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Precise micropatterning on three-dimensional (3D) surfaces is desired for a variety of applications, from microelectronics to metamaterials, which can be realized by transfer printing techniques. However, a nontrivial deficiency of this approach is that the transferred microstructures are adsorbed on the target surface with weak adhesion, limiting the applications to external force-free conditions. We propose a scalable "photolithography-transfer-plating" method to pattern stable and durable microstructures on 3D metallic surfaces with precise dimension and location control of the micropatterns. Surface patterning on metallic parts with different metals and isotropic and anisotropic curvatures is showcased. This method can also fabricate hierarchical structures with nanoscale vertical and microscale horizontal dimensions. The plated patterns are stable enough to mold soft materials, and the structure durability is validated by 24 h thermofluidic tests. We demonstrate micropatterned nickel electrodes for oxygen evolution reaction acceleration in hydrogen production, showing the potential of micropatterned 3D metallic surfaces for energy applications.

Nucleation and growth of calcium carbonate on surfaces is of broad importance in nature and technology, being essential to the calcification of organisms, while negatively impacting energy conversion through crystallization fouling, also called scale formation. Previous work studied how confinements, surface energies, and functionalizations affect nucleation and polymorph formation, with surface-water interactions and ion mobility playing important roles. However, the influence of surface nanostructures with nanocurvature-through pit and bump morphologies-on scale formation is unknown, limiting the development of scalephobic surfaces. Here, it is shown that nanoengineered surfaces enhance the nucleation rate by orders of magnitude, despite expected inhibition through effects like induced lattice strain through surface nanocurvature. Interfacial and holographic microscopy is used to quantify crystallite growth and find that nanoengineered interfaces experience slower individual growth rates while collectively the surface has 18% more deposited mass. Reconstructions through nanoscale cross-section imaging of surfaces coupled with classical nucleation theory-utilizing local nanocurvature effects-show the collective enhancement of nano-pits., (© 2024 Wiley‐VCH GmbH.)

Crystallization fouling, a process where scale forms on surfaces, is widespread in nature and technology, negatively affecting energy and water industries. Despite the effort, rationally designed surfaces that are intrinsically resistant to it remain elusive, due in part to a lack of understanding of how microfoulants deposit and adhere in dynamic aqueous environments. Here, we show that rational tuning of coating compliance and wettability works synergistically with microtexture to enhance microfoulant repellency, characterized by low adhesion and high removal efficiency of numerous individual microparticles and tenacious crystallites in a flowing water environment. We study the microfoulant interfacial dynamics in situ using a micro-scanning fluid dynamic gauge system, elucidate the removal mechanisms, and rationalize the behavior with a shear adhesive moment model. We then demonstrate a rationally developed coating that can remove 98% of deposits under shear flow conditions, 66% better than rigid substrates.

Natural salinity gradients are a promising source of so-called "blue energy", a renewable energy source that utilizes the free energy of mixing for power generation. One promising blue energy technology that converts these salinity gradients directly into electricity is reverse electrodialysis (RED). Used at its full potential, it could provide a substantial portion of the world's electricity consumption. Previous theoretical and experimental works have been done on optimizing RED devices, with the latter often focusing on precious and expensive metal electrodes. However, in order to rationally design and apply RED devices, we need to investigate all related transport phenomena─especially the fluidics of salinity gradient mixing and the redox electrolyte at various concentrations, which can have complex intertwined effects─in a fully functioning and scalable system. Here, guided by fundamental electrochemical and fluid dynamics theories, we work with an iron-based redox electrolyte with carbon electrodes in a RED device with tunable microfluidic environments and study the fundamental effects of electrolyte concentration and flow rate on the potential-driven redox activity and power output. We focus on optimizing the net power output, which is the difference between the gross power output generated by the RED device and the pumping power input, needed for salinity gradient mixing and redox electrolyte reactions. We find through this holistic approach that the electrolyte concentration in the electrode rinse solution is crucial for increasing the electrical current, while the pumping power input depends nonlinearly on the membrane separation distance. Finally, from this understanding, we designed a five cell-pair (CP) RED device that achieved a net power density of 224 mW m -2 CP -1 , a 60% improvement compared to the nonoptimized case. This study highlights the importance of the electrode rinse solution fluidics and composition when rationally designing RED devices based on scalable carbon-based electrodes.

Counteracting surface fogging to maintain surface transparency is important for a variety of applications including eyewear, windows and displays. Energy-neutral, passive approaches predominantly rely on engineering the surface wettability, but suffer from non-uniformity, contaminant deposition and lack of robustness, all of which substantially degrade durability and performance. Here, guided by nucleation thermodynamics, we design a transparent, sunlight-activated, photothermal coating to inhibit fogging. The metamaterial coating contains a nanoscopically thin percolating gold layer and is most absorptive in the near-infrared range, where half of the sunlight energy resides, thus maintaining visible transparency. The photoinduced heating effect enables sustained and superior fog prevention (4-fold improvement) and removal (3-fold improvement) compared with uncoated samples, and overall impressive performance, indoors and outdoors, even under cloudy conditions. The extreme thinness (~10 nm) of the coating-which can be produced by standard, readily scalable fabrication processes-enables integration beneath other coatings, rendering it durable even on highly compliant substrates., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Supercooled droplet freezing on surfaces occurs frequently in nature and industry, often adversely affecting the efficiency and reliability of technological processes. The ability of superhydrophobic surfaces to rapidly shed water and reduce ice adhesion make them promising candidates for resistance to icing. However, the effect of supercooled droplet freezing-with its inherent rapid local heating and explosive vaporization-on the evolution of droplet-substrate interactions, and the resulting implications for the design of icephobic surfaces, are little explored. Here we investigate the freezing of supercooled droplets resting on engineered textured surfaces. On the basis of investigations in which freezing is induced by evacuation of the atmosphere, we determine the surface properties required to promote ice self-expulsion and, simultaneously, identify two mechanisms through which repellency falters. We elucidate these outcomes by balancing (anti-)wetting surface forces with those triggered by recalescent freezing phenomena and demonstrate rationally designed textures to promote ice expulsion. Finally, we consider the complementary case of freezing at atmospheric pressure and subzero temperature, where we observe bottom-up ice suffusion within the surface texture. We then assemble a rational framework for the phenomenology of ice adhesion of supercooled droplets throughout freezing, informing ice-repellent surface design across the phase diagram., Competing Interests: Competing interestsThe authors declare no competing interests., (© The Author(s) 2023.)

Organic hydrophobic layers targeting sustained dropwise condensation are highly desirable but suffer from poor chemical and mechanical stability, combined with low thermal conductivity. The requirement of such layers to remain ultrathin to minimize their inherent thermal resistance competes against durability considerations. Here, we investigate the long-term durability and enhanced heat-transfer performance of perfluorodecanethiol (PFDT) coatings compared to alternative organic coatings, namely, perfluorodecyltriethoxysilane (PFDTS) and perfluorodecyl acrylate (PFDA), the latter fabricated with initiated chemical vapor deposition (iCVD), in condensation heat transfer and under the challenging operating conditions of intense flow (up to 9 m s -1 ) of superheated steam (111 °C) at high pressures (1.42 bar). We find that the thiol coating clearly outperforms the silane coating in terms of both heat transfer and durability. In addition, despite being only a monolayer, it clearly also outperforms the iCVD-fabricated PFDA coating in terms of durability. Remarkably, the thiol layer exhibited dropwise condensation for at least 63 h (>2× times more than the PFDA coating, which survived for 30 h), without any visible deterioration, showcasing its hydrolytic stability. The cost of thiol functionalization per area was also the lowest as compared to all of the other surface hydrophobic treatments used in this study, thus making it the most efficient option for practical applications on copper substrates.

Endothelial monolayers physiologically adapt to flow and flow-induced wall shear stress, attaining ordered configurations in which elongation, orientation, and polarization are coherently organized over many cells. Here, with the flow direction unchanged, a peculiar bi-stable (along the flow direction or perpendicular to it) cell alignment is observed, emerging as a function of the flow intensity alone, while cell polarization is purely instructed by flow directionality. Driven by the experimental findings, the parallelism between endothelia is delineated under a flow field and the transition of dual-frequency nematic liquid crystals under an external oscillatory electric field. The resulting physical model reproduces the two stable configurations and the energy landscape of the corresponding system transitions. In addition, it reveals the existence of a disordered, metastable state emerging upon system perturbation. This intermediate state, experimentally demonstrated in endothelial monolayers, is shown to expose the cellular system to a weakening of cell-to-cell junctions to the detriment of the monolayer integrity. The flow-adaptation of monolayers composed of healthy and senescent endothelia is successfully predicted by the model with adjustable nematic parameters. These results may help to understand the maladaptive response of in vivo endothelial tissues to disturbed hemodynamics and the progressive functional decay of senescent endothelia., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Surface icing is detrimental to applications ranging from transportation to biological systems. Soft elastomeric coatings can engender remarkably low ice adhesion strength, but mechanisms at the microscale and resulting ice extraction outcomes need to be understood. Here we investigate dynamic ice-elastomer interfacial events and show that the ice adhesion strength can actually vary by orders of magnitude due to the shear velocity. We study the detailed deformation fields of the elastomer using confocal traction force microscopy and elucidate the underlying mechanism. The elastomer initially undergoes elastic deformation having a shear velocity dependent threshold, followed by partial relaxation at the onset of slip, where velocity dependent "stick-slip" micropulsations are observed. The results of the work provide important information for the design of soft surfaces with respect to removal of ice, and utility to fields exemplified by adhesion, contact mechanics, and biofouling.

The global challenge of clean water scarcity needs to be confronted with novel sustainable, climate neutral solutions, over the entire spectrum of possible clean water availability. Atmospheric moisture represents a major untapped resource that can be harvested by sorbents, enabling water production in dry inland regions where it is needed. While benefiting from the utilization of an important renewable energy source, solar-driven, sorbent-based atmospheric water harvesting systems are inseparably based on a single water harvesting cycle per day, which severely limits the daily water productivity and the competitiveness of this very promising technology. Here, we rationally design an atmospheric water harvesting strategy, using durable hydrogel sorbents, that operates with sorption "ratcheting"─a large sequence of rapid adsorption and subsequent desorption steps─activated by direct sunlight. Employing theoretical considerations, we tailor the ratcheting timescales to the inherent sorption properties of the hydrogels, optimally exploiting their natural harvesting capabilities, while maintaining the sustainable utility of the daily cycle. Amplified by the favorable sorption properties and ratcheting stability of the sorbent, this strategy demonstrates an impressive ∼80% increase in water harvesting yield over the daily cycle systems. The generic nature of the ratcheting concept shows great potential to advance the water harvesting capabilities of a range of related systems.

Atmospheric water vapor is ubiquitous and represents a promising alternative to address global clean water scarcity. Sustainably harvesting this resource requires energy neutrality, continuous production, and facility of use. However, fully passive and uninterrupted 24-hour atmospheric water harvesting remains a challenge. Here, we demonstrate a rationally designed system that synergistically combines radiative shielding and cooling-dissipating the latent heat of condensation radiatively to outer space-with a fully passive superhydrophobic condensate harvester, working with a coalescence-induced water removal mechanism. A rationally designed shield, accounting for the atmospheric radiative heat, facilitates daytime atmospheric water harvesting under solar irradiation at realistic levels of relative humidity. The remarkable cooling power enhancement enables dew mass fluxes up to 50 g m -2 hour -1 , close to the ultimate capabilities of such systems. Our results demonstrate that the yield of related technologies can be at least doubled, while cooling and collection remain passive, thereby substantially advancing the state of the art., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

A liquid droplet dispensed over a sufficiently hot surface does not make contact but instead hovers on a cushion of its own self-generated vapor. Since its discovery in 1756, this so-called Leidenfrost effect has been intensively studied. Here we report a remarkable self-propulsion mechanism of Leidenfrost droplets against gravity, that we term Leidenfrost droplet trampolining. Leidenfrost droplets gently deposited on fully rigid surfaces experience self-induced spontaneous oscillations and start to gradually bounce from an initial resting altitude to increasing heights, thereby violating the traditionally accepted Leidenfrost equilibrium. We found that the continuously draining vapor cushion initiates and fuels Leidenfrost trampolining by inducing ripples on the droplet bottom surface, which translate into pressure oscillations and induce self-sustained periodic vertical droplet bouncing over a broad range of experimental conditions.

Superhydrophobic surfaces for repelling impacting water droplets are typically created by designing structures with capillary (antiwetting) pressures greater than those of the incoming droplet (dynamic, water hammer). Recent work has focused on the evolution of the intervening air layer between droplet and substrate during impact, a balance of air compression and drainage within the surface texture, and its role in affecting impalement under ambient conditions through local changes in the droplet curvature. However, little consideration has been given to the influence of the intervening air-layer thermodynamic state and composition, in particular when departing from standard atmospheric conditions, on the antiwetting behavior of superhydrophobic surfaces. Here, we explore the related physics and determine the working envelope for maintaining robust superhydrophobicity, in terms of the ambient pressure and water vapor content. With single-tier and multitier superhydrophobic surfaces and high-resolution dynamic imaging of the droplet meniscus and its penetration behavior into the surface texture, we expose a trend of increasing impalement severity with decreasing ambient pressure and elucidate a previously unexplored condensation-based impalement mechanism within the texture resulting from the compression, and subsequent supersaturation, of the intervening gas layer in low-pressure, humid conditions. Using fluid dynamical considerations and nucleation thermodynamics, we provide mechanistic understanding of impalement and further employ this knowledge to rationally construct multitier surfaces with robust superhydrophobicity, extending water repellency behavior well beyond typical atmospheric conditions. Such a property is expected to find multifaceted use exemplified by transportation and infrastructure applications where exceptional repellency to water and ice is desired., Competing Interests: The authors declare no competing interest.

Imparting and maintaining surface superhydrophobicity has been receiving significant research attention over the last several years, driven by a broad range of important applications and enabled by advancements in materials and surface nanoengineering. Researchers have investigated the effect of temperature on droplet-surface interactions, which poses additional challenges when liquid nucleation manifests itself, due to ensuing condensation into the surface texture that compromises its antiwetting behavior. Maintaining surface transparency at the same time poses an additional and significant challenge. Often, the solutions proposed are limited by working temperatures or are detrimental to visibility through the surface. Here we introduce a scalable method employing plasmonic photothermal metasurface composites, able to harvest sunlight and naturally heat the surface, sustaining water repellency and transparency under challenging environmental conditions where condensation and fogging would otherwise be strongly promoted. We demonstrate that these surfaces, when illuminated by sunlight, can prevent impalement of impacting water droplets, even when the droplet to surface temperature difference is 50 °C, by suppressing condensate formation within the texture, maintaining transparency. We also show how the same transparent metasurface coating could be combined and work collaboratively with hierarchical micro- and nanorough textures, resulting in simultaneous superior pressure-driven impalement resistance and avoidance of water nucleation and related possible frosting in supercooled conditions. Our work can find a host of applications as a sustainable solution against impacting water on surfaces such as windows, eyewear, and optical components.

Bitumen is a widely used material employed as a binder in pavement engineering and as a surface sealant in construction. Its surface microstructure and microscale properties have been shown to be temperature-dependent, with effects manifesting themselves on surface composition and texture, including the formation of the visually striking catana 'bee'-like structures. Despite the importance of a good performance of bitumen in subzero environments (<0°C), the behaviour of bitumen surface texture and composition at cold temperatures, affecting cracking, degradation and road icing, has received practically no attention. In particular, such knowledge is relevant to world regions experiencing long periods of subzero temperatures during the year. Employing advanced atomic force microscopy combined with infrared spectroscopy (AFM-IR) and an environmental chamber, we demonstrate the ability to characterise surface structure and composition with nanoscale precision for a broad range of temperatures. We show that cooling bitumen to subzero temperatures can have several interesting effects on its surface microtexture, nanotexture and composition, especially on its three surface domains, catana, peri and para. We found that the para domain coarsens and extends to form an interfacial transition domain (characterised by increasing surface roughness with peri domain composition) between the para and peri domains. We show that the catana and peri domains have a similar composition, but have different mechanical and chemical properties compared to the para domain. The essential findings of this work improve our understanding of the behaviour of bitumen in subzero environments, aiding us in our quest towards attaining better road and sealant performance., (© 2020 Royal Microscopical Society.)

Droplet interactions with compliant materials are familiar, but surprisingly complex processes of importance to the manufacturing, chemical, and garment industries. Despite progress-previous research indicates that mesoscopic substrate deformations can enhance droplet drying or slow down spreading dynamics-our understanding of how the intertwined effects of transient wetting phenomena and substrate deformation affect drying remains incomplete. Here we show that above a critical receding contact line speed during drying, a previously not observed wetting transition occurs. We employ 4D confocal reference-free traction force microscopy (cTFM) to quantify the transient displacement and stress fields with the needed resolution, revealing high and asymmetric local substrate deformations leading to contact line pinning, illustrating a rate-dependent wettability on viscoelastic solids. Our study has significance for understanding the liquid removal mechanism on compliant substrates and for the associated surface design considerations. The developed methodology paves the way to study complex dynamic compliant substrate phenomena.

Surface fogging is a common phenomenon that can have significant and detrimental effects on surface transparency and visibility. It affects the performance in a wide range of applications including windows, windshields, electronic displays, cameras, mirrors, and eyewear. A host of ongoing research is aimed at combating this problem by understanding and developing stable and effective antifogging coatings that are capable of handling a wide range of environmental challenges "passively" without consumption of electrical energy. Here we introduce an alternative approach employing sunlight to go beyond state-of-the-art techniques, such as superhydrophilic and superhydrophobic coatings, by rationally engineering solar absorbing metasurfaces that maintain transparency, while upon illumination induce localized heating to significantly delay the onset of surface fogging or decrease defogging time. For the same environmental conditions, we demonstrate that our metasurfaces are able to reduce defogging time by up to 4-fold and under supersaturated conditions inhibit the nucleation of condensate outperforming conventional state-of-the-art approaches in terms of visibility retention. Our research illustrates a durable and environmentally sustainable approach to passive antifogging and defogging for transparent surfaces. This work opens up the opportunity for large-scale manufacturing that can be applied to a range of materials, including polymers and other flexible substrates.

Macrotextured superhydrophobic surfaces can reduce droplet-substrate contact times of impacting water droplets; however, surface designs with similar performance for significantly more viscous liquids are missing, despite their importance in nature and technology such as for chemical shielding, food-staining repellency, and supercooled (viscous) water droplet removal in anti-icing applications. Here, we introduce a deterministic, controllable, and upscalable method to fabricate superhydrophobic surfaces with a 3D-printed architecture, combining arrays of alternating surface protrusions and indentations. We show a more than threefold contact time reduction of impacting viscous droplets up to a fluid viscosity of 3.7 mPa·s, which equals 3.7 times the viscosity of water at room temperature, covering the viscosity of many chemicals and supercooled water. On the basis of the combined consideration of the fluid flow within and the simultaneous droplet dynamics above the texture, we recommend future pathways to rationally architecture such surfaces, all realizable with the methodology presented here.

Surface icing affects the safety and performance of numerous processes in technology. Previous studies mostly investigated freezing of individual droplets. The interaction among multiple droplets during freezing is investigated less, especially on nanotextured icephobic surfaces, despite its practical importance as water droplets never appear in isolation, but in groups. Here we show that freezing of a supercooled droplet leads to spontaneous self-heating and induces strong vaporization. The resulting, rapidly propagating vapor front causes immediate cascading freezing of neighboring supercooled droplets upon reaching them. We put forth the explanation that, as the vapor approaches cold neighboring droplets, it can lead to local supersaturation and formation of airborne microscopic ice crystals, which act as freezing nucleation sites. The sequential triggering and propagation of this mechanism results in the rapid freezing of an entire droplet ensemble, resulting in ice coverage of the nanotextured surface. Although cascade freezing is observed in a low-pressure environment, it introduces an unexpected pathway of freezing propagation that can be crucial for the performance of rationally designed icephobic surfaces.

Ice nucleation from vapor presents a variety of challenges across a wide range of industries and applications including refrigeration, transportation, and energy generation. However, a rational comprehensive approach to fabricating intrinsically icephobic surfaces for frost formation-both from water condensation (followed by freezing) and in particular from desublimation (direct growth of ice crystals from vapor)-remains elusive. Here, guided by nucleation physics, we investigate the effect of material composition and surface texturing (atomically smooth to nanorough) on the nucleation and growth mechanism of frost for a range of conditions within the sublimation domain (0 °C to -55 °C; partial water vapor pressures 6 to 0.02 mbar). Surprisingly, we observe that on silicon at very cold temperatures-below the homogeneous ice solidification nucleation limit (<-46 °C)-desublimation does not become the favorable pathway to frosting. Furthermore, we show that surface nanoroughness makes frost formation on silicon more probable. We experimentally demonstrate at temperatures between -48 °C and -55 °C that nanotexture with radii of curvature within 1 order of magnitude of the critical radius of nucleation favors frost growth, facilitated by capillary condensation, consistent with Kelvin's equation. Our findings show that such nanoscale surface morphology imposed by design to impart desired functionalities-such as superhydrophobicity-or from defects can be highly detrimental for frost icephobicity at low temperatures and water vapor partial pressures (<0.05 mbar). Our work contributes to the fundamental understanding of phase transitions well within the equilibrium sublimation domain and has implications for applications such as travel, power generation, and refrigeration.

Inhibiting ice accumulation on surfaces is an energy-intensive task and is of significant importance in nature and technology where it has found applications in windshields, automobiles, aviation, renewable energy generation, and infrastructure. Existing methods rely on on-site electrical heat generation, chemicals, or mechanical removal, with drawbacks ranging from financial costs to disruptive technical interventions and environmental incompatibility. Here we focus on applications where surface transparency is desirable and propose metasurfaces with embedded plasmonically enhanced light absorption heating, using ultrathin hybrid metal-dielectric coatings, as a passive, viable approach for de-icing and anti-icing, in which the sole heat source is renewable solar energy. The balancing of transparency and absorption is achieved with rationally nanoengineered coatings consisting of gold nanoparticle inclusions in a dielectric (titanium dioxide), concentrating broadband absorbed solar energy into a small volume. This causes a > 10 °C temperature increase with respect to ambient at the air-solid interface, where ice is most likely to form, delaying freezing, reducing ice adhesion, when it occurs, to negligible levels (de-icing) and inhibiting frost formation (anti-icing). Our results illustrate an effective unexplored pathway toward environmentally compatible, solar-energy-driven icephobicity, enabled by respectively tailored plasmonic metasurfaces, with the ability to design the balance of transparency and light absorption.

Spontaneous removal of liquid, solidifying liquid and solid forms of matter from surfaces, is of significant importance in nature and technology, where it finds applications ranging from self-cleaning to icephobicity and to condensation systems. However, it is a great challenge to understand fundamentally the complex interaction of rapidly solidifying, typically supercooled, droplets with surfaces, and to harvest benefit from it for the design of intrinsically icephobic materials. Here we report and explain an ice removal mechanism that manifests itself simultaneously with freezing, driving gradual self-dislodging of droplets cooled via evaporation and sublimation (low environmental pressure) or convection (atmospheric pressure) from substrates. The key to successful self-dislodging is that the freezing at the droplet free surface and the droplet contact area with the substrate do not occur simultaneously: The frozen phase boundary moves inward from the droplet free surface toward the droplet-substrate interface, which remains liquid throughout most of the process and freezes last. We observe experimentally, and validate theoretically, that the inward motion of the phase boundary near the substrate drives a gradual reduction in droplet-substrate contact. Concurrently, the droplet lifts from the substrate due to its incompressibility, density differences, and the asymmetric freezing dynamics with inward solidification causing not fully frozen mass to be displaced toward the unsolidified droplet-substrate interface. Depending on surface topography and wetting conditions, we find that this can lead to full dislodging of the ice droplet from a variety of engineered substrates, rendering the latter ice-free., Competing Interests: The authors declare no conflict of interest.

Ice accumulation hinders the performance of, and poses safety threats for, infrastructure both on the ground and in the air. Previously, rationally designed superhydrophobic surfaces have demonstrated some potential as a passive means to mitigate ice accretion; however, further studies on material solutions that reduce impalement and the contact time for impacting supercooled droplets (high viscosity) and can also repel droplets that freeze during surface contact are urgently needed. Here we demonstrate the collaborative effect of substrate flexibility and surface micro/nanotexture on enhancing both icephobicity and the repellency of viscous droplets (typical of supercooled water). We first investigate the influence of increased viscosity (spanning from 0.9 to 1078 mPa·s using water-glycerol mixtures) on impalement resistance and the droplet-substrate contact time after impact. Then we examine the effect of droplet partial solidification on recoil and simulate more challenging icing conditions by impacting supercooled water droplets (down to -15 °C) onto flexible and rigid surfaces containing ice nucleation promoters (AgI). We demonstrate a passive mechanism for shedding partially solidified (recalescent) droplets-under conditions where partial solidification occurs much faster than the natural droplet oscillation-which does not rely on converting droplet surface energy into kinetic energy (classic recoil mechanism). Using an energy-based model (kinetic-elastic-capillary), we identify a previously unexplored mechanism whereby the substrate oscillation and velocity govern the rebound process, with low areal density and moderately stiff substrates acting to efficiently absorb the incoming droplet kinetic energy and rectify it back, allowing droplets to overcome adhesion and gravitational forces, and recoil. This mechanism applies for a range of droplet viscosities, spanning from low- to high-viscosity fluids and even ice slurries, which do not rebound from rigid superhydrophobic substrates. For a low-viscosity fluid, i.e., water, if the substrate oscillates faster than the droplet spreading and retraction, the action of the substrate is decoupled from the droplet oscillation, resulting in a reduction in the droplet-substrate contact time.

Separating petroleum hydrocarbons from water is an important problem to address in order to mitigate the disastrous effects of hydrocarbons on aquatic ecosystems. A rational approach to address the problem of marine oil-water separation is to disperse the oil with the aid of surfactants in order to minimize the formation of large slicks at the water surface and to maximize the oil-water interfacial area. Here we investigate the fundamental wetting and transport behavior of such surfactant-stabilized droplets and the flow conditions necessary to perform sieving and separation of these stabilized emulsions. We show that, for water-soluble surfactants, such droplets are completely repelled by a range of materials (intrinsically underwater superoleophobic) due to the detergency effect; therefore, there is no need for surface micro-/nanotexturing or chemical treatment to repel the oil and prevent fouling of the filter. We then simulate and experimentally investigate the effect of emulsion flow rate on the transport and impact behavior of such droplets on rigid meshes to identify the minimum pore opening (w) necessary to filter a droplet with a given diameter (d) in order to minimize the pressure drop across the mesh-and therefore maximize the filtering efficiency, which is strongly dependent on w. We define a range of flow conditions and droplet sizes where minimum droplet deformation is to be expected and therefore find that the condition of w ≈ d is sufficient for efficient separation. With this new understanding, we demonstrate the use of a commercially available filter-without any additional surface engineering or functionalization-to separate oil droplets (d < 100 μm) from a surfactant-stabilized emulsion with a flux of ∼11,000 L m -2 h -1 bar -1 . We believe these findings can inform the design of future oil separation materials.

Controlled handling of liquids and colloidal suspensions as they interact with surfaces, targeting a broad palette of related functionalities, is of great importance in science, technology, and nature. When small liquid volumes (drops on the order of microliters or nanoliters) need to be processed in microfluidic devices, contamination on the solid/liquid interface and loss of liquid due to adhesion on the transport channels are two very common problems that can significantly alter the process outcome, for example, the chemical reaction efficiency or the purity and the final concentration of a suspension. It is, therefore, no surprise that both levitation and minimal contact transport methods-including nonwetting surfaces-have been developed to minimize the interactions between liquids and surfaces. Here, we demonstrate contactless surface levitation and transport of liquid drops, realized by harnessing and sustaining the natural sublimation of a solid-carbon-dioxide-coated substrate to generate a continuous supporting vapor layer. The capability and limitations of this technique in handling liquids of extreme surface tension and kinematic viscosity values are investigated both experimentally and theoretically. The sublimating coating is capable of repelling many viscous and low-surface-tension liquids, colloidal suspensions, and non-Newtonian fluids as well, displaying outstanding omniphobic properties. Finally, we demonstrate how sublimation can be used for liquid transport, mixing, and drop coalescence, with a sublimating layer coated on an underlying substrate with prefabricated channels, conferring omniphobicity using a simple physical approach (i.e., phase change) rather than a chemical one. The independence of the surface levitation principle from material properties, such as electromagnetic, thermal or optical, surface energy, adhesion, or mechanical properties, renders this method attractive for a wide range of potential applications.

Inspired by manifestations in nature, microengineering and nanoengineering of synthetic materials to achieve superhydrophobicity has been the focus of much work. Generally, hydrophobicity is enhanced through the combined effects of surface texturing and chemistry; being durable, rigid materials are the norm. However, many natural and technical surfaces are flexible, and the resulting effect on hydrophobicity has been largely ignored. Here, we show that the rational tuning of flexibility can work synergistically with the surface microtexture or nanotexture to enhance liquid repellency performance, characterized by impalement and breakup resistance, contact time reduction, and restitution coefficient increase. Reduction in substrate areal density and stiffness imparts immediate acceleration and intrinsic responsiveness to impacting droplets (∼350 × g), mitigating the collision and lowering the impalement probability by ∼60% without the need for active actuation. Furthermore, we exemplify the above discoveries with materials ranging from man-made (thin steel or polymer sheets) to nature-made (butterfly wings)., Competing Interests: The authors declare no conflict of interest.

It is generally accepted that the hydrophilic property of graphene can be affected by the underlying substrate. However, the role of intrinsic vs substrate contributions and the related mechanisms are vividly debated. Here, we show that the intrinsic hydrophilicity of graphene can be intimately connected to the position of its Fermi level, which affects the interaction between graphene and water molecules. The underlying substrate, or dopants, can tune hydrophilicity by modulating the Fermi level of graphene. By shifting the Fermi level of graphene away from its Dirac point, via either chemical or electrical voltage doping, we show enhanced hydrophilicity with experiments and first principle simulations. Increased vapor condensation on graphene, induced by a simple shifting of its Fermi level, exemplifies applications in the area of interfacial transport phenomena.

Maintaining the non-wetting property of textured hydrophobic surfaces is directly related to the preservation of an intervening fluid layer (gaseous or immiscible liquid) between the droplet and substrate; once displaced, it cannot be recovered spontaneously as the fully penetrated Wenzel wetting state is energetically favorable. Here, we identify pathways for the "lifting" of droplets from the surface texture, enabling a complete Wenzel-to-Cassie-Baxter wetting state transition. This is accomplished by the hemiwicking of a transient (limited lifetime due to evaporation) low surface tension (LST) liquid, which is capable of self-assembling as an intervening underlayer, lifting the droplet from its impaled state and facilitating a skating-like behavior. In the skating phase, a critical substrate tilting angle is identified, up to which underlayer and droplet remain coupled exhibiting a pseudo-Cassie-Baxter state. For greater titling angles, the droplet, driven by inertia, detaches itself from the liquid intervening layer and transitions to a traditional Cassie-Baxter wetting state, thereby accelerating and leaving the underlayer behind. A model is also presented that elucidates the mechanism of mobility recovery. Ultimately, this work provides a better understanding of multiphase mass transfer of immiscible LST liquid-water mixtures with respect to establishing facile methods towards retaining intervening layers.

Spontaneous removal of condensed matter from surfaces is exploited in nature and in a broad range of technologies to achieve self-cleaning, anti-icing and condensation control. But despite much progress, our understanding of the phenomena leading to such behaviour remains incomplete, which makes it challenging to rationally design surfaces that benefit from its manifestation. Here we show that water droplets resting on superhydrophobic textured surfaces in a low-pressure environment can self-remove through sudden spontaneous levitation and subsequent trampoline-like bouncing behaviour, in which sequential collisions with the surface accelerate the droplets. These collisions have restitution coefficients (ratios of relative speeds after and before collision) greater than unity despite complete rigidity of the surface, and thus seemingly violate the second law of thermodynamics. However, these restitution coefficients result from an overpressure beneath the droplet produced by fast droplet vaporization while substrate adhesion and surface texture restrict vapour flow. We also show that the high vaporization rates experienced by the droplets and the associated cooling can result in freezing from a supercooled state that triggers a sudden increase in vaporization, which in turn boosts the levitation process. This effect can spontaneously remove surface icing by lifting away icy drops the moment they freeze. Although these observations are relevant only to systems in a low-pressure environment, they show how surface texturing can produce droplet-surface interactions that prohibit liquid and freezing water-droplet retention on surfaces.

Rough surfaces immersed under water remain practically dry if the liquid-solid contact is on roughness peaks, while the roughness valleys are filled with gas. Mechanisms that prevent water from invading the valleys are well studied. However, to remain practically dry under water, additional mechanisms need consideration. This is because trapped gas (e.g. air) in the roughness valleys can dissolve into the water pool, leading to invasion. Additionally, water vapor can also occupy the roughness valleys of immersed surfaces. If water vapor condenses, that too leads to invasion. These effects have not been investigated, and are critically important to maintain surfaces dry under water. In this work, we identify the critical roughness scale, below which it is possible to sustain the vapor phase of water and/or trapped gases in roughness valleys - thus keeping the immersed surface dry. Theoretical predictions are consistent with molecular dynamics simulations and experiments.

Icing of surfaces is commonplace in nature and technology, affecting everyday life and sometimes causing catastrophic events. Understanding (and counteracting) surface icing brings with it significant scientific challenges that requires interdisciplinary knowledge from diverse scientific fields such as nucleation thermodynamics and heat transfer, fluid dynamics, surface chemistry, and surface nanoengineering. Here we discuss key aspects and findings related to the physics of ice formation on surfaces and show how such knowledge could be employed to rationally develop surfaces with extreme resistance to icing (extraordinary icephobicity). Although superhydrophobic surfaces with micro-, nano-, or (often biomimetic) hierarchical roughnesses have shown in laboratory settings (under certain conditions) excellent repellency and low adhesion to water down to temperatures near or below the freezing point, extreme icephobicity necessitates additional important functionalities. Other approaches, such as lubricant-impregnated surfaces, exhibit both advantages and serious limitations with respect to icing. In all, a clear path toward passive surfaces with extreme resistance to ice formation remains a challenge, but it is one well worth undertaking. Equally important to potential applications is scalable surface manufacturing and the ability of icephobic surfaces to perform reliably and sustainably outside the laboratory under adverse conditions. Surfaces should possess mechanical and chemical stability, and they should be thermally resilient. Such issues and related research directions are also addressed in this article.

In situ assembly of high thermal conductivity materials in severely confined spaces is an important problem bringing with it scientific challenges but also significant application relevance. Here we present a simple, affordable, and reproducible methodology for synthesizing such materials, composed of hierarchical diamond micro/nanoparticle scaffolds and an ethylenediamine coating. An important feature of the assembly process is the utilization of ethylenediamine as an immobilizing agent to secure the integrity of the microparticle scaffolds during and after each processing step. After other liquid components employed in the scaffolds assembly dry out, the immobilization agent solidifies forming a stable coated particle scaffold structure. Nanoparticles tend to concentrate in the shell and neck regions between adjacent microparticles. The interface between core and shell, along with the concentrated neck regions of nanoparticles, significantly enhance the thermal conductivity, making such materials an excellent candidate as thermal underfills in the electronics industry, where efficient heat removal is a major stumbling block toward increasing packing density. We show that the presented structures exhibit nearly 1 order of magnitude improvement in thermal conductivity, enhanced temperature uniformity, and reduced processing time compared to commercially available products for electronics cooling, which underpins their potential utility.

Driven by its importance in nature and technology, droplet impact on solid surfaces has been studied for decades. To date, research on control of droplet impact outcome has focused on optimizing pre-impact parameters, e.g., droplet size and velocity. Here we follow a different, post-impact, surface engineering approach yielding controlled vectoring and morphing of droplets during and after impact. Surfaces with patterned domains of extreme wettability (high or low) are fabricated and implemented for controlling the impact process during and even after rebound--a previously neglected aspect of impact studies on non-wetting surfaces. For non-rebound cases, droplets can be morphed from spheres to complex shapes--without unwanted loss of liquid. The procedure relies on competition between surface tension and fluid inertial forces, and harnesses the naturally occurring contact-line pinning mechanisms at sharp wettability changes to create viable dry regions in the spread liquid volume. Utilizing the same forces central to morphing, we demonstrate the ability to rebound orthogonally-impacting droplets with an additional non-orthogonal velocity component. We theoretically analyze this capability and derive a We(-.25) dependence of the lateral restitution coefficient. This study offers wettability-engineered surfaces as a new approach to manipulate impacting droplet microvolumes, with ramifications for surface microfluidics and fluid-assisted templating applications.

Many important applications in fluid management could benefit from unidirectional transport through porous media via a simple, large-area, low-cost coating treatment; in essence, a fluid diode demonstrated herein for water using common cellulosic paper substrates. In electronics, the diode is an electrical component with asymmetric current transfer characteristics. A light (<2 g/m(2)) superhydrophobic conformal coating applied onto one side of a porous substrate is shown to create a liquid transport function analogous to the electronic diode, facilitating fluid movement in one direction under negligible penetration pressures, but opposing it in reverse up to greater pressures. The phenomenon is driven by capillary action and can be observed using any similarly-thin fluid barrier applied on only one side (i.e., wettability contrast) of an absorbent porous matrix. Diodic action and liquid transport rates are shown to be highly tunable, determined by fiber diameter and spacing, in combination with coating deposition amount. As an example, the device is used to separate an oil/water mixture, relying upon the surface tension differences of the mixture constituents, and may be implemented in multicomponent fluid filtration/separation technologies.

Surface tension driven transport of liquids on open substrates offers an enabling tool for open micro total analysis systems that are becoming increasingly popular for low-cost biomedical diagnostic devices. The present study uses a facile wettability patterning method to produce open microfluidic tracks that - due to their shape, surface texture and chemistry - are capable of transporting a wide range of liquid volumes (~1-500 μL) on-chip, overcoming viscous and other opposing forces (e.g., gravity) at the pertinent length scales. Small volumes are handled as individual droplets, while larger volumes require repeated droplet transport. The concept is developed and demonstrated with coatings based on TiO2 filler particles, which, when present in adequate (~80 wt.%) quantities within a hydrophobic fluoroacrylic polymer matrix, form composites that are intrinsically superhydrophobic. Such composite coatings become superhydrophilic upon exposure to UV light (390 nm). A commercial laser printer-based photo-masking approach is used on the coating for spatially selective wettability conversion from superhydrophobic to superhydrophilic. Carefully designed wedge-patterned surface tension confined tracks on the open-air devices move liquid on them without power input, even when acting against gravity. Simple designs of wettability patterning are used on versatile substrates (e.g., metals, polymers, paper) to demonstrate complex droplet handling tasks, e.g., merging, splitting and metered dispensing, some of which occur in 3-D geometries. Fluid transport rates of up to 350 μL s(-1) are attained. Applicability of the design on metal substrates allows these devices to be used also for other microscale engineering applications, e.g., water management in fuel cells.

We present a facile approach for the fabrication of low-cost surface biomicrofluidic devices on superhydrophobic paper created by drop-casting a fluoroacrylic copolymer onto microtextured paper. Wettability patterning is performed with a common household printer, which produces regions of varying wettability by simply controlling the intensity of ink deposited over prespecified domains. The procedure produces surfaces that are capable of selective droplet sliding and adhesion, when inclined. Using this methodology, we demonstrate the ability to tune the sliding angles of 10 μL water droplets in the range from 13° to 40° by printing lines of constant ink intensity and varied width from 0.1 mm to 2 mm. We also formulate a simple model to predict the onset of droplet sliding on printed lines of known width and wettability. Experiments demonstrate open-air surface microfluidic devices that are capable of pumpless transport, mixing and rapid droplet sampling (~0.6 μL at 50 Hz). Lastly, post treatment of printed areas with pH indicator solutions exemplifies the utility of these substrates in point-of-care diagnostics, which are needed at geographical locations where access to sophisticated testing equipment is limited or non-existent.

Low-cost, large-area, superhydrophobic coating treatments are of high value to technological applications requiring efficient liquid repellency. While many applications are envisioned, only few are realizable in practice due to either the high cost or low durability of such treatments. Recently, spray deposition of polymer-particle dispersions has been demonstrated as an excellent means for producing low-cost, large-area, durable, superhydrophobic composite coatings/films; however, such dispersions generally contain harsh or volatile solvents, which are required for solution processing of polymers as well as for dispersing hydrophobic nanoparticles, thus inhibiting scalability due to the increased cost in chemical handling and environmental safety concerns. Moreover, such coatings usually contain fluoropolymers due to their inherent low surface energy, a requirement for superhydrophobicity, but concerns over their biopersistence has provided an impetus for eliminating these chemicals. For spray coating, the former problem can be overcome by replacing organic solvents with water, but this situation seems paradoxical: Producing a highly water-repellent coating from an aqueous dispersion. We report a water-based, nonfluorinated dispersion for the formation of superhydrophobic composite coatings applied by spray on a variety of substrates. We stabilize hydrophobic components (i.e., polymer, nanoparticles) in water, by utilizing chemicals containing acid functional groups (i.e., acrylic acid) that can become ionized in aqueous environments under proper pH control (pH > 7). The functional polymer utilized in this study is a copolymer of ethylene and acrylic acid, while the particle filler is exfoliated graphite nanoplatelet (xGnP), which contains functional groups at its periphery. Once spray deposited and dried, the components become insoluble in water, thus promoting liquid repellency. Such coatings can find a wide range of applications due to their benign processing nature as well as the variety of substrates on which they can be deposited.

Surface tension confined (STC) open tracks for pumpless transport of low-surface tension liquids (e.g., acetone, ethanol, hexadecane) on microfluidic chips are fabricated using a large-area, wet-processing technique. Wettable, paraffin-wax, submillimeter-wide tracks are applied by a fountain-pen procedure on superoleophobic, fluoroacrylic-carbon nanofiber (CNF) composite coatings. The fabricated anisotropic wetting patterns confine the low-surface-tension liquids onto the flow tracks, driving them with meniscus velocities up to 3.1 cm s(-1). Scaling arguments and Washburn's equation provide estimates of the liquid velocities measured in the STC tracks. These tracks are also shown to act as rails for directional sliding control of mm-sized water droplets. The present facile top-down patterned wettability approach can be extended to deposit micrometer-wide tracks, which bear promise for pumpless handling of low-surface tension liquids (e.g., aqueous solutions containing alcohols or surfactants) in lab-on-a-chip type applications or in low power, high-throughput bio-microfluidics for health care applications.

Surfaces patterned with alternating (binary) superhydrophobic-superhydrophilic regions can be found naturally, offering a bio-inspired template for efficient fluid collection and management technologies. We describe a simple wet-processing, thermal treatment method to produce such patterns, starting with inherently superhydrophobic polysilsesquioxane-silica composite coatings prepared by spray casting nanoparticle dispersions. Such coatings become superhydrophilic after localized thermal treatment by means of laser irradiation or open-air flame exposure. When laser processed, the films are patternable down to ∼100 μm scales. The dispersions consist of hydrophobic fumed silica (HFS) and methylsilsesquioxane resin, which are dispersed in isopropanol and deposited onto various substrates (glass, quartz, aluminum, copper, and stainless steel). The coatings are characterized by advancing, receding, and sessile contact angle measurements before and after thermal treatment to delineate the effects of HFS filler concentration and thermal treatment on coating wettability. SEM, XPS and TGA measurements reveal the effects of thermal treatment on surface chemistry and texture. The thermally induced wettability shift from superhydrophobic to superhydrophilic is interpreted with the Cassie-Baxter wetting theory. Several micropatterned wettability surfaces demonstrate potential in pool boiling heat transfer enhancement, capillarity-driven liquid transport in open surface-tension-confined channels (e.g., lab-on-a-chip), and select surface coating applications relying on wettability gradients. Advantages of the present approach include the inherent stability and inertness of the organosilane-based coatings, which can be applied on many types of surfaces (glass, metals, etc.) with ease. The present method is also scalable to large areas, thus being attractive for industrial coating applications.

Super-repellent nanostructured composite coatings applied over large areas by spray and subsequent thermal treatment are reported. Solution blending of poly(vinylidene fluoride) and poly(ethyl 2-cyanoacrylate) is implemented to formulate filler particle dispersions used to apply these coatings. The wettability of these coatings is manipulated using hydrophobic poly(tetrafluoroethylene) and hydrophilic zinc oxide particle fillers or their combination. The resulting coatings feature contact angles up to 164 degrees for water and 154 degrees for a water and isopropyl alcohol mixture (9:1 weight ratio; surface tension approximately 40 mN/m). A self-cleaning ability is revealed by droplet roll-off angles below 10 degrees . The results show that the fillers affect the coating surface energy and surface roughness, in turn influencing the wettability of the coatings.