Ambient-mediated wetting on smooth surfaces.

A consensus was built in the first half of the 20th century, which was further debated more than 3 decades ago, that the wettability and condensation mechanisms on smooth solid surfaces are modified by the adsorption of organic contaminants present in the environment. Recently, disagreement has formed about this topic once again, as many researchers have overlooked contamination due to its difficulty to eliminate. For example, the intrinsic wettability of rare earth oxides has been reported to be hydrophobic and non-wetting to water. These materials were subsequently shown to display dropwise condensation with steam. Nonetheless, follow on research has demonstrated that the intrinsic wettability of rare earth oxides is hydrophilic and wetting to water, and that a transition to hydrophobicity occurs in a matter of hours-to-days as a consequence of the adsorption of volatile organic compounds from the ambient environment. The adsorption mechanisms, kinetics, and selectivity, of these volatile organic compounds are empirically known to be functions of the substrate material and structure. However, these mechanisms, which govern the surface wettability, remain poorly understood. In this contribution, we introduce current research demonstrating the different intrinsic wettability of metals, rare earth oxides, and other smooth materials, showing that they are intrinsically hydrophilic. Then we provide details on research focusing on the transition from wetting (hydrophilicity) to non-wetting (hydrophobicity) on somooth surfaces due to adsorption of volatile organic compounds. A state-of-the-art figure of merit mapping the wettability of different smooth solid surfaces to ambient exposure as a function of the surface carbon content has also been developed. In addition, we analyse recent works that address these wetting transitions so to shed light on how such processes affect droplet pinning and lateral adhesion. We then conclude with objective perspectives about research on wetting to non-wetting transitions on smooth solid surfaces in an attempt to raise awareness regarding this surface contamination phenomenon within the engineering, interfacial science, and physical chemistry domains.

Insight into the photocatalytic and photothermal effect in plasmon-enhanced water oxidation property of AuTNP@MnOx core-shell nanoconstruct.

The development of robust and efficient photocatalytic constructs for boosting the water oxidation reaction (WOR) is needed for establishing a sunlight-driven renewable energy infrastructure. Here, we synthesized plasmonic core-shell nanoconstructs consisting of triangular gold nanoprism (AuTNP) core with mixed manganese oxide (MnOx) shell for photoelectrocatalytic WOR. These constructs show electrocatalytic WOR with a low onset overpotential requirement of 270 mV at pH 10. Photoexcitation showed further enhancement of their catalytic activity resulting in ∼15% decrease of the onset overpotential requirement along with the generation of photocurrent density of up to 300 µA/cm2. We showed that such light-driven enhancement of AuTNP@MnOx dyad's catalytic activity toward the WOR process includes contributions from both photocatalytic (hot carriers driven) and photothermal effects with photothermal effect playing the major role for wavelength between 532 and 808 nm. The contribution from the photocatalytic effect is appreciable only for high-energy excitations near the interband region, while the photothermal effect largely dominates for lower energy excitations near the LSPR wavelengths of the dyad.

Ultra-resilient multi-layer fluorinated diamond like carbon hydrophobic surfaces.

Seventy percent of global electricity is generated by steam-cycle power plants. A hydrophobic condenser surface within these plants could boost overall cycle efficiency by 2%. In 2022, this enhancement equates to an additional electrical power generation of 1000 TWh annually, or 83% of the global solar electricity production. Furthermore, this efficiency increase reduces CO2 emissions by 460 million tons /year with a decreased use of 2 trillion gallons of cooling water per year. However, the main challenge with hydrophobic surfaces is their poor durability. Here, we show that solid microscale-thick fluorinated diamond-like carbon (F-DLC) possesses mechanical and thermal properties that ensure durability in moist, abrasive, and thermally harsh conditions. The F-DLC coating achieves this without relying on atmospheric interactions, infused lubricants, self-healing strategies, or sacrificial surface designs. Through tailored substrate adhesion and multilayer deposition, we develop a pinhole-free F-DLC coating with low surface energy and comparable Young's modulus to metals. In a three-year steam condensation experiment, the F-DLC coating maintains hydrophobicity, resulting in sustained and improved dropwise condensation on multiple metallic substrates. Our findings provide a promising solution to hydrophobic material fragility and can enhance the sustainability of renewable and non-renewable energy sources.

In Situ Opto-Hydrodynamic Characterization of Lubricant-Infused Surface Degradation.

Vapor condensation is widely used in industrial systems due to its effective heat and mass transfer when compared to single-phase thermal transport. In particular, dropwise condensation can significantly enhance heat transfer performance due to rapid droplet shedding and promotion of additional nucleation sites for vapor condensation. Recently, lubricant-infused surfaces (LISs) composed of superhydrophobic structures infused with a low surface tension lubricant have been shown to effectively promote dropwise condensation of a variety of fluids by forming chemically and topographically homogeneous low-surface-energy surfaces. However, depletion of the infused lubricant remains a critical limitation to developing durable LISs which can sustain prolonged dropwise condensation. Moreover, the observed degradation is difficult to detect especially during active condensation on the surface. Here, we introduce an optical measurement technique to quantify in situ and in operando lubricant drainage from LISs. The optical method allows for non-invasive, instantaneous, and accurate prediction of the lifespan of LISs. The method implements the analysis of sample transient transparency, with depletion leading to exposure of the structure and increased light scattering. Our work demonstrates the logarithmic relation between the amount of the lubricant remaining in the LIS and the optical transmittance of the LIS, validating our unique technique for estimating the durability of LISs.

Particulate-Droplet Coalescence and Self-Transport on Superhydrophobic Surfaces.

Particulate transport from surfaces governs a variety of phenomena including fungal spore dispersal, bioaerosol transmission, and self-cleaning. Here, we report a previously unidentified mechanism governing passive particulate removal from superhydrophobic surfaces, where a particle coalescing with a water droplet (∼10 to ∼100 µm) spontaneously launches. Compared to previously discovered coalescence-induced binary droplet jumping, the reported mechanism represents a more general capillary-inertial dominated transport mode coupled with particle/droplet properties and is typically mediated by rotation in addition to translation. Through wetting and momentum analyses, we show that transport physics depends on particle/droplet density, size, and wettability. The observed mechanism presents a simple and passive pathway to achieve self-cleaning on both artificial as well as biological materials as confirmed here with experiments conducted on butterfly wings, cicada wings, and clover leaves. Our findings provide insights into particle-droplet interaction and spontaneous particulate transport, which may facilitate the development of functional surfaces for medical, optical, thermal, and energy applications.

Ultrascalable Surface Structuring Strategy of Metal Additively Manufactured Materials for Enhanced Condensation.

Metal additive manufacturing (AM) enables unparalleled design freedom for the development of optimized devices in a plethora of applications. The requirement for the use of nonconventional aluminum alloys such as AlSi10Mg has made the rational micro/nanostructuring of metal AM challenging. Here, the techniques are developed and the fundamental mechanisms governing the micro/nanostructuring of AlSi10Mg, the most common metal AM material, are investigated. A surface structuring technique is rationally devised to form previously unexplored two-tier nanoscale architectures that enable remarkably low adhesion, excellent resilience to condensation flooding, and enhanced liquid-vapor phase transition. Using condensation as a demonstration framework, it is shown that the two-tier nanostructures achieve 6× higher heat transfer coefficient when compared to the best filmwise condensation. The study demonstrates that AM-enabled nanostructuring is optimal for confining droplets while reducing adhesion to facilitate droplet detachment. Extensive benchmarking with past reported data shows that the demonstrated heat transfer enhancement has not been achieved previously under high supersaturation conditions using conventional aluminum, further motivating the need for AM nanostructures. Finally, it has been demonstrated that the synergistic combination of wide AM design freedom and optimal AM nanostructuring method can provide an ultracompact condenser having excellent thermal performance and power density.

Life Span of Slippery Lubricant Infused Surfaces.

Since their discovery a decade ago, slippery liquid infused porous surfaces (SLIPSs) or lubricant infused surfaces (LISs) have been demonstrated time and again to have immense potential for a plethora of applications. Of these, one of the most promising is enhancing the energy efficiency of both thermoelectric and organic Rankine cycle power generation via enhanced vapor condensation. However, utilization of SLIPSs in the energy sector remains limited due to the poor understanding of their life span. Here, we use controlled conditions to conduct multimonth steam and ethanol condensation tests on ultrascalable nanostructured copper oxide structured surfaces impregnated with mineral and fluorinated lubricants having differing viscosities (9.7 mPa·s < µ < 5216 mPa·s) and chemical structures. Our study demonstrates that SLIPSs lose their hydrophobicity during steam condensation after 1 month due to condensate cloaking. However, these same SLIPSs maintain nonwetting after 5 months of ethanol condensation due to the absence of cloaking. Surfaces impregnated with higher viscosity oil (5216 mPa·s) increase the life span to more than 8 months of continuous ethanol condensation. Vapor shear tests revealed that SLIPSs do not undergo oil depletion during exposure to 10 m/s gas flows, critical to condenser implementation where single-phase superheated vapor impingement is prevalent. Furthermore, higher viscosity SLIPSs are shown to maintain good stability after exposure to 200 °C air. A subset of the durable SLIPSs did not show change in slipperiness after submerging in stagnant water and ethanol for up to 2 weeks, critical to condenser implementation where single-phase condensate immersion is prevalent. Our work not only demonstrates design methods and longevity statistics for slippery nanoengineered surfaces undergoing long-term dropwise condensation of steam and ethanol but also develops the fundamental design guidelines for creating durable slippery liquid infused surfaces.

The apparent surface free energy of rare earth oxides is governed by hydrocarbon adsorption.

The surface free energy of rare earth oxides (REOs) has been debated during the last decade, with some reporting REOs to be intrinsically hydrophilic and others reporting hydrophobic. Here, we investigate the wettability and surface chemistry of pristine and smooth REO surfaces, conclusively showing that hydrophobicity stems from wettability transition due to volatile organic compound adsorption. We show that, for indoor ambient atmospheres and well-controlled saturated hydrocarbon atmospheres, the apparent advancing and receding contact angles of water increase with exposure time. We examined the surfaces comprehensively with multiple surface analysis techniques to confirm hydrocarbon adsorption and correlate it to wettability transition mechanisms. We demonstrate that both physisorption and chemisorption occur on the surface, with chemisorbed hydrocarbons promoting further physisorption due to their high affinity with similar hydrocarbon molecules. This study offers a better understanding of the intrinsic wettability of REOs and provides design guidelines for REO-based durable hydrophobic coatings.

Ultra-thin self-healing vitrimer coatings for durable hydrophobicity.

Durable hydrophobic materials have attracted considerable interest in the last century. Currently, the most popular strategy to achieve hydrophobic coating durability is through the combination of a perfluoro-compound with a mechanically robust matrix to form a composite for coating protection. The matrix structure is typically large (thicker than 10 µm), difficult to scale to arbitrary materials, and incompatible with applications requiring nanoscale thickness such as heat transfer, water harvesting, and desalination. Here, we demonstrate durable hydrophobicity and superhydrophobicity with nanoscale-thick, perfluorinated compound-free polydimethylsiloxane vitrimers that are self-healing due to the exchange of network strands. The polydimethylsiloxane vitrimer thin film maintains excellent hydrophobicity and optical transparency after scratching, cutting, and indenting. We show that the polydimethylsiloxane vitrimer thin film can be deposited through scalable dip-coating on a variety of substrates. In contrast to previous work achieving thick durable hydrophobic coatings by passively stacking protective structures, this work presents a pathway to achieving ultra-thin (thinner than 100 nm) durable hydrophobic films.

A Deep Learning Perspective on Dropwise Condensation.

Condensation is ubiquitous in nature and industry. Heterogeneous condensation on surfaces is typified by the continuous cycle of droplet nucleation, growth, and departure. Central to the mechanistic understanding of the thermofluidic processes governing condensation is the rapid and high-fidelity extraction of interpretable physical descriptors from the highly transient droplet population. However, extracting quantifiable measures out of dynamic objects with conventional imaging technologies poses a challenge to researchers. Here, an intelligent vision-based framework is demonstrated that unites classical thermofluidic imaging techniques with deep learning to fundamentally address this challenge. The deep learning framework can autonomously harness physical descriptors and quantify thermal performance at extreme spatio-temporal resolutions of 300 nm and 200 ms, respectively. The data-centric analysis conclusively shows that contrary to classical understanding, the overall condensation performance is governed by a key tradeoff between heat transfer rate per individual droplet and droplet population density. The vision-based approach presents a powerful tool for the study of not only phase-change processes but also any nucleation-based process within and beyond the thermal science community through the harnessing of big data.

Fabrication Optimization of Ultra-Scalable Nanostructured Aluminum-Alloy Surfaces.

Aluminum and its alloys are widely used in various industries. Aluminum plays an important role in heat transfer applications, where enhancing the overall system performance through surface nanostructuring is achieved. Combining optimized nanostructures with a conformal hydrophobic coating leads to superhydrophobicity, which enables coalescence induced droplet jumping, enhanced condensation heat transfer, and delayed frosting. Hence, the development of a rapid, energy-efficient, and highly scalable fabrication method for rendering aluminum superhydrophobic is crucial. Here, we employ a simple, ultrascalable fabrication method to create boehmite nanostructures on aluminum. We systematically explore the influence of fabrication conditions such as water immersion time and immersion temperature, on the created nanostructure morphology and resultant nanostructure length scale. We achieved optimized structures and fabrication procedures for best droplet jumping performance as measured by total manufacturing energy utilization, fabrication time, and total cost. The wettability of the nanostructures was studied using the modified Cassie-Baxter model. To better differentiate performance of the fabricated superhydrophobic surfaces, we quantify the role of the nanostructure morphology to corresponding condensation and antifrosting performance through study of droplet jumping behavior and frost propagation dynamics. The effect of aluminum substrate composition (alloy) on wettability, condensation and antifrosting performance was investigated, providing important directions for proper substrate selection. Our findings indicate that the presence of trace alloying elements play a previously unobserved and important role on wettability, condensation, and frosting behavior via the inclusion of defect sites on the surface that are difficult to remove and act as pinning locations to increase liquid-solid adhesion. Our work provides optimization strategies for the fabrication of ultrascalable aluminum and aluminum alloy superhydrophobic surfaces for a variety of applications.

Scalable Slippery Omniphobic Covalently Attached Liquid Coatings for Flow Fouling Reduction.

Fouling and accretion have negative impacts on a plethora of processes. To mitigate heterogeneous nucleation of a foulant, lowering the surface energy and reducing surface roughness are desired. Here, we develop a multilayer coating to mitigate solution-based heterogeneous fouling for internal flows. The first layer is a sol-gel silicon dioxide (SiO2) coating, which acts as a corrosion barrier, creates the surface chemistry needed for covalent bonding of the slippery omniphobic covalently attached liquid (SOCAL), and ensures an atomically smooth (<1 nm) interface. The second layer bonded to SiO2 is SOCAL, which further reduces the nucleation rate due to its low surface energy (<12 mJ/m2). The presence of a consistent sol-gel SiO2 base coating to bind to the SOCAL enables application to various metallic substrates. The coating is solid, making it more durable when compared to alternative slippery liquid-infused surfaces (LIS) that suffer from lubricant loss. To demonstrate performance and scalability, we apply our coating to the internal walls of aluminum (Al) tubing and test its fouling performance in a flow-fouling setup with single-phase flow of synthetic seawater. The seawater consists of saturated calcium sulfide (CaSO4), and fouling is characterized in both laminar and turbulent flow regimes (Reynolds numbers 1030 to 9300). Our coating demonstrated a reduction in salt scale fouling by 95% when compared to uncoated Al tubes. Furthermore, we show our coating to withstand turbulent flow conditions, mechanical abrasion loading, and corrosive environments for durations much longer than LIS. Our work demonstrates a coating methodology applicable to a variety of metal substrates and internal passages to achieve antifouling in single-phase flows.

Lubricant-Infused Surfaces for Low-Surface-Tension Fluids: The Extent of Lubricant Miscibility.

Lubricant-infused surfaces (LISs) and slippery liquid-infused porous surfaces (SLIPSs) have shown remarkable success in repelling low-surface-tension fluids. The atomically smooth, defect-free slippery surface leads to reduced droplet pinning and omniphobicity. However, the presence of a lubricant introduces liquid-liquid interactions with the working fluid. The commonly utilized lubricants for LISs and SLIPSs, although immiscible with water, show various degrees of miscibility with organic polar and nonpolar working fluids. Here, we rigorously investigate the extent of miscibility by considering a wide range of liquid-vapor surface tensions (12-73 mN/m) and different categories of lubricants having a range of viscosities (5-2700 cSt). Using high-fidelity analytical chemistry techniques including X-ray photoelectron spectroscopy, nuclear magnetic resonance, thermogravimetric analysis, and two-dimensional gas chromatography, we quantify lubricant miscibility to parts per billion accuracy. Furthermore, we quantify lubricant concentrations in the collected condensate obtained from prolonged condensation experiments with ethanol and hexane to delineate mixing and shear-based lubricant drainage mechanisms and to predict the lifetime of LISs and SLIPSs. Our work not only elucidates the effect of lubricant properties on miscibility with various fluids but also develops guidelines for developing stable and robust LISs and SLIPSs.

Droplet Evaporation Dynamics of Low Surface Tension Fluids Using the Steady Method.

Droplet evaporation governs many heat- and mass-transfer processes germane in nature and industry. In the past 3 centuries, transient techniques have been developed to characterize the evaporation of sessile droplets. These methods have difficulty in reconciling transient effects induced by the droplet shape and size changes during evaporation. Furthermore, investigation of evaporation of microdroplets residing on wetting substrates, or fluids having low surface tensions (<30 mN/m), is difficult to perform using established approaches. Here, we use the steady method to study the microdroplet evaporation dynamics of low surface tension liquids. We start by employing the steady method to benchmark with water droplets having base radii (20 ≤ Rb ≤ 260 µm), apparent advancing contact angle (45° ≤ θa,app ≤ 162°), surface temperature (30 < Ts < 60 °C), and relative humidity (40% < ϕ < 60%). Following validation, evaporation of ethanol (≈22 mN/m), hexane (≈18 mN/m), and dodecane (≈25 mN/m) were studied for 90 ≤ Rb ≤ 400 µm and 10 < Ts < 25 °C. We elucidate the mechanisms governing the observed behavior using heat and mass transport scaling analysis during evaporation, demonstrating our steady technique to be particularly advantageous for microdroplets, where Marangoni and buoyant forces are negligible. Our work not only elucidates the droplet evaporation mechanisms of low surface tension liquids but also demonstrates the steady method as a means to study phase change processes.

Laplace Pressure Driven Single-Droplet Jumping on Structured Surfaces.

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.

Condensation of Satellite Droplets on Lubricant-Cloaked Droplets.

Condensation on lubricant-infused micro- or nanotextured superhydrophobic surfaces exhibits remarkable heat transfer performance owing to the high condensation nucleation density and efficient condensate droplet removal. When a low surface tension lubricant is used, it can spread on the condensed droplet and "cloak" it. Here, we describe a previously unobserved condensation phenomenon of satellite droplet formation on lubricant-cloaked water droplets using environmental scanning electron microscopy. The presence of satellite droplets confirms the cloaking behavior of common lubricants on water such as Krytox oils. More interestingly, we have observed satellite droplets on BMIm ionic liquid-infused surfaces, which is unexpected because BMIm was used in previous reports as a lubricant to eliminate cloaking during water condensation. Our studies reveal that the cloaking of BMIm on water droplets is theoretically favorable due to the fast timescale spreading during initial condensation when compared to the long timescale required for dissolution of the lubricant in water. We utilize a novel characterization approach based on Raman spectroscopy to confirm the existence of cloaking lubricant films on water droplets residing on lubricant-infused surfaces. The selected lubricants include Krytox oil, ionic liquid, and dodecane, which have drastically different surface tensions and polarities. In addition, spreading dynamics of cloaking and noncloaking lubricants on water droplets show that ionic liquid has the capability to mobilize water droplets spontaneously owing to cloaking and its relatively high surface tension. Our studies not only elucidate the physics governing cloaking and satellite droplet condensation phenomena at micro- and macroscales but also reveal a subset of previously unobserved lubricant-water interfacial interactions for a large variety of applications.

Dropwise condensation on solid hydrophilic surfaces.

Droplet nucleation and condensation are ubiquitous phenomena in nature and industry. Over the past century, research has shown dropwise condensation heat transfer on nonwetting surfaces to be an order of magnitude higher than filmwise condensation heat transfer on wetting substrates. However, the necessity for nonwetting to achieve dropwise condensation is unclear. This article reports stable dropwise condensation on a smooth, solid, hydrophilic surface (θa = 38°) having low contact angle hysteresis (<3°). We show that the distribution of nano- to micro- to macroscale droplet sizes (about 100 nm to 1 mm) for coalescing droplets agrees well with the classical distribution on hydrophobic surfaces and elucidate that the wettability-governed dropwise-to-filmwise transition is mediated by the departing droplet Bond number. Our findings demonstrate that achieving stable dropwise condensation is not governed by surface intrinsic wettability, as assumed for the past eight decades, but rather, it is dictated by contact angle hysteresis.

Stable Dropwise Condensation of Ethanol and Hexane on Rationally Designed Ultrascalable Nanostructured Lubricant-Infused Surfaces.

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-surface-tension fluids.

Hierarchical Condensation.

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.

Atmosphere-Mediated Superhydrophobicity of Rationally Designed Micro/Nanostructured Surfaces.

Superhydrophobicity has received significant attention over the past three decades owing to its significant potential in self-cleaning, anti-icing and drag reduction surfaces, energy-harvesting devices, antibacterial 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 because of 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, United States 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 coalescence-induced 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.