A Molecular Simulation Approach to Bond Reorganization in Epoxy Resins: From Curing to Deformation and Fracture

[Image: see text] We model bond formation and dissociation processes in thermosetting polymer networks from molecular dynamics simulations. For this, a coarsened molecular mechanics model is derived from quantum calculations to provide effective interaction potentials that enable million-atoms scale simulations. The importance of bond (re)organization is demonstrated for (i) simulating epoxy resin formation—for which our approach leads to realistic network models which can now account for degrees of curing up to 98%. Moreover, (ii) we elucidate the competition of bond dissociation and bond reformation during plastic deformation and fracture. On this basis, we rationalize the molecular mechanisms that account for the irreversible nature of damaging epoxy polymers by mechanical load.