Small Particle Driven Chain Disentanglements in Polymer Nanocomposites.

Using neutron spin-echo spectroscopy, x-ray photon correlation spectroscopy, and bulk rheology, we studied the effect of particle size on the single-chain dynamics, particle mobility, and bulk viscosity in athermal polyethylene oxide-gold nanoparticle composites. The results reveal a ≈25% increase in the reptation tube diameter with the addition of nanoparticles smaller than the entanglement mesh size (≈5  nm), at a volume fraction of 20%. The tube diameter remains unchanged in the composite with larger (20 nm) nanoparticles at the same loading. In both cases, the Rouse dynamics is insensitive to particle size. These results provide a direct experimental observation of particle-size-driven disentanglements that can cause non-Einstein-like viscosity trends often observed in polymer nanocomposites.