Rheology in shear and elongation and dielectric spectroscopy of polystyrene-block-poly(4-vinylpyridine) diblock copolymers


We elucidate the influence of composition (weight ratios of 89/11, 76/24 and 49/51) and morphology (spherical, cylindrical and lamellar) on the dielectric and viscoelastic properties in shear and elongation of anionically synthesized polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) diblock copolymers in the microphase-separated state. The temperature dependence of the response in both experiments is compared. The analysis of the linear regime shows the appearance of composition (superposition of moduli) and interfacial effects caused by microphase separation (low frequency shoulder, plateau and regime for dynamic moduli and Maxwell-Wagner-Sillars polarization in dielectric experiments). In shear and extensional flows with a constant deformation rate, a pronounced strain-softening behavior in case of a cylindrical and a lamellar morphology appears. For a high weight fraction of the majority phase and a spherical morphology, respectively, strain-softening is observed to a lesser extent. Consequently, strain-softening of diblock copolymer melts can be tuned by the weight/volume ratio of the two blocks.
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