Effect of Dispersity on the Conformation of Spherical Polymer Brushes

We show that dispersity (D̵) markedly alters the conformation of spherical polymer brushes. The average lengths (l_b) of poly(tert-butyl acrylate) (PtBA) brushes of varying D̵ grafted to nanoparticles were measured using dynamic light scattering. In the semidilute polymer brush (SDPB) regime, the l_b of PtBA and polymers from earlier studies of various D̵ could be cleanly collapsed onto a master curve as a function of the scaling variable N_wσ^1/3, where N_w is the weight-average degree of polymerization and σ is the grafting density. In the concentrated polymer brush (CPB) regime, however, l_b collapsed onto a bifurcated curve as a function of the scaling variable N_wσ^1/2, indicating D̵ more strongly affects the average length of brushes with low N_wσ^1/2. We propose that the stretching of the stem near the particle surface due to interchain interactions in the CPB regime leads to greater l_b in broad dispersity brushes of low but not high N_wσ^1/2.