Polymer diffusion in mixtures of polystyrene and polymethylstyrene studied by forced rayleigh scattering and photon correlation spectroscopy

Tracer diffusion coefficients D^* of both components were measured in mixtures of polystyrene (PS) and polymethylstyrene (PMS), a random copolymer from 60 wt.-% of m-methylstyrene and 40 wt.-% of p-methylstyrene. The results are interpreted in terms of the free-volume theory which yields master curves even for “asymmetric” mixtures of oligomer and polymer chains, if D^* is drawn versus the distance from the glass transition temperature, T–T_g. Whereas D^* was measured by the forced Rayleigh scattering technique, we also studied photon correlation spectroscopy in these mixtures and observed “slow modes” with decay constants that correspond to diffusion coefficients 2–3 decades smaller than the interdiffusion coefficient.