Segmental and secondary dynamics of nanoparticle-grafted oligomers

Abstract

The local segmental and secondary dynamics of tetramethylene oxide oligomer grafted to silica nanoparticles (NPs) were investigated as a function of grafting density and molecular weight. Grafting slows the segmental (α) dynamics, but gives rise to faster secondary (β) motions. Interestingly, the magnitude of these effects decreases with the extent of grafting (i.e., surface coverage), as well as with oligomer molecular weight. The disparity in dynamical effects reflects the decoupling of the segmental and more local β dynamics, the former is associated with stronger dynamic correlations that extend over a greater spatial range. This results in greater sensitivity to interactions, including tethering of the chains to the NP surface.