Colloidal glass transition in unentangled polymer nanocomposite melts

The linear and non-linear rheology of a high volume fraction particle filled unentangled polymer melt is measured. The particles in the polymer melt behave like hard spheres as the particle volume fraction is raised. At high volume fractions, the suspension develops a plateau elastic modulus. Over the frequency range of the elastic modulus plateau, the viscous modulus develops a minimum and a maximum. The frequencies of the two local extrema initially have critical power law scaling, suggesting the approach of a singular glass transition. At higher volume fractions in excess of the glass transition, the viscous modulus continues to show a well defined minimum and a well defined maximum. The non-linear moduli show a single perturbative yield point beyond which the suspension softens. The yielding behavior of the nanocomposite is shown to be sensitive to the strain frequency and the proximity of the strain frequency to the maximum frequency for the linear viscous modulus from linear rheology which characterizes thermal relaxation of glassy particle clusters in the zero strain limit. The linear and non-linear measurements are compared against a recently developed mechanical theory for colloidal glasses.