Understanding directed assembly of concentrated nanoparticles at energetically heterogeneous interfaces of
1Department of Chemical Engineering, Middle East Technical University, Dumlupınar Bulvarı No.1 Çankaya, Ankara 06800, Turkey.
Abstract:
Colloidal self-assembly has gained significant interest in scientific and technological advances. We investigated the self-assembly of the colloids at fluidic interfaces that mediate elastic interactions. Whereas past studies have reported the assembly of micrometer- or molecular-sized species at aqueous interfaces of liquid crystals (LCs), herein we study the assembly of intermediate-sized nanoparticles. Specifically, surface-modified silica nanoparticles (50 to 500 nm) were adsorbed at the liquid crystal-water interfaces and their positioning was investigated using electron microscopy after polymerization. The study revealed that the electric double layer forces and the elastic forces caused by LC strain are dominant in the assembly of nanoparticles and their contributions can be tuned to direct the self-assembly guided by the sub-interface symmetry of confined cholesteric LCs. At high ionic strengths, we observed a strong localization of nanoparticles at the defects, whereas intermediate strengths resulted in their partial enrichment into cholesteric fingerprint patterns with an interaction energy of ≈3 kBT. This result is comparable with the calculations based on the strength of the binary interactions of the nanoparticles. The findings also support the role of ion partitioning at the LC-aqueous interfaces on the formation of the assemblies. The results can be utilized for applications in sensors, microelectronics, and photonics.
