Droplet Size-Assisted Polysiloxane Architecting

Langmuir. 2023 Jan 10;39(1):377-388. doi: 10.1021/acs.langmuir.2c02607. Epub 2022 Dec 17.

Abstract

(Super)antiwetting shielding around engineering materials and protecting them against harsh environmental conditions have been achieved via growing various geometry polysiloxane (or silicone) patterns around them by using a droplet-assisted growth method, where the polymerization takes place inside of the water droplets acting as reaction vessels. The size and distribution of these reaction vessels are the main factors in making different geometry silicone patterns; however, very little is known about the fate of these droplets throughout the polymerization. Here, we propose keeping the relative humidity (% RH) inside the reactor stable throughout the polymerization as a new coating parameter to force the size of the reaction vessel water droplets to be the same for building simply shaped silicone rods with controlled geometry and distribution. In this manner, we grew simple geometry cylindric microrods on surfaces and could tune their length, diameter, inter-rod spacing, and thus the (super)hydrophobicity. Here, we also demonstrate that with changes in the amplitude and stability of the % RH, it is possible to fabricate different (super)hydrophobic nanograsses, conical silicone microrods, and isotropic silicone nanofilaments. The proposed new way of tuning initial and in situ reaction vessel droplet size can be used as a single factor to formulate different geometry silicone patterns with tunable dimensions, leading to different roughness and hydrophobicity. To a certain extent, the droplet size-assisted silicone shaping in this work provides a new way to control the length, diameter, morphology, inter-rod spacing, and thus the (super)hydrophobicity of the silicone patterns, especially those in the shape of simple cylindrical microrods. This control over silicone architecting will help to prepare new (super)hydrophobic coatings with more controlled morphology and thus wettability; on the contrary, it will support surface scientists modeling the connection between surface geometry and (super)antiwetting of such irregular pillared surfaces that remain elusive.