Effect of Condensed Water at an Alumina/Epoxy Resin Interface on Curing Reaction

The adhesion of epoxy adhesives to aluminum materials is an important issue in assembling parts for lightweight mobility. Aluminum surfaces typically possess an oxide layer, which readily adsorbs water. In this study, the aggregation states of water and its effect on the curing reaction were examined by placing a water layer between an amorphous alumina surface and a mixture of epoxy and amine components. This study used molecular dynamics simulations and density functional theory calculations. Before the reaction, water molecules strongly adsorbed onto the alumina surface, aggregating excess water. Some water diffused into the epoxy/amine mixture, accelerating the diffusion of unreacted substances. This led to faster reaction kinetics, particularly in proximity to the alumina surface. The adsorption of water molecules onto the alumina surface and the aggregation of excess water were similarly observed even after the curing process. Subsequently, the interaction between the alumina surface and various functional groups of the epoxy/amine mixture was evaluated before and after the reaction. Epoxy monomers had little interaction with the alumina surface before the reaction, whereas hydroxy groups formed by the ring-opening reaction of epoxy groups exhibited notable interaction. Conversely, sulfonyl and amino groups in amine compounds formed hydrogen bonds with OH groups on the alumina surface before the reaction. However, after the reaction, amino groups weakened their interaction with the alumina OH groups as they transformed from primary to tertiary during the curing reaction. Both epoxy and amine monomers/fragments similarly interacted with water molecules, both before and after the reaction. The insights gained from this study are expected to contribute to a better understanding of the impact of moisture absorption on the application of epoxy resins.