Jumping of coalescing condensate droplets from superhydrophobic surfaces is an interesting phenomenon which yields marked heat transfer enhancement over the more explored gravity-driven droplet removal mode in surface condensation, a phase change process of central interest to applications ranging from energy to water harvesting. However, when condensate microdroplets coalesce, they can also spontaneously propel themselves omnidirectionally on the surface independent of gravity and grow by feeding from droplets they sweep along the way. Here we observe and explain the physics behind this phenomenon of roaming of coalescing condensate microdroplets on solely nanostructured superhydrophobic surfaces, where the microdroplets are orders of magnitude larger than the underlaying surface nanotexture. We quantify and show that it is the inherent asymmetries in droplet adhesion during condensation, arising from the stochastic nature of nucleation within the nanostructures, that generates the tangential momentum driving the roaming motion. Subsequent dewetting during this conversion initiates a vivid roaming and successive coalescence process, preventing condensate flooding of the surface, and enhancing surface renewal. Finally, we show that the more efficient conversion process of roaming from excess surface energy to kinetic energy results in significantly improved heat transfer efficiency over condensate droplet jumping, the mechanism currently understood as maximum.
An effective pathway to enhance the heat transfer process is to induce the formation of highly mobile condensate droplets, employing micro‐nanoengineered superhydrophobic surfaces. However, the design of the topography of these surfaces for sustained high performance constitutes a significant scientific and technological challenge. Herein, the critical role of the correlation length of topography is demonstrated as an important factor when designing superhydrophobic surfaces for heat transfer applications. Specifically, it is shown that a) a high correlation length value corresponds to increased space between surface structures and higher lateral distances between nucleating droplets, which results in lower droplet departure diameter and significantly delayed flooding of the surface and b) correlation length has to surpass a critical value for dropwise condensation (DWC) to be sustained in hierarchical structured surfaces, when the droplets are growing in a partial Cassie state. Following this rationale, droplets are categorized in three different energy and wetting states (Wenzel droplets, Cassie droplets of low kinetic energy and high energy jumping droplets), depending on the correlation length of the topography. Heat transfer experiments demonstrate an increase of 126% in the heat transfer coefficient (HTC) of surfaces exhibiting the maximum correlation length when compared to the flat hydrophobic surface.
Heat exchangers are made of metals because of their high heat conductivity and mechanical stability. Metal surfaces are inherently hydrophilic, leading to inefficient filmwise condensation. It is still a challenge to coat these metal surfaces with a durable, robust, and thin hydrophobic layer, which is required for efficient dropwise condensation. Here, we report the nonstructured and ultrathin (∼6 nm) polydimethylsiloxane (PDMS) brushes on copper that sustain high-performing dropwise condensation in high supersaturation. Due to the flexible hydrophobic siloxane polymer chains, the coating has low resistance to drop sliding and excellent chemical stability. The PDMS brushes can sustain dropwise condensation for up to ∼8 h during exposure to 111 °C saturated steam flowing at 3 m·s-1, with a 5-7 times higher heat transfer coefficient compared to filmwise condensation. The surface is self-cleaning and can reduce the level of bacterial attachment by 99%. This low-cost, facile, fluorine-free, and scalable method is suitable for a great variety of heat transfer applications.
Water vapor condensation on metallic surfaces is critical to a broad range of applications, ranging from power generation to the chemical and pharmaceutical industries. Enhancing simultaneously the heat transfer efficiency, scalability, and durability of a condenser surface remains a persistent challenge. Coalescence-induced condensing droplet jumping is a capillarity-driven mechanism of self-ejection of microscopic condensate droplets from a surface. This mechanism is highly desired due to the fact that it continuously frees up the surface for new condensate to form directly on the surface, enhancing heat transfer without requiring the presence of the gravitational field. However, this condensate ejection mechanism typically requires the fabrication of surface nanotextures coated by an ultrathin (<10 nm) conformal hydrophobic coating (hydrophobic self-assembled monolayers such as silanes), which results in poor durability. Here, we present a scalable approach for the fabrication of a hierarchically structured superhydrophobic surface on aluminum substrates, which is able to withstand adverse conditions characterized by condensation of superheated steam shear flow at pressure and temperature up to approximate to 1.42 bar and approximate to 111 degrees C, respectively, and velocities in the range approximate to 3-9 m/s. The synergetic function of micro- and nanotextures, combined with a chemically grafted, robust ultrathin (approximate to 4.0 nm) poly-1H,1H,2H,2H-perfluorodecyl acrylate (pPFDA) coating, which is 1 order of magnitude thinner than the current state of the art, allows the sustenance of long-term coalescence-induced condensate jumping drop condensation for at least 72 h. This yields unprecedented, up to an order of magnitude higher heat transfer coefficients compared to filmwise condensation under the same conditions and significantly outperforms the current state of the art in terms of both durability and performance establishing a new milestone.
Superhydrophobic nanostructured surfaces can enhance water condensation efficiency by facilitating droplet departure via coalescence-induced jumping. However, condensed droplets tend to transit from a mobile jumping mode to a highly pinned state at high condensation heat flux because excessive water nucleates within the nanostructures and anchors the condensed droplets. The large pinned droplets act as a thermal barrier and insulate the cooling surface, thus severely degrading its heat transfer efficiency. This work developed a nanohierarchical structured surface by growing branched TiO2 nanorod arrays to prevent condensation-induced droplet pinning. After hydrophobization, the nano-hierarchical structure can spontaneously push the water out of nanostructures with an outward Laplace capillary pressure gradient when the droplet size is only at the nanoscale level. This effective de-wetting process maintains the high droplet mobility on the nano-hierarchical surface over a wide subcooling range, resulting in an up to similar to 90 % increase in heat transfer coefficient at a high heat flux of 132 kW center dot m(-2) compared to the single-tier nanorod surface. Our investigation of how the nanohierarchical structures fundamentally suppress the condensation-induced wetting on superhydrophobic surfaces represents a significant advance in understanding multiphase wetting phenomena and paves the way for the rational design of cooling surfaces.
Abstract Loss of transparency due to water vapor condensation, is a widespread problem across diverse applications such as windows, eyewear, displays, vehicles, and kitchenware. Conventional antifogging strategies relying on hydrophilic, or hydrophobic coatings, based on chemistry and/or nano-topography, can counteract up to mild water deposition, but lose functionality at excessive condensation environments. Here, we present a passive approach, rationally micropatterning an inherently hydrophilic hydrogel to maintain high transparency under supersaturation. Guided by optics and wetting theory, and employing a diffusion model to calculate related timescales of water film formation, we engineer a wicking structure on poly(ethylene glycol) diacrylate hydrogel, facilitating long-term sustainable filmwise condensation. Employing quantitative optical clarity measurements and visualization, we show that our approach clearly outperforms state of the art antifogging alternatives, retaining high optical clarity even in boiling environments. Facile fabrication and superior performance establish our microstructured hydrogel as an excellent choice for sustaining transparency under extreme condensation.
Dropwise condensation (DWC) is a phenomenon of common occurrence and significant utility in nature and technology. In energy applications, sustenance of DWC and avoidance of transition to film formation is directly related to efficient heat removal, ensuring high performance of related devices and processes. The efficiency of heat transfer in DWC depends on the heat transfer rates of individual droplets and the droplet size distribution. While the former can be summarily captured in engineering analysis through thermal resistance modeling, the theoretical analysis of the droplet size distribution involves assumptions often oversimplifying the complexity of droplet interactions, especially in the important sub–10 μm regime. Here, a modeling framework based on the thermal resistance approach is coupled with a dynamic model of droplet interactions: Droplet growth, coalescence, jumping, and removal of condensate due to gravity are all present during the unfolding of the phenomenon to accurately predict the droplet size distribution. The motivation is condensation experiments on superhydrophobic surfaces, namely rough aluminum substrates with a hydrophobic coating. Through the "interaction" of computations with measurements, the experimental findings are explained and critical parameters for condensation heat transfer on superhydrophobic surfaces are illuminated. Although larger droplets can be easily observed in experiments, it is shown that large droplets do not significantly affect heat transfer after reaching such state of growth. Instead, it is the small (with radius < 10 μm) and what we term "shadowed" droplets, i.e., the droplets grown in the shadow of the vertical projection area of the larger droplets, that play an important role in the heat transfer process. Due to the growth of these droplets and their concomitant shadowed coalescence and ensuing re-nucleation, the shift in the droplet size distribution towards smaller sizes is significant-enough to render the heat transfer rate rather insensitive to the presence of large droplets. In this regime, the effect of contact angle hysteresis on heat transfer is not crucial. Through the comparison with measurements, the dominant role of the density of nucleation sites on heat transfer is revealed and an estimation of the density of sites (∼105 mm−2) as a function of subcooling is extracted. Finally, the distribution of sites is found critical for heat transfer; an ordered distribution of sites outperforms random and clustered distributions.
Organic hydrophobic layers targeting sustained dropwise condensation are highly desirable but suffer from poor chemical and mechanical stability, combined with low thermal conductivity. The requirement of such layers to remain ultrathin to minimize their inherent thermal resistance competes against durability considerations. Here, we investigate the long-term durability and enhanced heat-transfer performance of perfluorodecanethiol (PFDT) coatings compared to alternative organic coatings, namely, perfluorodecyltriethoxysilane (PFDTS) and perfluorodecyl acrylate (PFDA), the latter fabricated with initiated chemical vapor deposition (iCVD), in condensation heat transfer and under the challenging operating conditions of intense flow (up to 9 m s–1) of superheated steam (111 °C) at high pressures (1.42 bar). We find that the thiol coating clearly outperforms the silane coating in terms of both heat transfer and durability. In addition, despite being only a monolayer, it clearly also outperforms the iCVD-fabricated PFDA coating in terms of durability. Remarkably, the thiol layer exhibited dropwise condensation for at least 63 h (>2× times more than the PFDA coating, which survived for 30 h), without any visible deterioration, showcasing its hydrolytic stability. The cost of thiol functionalization per area was also the lowest as compared to all of the other surface hydrophobic treatments used in this study, thus making it the most efficient option for practical applications on copper substrates.
Soft substrates enhance droplet nucleation during water vapor condensation because their deformability inherently reduces the energetic threshold for heterogeneous nucleation relative to rigid substrates. However, this enhancement is counteracted later in the condensation cycle, when substrate viscoelastic dissipation inhibits condensate droplet shedding. Here a polydimethylsiloxane (PDMS) based organogel is designed to overcome this limitation. It is shown that merely 5% bulk lubricant infusion in PDMS reduces viscoelastic dissipation in the substrate by nearly 28 times while doubling the droplet nucleation density. Parameters for water condensation on this organogel are correlated with material properties controlled by design, i.e., fraction and composition of uncrosslinked chains and shear modulus. It is demonstrated that the increase in nucleation density and reduction in precoalescence droplet growth rate is rather insensitive to the lubricant percentage in PDMS within the broad range investigated. These results indicate the presence of a lubricant layer on the substrate surface that cloaks the growing condensate droplets. This cloaking effect is visualized, and it is shown that cloaking occurs significantly faster on PDMS if it is infused with bulk lubricant. Overall, bulk lubricant infusion in PDMS enhances condensation and leads to a more than 40% higher dewing on the substrate.
Nanostructured surfaces usually exhibit complicated morphologies that cannot be described in terms of Euclidean geometry. Simultaneously, they do not constitute fully random noise fields to be characterized by simple stochastics and probability theory. In most cases, nanomorphologies consist of complicated mixtures of order and randomness, which should be described quantitatively if one aims to control their fabrication and properties. In this work, inspired by recent developments in complexity theory, we propose a method to measure nanomorphology complexity that is based on the deviation from the average symmetry of surfaces. We present the methodology for its calculation and the validation of its performance, using a series of synthetic surfaces where the proposed complexity measure obtains a maximum value at the most heterogeneous morphologies between the fully ordered and fully random cases. Additionally, we measure the complexity of experimental micro and nanostructured surfaces (polymeric and metallic), and demonstrate the usefulness of the proposed method in quantifying the impact of processing conditions on their morphologies. Finally, we hint at the relationship between the complexity measure and the functional properties of surfaces. (c) 2021 Elsevier Ltd. All rights reserved. Selection and peer-review under responsibility of the scientific committee of the International Conferences & Exhibition on Nanotechnologies, Organic Electronics & Nanomedicine - NANOTEXNOLOGY 2020.
A polytetrafluoroethylene-carbon nanofiber nanocomposite coating is applied on a copper substrate with an aluminum primer for superhydrophobicity to facilitate jumping dropwise condensation. While being durable and scalable, the coating delivers extreme heat transfer improvements up to ≈900%. More details can be found in article number 2001176 by Dimos Poulikakos and co-workers.
Condensation of water on metallic surfaces is critical for multiple energy conversion processes. Enhancement in condensation heat transfer efficiency often requires surface texturing and hydrophobicity, usually achieved through coatings, to maintain dropwise condensation. However, such surface treatments face conflicting challenges of minimal coating thermal resistance, enhanced coating durability, and scalable fabrication. This study presents a thin (≈2 µm) polytetrafluoroethylene–carbon nanofiber nanocomposite coating that meets these challenges and sustains coalescence‐induced jumping droplet condensation for extended periods under highly demanding condensation conditions. Coating durability is achieved through improved substrate adhesion by depositing a submicron thick aluminum primer layer. Carbon nanofibers in a polytetrafluoroethylene matrix increase coating thermal conductivity and promote spontaneous surface nanotexturing to achieve superhydrophobicity for condensate microdroplets. The coating material can be deposited through direct spraying, ensuring economical scalability and versatility for a wide range of substrates. No other coating is known for metallic surfaces that is able to sustain jumping dropwise condensation under shear of steam at 111 °C flowing at ≈3 m s −1 over the surface for 10 h and dropwise condensation for an additional 50 h. Up to ≈900% improvement in condensation heat transfer coefficient is achieved compared to conventional filmwise condensation.
Lubricant-infused surfaces (LIS) are highly efficient in repelling water and constitute a very promising family of materials for condensation processes occurring in a broad range of energy applications. However, the performance of LIS in such processes is limited by the inherent thermal resistance imposed by the thickness of the lubricant and supporting surface structure, as well as by the gradual depletion of the lubricant over time. Here, we present an ultrathin (∼70 nm) and conductive LIS architecture, obtained by infusing lubricant into a vertically grown graphene nanoscaffold on copper. The ultrathin nature of the scaffold, combined with the high in-plane thermal conductivity of graphene, drastically minimize earlier limitations, effectively doubling the heat transfer performance compared to a state-of-the-art CuO LIS surface. We show that the effect of the thermal resistance to the heat transfer performance of a LIS surface, although often overlooked, can be so detrimental that a simple nanostructured CuO surface can outperform a CuO LIS surface, despite filmwise condensation on the former. The present vertical graphene LIS is also found to be resistant to lubricant depletion, maintaining stable dropwise condensation for at least 24 h with no significant change of advancing contact angle and contact angle hysteresis. The lubricant consumed by the vertical graphene LIS is 52.6% less than that of the existing state-of-the-art CuO LIS, also making the fabrication process more economical.
Sustained dropwise condensation of water requires rapid shedding of condensed droplets from the surface. Here, we elucidate a microfluidic mechanism that spontaneously sweeps condensed microscale droplets without the need for the traditional droplet removal pathways such as use of superhydrophobicity for droplet rolling and jumping and utilization of wettability gradients for directional droplet transport among others. The mechanism involves self-generated, directional, cascading coalescence sequences of condensed microscale droplets along standard hydrophobic microgrooves. Each sequence appears like a spontaneous zipping process, can sweep droplets along the microgroove at speeds of up to ∼1 m/s, and can extend for lengths more than 100 times the microgroove width. We investigate this phenomenon through high-speed in situ microscale condensation observations and demonstrate that it is enabled by rapid oscillations of a condensate meniscus formed locally in a filled microgroove and pinned on its edges. Such oscillations are in turn spontaneously initiated by coalescence of an individual droplet growing on the ridge with the microgroove meniscus. We quantify the coalescence cascades by characterizing the size distribution of the swept droplets and propose a simple analytical model to explain the results. We also demonstrate that, as condensation proceeds on the hydrophobic microgrooved surface, the coalescence cascades recur spontaneously through repetitive dewetting of the microgrooves. Lastly, we identify surface design rules for consistent realization of the cascades. The hydrophobic microgrooved textures required for the activation of this mechanism can be realized through conventional, scalable surface fabrication methods on a broad range of materials (we demonstrate with aluminum and silicon), thus promising direct application in a host of phase-change processes.