Microstructural Dynamics and Rheology of Worm-like Diblock Copolymer Nanoparticle Dispersions under a Simple Shear and a Planar Extensional Flow.

Abstract

We investigate the shear and extensional flow behavior of dispersions composed of two types of worm-like nanoparticles (WLNPs) with comparable cross-sectional diameters, similar persistence lengths but differing contour lengths, and thus differing flexibility. By measuring the flow-induced birefringence (FIB) of WLNP dispersions in two contrasting microfluidic devices, we obtain an experimental quantification of the role of shearing and planar extensional flows at aligning a short and stiff WLNP (S-WLNP) and a relatively long and flexible WLNP (L-WLNP). We show that shear and extensional flows induce the alignment of both types of WLNPs. However, extensional deformations are more effective than shear deformations at triggering the onset of alignment of the WLNP. The difference between shear and extensional deformations for WLNP alignment is explained based on the ratio of extensional and shear viscosity of the solvent fluid (Trouton ratio of the solvent) and a structural parameter related to the WLNP extensibility and flexibility. Under shear flow, these WLNP dispersions display shear-thinning behavior, with an exponential reduction in viscosity with increasing alignment. Under extensional flow, the WLNP alignment leads to extensional thinning, making WLNP ideal additives for industrial and biotechnology formulations exposed to extensional dominated flows (e.g., jetting, spraying, and printing processes).