Probing the physical origins of droplet friction using a critically damped cantilever.

Previously, we and others have used cantilever-based techniques to measure droplet friction on various surfaces, but typically at low speeds U < 1 mm s-1; at higher speeds, friction measurements become inaccurate because of ringing artefacts. Here, we are able to eliminate the ringing noise using a critically damped cantilever. We measured droplet friction on a superhydrophobic surface over a wide range of speeds U = 10-5-10-1 m s-1 and identified two regimes corresponding to two different physical origins of droplet friction. At low speeds U < 1 cm s-1, the droplet is in contact with the top-most solid (Cassie-Baxter), and friction is dominated by contact-line pinning with Ffric force that is independent of U. In contrast, at high speeds U > 1 cm s-1, the droplet lifts off the surface, and friction is dominated by viscous dissipation in the air layer with Ffric ∝ U2/3 consistent with Landau-Levich-Derjaguin predictions. The same scaling applies for superhydrophobic and underwater superoleophobic surfaces despite their very different surface topographies and chemistries, i.e., the friction scaling law derived here is universal.

Emergent Collective Motion of Self-Propelled Condensate Droplets.

Recently, there is much interest in droplet condensation on soft or liquid or liquidlike substrates. Droplets can deform soft and liquid interfaces resulting in a wealth of phenomena not observed on hard, solid surfaces (e.g., increased nucleation, interdroplet attraction). Here, we describe a unique collective motion of condensate water droplets that emerges spontaneously when a solid substrate is covered with a thin oil film. Droplets move first in a serpentine, self-avoiding fashion before transitioning to circular motions. We show that this self-propulsion (with speeds in the 0.1-1 mm s^{-1} range) is fueled by the interfacial energy release upon merging with newly condensed but much smaller droplets. The resultant collective motion spans multiple length scales from submillimeter to several centimeters, with potentially important heat-transfer and water-harvesting applications.

Mitigating cavitation erosion using biomimetic gas-entrapping microtextured surfaces (GEMS).

Cavitation refers to the formation and collapse of vapor bubbles near solid boundaries in high-speed flows, such as ship propellers and pumps. During this process, cavitation bubbles focus fluid energy on the solid surface by forming high-speed jets, leading to damage and downtime of machinery. In response, numerous surface treatments to counteract this effect have been explored, including perfluorinated coatings and surface hardening, but they all succumb to cavitation erosion eventually. Here, we report on biomimetic gas-entrapping microtextured surfaces (GEMS) that robustly entrap air when immersed in water regardless of the wetting nature of the substrate. Crucially, the entrapment of air inside the cavities repels cavitation bubbles away from the surface, thereby preventing cavitation damage. We provide mechanistic insights by treating the system as a potential flow problem of a multi-bubble system. Our findings present a possible avenue for mitigating cavitation erosion through the application of inexpensive and environmentally friendly materials.

Proof-of-Concept for Gas-Entrapping Membranes Derived from Water-Loving SiO2/Si/SiO2 Wafers for Green Desalination.

Desalination through direct contact membrane distillation (DCMD) exploits water-repellent membranes to robustly separate counterflowing streams of hot and salty seawater from cold and pure water, thus allowing only pure water vapor to pass through. To achieve this feat, commercial DCMD membranes are derived from or coated with water-repellent perfluorocarbons such as polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF). However, the use of perfluorocarbons is limiting due to their high cost, non-biodegradability, and vulnerability to harsh operational conditions. Unveiled here is a new class of membranes referred to as gas-entrapping membranes (GEMs) that can robustly entrap air upon immersion in water. GEMs achieve this function by their microstructure rather than their chemical make-up. This work demonstrates a proof-of-concept for GEMs using intrinsically wetting SiO2/Si/SiO2 wafers as the model system; the contact angle of water on SiO2 is θo ≈ 40°. Silica-GEMs had 300 µm-long cylindrical pores whose diameters at the (2 µm-long) inlet and outlet regions were significantly smaller; this geometrically discontinuous structure, with 90° turns at the inlets and outlets, is known as the "reentrant microtexture". The microfabrication protocol for silica-GEMs entails designing, photolithography, chrome sputtering, and isotropic and anisotropic etching. Despite the water loving nature of silica, water does not intrude silica-GEMs on submersion. In fact, they robustly entrap air underwater and keep it intact even after six weeks (>106 seconds). On the other hand, silica membranes with simple cylindrical pores spontaneously imbibe water (< 1 s). These findings highlight the potential of the GEMs architecture for separation processes. While the choice of SiO2/Si/SiO2 wafers for GEMs is limited to demonstrating the proof-of-concept, it is expected that the protocols and concepts presented here will advance the rational design of scalable GEMs using inexpensive common materials for desalination and beyond.

Rendering SiO2/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars.

We present microfabrication protocols for rendering intrinsically wetting materials repellent to liquids (omniphobic) by creating gas-entrapping microtextures (GEMs) on them comprising cavities and pillars with reentrant and doubly reentrant features. Specifically, we use SiO2/Si as the model system and share protocols for two-dimensional (2D) designing, photolithography, isotropic/anisotropic etching techniques, thermal oxide growth, piranha cleaning, and storage towards achieving those microtextures. Even though the conventional wisdom indicates that roughening intrinsically wetting surfaces (θo < 90°) renders them even more wetting (θr < θo < 90°), GEMs demonstrate liquid repellence despite the intrinsic wettability of the substrate. For instance, despite the intrinsic wettability of silica θo ≈ 40° for the water/air system, and θo ≈ 20° for the hexadecane/air system, GEMs comprising cavities entrap air robustly on immersion in those liquids, and the apparent contact angles for the droplets are θr > 90°. The reentrant and doubly reentrant features in the GEMs stabilize the intruding liquid meniscus thereby trapping the liquid-solid-vapor system in metastable air-filled states (Cassie states) and delaying wetting transitions to the thermodynamically-stable fully-filled state (Wenzel state) by, for instance, hours to months. Similarly, SiO2/Si surfaces with arrays of reentrant and doubly reentrant micropillars demonstrate extremely high contact angles (θr ≈ 150°-160°) and low contact angle hysteresis for the probe liquids, thus characterized as superomniphobic. However, on immersion in the same liquids, those surfaces dramatically lose their superomniphobicity and get fully-filled within <1 s. To address this challenge, we present protocols for hybrid designs that comprise arrays of doubly reentrant pillars surrounded by walls with doubly reentrant profiles. Indeed, hybrid microtextures entrap air on immersion in the probe liquids. To summarize, the protocols described here should enable the investigation of GEMs in the context of achieving omniphobicity without chemical coatings, such as perfluorocarbons, which might unlock the scope of inexpensive common materials for applications as omniphobic materials. Silica microtextures could also serve as templates for soft materials.

Evaluating the potential of superhydrophobic nanoporous alumina membranes for direct contact membrane distillation.

HYPOTHESIS: Direct contact membrane distillation (DCMD) processes exploit water-repellant membranes to desalt warm seawaters by allowing only water vapor to transport across. While perfluorinated membranes/coatings are routinely used for DCMD, their vulnerability to abrasion, heat, and harsh chemicals necessitates alternatives, such as ceramics. Herein, we systematically assess the potential of ceramic membranes consisting of anodized aluminum oxide (AAO) for DCMD. EXPERIMENTS: We rendered AAO membranes superhydrophobic to accomplish the separation of hot salty water (343 K, 0.7 M NaCl) and cold deionized water (292 K) and quantified vapor transport. We also developed a multiscale model based on computational fluid dynamics, conjugate heat transfer, and the kinetic theory of gases to gain insights into our experiments. FINDINGS: The average vapor fluxes, J, across three sets of AAO membranes with average nanochannel diameters (and porosities) centered at 80 nm (32%), 100 nm (37%), and 160 nm (57%) varied by < 25%, while we had expected them to scale with the porosities. Our multiscale simulations unveiled how the high thermal conductivity of the AAO membranes reduced the effective temperature drive for the mass transfer. Our results highlight the limitations of AAO membranes for DCMD and might advance the rational development of desalination membranes.

Assessing omniphobicity by immersion.

HYPOTHESIS: Coating-free approaches to achieve liquid repellent, or omniphobic, surfaces could exploit inexpensive intrinsically wetting materials, such as polyethylene terephthalate and nylon, for applications such as liquid-vapor extraction and drag reduction. However, it is not clear whether the existing criteria for assessing coating-based omniphobicity, based on contact angles, would be reliable for coating-free approaches, especially considering localized defects/damages during manufacturing and usage. EXPERIMENTS: We assessed the omniphobicity of silica surfaces adorned with arrays of doubly reentrant pillars, cavities, and hybrid designs with sessile drops and on immersion in water and hexadecane through contact angle goniometry and confocal microscopy. FINDINGS: We demonstrate that the assessment of omniphobicity of surfaces derived from intrinsically wetting materials can be misleading, if solely based on the measurement of contact angles. Specifically, localized defects in microtextures consisting of pillars may lead to the spontaneous loss of omniphobicity and detecting them through contact angles can be difficult. We also demonstrate that the immersion of those surfaces into probe liquids may serve as a simple and quick 'litmus' test for omniphobicity. Thus, immersion as the additional criterion for omniphobicity might prove itself useful in the context of large-scale manufacturing.

Biomimetic coating-free surfaces for long-term entrapment of air under wetting liquids.

Trapping air at the solid-liquid interface is a promising strategy for reducing frictional drag and desalting water, although it has thus far remained unachievable without perfluorinated coatings. Here, we report on biomimetic microtextures composed of doubly reentrant cavities (DRCs) and reentrant cavities (RCs) that can enable even intrinsically wetting materials to entrap air for long periods upon immersion in liquids. Using SiO2/Si wafers as the model system, we demonstrate that while the air entrapped in simple cylindrical cavities immersed in hexadecane is lost after 0.2 s, the air entrapped in the DRCs remained intact even after 27 days (~106 s). To understand the factors and mechanisms underlying this ten-million-fold enhancement, we compared the behaviors of DRCs, RCs and simple cavities of circular and non-circular shapes on immersion in liquids of low and high vapor pressures through high-speed imaging, confocal microscopy, and pressure cells. Those results might advance the development of coating-free liquid repellent surfaces.

Doubly Reentrant Cavities Prevent Catastrophic Wetting Transitions on Intrinsically Wetting Surfaces.

Omniphobic surfaces, that is, which repel all known liquids, have proven of value in applications ranging from membrane distillation to underwater drag reduction. A limitation of currently employed omniphobic surfaces is that they rely on perfluorinated coatings, increasing cost and environmental impact and preventing applications in harsh environments. Thus, there is a keen interest in rendering conventional materials, such as plastics, omniphobic by micro/nanotexturing rather than via chemical makeup, with notable success having been achieved for silica surfaces with doubly reentrant micropillars. However, we found a critical limitation of microtextures comprising pillars that they undergo catastrophic wetting transitions (apparent contact angles, θr → 0° from θr > 90°) in the presence of localized physical damages/defects or on immersion in wetting liquids. In response, a doubly reentrant cavity microtexture is introduced, which can prevent catastrophic wetting transitions in the presence of localized structural damage/defects or on immersion in wetting liquids. Remarkably, our silica surfaces with doubly reentrant cavities could exhibit apparent contact angles, θr ≈ 135° for mineral oil, where the intrinsic contact angle, θo ≈ 20°. Further, when immersed in mineral oil or water, doubly reentrant microtextures in silica (θo ≈ 40° for water) were not penetrated even after several days of investigation. Thus, microtextures comprising doubly reentrant cavities might enable applications of conventional materials without chemical modifications, especially in scenarios that are prone to localized damages or immersion in wetting liquids, for example, hydrodynamic drag reduction and membrane distillation.