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Numerous studies have focused on designing functional surfaces that delay frost formation or reduce ice adhesion. However, solutions to the scientific challenges of developing antiicing surfaces remain elusive because of degradation such as mechanical wearing. Inspired by the discontinuous frost pattern on natural leaves, here we report findings on the condensation frosting process on surfaces with serrated structures on the millimeter scale, which is distinct from that on a conventional planar surface with microscale/nanoscale textures. Dropwise condensation, during the first stage of frosting, is enhanced on the peaks and suppressed in the valleys, causing frost to initiate from the peaks, regardless of surface chemistry. The condensed droplets in the valley are then evaporated due to the lower vapor pressure of ice compared with water, resulting in a frost-free zone in the valley, which resists frost propagation even on superhydrophilic surfaces. The dependence of the frost-free areal fraction on the geometric parameters and the ambient conditions is elucidated by both numerical simulations based on steady-state diffusion and an analytical method with an understanding of boundary conditions independent of surface chemistry. We envision that this study would provide a unified framework to design surfaces that can spatially control frost formation, crystal growth, diffusion-controlled growth of biominerals, and material deposition over a broad range of applications.
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Controlling dropwise condensation is fundamental to water-harvesting systems, desalination, thermal power generation, air conditioning, distillation towers, and numerous other applications. For any of these, it is essential to design surfaces that enable droplets to grow rapidly and to be shed as quickly as possible. However, approaches based on microscale, nanoscale or molecular-scale textures suffer from intrinsic trade-offs that make it difficult to optimize both growth and transport at once. Here we present a conceptually different design approach--based on principles derived from Namib desert beetles, cacti, and pitcher plants--that synergistically combines these aspects of condensation and substantially outperforms other synthetic surfaces. Inspired by an unconventional interpretation of the role of the beetle's bumpy surface geometry in promoting condensation, and using theoretical modelling, we show how to maximize vapour diffusion fluxat the apex of convex millimetric bumps by optimizing the radius of curvature and cross-sectional shape. Integrating this apex geometry with a widening slope, analogous to cactus spines, directly couples facilitated droplet growth with fast directional transport, by creating a free-energy profile that drives the droplet down the slope before its growth rate can decrease. This coupling is further enhanced by a slippery, pitcher-plant-inspired nanocoating that facilitates feedback between coalescence-driven growth and capillary-driven motion on the way down. Bumps that are rationally designed to integrate these mechanisms are able to grow and transport large droplets even against gravity and overcome the effect of an unfavourable temperature gradient. We further observe an unprecedented sixfold-higher exponent of growth rate, faster onset, higher steady-state turnover rate, and a greater volume of water collected compared to other surfaces. We envision that this fundamental understanding and rational design strategy can be applied to a wide range of water-harvesting and phase-change heat-transfer applications.
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Movimento (Física) , Transição de Fase , Água/química , Água/metabolismo , Animais , Biomimética , Cactaceae/anatomia & histologia , Cactaceae/metabolismo , Besouros/anatomia & histologia , Besouros/metabolismo , Difusão , Destilação , Gravitropismo , Plantas/anatomia & histologia , Plantas/metabolismo , Propriedades de Superfície , Temperatura , Fatores de Tempo , Volatilização , Abastecimento de ÁguaRESUMO
Fog collection is a promising solution to the worldwide water scarcity problem and is also of vital importance to industrial processes, such as recapturing water in cooling towers and mist elimination. To date, numerous studies have investigated the fog collection rate, a parameter that denotes the average performance over a long period of time. However, the initial period (referred to as onset time) between the start of the fog-laden flow and the actual collection of the captured liquid (a delay in time caused by droplet growth to a critical weight that exceeds droplet-surface retention force) has not been systematically understood. A longer onset time may result in a more serious clogging issue that deteriorates the collection rate and, hence, understanding this phenomenon is important. Here, we study how the onset time is determined by the capture and transport of fog using individual, vertical wires with various surface wettabilities and diameters, under different wind speeds. This approach allows us to derive a scaling law that correlates the onset time with the fog capture process and droplet-surface retention force, governed by aerodynamics and interfacial phenomena, respectively. In particular, the onset time decreases with an increasing rate of fog capture or a decreasing droplet-surface retention force. This study introduces an important aspect in the evaluation of fog collection and provides insights for the optimal design of fog collectors and mist eliminators.
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A multifunctional surface that enables control of wetting, optical reflectivity and mechanical damage of nanostructured interfaces is presented. Our approach is based on imprinting a periodic array of nanosized cones into a UV-curable polyurethane acrylate (PUA), resulting in a self-reinforcing egg-crate topography evenly distributed over large areas up to several cm(2) in size. The resulting surfaces can be either superhydrophilic or superhydrophobic (through subsequent application of an appropriate chemical coating), they minimize optical reflection losses over a broad range of wavelengths and a wide range of angles of incidence, and they also have enhanced mechanical resilience due to greatly improved redistribution of the normal and shearing mechanical loads. The transmissivity and wetting characteristics of the nanoscale egg-crate structure, as well as its resistance to mechanical deformation are analyzed theoretically. Experiments show that the optical performance together with self-cleaning or anti-fogging behavior of the inverted nanocone topography is comparable to earlier designs that have used periodic arrays of nanocones to control reflection and wetting. However the egg-crate structures are far superior in terms of mechanical robustness, and the ability to replicate this topography through several generations is promising for large-scale commercial applications where multifunctionality is important.
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Fog represents a large untapped source of potable water, especially in arid climates. Numerous plants and animals use textural and chemical features on their surfaces to harvest this precious resource. In this work, we investigate the influence of the surface wettability characteristics, length scale, and weave density on the fog-harvesting capability of woven meshes. We develop a combined hydrodynamic and surface wettability model to predict the overall fog-collection efficiency of the meshes and cast the findings in the form of a design chart. Two limiting surface wettability constraints govern the re-entrainment of collected droplets and clogging of mesh openings. Appropriate tuning of the wetting characteristics of the surfaces, reducing the wire radii, and optimizing the wire spacing all lead to more efficient fog collection. We use a family of coated meshes with a directed stream of fog droplets to simulate a natural foggy environment and demonstrate a five-fold enhancement in the fog-collecting efficiency of a conventional polyolefin mesh. The design rules developed in this work can be applied to select a mesh surface with optimal topography and wetting characteristics to harvest enhanced water fluxes over a wide range of natural convected fog environments.
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Água/química , Tempo (Meteorologia) , Hidrodinâmica , Estrutura Molecular , Tamanho da Partícula , Polienos/química , Propriedades de Superfície , MolhabilidadeRESUMO
We develop a theory to model the van der Waals interactions between liquid and graphene, including quantifying the wetting behavior of a graphene-coated surface. Molecular dynamics simulations and contact angle measurements were also carried out to test the theory. We show that graphene is only partially transparent to wetting and that the predicted highest attainable contact angle of water on a graphene-coated surface is 96°. Our findings reveal a more complex picture of wetting on graphene than what has been reported recently as complete "wetting transparency."
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Previously, we reported the creation of a fluorosilane (FOTS) modified pillar array silicon surface comprising ~3-µm-diameter pillars (6 µm pitch with ~7 µm height) that is both superhydrophobic and superoleophobic, with water and hexadecane contact angles exceeding 150° and sliding angles at ~10° owing to the surface fluorination and the re-entrant structure in the side wall of the pillar. In this work, the effects of surface texturing (pillar size, spacing, and height) on wettability, contact angle hysteresis, and "robustness" are investigated. We study the static, advancing, and receding contact angles, as well as the sliding angles as a function of the solid area fraction. The results reveal that pillar size and pillar spacing have very little effect on the static and advancing contact angles, as they are found to be insensitive to the solid area fraction from 0.04 to ~0.4 as the pillar diameter varies from 1 to 5 µm and the center-to-center spacing varies from 4.5 to 12 µm. On the other hand, sliding angle, receding contact angle, and contact angle hysteresis are found to be dependent on the solid area fraction. Specifically, receding contact angle decreases and sliding angle and hysteresis increase as the solid area fraction increases. This effect can be attributable to the increase in pinning as the solid area fraction increases. Surface Evolver modeling shows that water wets and pins the pillar surface whereas hexadecane wets the pillar surface and then penetrates into the side wall of the pillar with the contact line pinning underneath the re-entrant structure. Due to the penetration of the hexadecane drop into the pillar structure, the effect on the receding contact angle and hysteresis is larger relative to that of water. This interpretation is supported by studying a series of FOTS pillar array surfaces with varying overhang thickness. With the water drop, the contact line is pinned on the pillar surface and very little overhang thickness effect was observed. On the other hand, the hexadecane drop is shown to wet the pillar surface and the side wall of the overhang. It then pins at the lower edge of the overhang structure. A plot of the thickness of the overhang as a function of the static, advancing, and receding contact angles and sliding angle of hexadecane reveals that static, advancing, and receding contact angles decrease and sliding angle increases as the thickness of the overhang increases. A larger overhang effect is observed with octane due to its lower surface tension. The robustness of the pillar array surface against external pressure induced wetting and abrasion was modeled. Surface Evolver simulation (with the hexadecane drop) indicates that wetting breakthrough pressure as high as ~70 kPa is achievable with 0.5-µm-diameter pillar array FOTS surfaces. Mechanical modeling shows that bending of the pillars is the key failure by abrasion, which can be avoided with a short pillar structure. The path to fabricate a superoleophobic surface that can withstand the external force equivalent of a gentle cleaning blade (up to ~30 kPa) without wetting and abrasion failure is discussed.
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Water, abundant and ubiquitous in nature, is an easy yet powerful resource for the creatures to survive by putting together with their topologies interfacing their living environment. Here, a slippery, water-infusing surface (SWIS) that retains a thick and stable water layer on the membrane is presented, robustly maintaining the oil repellency against the pressure and friction of immiscible liquids. Inspired by the plant trichome structures and their function, grooved nanotrichome, formed on the fibrous membrane by the oxygen plasma etching, induces robust water lubrication on the SWIS. SWIS membrane repels and separates highly viscous and adhesive oils in air and underwater by preventing oils from adhering to the lubricating surface. Repeated tests both in air and underwater confirm the antiadhesion and self-cleaning properties of the SWIS. The SWIS oil scooper, fixed on a frame with a handle, successfully collects spilled oil on a pilot-scale oil spill site and a real ocean oil spill site by simply scooping and recovering the oil. In addition, SWIS membrane is expected to help protect environments with further applications such as oil-wastewater treatment and oil separation in food.
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Purificação da Água , Água , Lubrificantes , Lubrificação , Óleos/química , Água/químicaRESUMO
We provide a simple design chart framework to predict the apparent contact angle on a textured surface in terms of the equilibrium contact angle on a chemically identical smooth surface and details of the surface topography. For low surface tension liquids such as methanol (gamma(lv) = 22.7 mN/m) and octane (gamma(lv) = 21.6 mN/m), a solid-liquid-air composite interface on a textured surface is inherently metastable. Thus, on application of a sufficient pressure difference (e.g., an externally applied pressure or a sufficiently large Laplace pressure at small droplet size) the metastable composite interface transitions to a fully wetted interface. A dimensionless robustness factor is used to quantify the breakthrough pressure difference necessary to disrupt a metastable composite interface and to predict a priori the existence of a robust composite interface. The impact of the length scale (radius of the cylindrical features R varying from 18 to 114 microm) and the feature spacing ratio (D(*) = (R + D)/R varying from 2.2 to 5.1, where 2D is the spacing between the cylindrical features) on the robustness is illustrated by performing contact angle measurements on a set of dip-coated wire-mesh surfaces, which provide systematically quantifiable cylindrical texture. The design chart for a given feature size R shows how the two independent design parameters--surface chemistry as revealed in the equilibrium contact angle and texture spacing embodied in the dimensionless spacing ratio (D(*))--can be used to develop surfaces with desirably large values of the apparent contact angle and robustness of the metastable composite interface. Most revealing is the scaling of the robustness with the dimensionless parameter l(cap)/R (where l(cap = (gamma(lv)/rho g)(1/2) is the capillary length), which indicates clearly why, in the consideration of self-similar surfaces, smaller is better for producing omniphobic surfaces that resist wetting by liquids with low surface tension.
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Nanostructured glass with subwavelength hollow nanopillars of diameters of sub-65 nm was fabricated, showing high optical transmittance and ultralow diffuse reflectance. A simple process involving single-step plasma etching was used on a glass slide coated with a SiO2 sacrificial film. First, SiO2 nanodot structures were formed using plasma-induced anisotropic etching with CF4 plasma. The SiO2 nanodot array then became a secondary etching mask to form hollow nanopillars on the glass. The hollow structures formed at the upper part reaching up to the apex of the nanopillar had a lower solid fraction, while the lower part had a higher fraction. The refractive index (RI) gradually increased from 1.09 (near the value for air) to 1.42 (near the value for glass). Geometry-induced RI gradient enhanced light transmi, while it significantly reduced diffuse reflectance, particularly in the shorter wavelengths, thus suppressing the haziness or milky appearance of the nanostructured glass. Superhydrophilic and antifogging properties of nanostructured glasses and dental mirrored glasses were also demonstrated with water spraying and exhaled breath tests. Results showed that the wettability was enhanced in hydrophilicity and antifogging property by both the hydrophilic nature of the glass and the newly formed nanostructures. The nanostructured, superhydrophilic glass was also found to have easy cleaning nature against fine sand dust adhesion by simply blowing air or spraying water. Results of this study showed that such a hollow-pillared glass surface with gradient RI and special wettability could be applied in a variety of optical and optoelectronic applications requiring superwetting, such as optical windows for solar cell panels, display panels, light-emitting diodes, and medical devices even with curved surfaces.
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The development of liquid gating membrane (LGM) systems with tunable multiphase selectivity and antifouling properties is limited by the mechanical stability of the membrane materials. The mechanical integrity of most polymeric membranes can be compromised by deformation under harsh operating conditions (elevated temperatures, corrosive environments, foulants, etc.), ultimately leading to their failure. Here, a facile electrochemical approach to the fabrication of multifunctional metal-based liquid gating membrane systems is presented. The membrane porosity, pore size, and membrane surface roughness can be tuned from micro- to nanometer scale, enabling function under a variety of operating conditions. The prepared LGMs demonstrate controllable gas-liquid selectivity, superior resistance to corrosive conditions and fouling chemicals, and significant reduction of the transmembrane pressure required for the separation process, resulting in lower energy consumption. The stability of the gating liquid is confirmed experimentally through sustained fouling resistance and further supported by the interfacial energy calculations. The mechanically robust metal-based membrane systems reported in this study significantly extend the operating range of LGMs, prompting their applications in water treatment processes such as wastewater treatment, degassing, and multiphase separation.
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Low surface tension sebaceous liquids such as human fingerprint oils are readily deposited on high energy surfaces such as clean glass, leaving smudges that significantly lower transparency. There have been several attempts to prevent formation of these dactylograms on glass by employing oil-repellent textured surfaces. However, nanotextured superoleophobic coatings typically scatter visible light, and the intrinsic thermodynamic metastability of the composite superoleophobic state can result in failure of the oil repellency under moderate contact pressure. We develop titania-based porous nanoparticle coatings that are superoleophilic and highly transparent and which exhibit short time scales for decomposition of fingerprint oils under ultraviolet light. The mechanism by which a typical dactylogram is consumed combines wicking of the sebum into the nanoporous titania structure followed by photocatalytic degradation. We envision a wide range of applications because these TiO2 nanostructured surfaces remain photocatalytically active against fingerprint oils in natural sunlight and are also compatible with flexible glass substrates.
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This paper discusses the dynamic behavior of water drops impacting on inclined superhydrophobic surfaces. For a normal impact on a smooth hydrophobic surface, the spreading (or expansion) and retraction dynamics of an impacting drop varies from complete rebound to splashing depending on its Weber number, (We(d)), calculated using the impact speed and diameter d of the drop. For a slanted impact, on the other hand, the impact dynamics depends on two distinct Weber numbers, based on the velocity components normal, (We(nd)), and tangential, (We(td)), to the surface. Impact on superhydrophobic surfaces is even more complicated as the surfaces are covered with micro- to nano-scale texture. Therefore, we develop an expression for an additional set of two Weber numbers, (We(na), We(ta)), which are counterparts to the first set but use the gap distance a between asperities on the textured surface as the characteristic length. We correlate the derived Weber numbers with the impact dynamics on tilted surfaces covered with three different types of texture: (i) posts, (ii) ridges aligned with and (iii) ridges perpendicular to the impact direction. Results suggest that the first two Weber numbers, (We(nd), We(td)), affect the impact dynamics of a drop such as the degree of drop deformation as long as the superhydrophobicity remains intact. On the other hand, the Weber number We(na) determines the transition from the superhydrophobic Cassie-Baxter regime to the fully-wetted Wenzel regime. Accuracy of our model becomes lower at a high tilting angle (75°), due to the change in the transition mechanism.
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Birds in the cormorant (Phalacrocoracidae) family dive tens of metres into water to prey on fish while entraining a thin layer of air (a plastron film) within the microstructures of their feathers. In addition, many species within the family spread their wings for long periods of time upon emerging from water. To investigate whether wetting and wing-spreading are related to feather structure, microscopy and photographic studies have previously been used to extract structural parameters for barbs and barbules. In this work, we describe a systematic methodology to characterize the quasi-hierarchical topography of bird feathers that is based on contact angle measurements using a set of polar and non-polar probing liquids. Contact angle measurements on dip-coated feathers of six aquatic bird species (including three from the Phalacrocoracidae family) are used to extract two distinguishing structural parameters, a dimensionless spacing ratio of the barbule (D*) and a characteristic length scale corresponding to the spacing of defect sites. The dimensionless spacing parameter can be used in conjunction with a model for the surface topography to enable us to predict a priori the apparent contact angles of water droplets on feathers as well as the water breakthrough pressure required for the disruption of the plastron on the feather barbules. The predicted values of breakthrough depths in water (1-4 m) are towards the lower end of typical diving depths for the aquatic bird species examined here, and therefore a representative feather is expected to be fully wetted in a typical deep dive. However, thermodynamic surface energy analysis based on a simple one-dimensional cylindrical model of the feathers using parameters extracted from the goniometric analysis reveals that for water droplets on feathers of all six species under consideration, the non-wetting 'Cassie-Baxter' composite state represents the global energy minimum of the system. By contrast, for other wetting liquids, such as alkanes and common oils, the global energy minimum corresponds to a fully wetted or Wenzel state. For diving birds, individual feathers therefore spontaneously dewet once the bird emerges out of water, and the 'wing-spreading' posture might assist in overcoming kinetic barriers associated with pinning of liquid droplets that retard the rate of drying of the wet plumage of diving birds.
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Aves/fisiologia , Plumas/anatomia & histologia , Molhabilidade , Animais , Mergulho , Plumas/ultraestrutura , Especificidade da Espécie , Propriedades de Superfície , TermodinâmicaRESUMO
Designing multifunctional surfaces that have user-specified interactions with impacting liquids and with incident light is a topic of both fundamental and practical significance. Taking cues from nature, we use tapered conical nanotextures to fabricate the multifunctional surfaces; the slender conical features result in large topographic roughness, while the axial gradient in the effective refractive index minimizes reflection through adiabatic index-matching between air and the substrate. Precise geometric control of the conical shape and slenderness of the features as well as periodicity at the nanoscale are all keys to optimizing the multifunctionality of the textured surface, but at the same time, these demands pose the toughest fabrication challenges. Here we report a systematic approach to concurrent design of optimal structures in the fluidic and optical domains and a fabrication procedure that achieves the desired aspect ratios and periodicities with few defects and large pattern area. Our fabricated nanostructures demonstrate structural superhydrophilicity or, in combination with a suitable chemical coating, robust superhydrophobicity. Enhanced polarization-independent optical transmission exceeding 98% has also been achieved over a broad range of bandwidth and incident angles. These nanotextured surfaces are also robustly antifogging or self-cleaning, offering potential benefits for applications such as photovoltaic solar cells.