Lack of a unique kinetic pathway in the growth and decay of Pluronic micelles

We report kinetic experiments on dilute brine solutions of P84, P94 and P104 Pluronic copolymer micelles. The growth and the decay of micelles after temperature steps are measured by non-standard time resolved multi-angle photon correlation spectroscopy. Several concurrent mechanisms are at work during the very slow equilibration of solutions, namely insertion/expulsion of unimers, aggregation/dissociation of micellar aggregates, and fusion/budding of micellar aggregates. Their relative rates determine both the kinetic pathways and the morphologies of the micellar assemblies, which depend markedly on modest changes in the copolymer molecular weight. For the typical Pluronic copolymers investigated here, none of these elementary processes can be neglected if the resulting morphology is to be explained. This feature imposes multiple kinetic behaviours where growth and decay of Pluronic micelles become strongly dependent on the thermal history. We point out to some possible shortcomings in the studies of micellar growth kinetics by light scattering techniques. Extensive time-resolved multiangle measurements are a prerequisite for avoiding these pitfalls.