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Asymmetric block copolymers confined in a thin film

We have used a dynamic density functional theory (DDFT) for polymeric systems, to simulate the formation of micro phases in a melt of an asymmetric block copolymer, AnBm(fA=1/3), both in the bulk and in a thin film. In the DDFT model a polymer is represented as a chain of springs and beads. A spring mimics the stretching behavior of a chain fragment and the spring constant is calculated with the Gaussian chain approximation. Simulations were always started from a homogeneous system. We have mainly investigated the final morphology, adopted by the system. First, we have studied the bulk behavior. The diblock copolymer forms a hexagonal packed array of A-rich cylinders, embedded in a B-rich matrix. Film calculations have been done by confining a polymer melt in a slit. Both the slit width and surface-polymer interactions were varied. With the outcomes a phase diagram for confined films has been constructed. Various phases are predicted: parallel cylinders (C∥), perpendicular cylinders (C⊥), parallel lamella...