Equilibrium exchange kinetics in PEP-PEO block copolymer micelles. A time resolved SANS study

The chain exchange kinetics in polymeric micelles has been studied by a novel time resolved small angle neutron scattering (TR-SANS) technique. The system investigated was the amphiphilic block copolymer poly(ethylene-alt-propylene)-poly(ethylene oxide) (PEP-PEO) in water/N, N-dimethylformamide (DMF) mixtures as selective solvent for PEO. The TR-SANS technique exploits the large difference in scattering length density of deuterated and protonated species allowing for a detailed study of chain exchange kinetics with virtually no perturbation from equilibrium. The measured relaxation curves show a fast initial decay which gradually slows down at longer times. This extremely broad and heterogeneous decay drastically deviates from single exponential predicted by the scaling theory of Halperin and Alexander. Instead, the data appear to follow a logarithmic time dependence. This behavior most likely stems from a heterogeneous release of core chains caused by strong topological correlations inside the small micellar cores. (c) 2006 Elsevier B.V. All rights reserved.