Disk-like bicelles in block copolymer/homopolymer blends

Mixtures of micelle-forming and lamella-forming amphiphiles in solution can form disk-shaped bilayers, sometimes referred to as bicelles. Using self-consistent field theory (SCFT), we investigate the structure and stability of these aggregates in a blend of two species of PS-PDMS diblock with PDMS homopolymer at 225C. We find that the center of each disk is mainly composed of lamella-forming diblocks, while its thicker rim is mostly formed of micelle-forming diblocks. However, this segregation is not perfect, and the concentration of micelle formers is of the order of 10% on the flat central surface of the bicelle. We also find that the addition of micelle former to the mixture of lamella former and homopolymer is necessary for disk-like bicelles to be stable. Specifically, the free energy density of the disk has a minimum as a function of the disk radius when both micelle- and lamella-forming diblocks are present, indicating that the bicelles have a preferred, finite radius. However, it decays monotonically when only lamella former is present, indicating that the bicelle structure is always unstable with respect to further aggregation in these systems. Finally, we identify a concentration range where the bicelle is predicted to have a lower free energy density than the simple spherical, cylindrical and lamellar aggregates formed with similar amphiphile number fractions

Absence of Schroeder's Paradox in a Nanostructured Block Copolymer Electrolyte Membrane

This is a study of morphology, water uptake, and proton conductivity of a sulfonated polystyrene-block-polyethylene (PSS-PE) copolymer equilibrated in humid air with controlled relative humidity (RH), and in liquid water. Extrapolation of the domain size, water uptake, and conductivity obtained in humid air to RH = 100% allowed for an accurate comparison between the properties of PSS-PE hydrated in saturated vapor and in liquid water. We demonstrate that extrapolations of domain size and water uptake on samples equilibrated in humid air are consistent with measurements on samples equilibrated in liquid water. Small (5%) differences in proton conductivity were found in samples equilibrated in humid air and liquid water. We argue that differences in transport coefficients in disordered heterogeneous systems, particularly small differences, present no paradox whatsoever. Schroeder's Paradox, wherein properties of polymers measured in saturated water vapor are different from those obtained in liquid water, is thus not observed in the PSS-PE sample