Coexistence of crew-cut and starlike spherical micelles composed of copolymers with an annealed polyelectrolyte block.

Y. Lauw, F.A.M. Leermakers, M.A. Cohen Stuart, O.V. Borisov, E.B. Zhulina

    Research output: Contribution to journalArticleAcademicpeer-review

    26 Citations (Scopus)

    Abstract

    The self-assembly of block copolymer AmBn into spherical micelles is analyzed using a numerical self-consistent-field theory. A is the hydrophilic annealed polyacid and B the Hydrophobic part. The degree of polymerization for the polar moiety is fixed (m = 100), whereas that of the tail is varied (n = 100, 200, and 300). The charge in the annealed A block depends on both the pH and the added 1:1 electrolyte concentration ¿s. Beyond the cmc, the diblock copolymers form either low aggregation number starlike or large aggregation number crew-cut micelles. A nonmonotonic behavior of the micellar properties as a function of ¿s for fixed pH is found. For starlike micelles, the scaling of the aggregation number N agg with ¿s is in fair agreement with analytical predictions, i.e., Nagg ~ ¿s0.7-0.9. For the core radius, we find that Rcore ~ ¿s0.24-0.3, and for the corona thickness Tcorona ~ ¿s-0.08. For crew-cut micelles, the scaling exponents deviate significantly from analytical predictions. Upon increasing pH, a smooth transition from crew-cut to starlike micelles happens at high ¿s. Interestingly, a coexistence between these two different micellar sizes is possible for relatively low values of ¿s in a narrow pH range. The corresponding thermodynamics, phase diagram, and various structural properties are presented
    Original languageEnglish
    Pages (from-to)3628-3641
    JournalMacromolecules
    Volume39
    Issue number10
    DOIs
    Publication statusPublished - 2006

    Keywords

    • interacting chain molecules
    • statistical-theory
    • bilayer-membranes
    • mean-field
    • adsorption
    • model
    • thermodynamics
    • micellization
    • morphologies
    • polymers

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