Interdiffusion in dilute polymer mixtures. A subtle concentration effect

Dynamic light scattering has been used to investigate the diffusional dynamics in very dilute polystyrene/poly(propylene oxide), PS/PPO, polymer blends. Compared to previous investigations in the field, this system is more suitable for this type of investigation due to the significant refractive index difference between the two components and the fact that the matrix (PPO) dynamics do not interfere with the measurements. The tracer diffusion coefficient of PS thus obtained in the limit of infinite dilution scales as N−0.8±0.04PS with the PS degree of polymerization, i.e., behavior intermediate between the limits of nondraining Zimm and free‐draining Rouse behavior. The effect of the addition of a third component even at tracer concentrations on the diffusion dynamics was investigated both experimentally and theoretically in the framework of the dynamic random phase approximation. Similarities and differences between theory and experiment were found that are rather due to a modification of hydrodynamic interactions