No abstract

We experimentally and theoretically examine the influence of a double-chain cationic surfactant, didodecyldimethylammonium bromide (DDAB), on the wetting states and contact angles on superhydrophobic (SH) surfaces made of hydrophobic microcylinders. We use two types of micropatterns of different surface roughness, r, and packing fraction, ϕ, and vary nine dimensionless surfactant concentrations (C S), normalized by the critical micelle concentration (CMC), in the experiments. At low C S, some of the surfactant-laden droplets are in a gas-trapping, Cassie–Baxter (CB) state on the high-roughness microstructures. In contrast, some droplets are in a complete-wetting Wenzel (W) state on the low-roughness microtextures. We found that the contact angle of CB drops can be well predicted using a thermodynamic model considering surfactant adsorption at the liquid–vapor (LV) and solid–liquid (SL) interfaces. At high C S, however, all of the DDAB drops wet in a Wenzel mode. Based on a Gibbsian thermodynamic analysis, we find that for the two types of superhydrophobic surfaces used, the Wenzel state has the lowest thermodynamic energy and thus is more favorable theoretically. The CB state, however, is metastable at low C S due to a thermodynamic energy barrier. The metastable CB wetting state becomes more stable on the SH microtextures with greater ϕ and r, in agreement with our experimental observations. Finally, we generalize this surface-energy analysis to provide useful designs of surface parameters for a DDAB-laden surfactant droplet on the SH surface with a stable and robust CB state.

We report facile one- and two-step processes for the fabrication of transparent ultrahydrophobic surfaces and three-dimensional (3D)-printed superhydrophobic (SH) microstructures, respectively. In the one-step method, polydimethylsiloxane (PDMS) solution is treated thermally at 350 °C for 4 h, while PDMS-soot is generated and deposited on a glass slide to obtain a transparent SH surface without further chemical modification. For the two-step approach, SH surfaces are obtained by incorporating a 3D printing technique with a convenient hydrophobic coating method. Herein, we first 3D-print microstructured substrates with particular surface parameters, which are designed to facilitate a stable gas-trapping Cassie–Baxter (CB) wetting state based on a thermodynamic calculation. We subsequently coat the 3D-printed microstructures with candle soot (CS) or octadecyltrichlorosilane (OTS) solution to make superhydrophobic surfaces with mechanical durability. These surfaces exhibit an ultrahigh static water contact angle (CA, θ ≃ 158 ± 2 and 147 ± 2° for the CS and OTS coating, respectively) and a low roll-off angle for water droplets. Both static and dynamic (in terms of the advancing and receding) contact angles of a water droplet on the fabricated SH surfaces are in good agreement with the theoretical prediction of Cassie–Baxter contact angles. Furthermore, after a one-year-long shelf time, the SH substrates fabricated sustain good superhydrophobicity after ultrasonic water treatment and against several chemical droplets. All of these methods are simple, cost-effective, and highly efficient processes. The processes, design principle, and contact angle measurements presented here are useful for preparing transparent and superhydrophobic surfaces using additive manufacturing, which enables large-scale production and promisingly expands the application scope of utilizing self-cleaning superhydrophobic material.

Surfactant-laden sessile droplet evaporation plays a crucial role in a variety of omnipresent natural and technological applications, such as drying, coating, spray, and inkjet printing. Surfactant molecules can adsorb easily on interfaces and, hence, destructively ruin the useful gas-trapping wetting state (i.e., Cassie–Baxter, CB) of a drop on superhydrophobic (SH) surfaces. However, the influence of surfactant adsorption or concentration on evaporation modes has been rarely investigated so far. Here, we investigate the evaporation dynamics of aqueous didodecyldimethyl­ammonium bromide (DDAB) sessile droplet on SH surfaces made of regular hydrophobic micropillars, with various dimensionless surfactant concentrations (C S), primarily using experiments. We find that all drops initially form a CB state with a pinned base radius and evaporate in a mode of constant contact radius (CCR). Water and low-C S (=0.02) drop subsequently evaporate with a constant contact angle (CCA) mode, followed by a CCR mode and, eventually, a mixed-mode. By contrast, high-C S (of 0.25–1) droplets undergo a complex mixed mode, with rapidly increasing base radius, and finally a mixed mode, with slowly decreasing base radius and contact angle. The experimental data reveal that contact-angle-dependent evaporative mass flux, ṁ, collapses onto a nearly universal curve depending on C S. For the low-C S (of 0–0.25) drops, ṁ is lower and consistent with an evaporative cooling model, whereas high-C S (of 0.5–1) droplets are consistent with a pure vapor-diffusive model. We further show that the critical C S delineating these two evaporative models correlates with saturated surfactant adsorption on both liquid–solid and liquid–vapor interfaces.

Ionic liquids (ILs)salts in a liquid stateplay a crucial role in various applications, such as green solvents for chemical synthesis and catalysis, lubricants, especially for micro- and nanoelectromechanical systems, and electrolytes in solar cells. These applications critically rely on unique or tunable bulk properties of ionic liquids, such as viscosity, density, and surface tension. Furthermore, their interactions with different solid surfaces of various roughness and structures may uphold other promising applications, such as combustion, cooling, and coating. However, only a few systematic studies of IL wetting and interactions with solid surfaces exist. Here, we experimentally and theoretically investigate the dynamic wetting and contact angles (CA) of water and three kinds of ionic liquid droplets on hydrophobic microstructures of surface roughness (r = 2.61) and packing fraction (ϕ = 0.47) formed by micropillars arranged in a periodic pattern. The results show that, except for water, higher-viscosity ionic liquids have greater advancing and receding contact angles with increasing contact line velocity. Water drops initially form a gas-trapping, CB wetting state, whereas all three ionic liquid drops are in a Wenzel wetting state, where liquids penetrate and completely wet the microstructures. We find that an existing model comparing the global surface energies between a CB and a Wenzel state agrees well with the observed wetting states. In addition, a molecular dynamic model well predicts the experimental data and is used to explain the observed dynamic wetting for the ILs and superhydrophobic substrate. Our results further show that energy dissipation occurs more significantly in the three-phase contact line region than in the liquid bulk.