Eco-Friendly Fumed Nanosilica@Nanodiamond Hybrid Nanoparticles with Dual Sustainable Self-Healing and Barrier Anticorrosive Performances in Epoxy Coating.

Fumed nanosilica@nanodiamond attached by APTES [(3-aminopropyl) triethoxysilane], named FSiO@sND, was examined as an efficient anticorrosive nanohybrid for epoxy coating. Compared with fumed nanosilica (FSiO), nanodiamond (ND) moderated the hydrophilic nature of FSiO@sND and offered additional functional groups to the nanohybrid, i.e., carboxylic groups of ND and functional groups of APTES, while retaining the eco-friendly nature of FSiO in the hybrid nanoparticle. The hybrid nanoparticle showed pH-sensitive release behavior in which APTES is released considerably in an alkaline medium, acting as an efficient corrosion inhibitor. A thorough electrochemical impedance spectroscopy (EIS) study of scratched coatings in a 3.5% NaCl solution disclosed that FSiO@sND nanoparticles (at 0.33 wt % loading) conferred significant active/self-healing anticorrosion properties for the epoxy coatings, thanks to the release of APTES and the presence of carboxylic groups of ND taking part in forming a stable protective film on the substrate. Accordingly, epoxy/FSiO@sND coatings showed a corrosion improvement efficiency of 138% at an optimum immersion time of 5 h, which was higher than the 96% improvement for epoxy/FSiO coating. Epoxy/FSiO@sND intact coating showed much higher low-frequency impedance, i.e., 7.23 Ω·cm, compared with epoxy/FSiO2 coating, i.e., 5.44 Ω·cm, and neat epoxy coating, i.e., 5.71 Ω·cm, after 22 weeks of immersion in salty solution. This result along with a detailed analysis of EIS data for intact coatings suggested that FSiO@sND brought about strong barrier anticorrosive performance for epoxy coating. Such behavior was attributed to improved dispersion of nanohybrid in the epoxy matrix, enhanced cross-link density of the epoxy matrix, and improved coating/substrate adhesion caused by APTES and the carboxylic groups of ND.