Microscopic Dynamics of Polyethylene Glycol Chains Interacting with Silica Nanoparticles

We present high resolution neutron spectroscopic investigations of polyethylene glycol matrices interacting attractively with neat SiO₂ nanoparticles. We observe a very rich dynamical picture that significantly contradicts earlier conclusions on such systems. Investigating a short chain matrix we realized that a fraction of chains is attached at the nanoparticle surface suppressing completely its translational diffusion. Nevertheless these attached chains undergo an unchanged segmental dynamics seemingly forming a micellelike corona of chains attached with their OH end groups. Changing to methyl-terminated chains the picture changes drastically, now showing a tightly adsorbed layer that however is not glassy as often assumed but undergoes fast picosecond local dynamics. With the singular importance of end groups, mean field approaches are not applicable and future simulations should be redirected to model such unexpected phenomena.