Self-Limiting Processes in the Flame-Based Fabrication of Superhydrophobic Surfaces from Silicones

Outdoor applications of superhydrophobic coatings require synthetic approaches that allow their simple, fast, scalable, and environmentally benign deployment on large, heterogeneous surfaces and their rapid regeneration in situ. We recently showed that the thermal degradation of silicones by flames fulfills these characteristics by spontaneously structuring silicone surfaces into a hierarchical, textured structure that provides wear-resistant, healable superhydrophobicity. This paper elucidates how flame processing-a simple, rapid, and out-of-equilibrium process-can be so counterintuitively reliable and robust in producing such a complex structure. A comprehensive study of the effect of the processing speed and flame temperature on the chemical and physical properties of the coatings yielded three surprising results. (i) Three thermal degradation mechanisms drive the surface texturing: depolymerization (in the O₂-rich conditions of the surface), decomposition (in the O₂-poor conditions found a few micrometers from the surface), and pyrolysis at excessive temperatures. (ii) The operational condition is delimited by the onset of the depolymerization at low temperatures and the onset of pyrolysis at high temperatures. (iii) The remarkably wide operational conditions and robustness of this approach result from self-limiting growth and oxidation of the silicone particles that are responsible for the surface texturing and in the extent of their deposition. As a result of this analysis we show that superhydrophobic surfaces can be produced or regenerated with this approach at a speed of 15 cm s^-1 (i.e., the length of an airport runway in ∼4.5 h).