ContextWe report on atomic level of detail analyses of polymer composite models featuring epoxy resin interfaces to silica, iron oxide, and cellulose layers. Using “reactive” molecular dynamics simulations to explore epoxy network formation, resin hardening is investigated in an unprejudiced manner. This allows the detailed characterization of salt-bridges and hydrogen bonds at the interfaces. Moreover, our sandwich-type composite systems are subjected to tensile testing along the interface normal. To elucidate the role of relaxation processes, we contrast (i) direct dissociation of the epoxy-metal oxide/cellulose contact layer, (ii) constant strain-rate molecular dynamics studies featuring (visco-)elastic deformation and bond rupture of the epoxy resin, and (iii) extrapolated relaxation dynamics mimicking quasi-static conditions. While the fracture mechanism is clearly identified as interface dissociation of the composite constituents, we still find damaging of the nearby polymer phase. The observed plastic deformation and local cavitation are rationalized from the comparably large stress required for the dissociation of salt-bridges, hydrogen bonds, and van der Waals contacts. Indeed, the delamination of the contact layers of epoxy resins with slabs of silica, magnetite, and cellulose call for a maximum stress of 33, 26, and 21 MPa, respectively, as compared to 84 MPa required for bulk epoxy yielding.MethodsMolecular dynamics simulations using the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) code were augmented by a Monte Carlo–type procedure to probe epoxy bond formation (Macromolecules53(22): 9698–9705). The underlying interaction models are split into conventional Generalized Amber Force Fields (GAFF) for non-reacting moieties and a recently developed reactive molecular mechanics potential enabling epoxy bond formation and cleavage (ACS Polymers Au1(3): 165–174).