Asymmetric poly(ethylene-alt-propylene)-poly(ethylene oxide) micelles: A system with starlike morphology and interactions

We report on an experimental study of single particle properties and interactions of poly(ethylene-alt-propylene)-poly(ethylene oxide) (PEP-PEO) starlike micelles. The starlike regime is achieved by an extremely asymmetric block ratio (1:20) and the number of arms (functionality) is changed by varying the composition of the solvent (the interfacial tension). Small angle neutron scattering (SANS) data in the dilute regime can be modeled by assuming a constant density profile in the micellar core (compact core) and a starlike density profile in the corona (starlike shell). The starlike morphology of the corona is confirmed by a direct comparison with SANS measurements of dilute poly butadiene star solutions. Comparison of structure factors obtained by SANS measurements in the concentrated regime shows in addition that the interactions in the two systems are equivalent. Micellar structure factors at several packing fractions can be modeled by using the ultrasoft potential recently proposed for star polymers [Likos, Phys. Rev. Lett. 80, 4450 (1998)]. The experimental phase diagram of PEP-PEO micelles is quantitatively compared to theoretical expectations, finding good agreement for the location of the liquid-solid boundary and excellent agreement for the critical packing fraction where the liquid-to-bcc crystal transition takes place for f<70. The functionality, i.e., the coronal density, strongly influences the nature of the solid phase: for f<70 the system crystallizes into a bcc phase, high f>70 formation of amorphous arrested states prevents crystallization.