Nanorheology of Entangled Polymer Melts

We use molecular simulations to probe the local viscoelasticity of an entangled polymer melt by tracking the motion of embedded nonsticky nanoparticles (NPs). As in conventional microrheology, the generalized Stokes-Einstein relation is employed to extract an effective stress relaxation function G(GSE)(t) from the mean square displacement of NPs. G(GSE)(t) for different NP diameters d are compared with the stress relaxation function Gotthorn of a pure polymer melt. The deviation of G(GSE)(t) from G(t) reflects the incomplete coupling between NPs and the dynamic modes of the melt. For linear polymers, a plateau in G(GSE)(t) emerges as d exceeds the entanglement mesh size a and approaches the entanglement plateau in G(t) for a pure melt with increasing d. For ring polymers, as d increases towards the spanning size R of ring polymers, G(GSE)(t) approaches G(t) of the ring melt with no entanglement plateau.