Superhydrophobicity has received significant attention over the past three decades owing to its significant potential in self-cleaning and anti-icing surfaces, drag reduction, energy harvesting devices, anti-bacterial coatings, and enhanced heat transfer applications. Superhydrophobicity can be obtained via the roughening of an intrinsically hydrophobic surface, the creation of a re-entrant geometry, or by the roughening of a hydrophilic surface followed by a conformal coating of a hydrophobic material. Intrinsically hydrophobic surfaces have poor thermophysical properties such as thermal conductivity, and thus are not suitable for heat transfer applications. Re-entrant geometries, although versatile in applications where droplets are deposited, break down during spatially random nucleation and flood the surface. Chemical functionalization of rough metallic substrates, although promising, is not utilized due to the poor durability of conformal hydrophobic coatings. Here we develop a radically different approach to achieve stable superhydrophobicity. By utilizing laser processing and thermal oxidation of copper (Cu) to create a high surface energy hierarchical copper oxide (CuO), followed by repeatable and passive atmospheric adsorption of hydrophobic volatile organic compounds (VOCs), we show that stable superhydrophobicity with apparent advancing contact angles ≈ 160° and contact angle hysteresis as low as ≈ 20° can be achieved. We exploit the structure length scale and structure geometry dependent VOC adsorption dynamics to rationally design CuO nanowires with enhanced superhydrophobicity. To gain an understanding of the VOC adsorption physics, we utilized X-Ray Photoelectron and Ion Mass Spectroscopy to identify the chemical species deposited on our surfaces in two distinct locations: Urbana, IL, USA and Beijing, China. To test the stability of the atmosphere-mediated superhydrophobic surfaces during heterogeneous nucleation, we used high-speed optical microscopy to demonstrate the occurrence of dropwise condensation and stable coalescenceinduced droplet jumping. Our work not only provides rational design guidelines for developing passively-durable superhydrophobic surfaces with excellent flooding-resistance and self-healing capability, but also sheds light on the key role played by the atmosphere in governing wetting.
Vapor condensation is a widely used industrial process for transferring heat and separating fluids. Despite progress in developing low surface energy hydrophobic and micro/nanostructured superhydrophobic coatings to enhance water vapor condensation, demonstration of stable dropwise condensation of low-surface-tension fluids has not been achieved. Here, we develop rationally designed nanoengineered lubricant-infused surfaces (LISs) having ultralow contact angle hysteresis (<3°) for stable dropwise condensation of ethanol (γ ≈ 23 mN/m) and hexane (γ ≈ 19 mN/m). Using a combination of optical imaging and rigorous heat transfer measurements in a controlled environmental chamber free from noncondensable gases (<4 Pa), we characterize the condensation behavior of ethanol and hexane on ultrascalable nanostructured CuO surfaces impregnated with fluorinated lubricants having varying viscosities (0.496 < μ < 5.216 Pa•s) and chemical structures (branched versus linear, Krytox and Fomblin). We demonstrate stable dropwise condensation of ethanol and hexane on LISs impregnated with Krytox 1525, attaining about 200% enhancement in condensation heat transfer coefficient for both fluids compared to filmwise condensation on hydrophobic surfaces. In contrast to previous studies, we use 7 h of steady dropwise condensation experiments to demonstrate the importance of rational lubricant selection to minimize lubricant drainage and maximize LIS durability. This work not only demonstrates an avenue to achieving stable dropwise condensation of ethanol and hexane, it develops the fundamental design principles for creating durable LISs for enhanced condensation heat transfer of low-surfacetension fluids.
With the recent advances in surface fabrication technologies, condensation heat transfer has seen a renaissance. Hydrophobic and superhydrophobic surfaces have all been employed as a means to enhance condensate shedding, enabling micrometric droplet departure length scales. One of the main bottlenecks for achieving higher condensation efficiencies is the difficulty of shedding sub-10 μm droplets due to the increasing role played by surface adhesion and viscous limitations at nanometric length scales. To enable ultraefficient droplet shedding, we demonstrate hierarchical condensation on rationally designed copper oxide microhill structures covered with nanoscale features that enable large (∼100 μm) condensate droplets on top of the microstructures to coexist with smaller (<1 μm) droplets beneath. We use high-speed optical microscopy and focal plane shift imaging to show that hierarchical condensation is capable of efficiently removing sub-10-μm condensate droplets via both coalescence and divergent-track-assisted droplet self-transport toward the large suspended Cassie−Baxter (CB) state droplets, which eventually shed via classical gravitational shedding and thereby avoid vapor side limitations encountered with droplet jumping. Interestingly, experimental growth rate analysis showed that the presence of large CB droplets accelerates individual underlying droplet growth by ∼21% when compared to identically sized droplets not residing beneath CB droplets. Furthermore, the steady droplet shedding mechanism shifted the droplet size distribution toward smaller sizes, with ∼70% of observable underlying droplets having radii of ≤5 μm compared to ∼30% for droplets growing without shading. To elucidate the overall heat transfer performance, an analytical model was developed to show hierarchical condensation has the potential to break the limits of minimum droplet departure size governed by finite surface adhesion and viscous effects through the tailoring of structure length scale, coalescence, and self-transport. More importantly, abrasive wear tests showed that hierarchical condensation has good durability against mechanical damage to the surface. Our study not only demonstrates the potential of hierarchical condensation as a means to break the limitations of droplet jumping, it develops rational design guidelines for micro/nanostructured surfaces to enable excellent heat transfer performance as well as extended durability.
Droplet transport on, and shedding from, surfaces is ubiquitous in nature and is a key phenomenon governing applications including biofluidics, self-cleaning, anti-icing, water harvesting, and electronics thermal management. Conventional methods to achieve spontaneous droplet shedding enabled by surface−droplet interactions suffer from low droplet transport velocities and energy conversion efficiencies. Here, by spatially confining the growing droplet and enabling relaxation via rationally designed grooves, we achieve single-droplet jumping of micrometer and millimeter droplets with dimensionless jumping velocities v* approaching 0.95, significantly higher than conventional passive approaches such as coalescence-induced droplet jumping (v* ≈ 0.2−0.3). The mechanisms governing single-droplet jumping are elucidated through the study of groove geometry and local pinning, providing guidelines for optimized surface design. We show that rational design of grooves enables flexible control of droplet-jumping velocity, direction, and size via tailoring of local pinning and Laplace pressure differences. We successfully exploit this previously unobserved mechanism as a means for rapid removal of droplets during steam condensation. Our study demonstrates a passive method for fast, efficient, directional, and surface-pinning-tolerant transport and shedding of droplets having micrometer to millimeter length scales.
Scale formation presents an enormous cost to the global economy. Classical nucleation theory dictates that to reduce the heterogeneous nucleation of scale, the surface should have low surface energy and be as smooth as possible. Past approaches have focused on lowering surface energy via the use of hydrophobic coatings and have created atomically smooth interfaces to eliminate nucleation sites, or both, via the infusion of lowsurface-energy lubricants into rough superhydrophobic substrates. Although lubricant-based surfaces are promising candidates for antiscaling, lubricant drainage inhibits their utilization. Here, we develop methodologies to deposit slippery omniphobic covalently attached liquids (SOCAL) on arbitrary substrates. Similar to lubricant-based surfaces, SOCAL has ultralow roughness and surface energy, enabling low nucleation rates and eliminating the need to replenish the lubricant. To enable SOCAL coating on metals, we investigated the surface chemistry required to ensure high-quality functionalization as measured by ultralow contact angle hysteresis (<3°). Using a multilayer deposition approach, we first electrophoretically deposit (EPD) silicon dioxide (SiO 2 ) as an intermediate layer between the metallic substrate and SOCAL. The necessity of EPD SiO 2 is to smooth (<10 nm roughness) as well as to enable the proper surface chemistry for SOCAL bonding. To characterize antiscaling performance, we utilized calcium sulfate (CaSO 4 ) scale tests, showing a 20× reduction in scale deposition rate than untreated metallic substrates. Descaling tests revealed that SOCAL dramatically decreases scale adhesion, resulting in rapid removal of scale buildup. Our work not only demonstrates a robust methodology for depositing antiscaling SOCAL coatings on metals but also develops design guidelines for the creation of antifouling coatings for alternate applications such as biofouling and high-temperature coking.
SUMMARY Energy harvesting technology has recently gained attraction as it enables the utilization of diverse ambient energy sources. Reverse electrodialysis (RED) is such a technique that converts electrical energy from the concentration gradient between a concentrated solution (e.g., seawater) and a diluted solution (e.g., fresh water). We experimentally investigated a RED device using nanoporous polycarbonate track‐etch membranes. We performed the parametric study by varying the concentration differences, the pore size, and the electrolyte types. We characterized the RED performance in terms of maximum voltage, maximum current, and maximum power. The experimental results showed that the maximum voltage has a nonlinear dependency on the concentration difference with the highest value around the 100:1 concentration ratio. The maximum current and maximum power, on the other hand, monotonically increase as the concentration difference increases. We also found that the performance of the RED cell is enhanced with the decreased pore size in the experiments for the nominal diameter ranging from 15 to 100 nm. The results with different cations show that the electricity generation of the RED cell increases as the ion mobility increases or the valence number decreases. Copyright © 2013 John Wiley & Sons, Ltd.
Numerous natural surfaces have micro/nanostructures that result in extraordinary functionality, such as superhydrophobicity, self‐cleaning, antifogging, and antimicrobial properties. One such example is the cicada wing, where differences in nanopillar geometry and composition among species can impact and influence the degree of exhibited properties. To understand the relationships between surface topography and chemical composition with multifunctionality, the wing properties of Neotibicen pruinosus (superhydrophobic) and Magicicada cassinii (hydrophobic) cicadas are investigated at time points after microwave‐assisted extraction of surface molecules to characterize the chemical contribution to nanopillar functionality. Electron microscopy of the wings throughout the extraction process illustrates nanoscale topographical changes, while concomitant changes in hydrophobicity, bacterial fouling, and bactericidal properties are also measured. Extract analysis reveals the major components of the nanostructures to be fatty acids and saturated hydrocarbons ranging from C17 to C44. Effects on the antimicrobial character of a wing surface with respect to the extracted chemicals suggest that the molecular composition of the nanopillars plays both a direct and an indirect role in concert with nanopillar geometry. The data presented not only correlates the nanopillar molecular organization to macroscale functional properties, but it also presents design guidelines to consider during the replication of natural nanostructures onto engineered substrates to induce desired properties.
Coalescence-induced droplet jumping has the potential to enhance the performance of a variety of applications including condensation heat transfer, surface self-cleaning, anti-icing, and defrosting to name a few. Here, we study droplet jumping on hierarchical microgrooved and nanostructured smooth superhydrophobic surfaces. We show that the confined microgroove structures play a key role in tailoring droplet coalescence hydrodynamics, which in turn affects the droplet jumping velocity and energy conversion efficiency. We observed self-jumping of individual deformed droplets within microgrooves having maximum surface-to-kinetic energy conversion efficiency of 8%. Furthermore, various coalescence-induced jumping modes were observed on the hierarchical microgrooved superhydrophobic surface. The microgroove structure enabled high droplet jumping velocity (≈0.74U) and energy conversion efficiency (≈46%) by enabling the coalescence of deformed droplets in microgrooves with undeformed droplets on adjacent plateaus. The jumping velocity and energy conversion efficiency enhancements are 1.93× and 6.67× higher than traditional coalescence-induced droplet jumping on smooth superhydrophobic surfaces. This work not only demonstrates high droplet jumping velocity and energy conversion efficiency but also demonstrates the key role played by macroscale structures on coalescence hydrodynamics and elucidates a method to further control droplet jumping physics for a plethora of applications.
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