Unraveling Nanoscale Elastic and Adhesive Properties at the Nanoparticle/Epoxy Interface Using Bimodal Atomic Force Microscopy

The addition of a small fraction of solid nanoparticles to thermosetting polymers can substantially improve their fracture toughness, while maintaining various intrinsic thermomechanical properties. The underlying mechanism is largely related to the debonding process and subsequent formation of nanovoids at a nanoscale nanoparticle/epoxy interface, which is thought to be associated with a change in the structural and mechanical properties of the formed epoxy network at the interface compared with the matrix region. However, a direct characterization of the local physical properties at this nanoscale interface remains significantly challenging. Here, we employ a recently developed bimodal atomic force microscopy technique for the direct mapping of nanoscale elastic and adhesive responses of an amine-cured epoxy resin filled with ∼50 nm diameter silica nanoparticles. The obtained elastic modulus and dissipated energy maps with high spatial resolution evidence the existence of a ∼20-nm-thick interfacial epoxy layer surrounding the nanoparticles, which exhibits a reduced modulus and weaker adhesive response in comparison with the matrix properties. While the presence of such a soft and weak-adhesive interfacial layer is found not to affect the architecture of structural heterogeneities in the epoxy matrix, it conceivably supports the toughening mechanism related to the debonding and plastic nanovoid growth at the silica/epoxy interface. The incorporation of this soft interfacial layer into the Halpin-Tsai model also provides a good explanation for the effect of the silica fraction on the tensile modulus of cured epoxy nanocomposites.