This work presents the synthesis of monodisperse, mesoporous silica nanoparticles and their application as nanocontainers loaded with corrosion inhibitor (1H-benzotriazole (BTA)) and embedded in hybrid SiOx/ZrOx sol-gel coating for the corrosion protection of aluminum alloy. The developed porous system of mechanically stable silica nanoparticles exhibits high surface area (∼1000 m2·g(-1)), narrow pore size distribution (d∼3 nm), and large pore volume (∼1 mL·g(-1)). As a result, a sufficiently high uptake and storage of the corrosion inhibitor in the mesoporous nanocontainers was achieved. The successful embedding and homogeneous distribution of the BTA-loaded monodisperse silica nanocontainers in the passive anticorrosive SiOx/ZrOx film improve the wet corrosion resistance of the aluminum alloy AA2024 in 0.1 M sodium chloride solution. The enhanced corrosion protection of this newly developed active system in comparison to the passive sol-gel coating was observed during a simulated corrosion process by the scanning vibrating electrode technique (SVET). These results, as well as the controlled pH-dependent release of BTA from the mesoporous silica nanocontainers without additional polyelectrolyte shell, suggest an inhibitor release triggered by the corrosion process leading to a self-healing effect.

Organic coatings based on inhibitor loaded inorganic containers for smart corrosion inhibition are presented. The overall coating performance is strongly infl uenced by the containers as well as their inhibitor capacity, compatibility with the coating matrix, and size. The important effect of container size is described for the fi rst time in this work by investigating two types of mesoporous silica containers of different diameters: 80 and 700 nm. The coating physical properties (thickness and adhesion) are comparable for both container types. In contrast, the coating barrier properties are strongly infl uenced by the container size as assessed with electrochemical impedance spectroscopy (EIS). The incorporation of bigger containers reduces the coating resistance by a factor of two. Surprisingly, despite the similar amounts (20 wt%) of loaded inhibitor (2-mercaptobenzothiazole), different active inhibition ability is detected with the scanning vibrating electrode technique (SVET). Therefore, it is found that coatings with smaller containers exhibit better self-healing performance.

This work presents an effective anticorrosive coating for the industrially important aluminum alloy, AA2024-T3. The protective coating was designed by dispersing mesoporous silica nanocontainers, loaded with the nontoxic corrosion inhibitor, 2-mercaptobenzothiazole, in a hybrid sol-gel (SiOx/ZrOx) layer. The concentration of the embedded nanocontainers was varied (0.04-1.7 wt %) to ascertain the optimum conditions for anticorrosion performance. Attaining high efficiency was found to be a compromise between delivering sufficient corrosion inhibitor and preserving the coating barrier properties. The impact of nanocontainer concentration on the thickness and adhesion of freshly cured coatings was also investigated. The barrier properties of the intact coatings were assessed by electrochemical impedance spectroscopy. The active corrosion inhibition was evaluated during a simulated corrosion process by the scanning vibrating electrode technique. This study has led to a better understanding of the factors influencing the anticorrosion performance and properties of active anticorrosive coatings with embedded nanocontainers.

Application of mesoporous silica nanoparticles (MSNs) as delivery tools for self-healing coatings is limited by spontaneous leakage and specifically responsive release of small molecular inhibitors. In this work, a pH/sulfide ion responsive release system based on MSNs using a Cu-BTA complex forms at the openings of the mesopores into which BTA (corrosion inhibitor) and benzalkonium chloride (biocide) are loaded. The spontaneous leakage of active species is completely avoided and premature release of the loaded composition was lowered to 0.02. The responsive release begins when the pH is lower than 5 or [S^2-] is higher than 0.02 mM (about 0.6 ppm). The hybrid coating containing the responsive release system exhibits feedback self-healing property sensitive to lowering of pH and sulfide ion concentration and, at the same time, provides a high barrier level for a long time. Due to incorporation of biocide in the release system, the coating is also provided with antifouling properties