Heat-induced transition of polystyrene-block-poly(ethylene-co-propylene) micelles in decane and in dioxane

Dissolution of polystyrene-block-poly(ethylene co-propylene) (PS-PEP) in decane, a selective solvent for the PEP block, and dioxane, a selective solvent for the PS block, at room temperature leads to formation of metastable micellar structures, which convert into stable micelles with molar mass reduced several times after heating above similar to 50 degrees C. By comparing small-angle X-ray scattering (SAXS) and light scattering (LS) data, the following models of micellar structures are suggested: At room temperature, dissolution of PS-PEP in decane yields aggregates of micelles. These are detected by LS, while SAXS reflects the molar mass of individual micellar cores formed by PS blocks. At elevated temperature, these compound particles disaggregate and then reorganize into equilibrium micelles of reduced molar mass. Solutions of PS-PEP in dioxane at room temperature have a different character. The molar masses of the observed particles determined by SAXS are in a good agreement with LS results, so we can exclude aggregation of micelles in this solvent. Nevertheless, also here, after heat treatment, both SAXS and LS yield a molar mass that is about 5 times lower than that determined for unheated solutions. Metastable structures surviving from the solid-state morphology after dissolution in a selective solvent at room temperature may convert to classical equilibrium micelles only after heating.