term performance is well understood, they can no longer be used due to their proven Cr(VI) toxicity and carcinogenic effect. The search for alternative protection technologies for Mg alloys has been going on for at least a couple of decades. However, surface treatment systems with equivalent efficacies to that of Cr(VI)-based ones have only begun to emerge much more recently. It is still proving challenging to find sufficiently protective replacements for Cr(VI) that do not give rise to safety concerns related to corrosion, especially in terms of fulfilling the requirements of the transportation industry. Additionally, in overcoming these obstacles, the advantages of newly introduced technologies have to include not only health safety but also need to be balanced against their added cost, as well as being environmentally friendly and simple to implement and maintain. Anodizing, especially when carried out above the breakdown potential (technology known as Plasma Electrolytic Oxidation (PEO)) is an electrochemical oxidation process which has been recognized as one of the most effective methods to significantly improve the corrosion resistance of Mg and its alloys by forming a protective ceramic-like layer on their surface that isolates the base material from aggressive environmental agents. Part II of this review summarizes developments in and future outlooks for Mg anodizing, including traditional chromium-based processes and newly developed chromium-free alternatives, such as PEO technology and the use of organic electrolytes. This work provides an overview of processing parameters such as electrolyte composition and additives, voltage/current regimes, and post-treatment sealing strategies that influence the corrosion performance of the coatings. This large variability of the fabrication conditions makes it possible to obtain Cr-free products that meet the industrial requirements for performance, as expected from traditional Cr-based technologies.

Owing to the unique active corrosion protection characteristic of hexavalent chromium-based systems, they have been projected to be highly effective solutions against the corrosion of many engineering metals. However, hexavalent chromium, rendered a highly toxic and carcinogenic substance, is being phased out of industrial applications. Thus, over the past few years, extensive and concerted efforts have been made to develop environmentally friendly alternative technologies with comparable or better corrosion protection performance to that of hexavalent chromium-based technologies. The introduction of corrosion inhibitors to a coating system on magnesium surface is a cost-effective approach not only for improving the overall corrosion protection performance, but also for imparting active inhibition during the service life of the magnesium part. Therefore, in an attempt to resemble the unique active corrosion protection characteristic of the hexavalent chromium-based systems, the incorporation of inhibitors to barrier coatings on magnesium alloys has been extensively investigated. In Part III of the Review, several types of corrosion inhibitors for magnesium and its alloys are reviewed. A discussion of the state-of-the-art inhibitor systems, such as iron-binding inhibitors and inhibitor mixtures, is presented, and perspective directions of research are outlined, including in silico or computational screening of corrosion inhibitors. Finally, the combination of corrosion inhibitors with other corrosion protection strategies is reviewed. Several reported highly protective coatings with active inhibition capabilities stemming from the on-demand activation of incorporated inhibitors can be considered a promising replacement for hexavalent chromium-based technologies, as long as their deployment is adequately addressed.