Rearrangement of micelle structures during polymerization

Full text: Using small angle neutron scattering (SANS), we studied the shape transition of micelles of 11(methacryloyloxy)undecyltrimethylammonium bromide (MUTAB) as this tail-polymerisable cationic surfactant polymerized. Previous studies of such systems have suggested kinetic 'locking' of the micelle structure during polymerization. However, we found a transition from spheres (unpolymerised) to rods (at intermediate conversions) back to spheres (fully polymerized), see Figure 1. By comparing these results to the micelle shapes formed by the mixtures of 100% polymerized and unpolymerised MUTAB, we show that the shape transitions observed during polymerization are due to equilibrium structures that undergo rearrangement as the composition changes. In addition, atomic force microscopy (AFM) reveals that besides the monolayer of unpolymerised MUTAB, the rearranged structures of this surfmer in bulk, when polymerization proceeded, retained their shapes after adsorbing at mica/solution interface, providing potential for the manipulating of thin film structures. This understanding assists design of templating or encapsulating nanostructured materials.