Epoxy Coatings Containing Nature-Inspired Antifouling Compounds Loaded in Halloysite Nanocontainers

Marine biofouling is a major global concern affecting the marine industry, the environment, and public health. The accumulation of organisms on submerged surfaces causes significant economic losses, including increased fuel consumption, higher pollutant emissions, and accelerated corrosion. Antifouling (AF) coatings with biocides are widely used to prevent this problem. However, many conventional biocides have been banned due to toxicity, creating an urgent need for environmentally friendly alternatives. In previous studies, we synthesized a gallic acid derivative and three flavonoids that showed AF activity against the settlement of mussel larvae (Mytilus galloprovincialis) together with low ecotoxicity. In the present work, to further assess their potential in marine coatings and exploit the advantages of nanocarriers in protecting and prolonging bioactive effects, these compounds were loaded into halloysite nanotubes (HNTs) and incorporated into epoxy coatings. Coatings containing the same AF compounds in free form were also prepared for comparison. HNTs were characterized by scanning electron microscopy (SEM), and compound loading was quantified by thermogravimetric (TG) analysis. The resulting composites were analyzed by SEM and dynamic water contact angle measurements. Laboratory bioassays with M. galloprovincialis larvae showed that coatings containing HNT-loaded synthetic compounds generally reduced larval settlement more effectively than the corresponding coatings containing the same compounds directly dispersed in the epoxy matrix, with values below 20% after both 15 and 40 h of exposure for the best-performing formulation. These findings highlight the novelty of the proposed HNT-based delivery strategy for nature-inspired synthetic antifoulants and support its potential for the development of effective and environmentally safer AF coatings.