Orientation of Supramolecular Self-Organized Polymeric Nanostructures by Oscillatory Shear Flow

Macroscopic orientation of self-organized supramolecular polymeric materials has been demonstrated by oscillatory shear flow using in-situ small-angle X-ray scattering (SAXS). In the case when a homopolymer poly(4-vinylpyridine) and pentadecylphenol molecules are stoichiometrically complexed to form comb copolymer-like supermolecules, the self-organized lamellar local structures align parallel when sheared below the order−disorder transition temperature at 56 °C using 0.5 Hz frequency and 100% strain amplitude. Therefore, the hydrogen bonds between the phenolic and pyridine groups are strong enough to withstand the applied flow. In the case of a diblock copolymer of polystyrene and poly(4-vinylpyridine) stoichiometrically complexed with pentadecylphenol molecules to form the supermolecules, the self-organization yields lamellar- within -lamellar local structure near room temperature. The larger lamellar diblock copolymer structure showed a parallel orientation relative to the shearing plates upon shearing at 125 °C (i.e., above the order−disorder transition of the short length scale comb copolymer-like structure) with initially 0.5 Hz and finally 1 Hz, both at 50% strain amplitude. On cooling, the short length scale lamellar structure, consisting of poly(4-vinylpyridine) block and pentadecylphenol, is formed inside the layers of the comb copolymer-like material in perpendicular orientation.