Malo de Molina, P.P.Malo de MolinaIhlefeldt, F.F.IhlefeldtPrevost, S.S.PrevostHerfurth, C.C.HerfurthAppavou, M.-S.M.-S.AppavouLaschewsky, A.A.LaschewskyGradzielski, M.M.Gradzielski2022-03-042022-03-042015https://publica.fraunhofer.de/handle/publica/23978710.1021/acs.langmuir.5b00817The polymer architecture of telechelic or associative polymers has a large impact on the bridging of self-assembled structures. This work presents the phase behavior, small angle neutron scattering (SANS), dynamic light scattering (DLS), and fluorescence correlation spectroscopy (FCS) of a nonionic oil-in-water (O/W) microemulsion with hydrophobically end-capped multiarm polymers with functionalities f = 2, 3, and 4. For high polymer concentrations and large average interdroplet distance relative to the end-to end distance of the polymer, the system phase separates into a dense, highly connected droplet network phase, in equilibrium with a dilute phase. The extent of the two-phase region is larger for polymers with similar length but higher f. The interaction potential between the droplets in the presence of polymer has both a repulsive and an attractive contribution as a result of the counterbalancing effects of the exclusion by polymer chains and bridging between droplets. This study experimentally demonstrates that higher polymer functionalities induce a stronger attractive force between droplets, which is responsible for a more extended phase separation region, and correlate with lower collective droplet diffusivities and higher amplitude of the second relaxation time in DLS. The viscosity and the droplet self-diffusion obtained from FCS, however, are dominated by the end-capped chain concentration.en541journal article