Adsorption of Epoxy Oligomers on Iron Oxide Surfaces: The Importance of Surface Treatment and the Role of Entropy.

Epoxy-based coatings are widely used in a range of industries as protective coatings. The performance of the final solid-polymer system is dependent on the physicochemical properties of the interface and the interaction between the polymer and the solid substrate. In this study, we perform atomistic molecular dynamics simulations to investigate the binding of a common component in epoxy resins, diglycidyl ether of bisphenol A (DGEBA), on two iron oxide surfaces, hematite (0001) and magnetite (100), and investigate the effect of surface hydroxylation on the binding energy. We show that adsorption of DGEBA on hematite is more favorable than on magnetite and that the adsorbed molecules are highly localized on the pristine hematite surface but mobile on highly hydroxylated hematite surfaces and magnetite surfaces irregardless of surface hydroxylation fraction. A high degree of hydroxylation significantly reduces the binding energy of DGEBA on hematite but not on magnetite. The free-energy calculations confirm the trends observed upon hydroxylation, but the magnitude of the potential of mean force is lower than the binding energy due to the entropic contributions. Therefore, it can be suggested that DGEBA will adsorb more strongly on a surface containing a higher content of hematite than magnetite and that the presence of hydroxyl groups will weaken this adsorption. The presence of hydroxyl groups increases mobility of the chains, which can affect the coating rigidity.