The structural properties of neutral oil-in-water (O/W) microemulsions nanodroplets in the presence of telechelic polymers PEO modified with two hydrophobic end functions (PEO- 2m) were studied by Small-Angle Neutron Scattering (SANS). We show that the unknown attractive interaction introduced by the addition of PEO-2m, can could be balanced by a known repulsion interaction due to the addition of a cationic surfactant Cp +, which causes a progressive transformation of the bridges connecting the nanodroplets into loops. For this, we compute the structure factor S(q) with an effective pair potential, using the Ornstein Zernicke (OZ) integral equation approach with the Hypernetted Chain (HNC) closure relation. Generally, the agreement between the neutron scattering spectra and the numerical study is reasonable and allows a detailed description for each sample.

We use dynamic light scattering to investigate the effects of charge polydispersity and charge residence time on the dynamics of a micellar system. While in the corresponding uncharged system only one exponential relaxation is observed, two relaxation modes are seen when charging the micelles by adding charged co-surfactant molecules with a long residence time. We attribute the existence of these two relaxation modes to the combined effect of size polydispersity and charge polydispersity, i.e. frozen fluctuations of the number of charges per micelle. Further support to this scenario is provided by control experiments on a similar charged system, but where the charge residence time is short compared to the time scales probed by dynamic light scattering. Here, charge polydispersity is effectively suppressed due to the rapid exchange of charged molecules between micelles and only one single relaxation mode is seen, thereby demonstrating the key role of frozen charge fluctuations in the complex dynamics of our micellar system.

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