Entropy-driven segregation in epoxy-amine systems at a copper interface

Abstract

The composition of an epoxy resin at the interface with the adherend is usually different from that in the bulk due to the enrichment of a specific constituent, a characteristic called interfacial segregation. For better adhesion, it should be precisely understood how epoxy and amine molecules exist on the adherend surface and react with each other to form a three-dimensional network. In this study, the entropic factor of the segregation in a mixture of epoxy and amine at the copper interface before and after the curing reaction is discussed on the basis of a full-atomistic molecular dynamics (MD) simulation. Smaller molecules were preferentially segregated at the interface regardless of the epoxy and amine, and this segregation remained after the curing process. No segregation occurred at the interface for a combination composed of epoxy and amine molecules with a similar size. These findings make it clear that the size disparity between constituents affects the interfacial segregation via the packing and/or translational entropy. The curing reaction was slower near the interface than in the bulk, and a large amount of unreacted molecules remained there. Finally, the effect of molecular shape was also examined. Linear molecules were more likely to segregate than round-shaped ones even though they were similar in volume. We believe that these findings, which are difficult to obtain experimentally, contribute to the understanding of the interfacial adhesion phenomena on a molecular scale.