Surface Wrinkling on Polydimethylsiloxane Microspheres via Wet Surface Chemical Oxidation

Here we introduce a simple low-cost yet robust method to realize spontaneously wrinkled morphologies on spherical surfaces. It is based on surface chemical oxidation of aqueous-phase-synthesized polydimethylsiloxane (PDMS) microspheres in the mixed H2SO4/HNO3/H2O solution. Consequently, curvature and overstress-sensitive wrinkles including dimples and labyrinth patterns are successfully induced on the resulting oxidized PDMS microspheres. A power-law dependence of the wrinkling wavelength on the microsphere radius exists. The effects of experimental parameters on these tunable spherical wrinkles have been systematically investigated, when the microspheres are pre-deposited on a substrate. These parameters include the radius and modulus of microspheres, the mixed acid solution composition, the oxidation duration, and the water washing post-treatment. Meanwhile, the complicated chemical oxidation process has also been well studied by in-situ optical observation via the microsphere system, which represents an intractable issue in a planar system. Furthermore, we realize surface wrinkled topographies on the whole microspheres at a large scale, when microspheres are directly dispersed in the mixed acid solution for surface oxidation. These results indicate that the introduced wet surface chemical oxidation has the great potential to apply to other complicated curved surfaces for large-scale generation of well-defined wrinkling patterns, which endow the solids with desired physical properties.