Size dependent influence of contact line pinning on wetting of nano-textured/patterned silica surfaces

Abstract

Wetting behavior on a heterogeneous surface undergoes contact angle hysteresis as the droplet stabilized at a metastable state with a contact angle significantly different from its equilibrium value due to contact line pinning. However, there is a lack of consensus on how to calculate the influence of pinning forces. In general, the pinning effect can be characterized as (i) microscopic behavior when a droplet is pinned and the contact angle increases/decreases as the droplet volume increases/decreases and (ii) macroscopic behavior as the pinning effects decrease and ultimately, disappear with the increase of the droplet size. The current work studied both behaviors using molecular dynamics (MD) simulation with more than 300 different size water droplets on silica surfaces with three different patterns across two different wetting conditions. Results showed that the contact angle increases linearly with increasing droplet volume through the microscopic behavior, while the droplet is pinned on top of a certain number of patterns. When we normalized the droplet size with the corresponding pattern size, we observed a “wetting similarity” that linear microscopic contact angle variations over different size heterogeneities continuously line up. This shows that the pinning force remains constant and the resulting pinning effects are scalable by the size ratio between the droplet and pattern, independent of the size-scale. The slope of these microscopic linear variations decreases with an increase in the droplet size as observed through the macroscopic behavior. We further found a universal behavior in the variation of the corresponding pinning forces, independent of the wetting condition. In macroscopic behavior, pinning effects become negligible and the contact angle reaches the equilibrium value of the corresponding surface when the diameter of the free-standing droplet is approximately equal to 24 times the size of the surface structure. We found that the pinning effect is scalable with the droplet volume, not the size of the droplet base.