Effect of Surfactant Selectivity on Shape and Inner Morphology of Triblock Terpolymer Microparticles

The confined assembly of block copolymers (BCPs) has become a useful tool to prepare microparticles with controlled anisotropy and inner structure. While a solid understanding of the behavior of AB diblock copolymers exists, knowledge on the parameters affecting ABC triblock terpolymer assembly is much more limited. In this work, the effect of block-selective surfactants, sodium-4-vinylbenzenesulfonate (VBS) and sodium dodecylsulfate (SDS), is analyzed in the evaporation-induced confined assembly (EICA) of a polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock terpolymer (SBM). Despite using the same terpolymer and emulsification process, SDS results in ellipsoidal microparticles with axially stacked lamellae, while VBS results in spherical microparticles with concentric lamellae or 3D spiral morphology. This change in morphology upon switching the surfactant is further substantiated by molecular simulations and enhances the understanding of terpolymer microphase separation in confinement.