Control of Buckling of Colloidal Supraparticles

TL;DR

This paper demonstrates how controlling particle-surfactant interactions through pH manipulation during emulsion templating enables precise control over the buckling and final morphology of colloidal supraparticles.

Contribution

It introduces a method to control supraparticle morphology by tuning the timing of interfacial adsorption via pH adjustments during assembly.

Findings

Buckling is influenced by particle-surfactant interactions.

pH manipulation allows control over supraparticle morphology.

Final structures range from buckled to smooth surfaces.

Abstract

Clusters of colloidal particles, often termed supraparticles, can provide more functionality than the individual particles they consist of. Since these functionalities are determined by the arrangement of the primary particles within a supraparticle, controlling the structure formation process is of fundamental importance. Here, we show how buckling is determined by particle-surfactant interactions and how the final morphology of the formed supraparticles can be controlled by manipulating these interactions in time. We use water/oil emulsions to template supraparticle formation and tailor the interactions of negatively charged colloidal particles with the surfactants stabilizing the water/oil-interface via the local pH within the aqueous droplet. At low pH, protonation of the anionic headgroup of the surfactant decreases electrostatic repulsion of the particles, facilitates interfacial adsorption, and subsequently causes buckling. We show that the local pH of the aqueous phase continuously changes during the assembly process. We gain control over the formation pathway by determining the point in time when interfacial adsorption is enabled, which we control via the initial pH. As a consequence, the final supraparticle morphology can be tailored at will, from fully buckled structures, via undulated surface morphologies to spherically rough and spherically smooth supraparticles and crystalline colloidal clusters.