Segmental relaxation behavior of polystyrene chains in the cores of collapsed dry micelles tethered on the micelle film surface by a poly(acrylic acid) corona.

We present an experimental investigation of the segmental relaxation behavior of polystyrene (PS) chains that are confined in a micellar core tethered by a poly(acrylic acid) (PAA) block corona on the dry film surface, along with various core density and molecular weight of PS block from below to well above the entanglement molecular weight. The results show that the onset temperature of PS chain rearrangement (T(onset)), which was much lower than the T(bulk)(g) of the corresponding PS block and higher than T(film)(g) of ultrathin PS films with corresponding thickness and molecular weights, generally increases with increasing density of the micelle core. It was found that the difference in ΔT(onset) with increasing relative density ρ/ρmin obtained from PS154-b-PAA49 and PS278-b-PAA47 micelles was large, while these from PS278-b-PAA47 and PS404-b-PAA63 was negligible, suggesting that entanglement has considerable influence on the density dependence of the T(onset) of PS chains under confinement in the micelle core on the film surface.