Abstract

We describe morphological variations in binary mixtures of a poly(styrene-b-2-vinylpyridine) diblock copolymer (SP) (Mw = 151K) and poly(4-hydroxystyrene)s (Mw = 8K, 14K, 52K) (H8, H14, H52) as a function of molecular weight of homopolymer H and as a function of blend ratio. Transmission electron microscopy reveals ordered nanophase-separated structures for all samples regardless of molecular weight and the amount of homopolymer added. As much as 28-fold homopolymer H52, which has a Mw higher than that of the P block, can be added to the SP block copolymer without inducing macrophase separation. This unusual miscibility is apparently due to the affinity of P for H via hydrogen-bonding interactions. Furthermore, at a constant volume fraction of polystyrene (ϕs of 0.48) and an H/P ratio of 3.2, a structural transition from hexagonally packed cylinders to lamellae occurs upon increasing the Mw of the homopolymer. The small-angle X-ray scattering (SAXS) data obtained for these blends show that the intercylind...

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