The effect of polymers on the phase behavior of balanced microemulsions: diblock-copolymer and comb-polymers

The effect of some amphipilic diblock-copolymers and comb-polymers on a balanced Winsor III microemulsion system is investigated with the quaternary system n-octyl-β-d-glucoside/1-octanol/n-octane/D₂O as basis system. The diblock-copolymers are polyethyleneoxide-co-polydodecenoxide (PEO _x PEDODO _y ) and polyethyleneoxide-co-polybutyleneoxide (PEO _x PEBU _y ), constituted of a straight chain hydrophilic part and a bulky hydrophobic part. Addition of the diblock-copolymer leads to an enhancement of the swelling of the middle phase by uptake of water and oil; a maximum boosting factor of 6 was obtained for PEO₁₁₁PEDODO₂₅. Nuclear magnetic resonance diffusometry yields the self-diffusion coefficients of all the components in the system. The diffusion experiments provide information on how the microstructure of the bicontinuous microemulsion changes upon addition of the polymers. The reduced self-diffusion coefficients of water and oil are sensitive to the type of polymer that is incorporated in the film. For the diblock-copolymers, as mainly used here, the reduced self-diffusion coefficient of oil and water will respond to how the polymer bends the film. When the film bends away from water, the reduced self-diffusion of the water will increase, whereas the oil diffusion will decrease due to the film acting as a barrier, hindering free diffusion. The self-diffusion coefficient of the polymer and surfactant are similar in magnitude and both decrease slightly with increasing polymer concentration.