Distribution of Silicone Oils in PDMS and Epoxy–PDMS-Based Antifouling Coatings

Biofouling is an issue of global significance that impairs marine infrastructure, causes increased fuel consumption and greenhouse gas emissions, and threatens biodiversity. Since the year 2000, self-polishing copolymer (SPC) coatings and fouling release coatings (FRCs) dominate the fouling protection coatings market. SPC technology is based on the controlled release of biocides using a mixture of acrylic and natural binders as a delivery system. FRC technology is based on PDMS providing surface properties that resist attachment of fouling organisms. FRCs often contain surface modifying agents, such as free silicone oils, to tune the physicochemical properties of the surface. However, the long-term efficacy of these agents and their migration and distribution in PDMS-based coatings have not been well studied. In this study, we employed time-of-flight secondary ion mass spectrometry (ToF-SIMS) combined with multivariate analysis to examine the distribution of silicone oils as a function of exposure to artificial seawater (ASW). The results show that pure PDMS-based coatings allow uniform distribution of silicone oils with robust behavior upon ASW exposure. In contrast, epoxy–PDMS-based coatings displayed phase separation of the oils, which strongly altered their surface chemistry. Our findings suggest that the modification of mobile oils is critical to the performance of marine antifouling coatings. Furthermore, the presence of other ingredients of commercial coating formulations strongly affected the distribution of mobile oils. This study lays the foundation for future systematic research aimed at developing predictive models to optimize fouling protection coatings for the marine industry.