Structure of The Diblock Co-Polywer Aggregates in Solution

We have employed a variety of scattering techniques to study the structure of diblock copolymer aggregates in solution The system of interest is an anionically prepared poly(styrene-isoprene) diblock copolymer (PS-PI) with well defined molecular weight and composition. When the diblock copolymer is added to decane, which dissolves the polyisoprene but not the polystyrene, we observe that polymeric micelles form at concentrations above a critical micellar concentration. The aggregation number is determined by light scattering and neutron scattering to be roughly 120. The micellar aggregate consists of a spherical polystyrene core with a mean radius of 105 A surrounded by a PI corona. The size distribution is quite narrow (<10%). The PS core is swollen with the solvent by roughly a factor of 2 in volume. By combining dynamic light scattering and SANS, we determined the thickness of the corona to be 50 A, which is 70% larger than the radius of gyration of a free PI chain of the same molecular weight in a good solvent. Furthermore, SANS measurements suggest that the aggregates form an ordered phase at the nominal cross-over concentration as it is expected for a highly functionalized star-branched macromolecules in solution.