Small-Angle Neutron Scattering and Theoretical Investigation of Poly(ethylene oxide)−Poly(propylene oxide)−Poly(ethylene oxide) Stabilized Oil-in-Water Microemulsions

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Abstract
The aim of this study is to determine the effects of oil solutes and alcohol cosolvents on the structure of oil-in-water microemulsions stabilized by poly(ethylene oxide)−poly(propylene oxide)−poly(ethylene oxide) (PEO−PPO−PEO) triblock copolymers. The systems investigated involved the solubilization of 1,3,5-trimethylbenzene or 1,2-dichlorobenzene by P123 (EO20−PO70−EO20) pluronic surfactant micelles in water and water + ethanol solvents. The structures of these swollen micelles were determined by small-angle neutron scattering (SANS). A thermodynamic model was employed to interpret the characterization data. The results of the thermodynamic model for micellization agreed well with the SANS data from samples of micelles swollen by both oils. The model predicted the size of the micelles within 5% accuracy using only one fitting parameter, the micelle polydispersity. Ethanol had significantly different effects on the polymer micelles that contained solubilized oil compared to pure polymer micelles. For pure polymer micelles, the addition of ethanol increased the solubility of the polymer and, therefore, decreased the total volume fraction of micelles, while for polymer−oil aggregates, ethanol tended to have a positive effect on the volume fraction of micelles. SANS results showed that the greatest divergence from pure aqueous solvent results occurred at oil concentrations above the microemulsion stability limit.