Macromolecules, Vol.39, No.10, 3628-3641, 2006
Coexistence of crew-cut and starlike spherical micelles composed of copolymers with an annealed polyelectrolyte block
The self-assembly of block copolymer A(m)B(n) 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 phi(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 phi(s) for fixed pH is found. For starlike micelles, the scaling of the aggregation number N-agg with phi(s) is in fair agreement with analytical predictions, i.e., N-agg similar to phi(s) (0.7- 0.9). For the core radius, we find that R-core similar to phi(s) (0.24- 0.3), and for the corona thickness T-corona similar to phi(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 phi(s). Interestingly, a coexistence between these two different micellar sizes is possible for relatively low values of phi(s) in a narrow pH range. The corresponding thermodynamics, phase diagram, and various structural properties are presented.