RESUMEN
In this study, the wetting and dewetting behaviors of water nanodroplets containing various molecule numbers on nanopillar-arrayed surfaces in the presence or absence of an external electric field are investigated via molecular dynamics (MD) simulations, aiming to examine whether there is a scale effect. The results show that, in the absence of an electric field, nanodroplets on coexisting Cassie/Wenzel surfaces may be in the Cassie or the Wenzel state depending on their initial states, and apparent contact angles of the Cassie or Wenzel nanodroplets increase monotonously with increasing the droplet size. Energy analysis shows that on the same coexisting Cassie/Wenzel surface, when an electric field is imposed, a small nanodroplet possesses a lower energy barrier separating the Cassie state from the Wenzel state. Therefore, the small nanodroplet is easier to collapse into the Wenzel state. Moreover, the spontaneous Wenzel-to-Cassie dewetting transition is not observed for the nanodroplets after the removal of the electric field because the Wenzel state is a globally stable energetic state. With the same pillar geometry, both the wetting transition and the dewetting transition are significantly modified for liquids with higher intrinsic contact angles. The energy barrier of the wetting transition increases for both the large and small nanodroplets, meaning that the Cassie state becomes more robust. The energy curve shows that the Wenzel state of the large nanodroplet has higher energy so that the droplet can return to the Cassie state when removing the electric field. Intriguingly, although the small Wenzel nanodroplet has lower energy in the presence of the electric field, the dewetting transition still occurs. The increased solid-liquid interfacial tension when removing the electric field is responsible for this abnormal result. The wetting and dewetting transitions follow different energy pathways, leading to a hysteresis energy loop. There exists a critical water molecule number separating the unstable/stable Wenzel configurations, above which the Cassie state is energetically favorable and the dewetting transition can occur spontaneously after removing the electric field.
RESUMEN
Sweeping deposited particles is absolutely essential in order to maintain the excellent functionality of superhydrophobic surfaces. Many methods have been proposed to sweep microparticles deposited on tips of micro/nanostructures. However, how to sweep nanoparticles trapped in cavities of superhydrophobic surfaces has remained an outstanding issue. Here, we show that harnessing the reversible wetting transition provides a feasible way to sweep such nanoparticles. Using molecular dynamics simulations, we demonstrate that the electrically induced CB-W wetting transition makes liquid intrude into a groove and wet a trapped hydrophilic nanoparticle; however, once the electric field is removed, a spontaneous W-CB dewetting transition happens, and the extruded liquid transports the hydrophilic nanoparticle to the groove top, successfully picking up the trapped hydrophilic nanoparticle. We further find that the adhesion between the nanoparticle and groove bottom wall hinders the successful pickup, and picking up such a nanoparticle requires a stronger particle hydrophilicity. With the introduction of amphiphilic Janus particles into a liquid, we exhibit that the electrically induced reversible wetting transition can also successfully pick up a trapped hydrophobic nanoparticle. By means of calculations of the potential of mean force (PMF), we reveal pathways of both the CB-W wetting transition and the W-CB dewetting transition and hence answer why and how a hydrophilic or a hydrophobic nanoparticle is picked up successfully.
RESUMEN
When droplets are placed on hydrophobic textured surfaces, different wetting states Cassie-Baxter (CB) state or Wenzel (W) state may occur depending on materials and structures of surfaces, types and sizes of droplets, thermal fluctuations, and external stimuli. The wetting transition from the CB to the W state and the opposite process have attracted a great deal of attention because of their primary importance for designing and fabricating textured surfaces. In this work, molecular dynamics (MD) simulations are employed to understand the mechanism behind the CB-to-W transition for a nanoscale water film placed on a surface decorated with a single nanogroove when an external electric field is applied. The free energy variation during the transition process is computed on the basis of the restrained MD simulations. Water intrusion into the groove is observed by simulation snapshots, which provides direct evidence for the electric field-induced CB-to-W transition. In the previous experiments, however, only a sharp reduction in the apparent contact angle is employed to judge whether the transition takes place. The free energy curves reveal that there are two energy barriers separating the CB and W states (Δ E1) as well as separating the W and CB states (Δ E2). Owing to the presence of Δ E1, although the CB state has a higher free energy than the W state, it cannot spontaneously convert to the W state. When the external energy input exceeds Δ E1, the CB-to-W transition can be triggered, otherwise the transition will stop, and the water film will return to the CB state. Moreover, it is found that the maximum of free energy always occurs after the film touches the groove bottom. Thus, the requirement that the film should touch the groove bottom is responsible for the presence of the energy barrier Δ E1. Finally, the dependence of the two energy barriers on the electric field strength, groove aspect ratio, and intrinsic contact angle of the groove is also discussed.