Probing the Nanostructure and Reactivity of Epoxy–Amine Interphases

High Resolution Image Download MS PowerPoint Slide Understanding and controlling the structure of interphase regions in epoxy resins have been a long-standing goal in high-performance composite and coating development, since these are widely considered to be weak points in the microstructure of these materials, determining key properties such as fracture strength and barrier performance. These buried nanoscale regions are, however, inaccessible to conventional analytical techniques, and little is understood about their underlying formation mechanism. Here, we combine molecular dynamics (MD) simulation with nanoscale infrared chemical mapping to develop new understanding of the interphase using model epoxy–amine binders composed of diglycidyl ether of bisphenol A (DGEBA) cross-linked using m -xylylenediamine (MXDA). Iron oxide powders are used as exemplary surfaces, where we demonstrate that the electrostatic binding energies between the amine cross-linker and particles range from repulsive (magnetite, Fe 3 O 4 ) to weakly attractive (hematite, Fe 2 O 3 ) to strong immobilization (goethite, FeOOH). We find that interfacial binding occurs upon mixing and determines the overall level of residual amine content in the bulk matrix but does not correlate with a detectable amine depletion in the vicinity of particles. In all cases, an excess of both epoxy and amine functionality is detected close to particles, and the extent of matrix undercuring is found to be dependent on the entropic segregation of the unreacted material during the ambient cure. Detailed MD simulations demonstrate that spatial segregation of the unreacted precursors is expected in the interphase, leading to the experimental observation that, even after extensive postcure heating, individual particles remain embedded in a nanoscale underdeveloped environment.