Elucidating the Effects of Chemisorbed Water Molecules on the Adhesive Interactions of Epoxy Resin to γ-Alumina Surfaces

The adhesion mechanism of epoxy resin to the gamma-alumina (110) surface was investigated using first-principles density functional theory (DFT). Aluminum materials are lightweight and are used in a wide range of industrial fields. Its surface is oxidized to alumina, and the stable surface is known as the gamma-alumina (110) surface. The coverage of hydroxy groups by chemisorbed water molecules on this surface varied depending on the pretreatment temperature. In this study, we investigated the adhesive interactions of epoxy resin on four alumina surfaces with different densities of surface hydroxy groups (0, 3, 6, and 9 OH/nm(2)) and have discussed their effects. At each interface, the energy curves of the vertically displaced epoxy resin were calculated and the adhesive forces were estimated by differentiating these curves. As the coverage of the surface hydroxy groups increased from 0 to 6 OH/nm(2), the adhesive strength gradually decreased. However, the adhesive strength at 9 OH/nm(2) was relatively large and almost equal to that at 3 OH/nm(2). This inverse volcano-type behavior was analyzed via the decomposition of adhesive forces and the crystal orbital Hamilton population (COHP). The decomposition of adhesive forces into DFT and dispersion components revealed that the inverse volcano-type behavior is derived from the DFT component, and the interfacial interactions owing to the DFT component are accompanied by charge transfer. These were investigated using a COHP analysis, which revealed that this behavior was caused by changes in the activity of the aluminum atoms on the surface and surface reconstruction by chemisorbed water molecules. It is noteworthy that the adhesive strength for 9 OH/nm(2) was only 6.9% lower than that for 0 OH/nm(2) wherein the chemisorbed water molecules were completely removed from the surface. These results are expected to provide a guideline for the adhesion of epoxy resin to aluminum materials.