Asymmetric polymer mixtures in good solvents: A light scattering study.

Dilute solutions of asymmetric polystyrene/poly(methyl methacrylate) (PS/PMMA) mixtures in toluene and tetrahydrofuran (THF) are investigated by static and dynamic light scattering (SLS and DLS). Both solvents are good solvents for each of the two polymers. In toluene, the PMMA refractive index increment is close to zero and SLS provides a direct measurement of the PS static scattering functions. DLS correlatively leads to a single relaxation mode connected with these PS chains. Contrarily, two modes well separated in time are observed for identical PS/PMMA mixtures in THF. Scattering from the PMMA chains is no longer negligible and partial static scattering functions can only be obtained through SLS-DLS combination. For identical polymer concentration and PS/PMMA mixture composition, PS scattering functions are then found to be different in both solvents. The difference increases with concentration and is only partly due to distinct thermodynamic parameters according to the solvent. PMMA scattering functions lead to similar conclusions. The Random Phase Approximation (RPA) describes all scattering functions. However, the SLS-DLS combination affords a reasonable approximation for extracting the partial static scattering functions only for the lowest concentrations, i.e. provided the cross polymer correlation term remains negligible.