Topological Paths and Transient Morphologies during Formation of Mesoporous Block Copolymer Membranes

We systematically investigated the structure formation pathways and transient morphologies involved in the formation of mesoporous membranes by the self-assembly of block copolymers during nonsolvent-induced phase separation. Using AFM, SEM, and in situ synchrotron SAXS, we mapped the topological paths and characteristic transient structures into a ternary phase diagram. We focused on the stability region of an ordered pore phase which is relevant for the generation of integral asymmetric isoporous membranes. We could identify several characteristic morphologies, i.e., spinodal networks, sphere percolation networks, ordered pore structures, and disordered and ordered cylinder arrangements together with transient structures connecting their stability regions. With given evaporation rates for the pure solvents, we calculated the corresponding composition trajectories in the phase diagram to identify suitable experimental conditions in terms of initial polymer volume fraction, solvent composition, and immersion time to trap the desired pore structure.