Formation of Perpendicular Three-Dimensional Network Nanostructures in ABC-Star Copolymers

Perpendicular arrangements in hierarchical nanostructures show superior mechanical properties and provide great opportunities for the development of advanced membranes because different channels are connected by the perpendicular blocks. To obtain these perpendicular hierarchical nanostructures, we use a simple ABC-star terpolymer because of the existence of a conjunction point by using the A block as a polymer network template, which guides the BC phase separation accordingly. When χ_BC is 10, the formed phase and the corresponding phase diagram of ABC-star are similar to those of the AB₂ triblock because of the mixture between the B and C blocks. Interestingly, at increased χ_BC, the B and C blocks phase separate, leading to the formation of a series of perpendicular nanostructures, including perpendicular lamellae-in-lamellae (L_⊥), perpendicular lamellae-in-cylinder (C_⊥), and even perpendicular three-dimensional polymer networks (G_⊥). The corresponding stability regime of each phase is identified through the dedicated comparison of free energy, which can well explain the missing phases in Monte Carlo simulations. Our proposed design route according to the target structures and the calculated phase diagram can provide useful guidance for the experimental observation of these perpendicular nanostructures.