Time-Dependent Wetting Behavior of PDMS Surfaces with Bioinspired, Hierarchical Structures

Wetting of rough surfaces involves time-dependent effects, such as surface deformations, nonuniform filling of surface pores within or outside the contact area, and surface chemistries, but the detailed impact of these phenomena on wetting is not entirely clear. Understanding these effects is crucial for designing coatings for a wide range of applications, such as membrane-based oil–water separation and desalination, waterproof linings/windows for automobiles, aircrafts, and naval vessels, and antibiofouling. Herein, we report on time-dependent contact angles of water droplets on a rough polydimethylsiloxane (PDMS) surface that cannot be completely described by the conventional Cassie–Baxter or Wenzel models or the recently proposed Cassie-impregnated model. Shells of sand dollars (Dendraster excentricus) were used as lithography-free, robust templates to produce rough PDMS surfaces with hierarchical, periodic features ranging from 1 × 10^–7 to 1 × 10^–4 m. Under saturated vapor conditions, we found that in the short term (<1 min), the contact angle of a sessile water droplet on the templated PDMS, θ_SDT = 140 ± 3°, was accurately described by the Cassie–Baxter model (predicted θ_SDT = 137°); however, after 90 min, θ_SDT fell to 110°. Fluorescent confocal microscopy confirmed that the initial reduction in θ_SDT to 110° (the Wenzel limit) was primarily a Cassie–Baxter to Wenzel transition during which pores within the contact area filled gradually, and more rapidly for ethanol–water mixtures. After 90 min, the contact line of the water droplet became pinned, perhaps caused by viscoelastic deformation of the PDMS around the contact line, and a significant volume of water began to flow from the droplet to pores outside the contact region, causing θ_SDT to decrease to 65° over 48 h on the rough surface. The system we present here to explore the concept of contact angle time dependence (dynamics) and modeling of natural surfaces provides insights into the design and development of long- and short-lived coatings.