Direct observation of nanoparticle-surfactant assembly and jamming at the water-oil interface
Yu Chai, Jaffar Hasnain, Kushaan Bahl, Matthew Wong, Dong Li, Phillip L. Geissler, Paul Y. Kim, Yufeng Jiang, Peiyang Gu, Siqi Li, Dangyuan Lei, Brett A. Helms, Thomas P. Russell, Paul D. Ashby
Abstract
Electrostatic interactions between nanoparticles (NPs) and functionalized ligands lead to the formation of NP surfactants (NPSs) that assemble at the water-oil interface and form jammed structures. To understand the interfacial behavior of NPSs, it is necessary to understand the mechanism by which the NPSs attach to the interface and how this attachment depends on the areal coverage of the interface. Through direct observation with high spatial and temporal resolution, using laser scanning confocal microscopy and in situ atomic force microscopy (AFM), we observe that early-stage attachment of NPs to the interface is diffusion limited and with increasing areal density of the NPSs, further attachment requires cooperative displacement of the previously assembled NPSs both laterally and vertically. The unprecedented detail provided by in situ AFM reveals the complex mechanism of attachment and the deeply nonequilibrium nature of the assembly.