Effect of crosslink formation on heat conduction in amorphous polymers

We performed molecular dynamics (MD) simulations on amorphous polyethylene (PE) and polystyrene (PS) in order to elucidate the effect of crosslinks between polymer chains on heat conduction. In each polymer system, thermal conductivities were measured for a range of crosslink concentration by using nonequilibrium MD techniques. PE comprised of 50 carbon atom long chains exhibited slightly higher conductivity than that of 250 carbon atom long chains at the standard state. In both cases for PE, crosslinking significantly increased conductivity and the increase was more or less proportional to the crosslink density. On the other hand, in the PS case, although the thermal conductivity increased with the crosslinking, the magnitude of change in thermal conductivity was relatively small. We attribute this difference to highly heterogeneous PS based network including phenyl side groups. In order to elucidate the mechanism for the increase of thermal conductivity with the crosslink concentration, we decomposed energy transfer into modes associated with various bonded and non-bonded interactions.