Phase-dependent shear-induced order of nanorods in isotropic and nematic wormlike micelle solutions

Abstract

Small angle X-ray scattering with in situ shear was employed to study the assembly and ordering of dispersions of gold nanorods within wormlike micelle solutions formed by the surfactant cetylpyridinium chloride (CPyCl) and counter-ion sodium salicylate (NaSal). Above a threshold CPyCl concentration but below the isotropic-to-nematic transition of the micelles, the nanorods self-assembled under quiescent conditions into isotropically oriented domains with hexagonal order. Under steady shear at rates between 0.5 and 7.5 s⁻¹, the nanorod assemblies acquired macroscopic orientational order in which the hexagonal planes were coincident with the flow-vorticity plane. The nanorods could be re-dispersed by strong shear but re-assembled following cessation of the shear. In the nematic phase of the micelles at higher surfactant concentration, the nanorods did not acquire hexagonal order but instead formed smectic-like layers in the gradient–vorticity plane under shear. Finally, at still higher surfactant concentration, where the micelles form a hexagonal phase, the nanorods showed no translational ordering but did acquire nematic-like order under shear due to alignment in the flow. Depletion forces mediated by the wormlike micelles are identified as the driving mechanism for this sequence of nanorod ordering behaviors, suggesting a novel mechanism for controlled, reconfigurable assembly of nanoparticles in solution.