Grafting density dominant glass transition of dry polystyrene brushes

The effects of the grafting densities (σ_p), molecular weights (M_n) and thicknesses of dry polystyrene (PS) brushes on their glass transition temperature (T) were investigated by ellipsometry. The results show that T strongly depends on the grafting density of the PS brushes. The T of the PS brushes with σ_p > 0.30 increases with decreasing M_n (or brush thickness) and is mainly dominated by entropic effects, in which the grafted chains are highly extended along the film thickness direction resulting in a sharp reduction in configurational entropy. The T of PS brushes with σ_p < 0.30 decreases with decreasing M_n (or brush thickness) which is mainly dominated by surface effects. For intermediate-density brushes (σ_p = 0.30), T becomes independent of M_n or brush thickness. The reason for this grafting density dependence of T is attributed to the transition of the PS brush conformation from mushroom-to-brush.