Flat Hydrophobic Surface Research Articles

Distribution, coalescence, and freezing characteristics of water droplets on surfaces with different wettabilities under subfreezing convective flow

This paper investigates the effects of surface wettability and surface initial conditions on early frost formation for hydrophobic, hydrophilic, and bare aluminum flat surfaces. The new data revealed that the average droplet sizes were larger and droplet size distributions were wider for the hydrophilic surface than for the hydrophobic and bare aluminum surfaces. This was due to a coalescence phenomenon occurring before the droplets froze into ice beads. Because of the relative high sub-freezing plate temperatures used in this work, the surface wettability of the plates had a smaller impact on the freezing time. Supersaturation degree and temperature difference between the air stream and the surface controlled freezing times for all different surface wettability types. When testing was conducted without cleaning the surfaces in between individual test runs, a film deposited on the surfaces which smoothed surface imperfections, inhibited surface wettability effects on droplet size and shape, and delayed freezing. A large variation in the frost nucleation behavior was measured in the present work due to intentionally different generated initial surface cleanness conditions. This finding could explain some of the significant deviations observed in data from literature studies when comparing freezing times and droplet diameters for similar coatings and similar tests conditions.

Numerical study of droplet evaporation on heated flat and micro-pillared hydrophobic surfaces by using the lattice Boltzmann method

The evaporation processes of sessile droplets on both heated flat and structured hydrophobic surfaces are numerically studied by using a thermal multi-phase lattice Boltzmann model. The contact-line dynamics and heat transfer regarding the evaporation of droplets are simulated and the effects of the heat conductivity, wettability, and roughness of the substrate on the droplet evaporation are investigated. The results indicate that the different evaporation modes of the droplets on the rough surfaces are attributed to the microscopic “stick–slip” motion of the contact line. The constant contact angle (CCA) mode of droplet evaporation on the rough hydrophobic surface can be regarded as a macroscopic average of the microscopic “stick–slip” processes with a short stick period and small change in apparent contact angle. The weaker stick effect of the surface with a higher hydrophobicity and smaller solid fraction makes the droplet evaporation more likely to occur in the CCA manner.

Density Maximization of One-Step Electrodeposited Copper Nanocones and Dropwise Condensation Heat-Transfer Performance Evaluation.

Currently, it is still a great challenge to obtain copper-based high-efficient dropwise condensation heat transfer (CHT) interfaces via template-free electrodepositing technologies. Here, we report that the density of template-free electrodeposited copper nanocones can maximally reach 1.5 × 106/mm2 by the synergistic control of substrate surface roughness, poly(ethylene glycol) (PEG) molecular weight, and PEG concentration. After thiol modification, the densely packed copper nanocone samples can present low-adhesive superhydrophobicity and condensate microdrop self-jumping function at ambient environment. Condensation heat and mass transfer characterizations show that the CHT coefficient of copper surfaces can maximally enhance 98% for 20 °C vapor and 51% for 40 °C vapor by in situ growth of superhydrophobic densely packed copper nanocones. Although the dropwise condensation mode can change from the jumping mode to the mixed jumping and sweeping mode and the shedding-off mode along with the increase of surface subcooling and vapor temperature, the CHT performance of the nanosample is still superior to that of the contrast flat hydrophobic surface during the whole testing range of surface subcooling. As vapor temperature increases to 80 °C, the CHT performance of the nanosample is inferior to that of the contrast sample. The CHT enhancement under low-temperature vapor should be ascribed to the enhancement of small-drop mass transfer ability caused by low-adhesive superhydrophobicity nature of nanosample surfaces. Their performance degradation mainly results from increased drop-drop drag force along with the increase of surface subcooling and vapor temperature. In sharp contrast, the CHT deterioration under high-temperature vapor should be ascribed to larger drop-surface adhesion and drop-drop drag force. The former is caused by vapor penetration, whereas the latter is caused by the dramatically increased nucleation density and growth rate of condensates. These findings would help design and develop copper-based high-efficiency condensation heat transfer interfaces.

Distinct Interaction of Lytic Polysaccharide Monooxygenase with Cellulose Revealed by Computational and Biochemical Studies.

A distinct interaction pattern of lytic polysaccharide monooxygenases (LPMOs) with their insoluble substrate, cellulose, was revealed through the combination of computational and biochemical approaches. The results indicated that the enzymes can stably bind on the flat hydrophobic surface of cellulose via the interactions of the key residues located in the axis across the conserved distal tyrosine residue and copper ion with two adjacent cellulose chains. Further studies on the correlation of substrate binding and H2O2 accumulation suggested that LPMOs involved in the productive binding on the insoluble polysaccharides not only fail to accumulate H2O2 but also consume the H2O2 produced by the unbound molecules under the lab condition. This was further substantiated by quantum-mechanical calculations. These findings broadened our knowledge of the interaction between enzymes and insoluble substrates and deepened our understanding of the role that H2O2 plays in LPMO activity.

Atomic-scale mapping of hydrophobic layers on graphene and few-layer MoS2 and WSe2 in water

The structure and the role of the interfacial water in mediating the interactions of extended hydrophobic surfaces are not well understood. Two-dimensional materials provide a variety of large and atomically flat hydrophobic surfaces to facilitate our understanding of hydrophobic interactions. The angstrom resolution capabilities of three-dimensional AFM are exploited to image the interfacial water organization on graphene, few-layer MoS2 and few-layer WSe2. Those interfaces are characterized by the existence of a 2 nm thick region above the solid surface where the liquid density oscillates. The distances between adjacent layers for graphene, few-layer MoS2 and WSe2 are ~0.50 nm. This value is larger than the one predicted and measured for water density oscillations (~0.30 nm). The experiments indicate that on extended hydrophobic surfaces water molecules are expelled from the vicinity of the surface and replaced by several molecular-size hydrophobic layers.

Measurement of entropic force from polymers attached to a pyramidal tip

The measurement of the boundary shape dependence of the entropic force from long polymers was attempted. The pyramidal cone-plate geometry was chosen. The polymer molecules were covalently bound to a well-defined Au patch at the apex of a pyramidal cantilever tip of the atomic force microscope (AFM). A smooth hydrophobic plate was used as the second boundary to confine the polymer molecules. The use of the hydrophobic plate allows neglect of polymer adhesion forces. The measurements were made in salt water solution to decrease the effect of electrostatic forces from any uncompensated charges on the boundary. As the functionalized AFM tip approaches the flat hydrophobic surface, the induced entropic forces were measured as a function of the separation distance. The measured force-distance curves are compared with a model of polymer-mediated entropic force between scale-free objects and the Alexander–de Gennes (AdG) theory for a polymer brush.

Controlling shedding characteristics of condensate drops using electrowetting

We show here that ac electrowetting (ac-EW) with structured electrodes can be used to control the gravity-driven shedding of drops condensing onto flat hydrophobic surfaces. Under ac-EW with straight interdigitated electrodes, the condensate drops shed with relatively small radii due to the ac-EW-induced reduction of contact angle hysteresis. The smaller shedding radius, coupled with the enhanced growth due to coalescence under EW, results in an increased shedding rate. We also show that the condensate droplet pattern under EW can be controlled, and the coalescence can be further enhanced, using interdigitated electrodes with zigzag edges. Such enhanced coalescence in conjunction with the electrically induced trapping effect due to the electrode geometry results in a larger shedding radius, but a lower shedding rate. However, the shedding characteristics can be further optimized by applying the electrical voltage intermittently. We finally provide an estimate of the condensate volume removed per unit time in order to highlight how it is enhanced using ac-EW-controlled dropwise condensation.

Breath Figures under Electrowetting: Electrically Controlled Evolution of Drop Condensation Patterns.

We show that electrowetting (EW) with structured electrodes significantly modifies the distribution of drops condensing onto flat hydrophobic surfaces by aligning the drops and by enhancing coalescence. Numerical calculations demonstrate that drop alignment and coalescence are governed by the drop-size-dependent electrostatic energy landscape that is imposed by the electrode pattern and the applied voltage. Such EW-controlled migration and coalescence of condensate drops significantly alter the statistical characteristics of the ensemble of droplets. The evolution of the drop size distribution displays self-similar characteristics that significantly deviate from classical breath figures on homogeneous surfaces once the electrically induced coalescence cascades set in beyond a certain critical drop size. The resulting reduced surface coverage, coupled with earlier drop shedding under EW, enhances the net heat transfer.

Behavior of an evaporating water droplet on lubricant-impregnated nano-structured surface

The behavior of an evaporating water droplet on lubricant-impregnated nano-structured surface (LINS) was investigated experimentally. For comparison, the flat hydrophobic surface (FHS) and superhydrophobic nano-structured surface (SHNS) were also prepared and tested. The initial water contact angles (WCAs) of LINS, FHS, and SHNS showed 108°, 103°, and 153°, respectively, and their WCA hysteresis (WCAH) were 2°, 30°, and 23°, respectively. During the evaporation of water droplet, FHS showed a typical constant contact radius (CCR) mode. On the contrary, SHNS and LINS showed more complicated mixed mode. These differences of evaporation modes were closely related to the total evaporation time. Initial WCA of LINS was between FHS and SHNS, but the water droplet on LINS showed the longest total evaporation time in the test surfaces. This may be because LINS has the water droplet of the high aspect ratio during the evaporation and the low thermal effusivity. In such a case, the large height of water droplet plays a role to the longer thermal resistance path, which can result in extending the total evaporation time.

Simple Calculation Method of Shearing Characteristics for a Water Droplet between Two Parallel Hydrophobic Flat Surfaces

Simple Calculation Method of Shearing Characteristics for a Water Droplet between Two Parallel Hydrophobic Flat Surfaces

Drying droplet deposited on poor wetting substrate: beyond the lubrication approximation

Evaporating sessile droplet of aqueous solution deposited on hydrophobic surface is an urgent object of theoretical modeling (evaporation dynamics, microfluidics inside the drop, particle dynamics in evaporating drop, etc) and applied researches (printing technologies, nanoparticle ensemble self-assembly processes, hydrophobic coatings, etc). Although self-assembly investigation in evaporating droplet of colloidal solution on smooth surfaces with quite acute contact angles has been widely studied recently for liquids of different properties, nanoparticles ensemble self-assembly processes in droplet deposited on hydrophobic and superhydrophobic surfaces has not received much attention up to date. This work includes the analysis of application of existing droplet evaporation models, the boundary conditions for the hydrodynamic flows on the drop surface, as well as the nanoparticle dynamics in the volume of aqueous solution droplet deposited on hydrophobic flat surface, and the dried pattern formation processes modelling.

Patterned Polymer Coatings Increase the Efficiency of Dew Harvesting.

Micropatterned polymer surfaces, possessing both topographical and chemical characteristics, were prepared on three-dimensional copper tubes and used to capture atmospheric water. The micropatterns mimic the structure on the back of a desert beetle that condenses water from the air in a very dry environment. The patterned coatings were prepared by the dewetting of thin films of poly-4-vinylpyridine (P4VP) on top of polystyrene films (PS) films, upon solvent annealing, and consist of raised hydrophilic bumps on a hydrophobic background. The size and density distribution of the hydrophilic bumps could be tuned widely by adjusting the initial thickness of the P4VP films: the diameter of the produced bumps and their height could be varied by almost 2 orders of magnitude (1-80 μm and 40-9000 nm, respectively), and their distribution density could be varied by 5 orders of magnitude. Under low subcooling conditions (3 °C), the highest rate of water condensation was measured on the largest (80 μm diameter) hydrophilic bumps and was found to be 57% higher than that on flat hydrophobic films. These subcooling conditions are achieved spontaneously in dew formation, by passive radiative cooling of a surface exposed to the night sky. In effect, the pattern would result in a larger number of dewy nights than a flat hydrophobic surface and therefore increases water capture efficiency. Our approach is suited to fabrication on a large scale, to enable the use of the patterned coatings for water collection with no external input of energy.

A biophysical vascular bubble model for devising decompression procedures.

Vascular bubble models, which present a realistic biophysical approach, hold great promise for devising suitable diver decompression procedures. Nanobubbles were found to nucleate on a flat hydrophobic surface, expanding to form bubbles after decompression. Such active hydrophobic spots (AHS) were formed from lung surfactants on the luminal aspect of ovine blood vessels. Many of the phenomena observed in these bubbling vessels correlated with those known to occur in diving. On the basis of our previous studies, which proposed a new model for the formation of arterial bubbles, we now suggest the biophysical model presented herein. There are two phases of bubble expansion after decompression. The first is an extended initiation phase, during which nanobubbles are transformed into gas micronuclei and begin to expand. The second, shorter phase is one of simple diffusion‐driven growth, the inert gas tension in the blood remaining almost constant during bubble expansion. Detachment of the bubble occurs when its buoyancy exceeds the intermembrane force. Three mechanisms underlying the appearance of arterial bubbles should be considered: patent foramen ovale, intrapulmonary arteriovenous anastomoses, and the evolution of bubbles in the distal arteries with preference for the spinal cord. Other parameters that may be quantified include age, acclimation, distribution of bubble volume, AHS, individual sensitivity, and frequency of bubble formation. We believe that the vascular bubble model we propose adheres more closely to proven physiological processes. Its predictability may therefore be higher than other models, with appropriate adjustments for decompression illness (DCI) data.

Evaporation Flux Distribution of Drops on a Hydrophilic or Hydrophobic Flat Surface by Molecular Simulations.

The evaporation flux distribution of sessile drops is investigated by molecular dynamic simulations. Three evaporating modes are classified, including the diffusion dominant mode, the substrate heating mode, and the environment heating mode. Both hydrophilic and hydrophobic drop-substrate interactions are considered. To count the evaporation flux distribution, which is position dependent, we proposed an azimuthal-angle-based division method under the assumption of spherical crown shape of drops. The modeling results show that the edge evaporation, i.e., near the contact line, is enhanced for hydrophilic drops in all the three modes. The surface diffusion of liquid molecular absorbed on solid substrate for hydrophilic cases plays an important role as well as the space diffusion on the enhanced evaporation rate at the edge. For hydrophobic drops, the edge evaporation flux is higher for the substrate heating mode, but lower than elsewhere of the drop for the diffusion dominant mode; however, a nearly uniform distribution is found for the environment heating mode. The evidence shows that the temperature distribution inside drops plays a key role in the position-dependent evaporation flux.

Determination of the adhesion energy of liquid droplets on a hydrophobic flat surface considering the contact area

The formation of liquid droplets on a hydrophobic surface and continuous droplet removal is beneficial in the design of various engineering devices. A liquid droplet on an inclined hydrophobic surface may roll down or attach to the surface depending on the balance among the associated forces. A series of experiments is performed in order to measure the inclination angle of a hydrophobic surface that makes a liquid droplet begin to slide or roll down. Various sizes of sessile drops of deionized water, ethylene glycol, and methylene iodide are examined. The existing adhesion force models have not been successful in predicting the sliding angle because they do not consider the area where the liquid droplet and solid surface are in contact with each other, but rather they consider the length of the periphery of the contact area. In this study, a new method to predict the adhesion energy of a droplet on a flat solid surface is proposed. The proposed method is based on the relationship between the solid and liquid contact area using moment of force analyses. Analyzing the experimental data using the proposed method, the adhesion energy per unit area is evaluated to have a constant value regardless of the droplet volume. The new definition of adhesion energy per unit area is appropriate for describing the movement of a liquid on a hydrophobic solid surface.

Hydrogel Inverse Replicas of Breath Figures Exhibit Superoleophobicity Due to Patterned Surface Roughness

The wetting behavior of a surface depends on both its surface chemistry and the characteristics of surface morphology and topography. Adding structure to a flat hydrophobic or oleophobic surface increases the effective contact angle and thus the hydrophobicity or oleophobicity of the surface, as exemplified by the lotus leaf analogy. We describe a simple strategy to introduce micropatterned roughness on surfaces of soft materials, utilizing the template of hexagonally packed pores of breath figures as molds. The generated inverse replicas represent micron scale patterned beadlike protrusions on hydrogel surfaces. This added roughness imparts superoleophobic properties (contact angle of the order of 150° and greater) to an inherently oleophobic flat hydrogel surface, when submerged. The introduced pattern on the hydrogel surface changes morphology as it swells in water to resemble morphologies remarkably analogous to the compound eye. Analysis of the wetting behavior using the Cassie-Baxter approximation leads to estimation of the contact angle in the superoleophobic regime and in agreement with the experimental value.

Wetting hysteresis induced by temperature changes: Supercooled water on hydrophobic surfaces

The state and stability of supercooled water on (super)hydrophobic surfaces is crucial for low temperature applications and it will affect anti-icing and de-icing properties. Surface characteristics such as topography and chemistry are expected to affect wetting hysteresis during temperature cycling experiments, and also the freezing delay of supercooled water. We utilized stochastically rough wood surfaces that were further modified to render them hydrophobic or superhydrophobic. Liquid flame spraying (LFS) was utilized to create a multi-scale roughness by depositing titanium dioxide nanoparticles. The coating was subsequently made non-polar by applying a thin plasma polymer layer. As flat reference samples modified silica surfaces with similar chemistries were utilized. With these substrates we test the hypothesis that superhydrophobic surfaces also should retard ice formation. Wetting hysteresis was evaluated using contact angle measurements during a freeze–thaw cycle from room temperature to freezing occurrence at −7°C, and then back to room temperature. Further, the delay in freezing of supercooled water droplets was studied at temperatures of −4°C and −7°C. The hysteresis in contact angle observed during a cooling–heating cycle is found to be small on flat hydrophobic surfaces. However, significant changes in contact angles during a cooling–heating cycle are observed on the rough surfaces, with a higher contact angle observed on cooling compared to during the subsequent heating. Condensation and subsequent frost formation at sub-zero temperatures induce the hysteresis. The freezing delay data show that the flat surface is more efficient in enhancing the freezing delay than the rougher surfaces, which can be rationalized considering heterogeneous nucleation theory. Thus, our data suggests that molecular flat surfaces, rather than rough superhydrophobic surfaces, are beneficial for retarding ice formation under conditions that allow condensation and frost formation to occur.

Perpetual superhydrophobicity.

A liquid droplet placed on a geometrically textured surface may take on a "suspended" state, in which the liquid wets only the top of the surface structure, while the remaining geometrical features are occupied by vapor. This superhydrophobic Cassie-Baxter state is characterized by its composite interface which is intrinsically fragile and, if subjected to certain external perturbations, may collapse into the fully wet, so-called Wenzel state. Restoring the superhydrophobic Cassie-Baxter state requires a supply of free energy to the system in order to again nucleate the vapor. Here, we use microscopic classical density functional theory in order to study the Cassie-Baxter to Wenzel and the reverse transition in widely spaced, parallel arrays of rectangular nanogrooves patterned on a hydrophobic flat surface. We demonstrate that if the width of the grooves falls below a threshold value of ca. 7 nm, which depends on the surface chemistry, the Wenzel state becomes thermodynamically unstable even at very large positive pressures, thus realizing a "perpetual" superhydrophobic Cassie-Baxter state by passive means. Building upon this finding, we demonstrate that hierarchical structures can achieve perpetual superhydrophobicity even for micron-sized geometrical textures.

Fabrication of copper-based ZnO nanopencil arrays with high-efficiency dropwise condensation heat transfer performance

A copper-based zinc oxide nanopencil array film was reported. Compared with hydrophobic flat Cu surface, it exhibits condensate microdrop self-propelling function and maximal ∼140% enhancement in dropwise condensation heat transfer coefficient.

The effect of surface modification on initial ice formation on aluminum surfaces

One of the most promising energy saving methods in cold climate areas is heat recovery in ventilation system by using air-to-air heat exchangers. However, due to a higher humidity in the exhaust air, there is a risk of ice formation on the heat exchanger fins at subzero temperatures. Since the main material of heat exchanger fins is aluminum, this paper focuses on the effect of aluminum wettability on the initial stages of ice formation. The ice growth was studied on bare as well as hydrophilically and hydrophobically modified surfaces of aluminum (8011A) sheets, commonly used in heat exchangers, at different psychrometric parameters. The obtained results show that the surface modification of aluminum plays a crucial role in the ice formation. We demonstrated that flat hydrophobic surfaces exhibit slower ice growth and denser ice layers, hence making this type of treatment preferable for aluminum heat exchangers. Furthermore we provide an explanation for a commonly observed phenomenon that bare aluminum surfaces are characterized by a faster ice growth and less dense ice layer as compared to both hydrophilically and hydrophobically modified surfaces.