Effect of surface texturing on superoleophobicity, contact angle hysteresis, and "robustness"

Abstract

Previously, we reported the creation of a fluorosilane (FOTS) modified pillar array silicon surface comprising ~3-μm-diameter pillars (6 μm pitch with ~7 μm height) that is both superhydrophobic and superoleophobic, with water and hexadecane contact angles exceeding 150° and sliding angles at ~10° owing to the surface fluorination and the re-entrant structure in the side wall of the pillar. In this work, the effects of surface texturing (pillar size, spacing, and height) on wettability, contact angle hysteresis, and "robustness" are investigated. We study the static, advancing, and receding contact angles, as well as the sliding angles as a function of the solid area fraction. The results reveal that pillar size and pillar spacing have very little effect on the static and advancing contact angles, as they are found to be insensitive to the solid area fraction from 0.04 to ~0.4 as the pillar diameter varies from 1 to 5 μm and the center-to-center spacing varies from 4.5 to 12 μm. On the other hand, sliding angle, receding contact angle, and contact angle hysteresis are found to be dependent on the solid area fraction. Specifically, receding contact angle decreases and sliding angle and hysteresis increase as the solid area fraction increases. This effect can be attributable to the increase in pinning as the solid area fraction increases. Surface Evolver modeling shows that water wets and pins the pillar surface whereas hexadecane wets the pillar surface and then penetrates into the side wall of the pillar with the contact line pinning underneath the re-entrant structure. Due to the penetration of the hexadecane drop into the pillar structure, the effect on the receding contact angle and hysteresis is larger relative to that of water. This interpretation is supported by studying a series of FOTS pillar array surfaces with varying overhang thickness. With the water drop, the contact line is pinned on the pillar surface and very little overhang thickness effect was observed. On the other hand, the hexadecane drop is shown to wet the pillar surface and the side wall of the overhang. It then pins at the lower edge of the overhang structure. A plot of the thickness of the overhang as a function of the static, advancing, and receding contact angles and sliding angle of hexadecane reveals that static, advancing, and receding contact angles decrease and sliding angle increases as the thickness of the overhang increases. A larger overhang effect is observed with octane due to its lower surface tension. The robustness of the pillar array surface against external pressure induced wetting and abrasion was modeled. Surface Evolver simulation (with the hexadecane drop) indicates that wetting breakthrough pressure as high as ~70 kPa is achievable with 0.5-μm-diameter pillar array FOTS surfaces. Mechanical modeling shows that bending of the pillars is the key failure by abrasion, which can be avoided with a short pillar structure. The path to fabricate a superoleophobic surface that can withstand the external force equivalent of a gentle cleaning blade (up to ~30 kPa) without wetting and abrasion failure is discussed.