Study of temperature dependence of thermal conductivity in cross-linked epoxies using molecular dynamics simulations with long range interactions

In this work, we demonstrate the use of the Green–Kubo integral of the heat flux autocorrelation function, incorporating long-range corrections to model the thermal conductivity versus temperature relationship of cross-linked polymers. The simulations were performed on a cross-linked epoxy made from DGEBA and a curing agent (diamino diphenyl sulfone) using a consistent valence force field (CVFF). A dendrimeric approach was utilized for building equilibrated cross-linked structures that allowed replication of the experimental dilatometric curve for the epoxy system. We demonstrate that the inclusion of a long-range correction within the Ewald/PPPM approach brings the results close to experimentally measured conductivity within an error of 10% while providing a good prediction of the relationship of thermal conductivity versus temperature. This method shows significant promise towards the computation of thermal conductivity from simulations even before synthesis of the polymer for purposes of materials by design.