Controlling the kinetics of viscoelastic phase separation through self-assembly of spherical nanoparticles or block copolymers.

Viscoelastic phase separation (VPS) can produce a network structure of the minor phase, which needs to be stabilized for designing a heterogeneous structure with desired mechanical and electrical functions. In this work, we investigate the stabilization of the VPS-induced network structure in a dynamically asymmetric PS/PVME blend by incorporation of a SEBS-g-MA block copolymer or dimethyldichlorosilane modified nanosilica. The addition of SEBS-g-MA retards the volume shrinking process and slows down the kinetics of phase separation due to its localization at the PS/PVME interfaces. Consequently, in the later stage of VPS, phase inversion occurs at longer times with respect to the neat blend due to the decreased interfacial tension. In contrast, hydrophobic nanoparticles self-assemble in the bulk of PS-rich phase and restrain the dynamics of polymer chains enhancing the dynamic asymmetry of the system. The efficiency of nanoparticles in controlling the kinetics of phase separation is found to be superior compared to block copolymer-based compatibilizers indicating the significance of chain dynamics. Moreover, beyond a critical nanoparticle volume fraction, phase separation is pinned due to particle percolation within the PS-rich phase, yielding a kinetically trapped VPS-induced network structure.