How Surfactants Affect Droplet Wetting on Hydrophobic Microstructures

Surfactants, as amphiphilic molecules, adsorb easily at interfaces and can detrimentally destroy the useful, gas-trapping wetting state (Cassie–Baxter, CB) of a drop on superhydrophobic surfaces. Here, we provide a quantitative understanding of how surfactants alter the wetting state and contact angle of aqueous drops on hydrophobic microstructures of different roughness (r) and solid fraction (ϕ). Experimentally, at low surfactant concentrations (C), some drops attain a homogeneous wetting state (Wenzel, W), while others attain the CB state whose large contact angles can be predicted by a thermodynamic model. In contrast, all of our high-C drops attain the Wenzel state. To explain this observed transition, we consider the free energy and find that, theoretically, for our surfaces the W state is always preferred, while the CB state is metastable at low C, consistent with experimental results. Furthermore, we provide a beneficial blueprint for stable CB states for applications exploiting superhydrophobicity.