Halloysite clay nanotubes loaded with corrosion inhibitors benzotriazole (BTA), 2-mercaptobenzimidazole (MBI), and 2-mercaptobenzothiazole (MBT) were used as additives in self-healing composite paint coating of copper. These inhibitors form protective films on the metal surface and mitigate corrosion. Mechanisms involved in the film formation have been studied with optical and electron microscopy, UV-vis spectrometry, and adhesivity tests. Efficiency of the halloysite lumen loading ascended in the order of BTA < MBT < MBI; consequently, MBI and MBT halloysite formulations have shown the best protection. Inhibitors were kept in the tubes buried in polymeric paint layer for a long time and release was enhanced in the coating defects exposed to humid media with 20-50 h, sufficient for formation of protective layer. Anticorrosive performance of the halloysite-based composite acrylic and polyurethane coatings have been demonstrated for 110-copper alloy strips exposed to 0.5 M aqueous NaCl for 6 months.

The use of natural halloysite clay tubes 50 nm in diameter as nanocontainers for loading, storing, and slowly releasing organic corrosion inhibitors is described. Loaded nanotubes can be mixed well with many polymers and dyes in amounts of 5-10 wt % to form a ceramic framework (which increases the strength of halloysite composites by 30-50%), increase the adhesion of these coatings to metals, and allow for the slow release of corrosion inhibitors in defects of coatings. A significant improvement of protective anticorrosion properties of polyacryl and polyurethane coatings containing ceramic nanotubes loaded with benzotriazole and hydroxyquinoline is demonstrated.