The stress deformation response influenced by the chain rigidity for mesostructures in diblock copolymers

Abstract

A self-consistent field theory formalism based on the wormlike chain model is developed to investigate the stress–strain relation for mesostructures in diblock copolymers under the influence of chain rigidity, involving the adjustable simulation cell in the non-orthogonal coordinates by means of optimization of free energy. We elucidate the effect of the chain persistency broadly spanning from the Gaussian chain to the rigid rodlike chain on the elastic response of mesophases that deviate from the initial equilibrium structures. We analytically and numerically demonstrate that our current approach in the long chain limit recovers to the Gaussian-chain-based theory. Being ascribed to the distinct conformational behaviors for flexible chains and rigid rodlike chains, the tensile and compressive stresses applied to lamellae exhibit asymmetric deformation behaviors and the shear stress applied to the initial equilibrium hexagonal cylinders results in noticeable deviations in the shape and spatial arrangement of cylindroids for various chain rigidity values. For the zero stress, in addition, our approach can be straightforwardly utilized to explore the optimal size and shape of the simulation cell in order to achieve a stress free configuration of systems.