Macromolecules, Vol.29, No.16, 5297-5305, 1996
Frs Study of Diffusional Processes in Block Copolymer/Homopolymer Blends Containing Glassy Spherical Micelles
Forced Rayleigh scattering (FRS) was used to study diffusional processes in block copolymer/homopolymer blend systems forming spherical microdomains. Materials used were an asymmetric polystyrene-bloch-polyisoprene copolymer (M(n) = 74 000, 21 wt % polystyrene) labeled with photosensitive dyes (o-nitrostilbene or fluorescein) at the end of polystyrene block chains (b-PS) and two kinds of homopolyisoprene (HPI) (M(n) = 23 000, M(n) = 90 000). Using the lower molecular weight HPI for blending with the block copolymer, b-PS spheres with coronas of polyisoprene block chains (b-PI) strongly swollen by the matrix HPI are obtained (wet-brush system), whereas the HPI matrix having higher M(n) yields much less swollen coronas of b-PI (dry-brush system). The differences between these two systems in structural and dynamical behavior were found by small-angle X-ray scattering and FRS studies, respectively. To exclude chain release from the spherical micelles during the measurements, diffusion has been studied close to the T-g of b-PS microdomains. Unexpectedly, FRS signals differed strongly if measured well below or slightly above the T-g of PS microdomains in both intensity and corresponding diffusional processes.
Keywords:FORCED RAYLEIGH-SCATTERING;COPOLYMER HOMOPOLYMER BLENDS;CUBIC LATTICE SYSTEMS;ORDERED STRUCTURE;PARACRYSTALLINE DISTORTION;ELASTIC-SCATTERING;MOLECULAR-WEIGHT;PHASE-EQUILIBRIA;SELF-DIFFUSION;MIXTURES