Diffusion in microstructured block copolymer solutions

This work explores the effect of heterogeneity of chemical composition on tracer diffusion, when the characteristic size of the heterogeneities approaches that of the diffusing molecule. A heterogeneous environment is created by the self-assembly of diblock copolymers in solution. The system chosen for this study is polystyrene-polyisoprene diblock copolymers in toluene, which is a common solvent for the two blocks. Above a certain critical concentration, these systems are known to microphase separate into swollen domains of polystyrene and polyisoprene. Diffusion of homopolystyrene through the microstructure is measured in this work. The characteristics of the microstructure are varied by studying block copolymers of different molecular weights and compositions. The tracer diffusion coefficients of the labelled polystyrenes are measured by forced Rayleigh scattering, while the microstructure of the matrix is inferred from small angle X-ray scattering measurements. In this paper, we report results for the diffusion of polystyrenes (molecular weights 3.2 × 104 and 9.0 × 104) in microstructured solutions of three copolymers. Two copolymer samples forming lamellae of alternating polystyrene and polyisoprene microphases and one sample forming polystyrene cylinders embedded in a polyisoprene matrix have been examined. The data indicate that the tracer diffusion coefficient of 3.2 × 104 molecular weight polystyrene in lamellar and cylindrical solutions is comparable to that of the homopolymer in a homogeneous solution of the same concentration. In contrast, the diffusion of 9.0 × 104 molecular weight polystyrene is substantially slower in the structured solutions than in unstructured solutions of the same concentration. For example, the diffusion coefficient of 9.0 × 104 molecular weight polystyrene in a 47% block copolymer solution with cylindrical microstructure is lower than its value in a homogeneous solution of the same concentration by a factor of 30.