Complex Polymeric Microstructures with Programmable Architecture via Pickering Emulsion-Templated In Situ Polymerization

Aside from smooth and spherical microcapsules, the concept of tailoring complex polymeric microstructures is being taken a step ahead due to their great demand in various applications and fundamental studies in the subjects of microfluidics and nanotechnology. Size, shape, and morphology are of paramount importance for their functional performance and various applications. However, simple, inexpensive, versatile, and high-throughput techniques for fabricating microcapsules with controlled morphology remain a bottleneck for discoveries in the subject of polymer colloids. In this paper, we directly fulfill this need by reporting a novel approach of Pickering emulsion-templated in situ polymerization for tailoring complex polymeric microstructures comprised of a composite shell of titanium dioxide nanoparticle (TiO2 NP)-embedded poly(melamine-urea-formaldehyde) (polyMUF) and a core of hexadecane (HD, soft template). At first, we hydrophobize TiO2 NPs by chemisorbing long-chain biobased myristic acid via a bidentate chelating complex and precisely tune their wettability by varying the grafting density of myristic acid to obtain highly stable oil-in-water (O/W) Pickering emulsion. Thereafter, we employ the optimized TiO2 NPs in the intended encapsulation strategy that enables various microstructures and morphologies with the particle diameter ranging from 5 to 20 μm. Careful manipulation of reaction parameters and copolymer components leads to novel complex microstructures: smooth, raspberry-like, partially budded, hollow, filled, single-holed, and closed-cell-like microstructures. Particle properties such as morphology, size, shell thickness, and core content are governed by the TiO2 NP content, core-to-shell ratio, copolymer component, conversion, and pH value. Based on the results of a series of control experiments, novel mechanisms for the formation of various such microstructures are proposed.