Copolymers micelle relaxation dynamics

We argue that the above features of star dynamics are generic for soft systems of the core-shell type for which stars serve as prototype. Support for this comes from the dynamic light scattering (DLS) investigation of large block copolymer micelles, where all three relaxation modes, i.e., cooperative, structural and selfdiffusion are observed [188]. In particular, the star model discussed above applies to core-shell particles with a small spherical core relative to the chain (shell) dimensions. For a surface number density a = f / (47i r ) the polymer layer thickness under good solvent conditions is L ... 

Keywords Block copolymer micelles Fluorescence anisotropy Fluorescence correlation spectroscopy Molecular dynamics simulations Monte Carlo simulations Solvent relaxation method Time-resolved fluorescence... 

This analysis has been extended to allow for the de-grafting dynamics in the case of aggregated diblock copolymers ". The resulting Kramers type rate theory enables the analysis of the relaxation dynamics of copolymeric micelles". Related studies were reported by Ligoure and Liebler and by Johner and Joanny who respectively considered copolymer adsorption out of non-selective and selective solvents. 

There continues to be extensive interest in latexes and micellar systems. The structure of acrylic latex particles has been investigated by non-radiative energy transfer by labelling the co-monomers with fluorescent acceptor-donor systems. Phase separations could also be measured in this way. Excimer fluorescence has been used to measure the critical micelle temperature in diblock copolymers of polystyrene with ethylene-propylene and the results agree well with dynamic light scattering measurements. Fluorescence anisotropy has been used to measure adsorption isotherms of labelled polymers to silica as well as segmental relaxation processes in solutions of acrylic polymers. In the latter case unusual interactions were indicated between the polymers and chlorinated hydrocarbon solvents. Fluorescence analysis of hydrophobically modifled cellulose have shown the operation of slow dynamic processes while fluorescence... 

The main part is then devoted to the equilibrium exchange kinetics of selected PEP-PEO micellar systems. We report on TR-SANS measurements in pure water that, independently of block copolymer molecular weight, composition, and temperature, revealed frozen micelles. This review further concerns the effect of tuning the kinetics by addition of co-solvents, i.e., reduction of y. The relaxation behavior of some selected systems revealing chain exchange dynamics that can be resolved by TR-SANS wfll be presented, followed by a discussion of the main observation, namely, the unexpected appearance of a pseudo-logarithmic time decay of the relaxation function. 

---