Intrinsic Water Transport in Moisture-Capturing Hydrogels.

Moisture-capturing hydrogels have emerged as attractive sorbent materials capable of converting ambient humidity into liquid water. Recent works have demonstrated exceptional water capture capabilities of hydrogels while simultaneously exploring different strategies to accelerate water capture and release. However, on the material level, an understanding of the intrinsic transport properties of moisture-capturing hydrogels is currently missing, which hinders their rational design. In this work, we combine absorption and desorption experiments of macroscopic hydrogel samples in pure vapor with models of water diffusion in the hydrogels to demonstrate the first measurements of the intrinsic water diffusion coefficient in hydrogel-salt composites. Based on these insights, we pattern hydrogels with micropores to significantly decrease the required absorption and desorption times by 19% and 72%, respectively, while reducing the total water capacity of the hydrogel by only 4%. Thereby, we provide an effective strategy toward hydrogel material optimization, with a particular significance in pure-vapor environments.

Spontaneous droplet trampolining on rigid superhydrophobic surfaces.

Spontaneous removal of condensed matter from surfaces is exploited in nature and in a broad range of technologies to achieve self-cleaning, anti-icing and condensation control. But despite much progress, our understanding of the phenomena leading to such behaviour remains incomplete, which makes it challenging to rationally design surfaces that benefit from its manifestation. Here we show that water droplets resting on superhydrophobic textured surfaces in a low-pressure environment can self-remove through sudden spontaneous levitation and subsequent trampoline-like bouncing behaviour, in which sequential collisions with the surface accelerate the droplets. These collisions have restitution coefficients (ratios of relative speeds after and before collision) greater than unity despite complete rigidity of the surface, and thus seemingly violate the second law of thermodynamics. However, these restitution coefficients result from an overpressure beneath the droplet produced by fast droplet vaporization while substrate adhesion and surface texture restrict vapour flow. We also show that the high vaporization rates experienced by the droplets and the associated cooling can result in freezing from a supercooled state that triggers a sudden increase in vaporization, which in turn boosts the levitation process. This effect can spontaneously remove surface icing by lifting away icy drops the moment they freeze. Although these observations are relevant only to systems in a low-pressure environment, they show how surface texturing can produce droplet-surface interactions that prohibit liquid and freezing water-droplet retention on surfaces.

Spontaneous self-dislodging of freezing water droplets and the role of wettability.

Spontaneous removal of liquid, solidifying liquid and solid forms of matter from surfaces, is of significant importance in nature and technology, where it finds applications ranging from self-cleaning to icephobicity and to condensation systems. However, it is a great challenge to understand fundamentally the complex interaction of rapidly solidifying, typically supercooled, droplets with surfaces, and to harvest benefit from it for the design of intrinsically icephobic materials. Here we report and explain an ice removal mechanism that manifests itself simultaneously with freezing, driving gradual self-dislodging of droplets cooled via evaporation and sublimation (low environmental pressure) or convection (atmospheric pressure) from substrates. The key to successful self-dislodging is that the freezing at the droplet free surface and the droplet contact area with the substrate do not occur simultaneously: The frozen phase boundary moves inward from the droplet free surface toward the droplet-substrate interface, which remains liquid throughout most of the process and freezes last. We observe experimentally, and validate theoretically, that the inward motion of the phase boundary near the substrate drives a gradual reduction in droplet-substrate contact. Concurrently, the droplet lifts from the substrate due to its incompressibility, density differences, and the asymmetric freezing dynamics with inward solidification causing not fully frozen mass to be displaced toward the unsolidified droplet-substrate interface. Depending on surface topography and wetting conditions, we find that this can lead to full dislodging of the ice droplet from a variety of engineered substrates, rendering the latter ice-free.

Extreme Water Uptake of Hygroscopic Hydrogels through Maximized Swelling-Induced Salt Loading.

Hygroscopic hydrogels are emerging as scalable and low-cost sorbents for atmospheric water harvesting, dehumidification, passive cooling, and thermal energy storage. However, devices using these materials still exhibit insufficient performance, partly due to the limited water vapor uptake of the hydrogels. Here, the swelling dynamics of hydrogels in aqueous lithiumchloride solutions, the implications on hydrogel salt loading, and the resulting vapor uptake of the synthesized hydrogel-salt composites are characterized. By tuning the salt concentration of the swelling solutions and the cross-linking properties of the gels, hygroscopic hydrogels with extremely high salt loadings are synthesized, which enable unprecedented water uptakes of 1.79 and 3.86 gg-1 at relative humidity (RH) of 30% and 70%, respectively. At 30% RH, this exceeds previously reported water uptakes of metal-organic frameworks by over 100% and of hydrogels by 15%, bringing the uptake within 93% of the fundamental limit of hygroscopic salts while avoiding leakage problems common in salt solutions. By modeling the salt-vapor equilibria, the maximum leakage-free RH is elucidated as a function of hydrogel uptake and swelling ratio. These insights guide the design of hydrogels with exceptional hygroscopicity that enable sorption-based devices to tackle water scarcity and the global energy crisis.

Design of a Compact Multicyclic High-Performance Atmospheric Water Harvester for Arid Environments.

Water scarcity remains a grand challenge across the globe. Sorption-based atmospheric water harvesting (SAWH) is an emerging and promising solution for water scarcity, especially in arid and noncoastal regions. Traditional approaches to AWH such as fog harvesting and dewing are often not applicable in an arid environment (<30% relative humidity (RH)), whereas SAWH has demonstrated great potential to provide fresh water under a wide range of climate conditions. Despite advances in materials development, most demonstrated SAWH devices still lack sufficient water production. In this work, we focus on the adsorption bed design to achieve high water production, multicyclic operation, and a compact form factor (high material loading per heat source contact area). The modeling efforts and experimental validation illustrate an optimized design space with a fin-array adsorption bed enabled by high-density waste heat, which promises 5.826 Lwater kgsorbent -1 day-1 at 30% RH within a compact 1 L adsorbent bed and commercial adsorbent materials.

Freezing-induced wetting transitions on superhydrophobic surfaces.

Supercooled droplet freezing on surfaces occurs frequently in nature and industry, often adversely affecting the efficiency and reliability of technological processes. The ability of superhydrophobic surfaces to rapidly shed water and reduce ice adhesion make them promising candidates for resistance to icing. However, the effect of supercooled droplet freezing-with its inherent rapid local heating and explosive vaporization-on the evolution of droplet-substrate interactions, and the resulting implications for the design of icephobic surfaces, are little explored. Here we investigate the freezing of supercooled droplets resting on engineered textured surfaces. On the basis of investigations in which freezing is induced by evacuation of the atmosphere, we determine the surface properties required to promote ice self-expulsion and, simultaneously, identify two mechanisms through which repellency falters. We elucidate these outcomes by balancing (anti-)wetting surface forces with those triggered by recalescent freezing phenomena and demonstrate rationally designed textures to promote ice expulsion. Finally, we consider the complementary case of freezing at atmospheric pressure and subzero temperature, where we observe bottom-up ice suffusion within the surface texture. We then assemble a rational framework for the phenomenology of ice adhesion of supercooled droplets throughout freezing, informing ice-repellent surface design across the phase diagram.

Leidenfrost droplet trampolining.

A liquid droplet dispensed over a sufficiently hot surface does not make contact but instead hovers on a cushion of its own self-generated vapor. Since its discovery in 1756, this so-called Leidenfrost effect has been intensively studied. Here we report a remarkable self-propulsion mechanism of Leidenfrost droplets against gravity, that we term Leidenfrost droplet trampolining. Leidenfrost droplets gently deposited on fully rigid surfaces experience self-induced spontaneous oscillations and start to gradually bounce from an initial resting altitude to increasing heights, thereby violating the traditionally accepted Leidenfrost equilibrium. We found that the continuously draining vapor cushion initiates and fuels Leidenfrost trampolining by inducing ripples on the droplet bottom surface, which translate into pressure oscillations and induce self-sustained periodic vertical droplet bouncing over a broad range of experimental conditions.

Cascade Freezing of Supercooled Water Droplet Collectives.

Surface icing affects the safety and performance of numerous processes in technology. Previous studies mostly investigated freezing of individual droplets. The interaction among multiple droplets during freezing is investigated less, especially on nanotextured icephobic surfaces, despite its practical importance as water droplets never appear in isolation, but in groups. Here we show that freezing of a supercooled droplet leads to spontaneous self-heating and induces strong vaporization. The resulting, rapidly propagating vapor front causes immediate cascading freezing of neighboring supercooled droplets upon reaching them. We put forth the explanation that, as the vapor approaches cold neighboring droplets, it can lead to local supersaturation and formation of airborne microscopic ice crystals, which act as freezing nucleation sites. The sequential triggering and propagation of this mechanism results in the rapid freezing of an entire droplet ensemble, resulting in ice coverage of the nanotextured surface. Although cascade freezing is observed in a low-pressure environment, it introduces an unexpected pathway of freezing propagation that can be crucial for the performance of rationally designed icephobic surfaces.

3D-Printed Surface Architecture Enhancing Superhydrophobicity and Viscous Droplet Repellency.

Macrotextured superhydrophobic surfaces can reduce droplet-substrate contact times of impacting water droplets; however, surface designs with similar performance for significantly more viscous liquids are missing, despite their importance in nature and technology such as for chemical shielding, food-staining repellency, and supercooled (viscous) water droplet removal in anti-icing applications. Here, we introduce a deterministic, controllable, and upscalable method to fabricate superhydrophobic surfaces with a 3D-printed architecture, combining arrays of alternating surface protrusions and indentations. We show a more than threefold contact time reduction of impacting viscous droplets up to a fluid viscosity of 3.7 mPa·s, which equals 3.7 times the viscosity of water at room temperature, covering the viscosity of many chemicals and supercooled water. On the basis of the combined consideration of the fluid flow within and the simultaneous droplet dynamics above the texture, we recommend future pathways to rationally architecture such surfaces, all realizable with the methodology presented here.

Honeycomb-structured metasurfaces for the adaptive nesting of endothelial cells under hemodynamic loads.

The thrombogenicity of artificial materials comprising ventricular assist devices (VADs) limits their long-term integration in the human body. A living endothelium covering the luminal surface can provide a safe interface working compatibly with blood and circumventing this problem. However, the survival of endothelial cells is endangered by non-physiological hemodynamic conditions generated by VAD function, including high wall shear stress and deformation. Here, we introduce a surface topography comprising hexagonal honeycomb shelters in which cells remodel to generate coherently organized patterns of subcellular compartments. The resulting hexagonal array shows resistance to supraphysiological loads maintaining endothelium integrity and avoiding local discontinuities.

Morphing and vectoring impacting droplets by means of wettability-engineered surfaces.

Driven by its importance in nature and technology, droplet impact on solid surfaces has been studied for decades. To date, research on control of droplet impact outcome has focused on optimizing pre-impact parameters, e.g., droplet size and velocity. Here we follow a different, post-impact, surface engineering approach yielding controlled vectoring and morphing of droplets during and after impact. Surfaces with patterned domains of extreme wettability (high or low) are fabricated and implemented for controlling the impact process during and even after rebound--a previously neglected aspect of impact studies on non-wetting surfaces. For non-rebound cases, droplets can be morphed from spheres to complex shapes--without unwanted loss of liquid. The procedure relies on competition between surface tension and fluid inertial forces, and harnesses the naturally occurring contact-line pinning mechanisms at sharp wettability changes to create viable dry regions in the spread liquid volume. Utilizing the same forces central to morphing, we demonstrate the ability to rebound orthogonally-impacting droplets with an additional non-orthogonal velocity component. We theoretically analyze this capability and derive a We(-.25) dependence of the lateral restitution coefficient. This study offers wettability-engineered surfaces as a new approach to manipulate impacting droplet microvolumes, with ramifications for surface microfluidics and fluid-assisted templating applications.