Understanding the Rheology of Polymer–Polymer Interfaces Covered with Janus Nanoparticles: Polymer Blends versus Particle Sandwiched Multilayers

Abstract

Interfacial rheology is crucial in dictating morphology and ultimate properties of particle-stabilized polymer blends, but is challenging to be determined. In this study, a fully polymeric dumbbell-shaped Janus nanoparticle (JNP) of polymethyl methacrylate (PMMA) and polystyrene (PS) spheres with equal sizes (∼80 nm) was prepared and used as an efficient compatibilizer for PMMA/PS blends. The JNPs were preferentially localized at the PMMA/PS interface, thereby reducing the interfacial tension and refining the morphology in both droplet-matrix and co-continuous type blends, whereby a JNP concentration ∼2.5 wt % is sufficient to reach a saturation in droplet size reduction due to compatibilization. Based on the linear viscoelastic moduli and corresponding relaxation spectra (H(τ)*τ) of JNP-compatibilized droplet-matrix blends, besides the droplet shape relaxation time (τF), a longer relaxation time (τβ), typically related to interfacial viscoelasticity, was readily identified. The dependence of τβ on the JNP concentration (WJNPs) was significantly dominated by the droplet size reduction induced by the JNP compatibilization, with τβ decreasing with increasing WJNPs. The viscoelastic properties extracted from τβ typically originate from a combination of gradients in interfacial tension due to the particle redistribution at the droplet interface (Marangoni stresses) and the deviatoric stresses of intrinsic rheological origin. The latter originate from the intrinsic viscoelasticity of the particle-laden interface, which is enhanced by particle jamming and particle–polymer interactions, such as entanglements between chains from the polymeric spheres and those penetrating from the bulk into the spheres. To address the challenge of isolating these contributions, a JNP-sandwiched PMMA/PS multilayer structure was designed to exclude the effect of Marangoni stresses and droplet curvature, thus having no τF but a new relaxation (τ′β), which characterizes the contribution of intrinsic interfacial viscoelasticity. The τ′β was observed to increase with JNP coverage (Σ) following the Vogel–Fulcher–Tammann model that is typically used to describe the divergent behavior of the “cage” effect in classical colloidal glasses. Moreover, a multimode Maxwell model fitting allows to split the interfacial relaxation into the confined diffusion of JNPs within their cage and the entanglements between the JNPs and the bulk.