Superhydrophobic surfaces for extreme environmental 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.

Ultrathin Durable Organic Hydrophobic Coatings Enhancing Dropwise Condensation Heat Transfer.

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.

Spontaneous droplet trampolining on rigid superhydrophobic surfaces.

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.

Spontaneous self-dislodging of freezing water droplets and the role of wettability.

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.

Transparent Metasurfaces Counteracting Fogging by Harnessing Sunlight.

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.

Superhydrophobicity enhancement through substrate flexibility.

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).

Imparting Icephobicity with Substrate Flexibility.

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.

Contactless Transport and Mixing of Liquids on Self-Sustained Sublimating Coatings.

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.

Detergency and Its Implications for Oil Emulsion Sieving and Separation.

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.

On the Mechanism of Hydrophilicity of Graphene.

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.

Physics of icing and rational design of surfaces with extraordinary icephobicity.

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.

Transparent sunlight-activated antifogging metamaterials.

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.

Freezing-induced wetting transitions on superhydrophobic surfaces.

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.

Imparting scalephobicity with rational microtexturing of soft materials.

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.

Engineering Electrode Rinse Solution Fluidics for Carbon-Based Reverse Electrodialysis Devices.

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.

Microscale investigation on interfacial slippage and detachment of ice from soft materials.

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.

Enhanced Atmospheric Water Harvesting with Sunlight-Activated Sorption Ratcheting.

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.

Bistability of Dielectrically Anisotropic Nematic Crystals and the Adaptation of Endothelial Collectives to Stress Fields.

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.

Leidenfrost droplet trampolining.

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.

Exploiting radiative cooling for uninterrupted 24-hour water harvesting from the atmosphere.

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.