Simultaneous uniaxial extensional deformation and cylindrical confinement of block copolymers using non-equilibrium molecular dynamics

Abstract

Using coarse-grained nonequilibrium molecular dynamics, symmetric block copolymers are simulated under the combined effects of cylindrical confinement and uniaxial extensional deformation. For a given confinement diameter, a block copolymer (BCP) will self-assemble into a fixed number of concentric cylinder lamellae at equilibrium. The changing diameter during uniaxial extensional deformation therefore is expected to affect the morphology of the BCPs. The aim of this study is to investigate the interplay of deformation and confinement on BCP morphology by varying the simulation strain rate and diameter. Two different simulation approaches are conducted: constant time simulations with varying initial diameter and constant strain simulations with varying simulation time. A comparison of self-assembly at different strain rates shows that for low strain rates, near-equilibrium morphology can form despite the deformation, while for progressively higher strain rates, extra lamellae and disordered morphologies appear. By defining a Weissenberg number based on the deformation and polymer self-assembly time-scales, the morphologies at different strain rates and diameters are explained. Using the time scale analysis, ordered morphologies appear for Wi < 1, while extra lamellae and disordered morphologies occur at Wi > 1. For the latter case, the cylinder diameter shrinks too quickly for polymers to form the equilibrium morphology, which results in a mixture of lamellar structures along the cylinder length.