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Theory of Binary Mixtures of Diblock Copolymers: A New Route to the Double-Diamond & Plumber’s Nightmare Phases

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We study the formation of novel bicontinuous phases in binary mixtures of AB diblock copolymers (DBCP) using the polymeric self-consistent field theory. We predict that the bicontinuous double-diamond (DD) and plumber’s nightmare (P) phases, which are metastable phases of neat diblock copolymers, could be stablized in gyroid-forming A-minority DBCPs via the blending of specifically designed A-majority DBCPs. The mechanisms of stabilizing different bicontinuous phases are revealed by analyzing the spatial distribution of the different DBCPs. It is found that the A-majority DBCPs residing mainly in the nodes of the structure, thus alleviating the packing frustration of the A-blocks. Furthermore, a local segregation of the two DBCPs occurs at the AB interface, thus regulating the local curvature of the interfaces. A synergetic interplay of these two mechanisms results in a larger stable region of the DD and P phases via the addition of tailored A-majority DBCPs. The theoretical study provides an efficient route to obtain novel bicontinuous phases.

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