Fundamental Limits of the Spatial Control of Heterogeneous Nucleation on Biphilic Surfaces.

Condensation of water vapor on nonwetting surfaces, termed dropwise condensation, leads to rapid droplet removal and significantly improves heat transfer compared to wetting surfaces. However, the spatial distribution of heterogeneous nucleation sites during dropwise condensation is random. Furthermore, the low surface energy of the nonwetting substrate reduces the nucleation rate as predicted by classical nucleation theory. To achieve higher nucleation rates, biphilic surfaces having low nucleation energy barriers that rely on spatial heterogeneity of surface chemistry have been developed. Here, we use a robust method to create biphilic surfaces on flat and micropillar samples having various dimensions (pillar lengths: 10-15 µm, pillar heights: 0-15 µm) by utilizing lift-off microfabrication. Our fabrication approach leads to hydrophilic pillar tops and hydrophobic pillar sides and surrounding basal areas. To study water vapor condensation on the biphilic surfaces, we utilized optical microscopy in a controlled temperature and humidity environment. Interestingly, our studies show that while the majority of nucleation (≈100%) occurred only on the hydrophilic areas (pillar tops) for small pillar center-to-center spacing (pitch), the spatial control of heterogeneous nucleation broke down when the pitch increased. For larger pitches, we observed the nucleation of water droplets on the hydrophobic base in conjunction with hydrophilic pillar tops. Using theoretical models of vapor diffusion coupled with heat transfer and three-dimensional (3D) numerical simulations, we show that nucleation initiation on hydrophilic pillar tops leads to the formation of dry zones, preventing nucleation on hydrophobic regions. However, with increasing pitch, part of the hydrophobic region no longer feels the presence of the vapor depletion zone, resulting in subsequent nucleation at defect sites on the hydrophobic regions at the base. Our study offers insights into the fundamental limitations of biphilic condensation and offers avenues for their further improvement for applications such as boiling, icing, evaporation, and condensation.

Role of Thin Film Adhesion on Capillary Peeling.

The capillary force can peel off a substrate-attached film if the adhesion energy (Gw) is low. Capillary peeling has been used as a convenient, rapid, and nondestructive method for fabricating free-standing thin films. However, the critical value of Gw, which leads to the transition between peeling and sticking, remains largely unknown. As a result, capillary peeling remains empirical and applicable to a limited set of materials. Here, we investigate the critical value of Gw and experimentally show the critical adhesion (Gw,c) to scale with the water-film interfacial energy (≈0.7γfw), which corresponds well with our theoretical prediction of Gw,c = γfw. Based on the critical adhesion, we propose quantitative thermodynamic guidelines for designing thin film interfaces that enable successful capillary peeling. The outcomes of this work present a powerful technique for thin film transfer and advanced nanofabrication in flexible photovoltaics, battery materials, biosensing, translational medicine, and stretchable bioelectronics.

High-Throughput Stamping of Hybrid Functional Surfaces.

Hydrophobic-hydrophilic hybrid surfaces, sometimes termed biphilic surfaces, have shown potential to enhance condensation and boiling heat transfer, anti-icing, and fog harvesting performance. However, state of art techniques to develop these surfaces have limited substrate selection, poor scalability, and lengthy and costly fabrication methods. Here, we develop a simple, scalable, and rapid stamping technique for hybrid surfaces with spatially controlled wettability. To enable stamping, rationally designed and prefabricated polydimethylsiloxane (PDMS) stamps, which are reusable and independent of the substrate and functional coating, were used. To demonstrate the stamping technique, we used silicon wafer, copper, and aluminum substrates functionalized with a variety of hydrophobic chemistries including heptadecafluorodecyltrimethoxy-silane, octafluorocyclobutane, and slippery omniphobic covalently attached liquids. Condensation experiments and microgoniometric characterization demonstrated that the stamped surfaces have global hydrophobicity or superhydrophobicity with localized hydrophilicity (spots) enabled by local removal of the functional coating during stamping. Stamped surfaces with superhydrophobic backgrounds and hydrophilic spots demonstrated stable coalescence induced droplet jumping. Compared to conventional techniques, our stamping method has comparable prototyping cost with reduced manufacturing time scale and cost. Our work not only presents design guidelines for the development of scalable hybrid surfaces for the study of phase change phenomena, it develops a scalable and rapid stamping protocol for the cost-effective manufacture of next-generation hybrid wettability surfaces.

Durability and Degradation Mechanisms of Antifrosting Surfaces.

Rapid implementation of renewable energy technologies has exacerbated the potential for economic loss and safety concerns caused by ice and frost accretion, which occurs on the surfaces of wind turbine blades, photovoltaic panels, and residential and electric vehicle air-source heat pumps. The past decade has seen advances in surface chemistry and micro- and nanostructures that can promote passive antifrosting and enhance defrosting. However, the durability of these surfaces remains the major obstacle preventing real-life applications, with degradation mechanisms remaining poorly understood. Here, we conducted durability tests on antifrosting surfaces, including superhydrophobic, hydrophobic, superhydrophilic, and slippery liquid-infused surfaces. For superhydrophobic surfaces, we demonstrate durability with progressive degradation for up to 1000 cycles of atmospheric frosting-defrosting and month-long outdoor exposure tests. We show that progressive degradation, as reflected by increased condensate retention and reduced droplet shedding, results from molecular-level degradation of the low-surface-energy self-assembled monolayer (SAM). The degradation of the SAM leads to local high-surface-energy defects, which further deteriorate the surface by promoting accumulation of atmospheric particulate matter during cyclic condensation, frosting, and melt drying. Furthermore, cyclic frosting and defrost tests demonstrate the durability and degradation mechanisms of other surfaces to show, for example, the loss of water affinity of superhydrophilic surfaces after 22 days due to atmospheric volatile organic compound (VOC) adsorption and significant lubricant drainage for lubricant-infused surfaces after 100 cycles. Our work reveals the degradation mechanism of functional surfaces during exposure to long-term frost-defrost cycling and elucidates guidelines for the development of future surfaces for real-life antifrosting/icing applications.

Defect-Density-Controlled Phase-Change Phenomena.

Juxtaposing hydrophilicity and hydrophobicity on the same surface, known as hybrid surface engineering, can enhance phase-change heat transfer. However, controlling hydrophilicity on hybrid surfaces in a scalable fashion is a challenge, limiting their application. Here, using widely available metal meshes with variable dimensions and by controlling the patterning pressure, we scalably fabricate hybrid surfaces having spot and gridlike patterns using stamping. Using fog harvesting in a controlled chamber, we show that optimized hybrid surfaces have a ∼37% higher fog harvesting rate when compared to homogeneous superhydrophobic surfaces. Furthermore, condensation frosting experiments reveal that, on grid-patterned hybrid surfaces, frost propagates at ∼160% higher velocity and provides ∼20% less frost coverage when compared to homogeneous superhydrophobic surfaces. During defrost, our hybrid surfaces retain more water when compared to superhydrophobic surfaces due to the presence of hydrophilic patterns and melt water pinning. We adapt our fabrication technique to roll-to-roll patterning, demonstrating wettability contrast on round metallic geometries via atmospheric water vapor condensation. This work provides guidelines for the rapid, substrate-independent, and scalable fabrication of hybrid wettability surfaces for a wide variety of applications.

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.

A Lipid-Inspired Highly Adhesive Interface for Durable Superhydrophobicity in Wet Environments and Stable Jumping Droplet Condensation.

Creating thin (<100 nm) hydrophobic coatings that are durable in wet conditions remains challenging. Although the dropwise condensation of steam on thin hydrophobic coatings can enhance condensation heat transfer by 1000%, these coatings easily delaminate. Designing interfaces with high adhesion while maintaining a nanoscale coating thickness is key to overcoming this challenge. In nature, cell membranes face this same challenge where nanometer-thick lipid bilayers achieve high adhesion in wet environments to maintain integrity. Nature ensures this adhesion by forming a lipid interface having two nonpolar surfaces, demonstrating high physicochemical resistance to biofluids attempting to open the interface. Here, developing an artificial lipid-like interface that utilizes fluorine-carbon molecular chains can achieve durable nanometric hydrophobic coatings. The application of our approach to create a superhydrophobic material shows high stability during jumping-droplet-enhanced condensation as quantified from a continual one-year steam condensation experiment. The jumping-droplet condensation enhanced condensation heat transfer coefficient up to 400% on tube samples when compared to filmwise condensation on bare copper. Our bioinspired materials design principle can be followed to develop many durable hydrophobic surfaces using alternate substrate-coating pairs, providing stable hydrophobicity or superhydrophobicity to a plethora of applications.

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.

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.

Microscale Confinement and Wetting Contrast Enable Enhanced and Tunable Condensation.

Dropwise condensation represents the upper limit of thermal transport efficiency for liquid-to-vapor phase transition. A century of research has focused on promoting dropwise condensation by attempting to overcome limitations associated with thermal resistance and poor surface-modifier durability. Here, we show that condensation in a microscale gap formed by surfaces having a wetting contrast can overcome these limitations. Spontaneous out-of-plane condensate transfer between the contrasting parallel surfaces decouples the nanoscale nucleation behavior, droplet growth dynamics, and shedding processes to enable minimization of thermal resistance and elimination of surface modification. Experiments on pure steam combined with theoretical analysis and numerical simulation confirm the breaking of intrinsic limits to classical condensation and demonstrate a gap-dependent heat-transfer coefficient with up to 240% enhancement compared to dropwise condensation. Our study presents a promising mechanism and technology for compact energy and water applications where high, tunable, gravity-independent, and durable phase-change heat transfer is required.

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.

Extreme Antiscaling Performance of Slippery Omniphobic Covalently Attached Liquids.

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 low-surface-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 (SiO2) as an intermediate layer between the metallic substrate and SOCAL. The necessity of EPD SiO2 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 (CaSO4) 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.