Conformational Study on Thin Films of Symmetric AnB2nAn Triblock Copolymer

Abstract

AbstractSummary: The behavior of symmetric AnB2nAn triblock copolymer films confined between two hard neutral walls was explored by Monte Carlo simulation. The thicknesses of the films were between ≈1Rg0 and ≈7Rg0, where Rg0 is the unperturbed radius of gyration in the bulk. The confinement leads to a lamellar structure normal to the wall and the order‐disorder transition (ODT) temperature was found to be a function of film thickness. When the film thickness (D) was less than a critical value, DC, which is between 3Rg0 and 4Rg0, the ODT temperature (T*ODT) reduced by chain length N (T*ODT/N) decreased with decreasing film thickness. However, T*ODT/N was nearly independent of the film thickness when it was greater than DC. In the case of strong confinement (D < DC), the B block shrinks along the direction perpendicular to the wall and stretches along the direction parallel to the wall with decreasing film thickness, and the volume occupied by the B block shrinks. Under weak confinement conditions (D > DC), the volume of the B block is nearly independent of film thickness. The conformations of the B block in the disordered state are quite different from those in the lamellae. If the film is thick enough, the volume of the B block approaches its value in the unperturbed state, regardless of the morphology. When temperature decreases, the B block stretches in the direction perpendicular to the A/B interface and shrinks in the other two directions. In addition, decreasing the temperature leads to the chains adopting two main extreme conformations, coiling or stretching as much as they can. The scaling behavior of the fraction of bridge chains vs. the temperature obtained in the weak segregation limit was different from that predicted in the strong segregation limit.Schematic diagram of the X, Y and Z axis definition.magnified imageSchematic diagram of the X, Y and Z axis definition.