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.

Droplet Jumping: Effects of Droplet Size, Surface Structure, Pinning, and Liquid Properties.

Coalescence-induced droplet jumping has the potential to enhance the efficiency of a plethora of applications. Although binary droplet jumping is quantitatively understood from energy and hydrodynamic perspectives, multiple aspects that affect jumping behavior, including droplet size mismatch, droplet-surface interaction, and condensate thermophysical properties, remain poorly understood. Here, we develop a visualization technique utilizing microdroplet dispensing to study droplet jumping dynamics on nanostructured superhydrophobic, hierarchical superhydrophobic, and hierarchical biphilic surfaces. We show that on the nanostructured superhydrophobic surface the jumping velocity follows inertial-capillary scaling with a dimensionless velocity of 0.26 and a jumping direction perpendicular to the substrate. A droplet mismatch phase diagram was developed showing that jumping is possible for droplet size mismatch up to 70%. On the hierarchical superhydrophobic surface, jumping behavior was dependent on the ratio between the droplet radius Ri and surface structure length scale L. For small droplets ( Ri ≤ 5 L), the jumping velocity was highly scattered, with a deviation of the jumping direction from the substrate normal as high as 80°. Surface structure length scale effects were shown to vanish for large droplets ( Ri > 5 L). On the hierarchical biphilic surface, similar but more significant scattering of the jumping velocity and direction was observed. Droplet-size-dependent surface adhesion and pinning-mediated droplet rotation were responsible for the reduced jumping velocity and scattered jumping direction. Furthermore, droplet jumping studies of liquids with surface tensions as low as 38 mN/m were performed, further confirming the validity of inertial-capillary scaling for varying condensate fluids. Our work not only demonstrates a powerful platform to study droplet-droplet and droplet-surface interactions but provides insights into the role of fluid-substrate coupling as well as condensate properties during droplet jumping.

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.