Thermal Properties of Particle Brush Materials: Effect of Polymer Graft Architecture on the Glass Transition Temperature in Polymer-Grafted Colloidal Systems

The governing parameters controlling the glass transition temperature of polymer-grafted particle systems are analyzed for the particular case of polystyrene (PS)-grafted silica colloids in the dense grafting limit. At a given degree of polymerization of surface-grafted chains the glass transition temperature is found to increase as compared to linear chain polymers of equivalent degree of polymerization. The difference in the glass transition temperature between polymer-grafted particle systems and their respective linear polymer analogs increases with decreasing degree of polymerization of surface-grafted chains and levels off at similar plateau values for particle brushes of distinct particle core size. The trend toward increased glass transition temperature is interpreted as a consequence of the increased steric hindrance in polymer-grafted particles that counteracts the relaxation of surface-grafted polymer chains. The increase in glass transition temperature is shown to be approximately consistent with the chain conformational regimes that are predicted on the basis of a Daoud-Cotton type scaling model.