We have studied the solubilization behavior of tributylphosphate (TBP) in aqueous solutions of L64-Pluronics, using light and small angle neutron scattering (SANS). Varying the temperature and the oil content, the system presents a nontrivial phase behavior. In particular, at 308 K, a first solubilization followed by an emulsification failure and a resolubilization is found. We have measured the microstructure by SANS and characterized the microemulsion droplet core size, corona thickness, polydispersity, and interactions. It is shown that at low oil content, the system is made of small swollen micelles. After the phase separation, the resolubilization is carried by larger oil droplets decorated by copolymer. From specific surface measurements at large angles, a surprising change in surfactant conformation is found to accompany this morphological evolution which is also supported by previous results obtained from ¹H NMR experiments. In independent measurements, our structural modeling is confirmed using contrast-variation SANS.
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