Macromolecules, Vol.39, No.26, 9497-9507, 2006
Spontaneous curvatures of copolymer interfaces in poor solvents: Monolayer morphology
We compute phase diagrams for dilute AB diblock copolymers in poor solvent in the strong segregation limit (SSL), as function of the copolymer volume fractions, from physics derived directly from the properties of the single diblock copolymer and the interfacial surface tension between the solvent and the copolymer. We allow both volumetric as well as stiffness asymmetry between the two diblock components. We also allow for the possibility of reversion of the morphologies, which represent a system that is continuous in polymer rather than solvent. Thereby, we can map transitions between various phases with, e.g., bicontinuous and continuous structures in either solvent or copolymer. We show that the energetically favorable morphologies in the SSL are different from the morphologies in the more studied weak segregation limit (WSL). Transitions from spherical to cylindrical and from cylindrical to bicontinuous phases are observed with increased asymmetry. A remarkable result is that spherical micelles are not favored for very asymmetric polymers except when the solvent-copolymer interaction is very low.