Disk-shaped bicelles in block copolymer/homopolymer blends

TL;DR

This study uses self-consistent field theory to analyze the structure and stability of disk-shaped bicelles formed in block copolymer/homopolymer blends, revealing conditions for their thermodynamic stability.

Contribution

It provides a theoretical investigation of bicelle formation in block copolymer blends, identifying the compositional conditions for their stability and preferred size.

Findings

Bicelles have a lamella-rich center and micelle-rich rim.

Addition of micelle-formers stabilizes bicelles.

Bicelles can be thermodynamically stable within certain concentrations.

Abstract

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 cylindrical and lamellar aggregates, and so might be thermodynamically stable.