Rough Superhydrophobic Surfaces Research Articles

Constructing carbon nanotube (CNTs)/silica superhydrophobic coating with multi-stage rough structure for long-term anti-corrosion and low-temperature anti-icing in the marine environment

The rough superhydrophobic surface is beneficial for capturing more gases underwater, which enhances corrosion and ice resistance for marine equipment. In this work, a PVAc-PVDF-FMCS (PPFMCS) multi-stage rough superhydrophobic coating was manufactured by a cold spraying method, significantly improving the anti-corrosion and anti-icing of aluminium alloy. The point-line structure was designed by cross-linking between multi-walled carbon nanotubes (MWCNTs) and silicon dioxide (SiO2), which facilitated the formation of multi-stage rough surface. The porous skeleton and interfacial adhesion of the PPFMCS coating were attributed to the introduction of polyvinylidenefluoride (PVDF) and polyvinylacetate (PVAc), respectively. The PPFMCS coating had good superhydrophobicity with a water contact angle of 163.5°, while exhibiting the outstanding performance of long-term anti-corrosion and anti-icing. The |Z|0.01 Hz value of the PPFMCS coating was still 9.62 × 109 Ω cm2 in 3.5 wt% NaCl solution for 35 days, only two orders of magnitude lower than that of the original coating, the equivalent circuits were further investigated and the metal protection is evaluated on the shore or in the deep ocean of the South China Sea. The PPFMCS coating was able to obviously delay icing for 5 min at −20 °C, the ice adhesion of its surface was as low as 85.5 kPa. The icing phase transition was analysed by a thermodynamic method. The coating also had good stability and drag reduction performance. This high-performance coating based on point-line structural design is expected to have practical applications in marine transportation, oil exploration and polar exploration.

Prolonged Lifespan of Superhydrophobic Thin Films and Coatings Using Recycled Polyethylene.

High-density polyethylene (HDPE) waste poses a significant environmental challenge due to its non-biodegradable nature and the vast quantities generated annually. However, conventional recycling methods are energy-intensive and often yield low-quality products. Herein, HDPE waste is upcycled into anti-aging, superhydrophobic thin films suitable for outdoor applications. A two-layer spin-casting method combined with heating-induced crosslinking is utilized to produce an exceptionally rough superhydrophobic surface, featuring a root mean square (RMS) roughness of 50 nm, an average crest height of 222 nm, an average trough depth of -264 nm, and a contact angle (CA) of 148°. To assess durability, weathering tests were conducted, revealing the films' susceptibility to degradation under harsh conditions. The films' resistance to environmental factors is improved by incorporating a UV absorber, maintaining their hydrophobic properties and mechanical strength. Our research demonstrates a sustainable method for upcycling waste into high-performance, weather-resistant, superhydrophobic films.

Freezing Characteristics of a Water Droplet on a Multiscale Superhydrophobic Surface.

Superhydrophobic surfaces have the potential to retard ice formation owing to their super water-repellant nature arising from high static contact angle and low contact angle hysteresis. Most of the previous studies have focused on patterned surfaces with mono-scaled prismatic structures. In contrast, the freezing behavior on multiscaled rough superhydrophobic surfaces that are of practical significance is relatively little studied. This article presents, for the first time, the freezing dynamics of a water droplet interacting with multiscale fractal superhydrophobic surfaces which validates well with experimental measurements. It is shown that the dual effects of increased contact angle and poor interfacial conduction due to trapped air cavities within the roughness features of the superhydrophobic surface lead to increasing freezing time with increasing surface hydrophobicity, determined as a function of the fractal surface parameters. A comparison of the freezing dynamics of sessile droplets of identical contact angle on a smooth versus a rough superhydrophobic surface shows that interfacial asperity thermal resistance contributes to over 14% increase in the freeze time. It is further shown that by tailoring the multiscale characteristics, the freeze time may be increased by up to 7-fold compared to freezing on a smooth surface. The application of the numerical model to studying ice formation on several practical superhydrophobic surfaces of a range of metallic materials and fabrication methods is also discussed, which offers guidelines for the design of anti-icing surfaces in practice.

Design and performance optimization of self-cleaning coating on decorative UHPC surface

After long-term use, decorative UHPC may adhere to pollutants due to its hydrophilicity, which affects its aesthetics. Due to the smooth and dense exposed surface of UHPC, ordinary self-cleaning coatings have poor adhesion on its surface and are prone to peeling off due to rain wash in the environment, which cannot maintain the self-cleaning performance of UHPC for a long time. In this paper, a modified self-cleaning coating with a double layer structure was designed. The bottom layer is an epoxy resin (ER) adhesive layer to improve the adhesion performance of the coating to UHPC. The surface layer is a polymethylhydrosiloxane (PMHS) modified nano-SiO2 superhydrophobic layer, which satisfies the self-cleaning characteristics while constructing a regular rough superhydrophobic surface on the UHPC surface. The prepared superhydrophobic UHPC showed good self-cleaning performance, with a static water contact angle of 156.5and a sliding angle of only about 2.2. The performance test results show that the double-layer structure design makes the superhydrophobic coating have good wear resistance, water erosion resistance and excellent chemical stability. The surface functional groups, micro-area morphology and roughness were characterized by Fourier transform infrared spectrometer, scanning electron microscopy, optical profiler and atomic force microscopy, respectively. The reasons for the excellent self-cleaning performance and long-term stability of the coating were explained.

Jeffery’s paradox for the rotation of a single ‘stick–slip’ cylinder

We consider the problem of determining the two-dimensional fluid velocity due to the rotation of an infinitely-long ‘stick–slip’ cylinder in an otherwise quiescent Stokes flow. Stick–slip boundary conditions are introduced as a model of a rough superhydrophobic surface, via a distribution of alternating solid–liquid (stick) and gas–liquid (slip) interfaces. This leads to a mixed boundary-value problem for Stokes flow. Complex variable techniques are employed to transform the flow problem into a Hilbert problem, which involves finding a function analytic in a plane region assuming that on some portions of the boundary its real part is known, while on others its imaginary part is given. We solve the Hilbert problem to obtain semi-analytic expressions for all the pertinent fluid-dynamic quantities. We find that in the general aperiodic case there is no solution in which the velocity of the fluid vanishes at infinity. This is a form of Jeffery’s paradox, typically associated with viscous flow due to the counter-rotation of two equal rigid cylinders. Our work provides the first example of Jeffery’s paradox due to the rotation of a single cylinder.

Biphilic jumping-droplet condensation

Jumping-droplet condensation on rough superhydrophobic surfaces exhibits increased heat-transfer rates when compared with dropwise condensation on smooth hydrophobic surfaces. However, the performance of superhydrophobic surfaces is limited by the low individual droplet growth rates associated with their extreme apparent advancing contact angles. Here, we report that biphilic surfaces having smooth, low-surface-energy spots on a superhydrophobic background exhibit a 10× higher jumping-droplet condensation heat-transfer coefficient when compared with homogeneous superhydrophobic surfaces. Our detailed condensation heat-transfer modeling coupled with numerical simulations of binary and coordinated droplet coalescence show that spot wettability should not be optimized toward minimizing droplet nucleation energy barriers. Rather, spot wettability should be optimized to minimize droplet adhesion while maximizing individual droplet growth rates. Model-predicted design optimization of a variety of biphilic surfaces is validated against experiments. Our findings provide design guidelines for biphilic surface development to maximize condensation heat transfer.

Bouncing of cloud-sized microdroplets on superhydrophobic surfaces

The control of microdroplet impact on superhydrophobic surfaces (SHSs) is becoming imperative owing to its effect on several industrial applications, such as corrosion protection, self-cleaning, ice resisting, and de-icing. While most of the experimental studies on the impact dynamics of droplets are based on macrodroplets, it is unclear how the obtained results can be applied to microdroplet impact on SHSs. In this work, a comprehensive experimental analysis ranging from millimeter- to micrometer-sized droplets using a novel drop on demand microdispensing system is performed. Several SHSs were synthesized to control droplet impact by enforcing bouncing on the surface during the impingement process. The current analysis focuses on experimentally capturing and analyzing the impact behavior of cloud-sized microdroplets and macrodroplets (D0 = 10 μm–2500 μm) upon SHS impact, with hysteresis, under controlled environmental conditions. Different droplet impact parameters, such as droplet contact time, maximum spreading diameter, and restitution coefficient, were experimentally obtained. Interestingly, this investigation highlighted a contrast in the behavior of microdroplets and macrodroplets upon impact on rough SHSs. It was found that critical parameters controlling droplet dynamics, such as the maximum spreading diameter and coefficient of restitution, cannot be described by current models in the literature. A preliminary theoretical model based on energy balance and accounting for the substrate hysteresis is proposed to explain some of these findings. Finally, the effect of SHS roughness on the bouncing of cloud-sized microdroplets (D0 = 10 μm–100 μm) was examined in the context of synthesizing SHSs.

One-step fabrication of Salvinia-inspired superhydrophobic surfaces with High adhesion

Superhydrophobic surfaces with either low or high adhesion have great significance in numerous engineering domains. Salvinia, a common aquatic plant which has hydrophobic micro hair with a hydrophilic tip on the top, is a nature superhydrophobic surface with high adhesion. Here, inspired by salvinia, a superhydrophobic surface with high adhesion is fabricated by simple polymerization of dopamine (DA) onto nanotips of micro/nanostructured superhydrophobic surface. When the rough superhydrophobic surface is immersed in the DA solution, air is trapped in valley between the micro/nanostructures and discontinuous three-phase contact line (TCL) forms immediately. The polydopamine (PDA) adhesion only occurs on very tips of the micro/nanostructures, while the other ravine part of the micro/nanostructures remained hydrophobic, what endows the superhydrophobic surface numerous hydrophilic tiny tips like the hairs of salvinia leaf. The salvinia-like surface showed superhydrophobic but high adhesive property. This work unfolds more applicabilities of superhydrophobic surface and promotes the application of the superhydrophobic surface.

Wall-bounded flow over a realistically rough superhydrophobic surface

Direct numerical simulation (DNS) is performed for two wall-bounded flow configurations: laminar Couette flow at $Re=740$ and turbulent channel flow at $Re_{\unicode[STIX]{x1D70F}}=180$, where $\unicode[STIX]{x1D70F}$ is the shear stress at the wall. The top wall is smooth and the bottom wall is a realistically rough superhydrophobic surface (SHS), generated from a three-dimensional surface profile measurement. The air–water interface, which is assumed to be flat, is simulated using the volume-of-fluid (VOF) approach. The two flow cases are studied with varying interface heights $h$ to understand its effect on slip and drag reduction ($DR$). For the laminar Couette flow case, the presence of the surface roughness is felt up to $40\,\%$ of the channel height in the wall-normal direction. Nonlinear dependence of $DR$ on $h$ is observed with three distinct regions. A nonlinear curve fit is obtained for gas fraction $\unicode[STIX]{x1D719}_{g}$ as a function of $h$, where $\unicode[STIX]{x1D719}_{g}$ determines the amount of slip area exposed to the flow. A power law fit is obtained from the data for the effective slip length as a function of $\unicode[STIX]{x1D719}_{g}$ and is compared to those derived for structured geometry. For the turbulent channel flow, statistics of the flow field are compared to that of a smooth wall to understand the effects of roughness and $h$. Four cases are simulated ranging from fully wetted to fully covered and two intermediate regions in between. Scaling laws for slip length, slip velocity, roughness function and $DR$ are obtained for different penetration depths and are compared to past work for structured geometry. $DR$ is shown to depend on a competing effect between slip velocity and turbulent losses due to the Reynolds shear stress contribution. Presence of trapped air in the cavities significantly alters near-wall flow physics where we examine near-wall structures and propose a physical mechanism for their behaviour. The fully wetted roughness increases the peak value of turbulent intensities, whereas the presence of the interface suppresses them. The pressure fluctuations have competing contributions between turbulent pressure fluctuations and stagnation due to asperities, the near-wall structure is altered and breaks down with increasing slip. Overall, there exists a competing effect between the interface and the asperities, the interface suppresses turbulence whereas the asperities enhance them. The present work demonstrates DNS over a realistic multiphase SHS for the first time, to the best of our knowledge.

Influence of textural statistics on drag reduction by scalable, randomly rough superhydrophobic surfaces in turbulent flow

We investigate the influence of statistical measures of surface roughness on the turbulent drag reduction (DR) performance of four scalable, randomly rough superhydrophobic (SH) textures. Each surface was fabricated using readily scalable surface texturing processes to generate a random, self-affine height profile on the base substrate. The frictional drag on all four SH surfaces was measured when fully submerged in shear-driven turbulent flow inside a bespoke Taylor-Couette apparatus at Reynolds numbers in the range 1 × 104 ≲ Re ≲ 1 × 105. An “effective” slip length quantifying the overall drag-reducing ability for each surface was extracted from the resulting Prandtl-von Kármán friction plots. Reductions in the frictional drag of up to 26% were observed, with one of the hierarchically textured surfaces exceeding a wall shear stress of 26 Pa (corresponding to a Reynolds number Re ≈ 7 × 104) before the onset of flow-induced plastron collapse. The surface morphology of each texture was characterized using noncontact optical profilometry, and the influence of various statistical measures of roughness on the effective slip length was explored. The lateral autocorrelation length was identified as the key textural parameter determining the drag-reducing ability for randomly rough SH textures, playing the role analogous to the spatial periodicity of regularly patterned SH surfaces. A large autocorrelation length, a small surface roughness, and the presence of hierarchical roughness features were observed to be the three important design requirements for scalable SH textures for optimal DR in turbulent flows.

Superhydrophobic Coatings for Improved Performance of Electrical Insulators

AbstractDielectric strength of electrical insulators is adversely affected by both wet conditions and surface roughness due to accelerated dielectric breakdown. While textured superhydrophobic coatings (i.e., coatings that are extremely repellent to water) can prevent the accumulation of water and help retain the dielectric strength of insulators under wet conditions, it is unclear whether or not the presence of texture (i.e., surface roughness) allows the retention of the dielectric strength of insulators. In this work, through a series of systematic experiments and analysis, it is concluded that porous superhydrophobic coatings rather than rough monolithic superhydrophobic surfaces allow the retention of dielectric strength of insulators under wet conditions in spite of the surface roughness. The insights from this work can enable the design of electrical insulators with improved performance and increased longevity.

Dropwise Condensation on Superhydrophobic Microporous Wick Structures

Previous research in dropwise condensation (DWC) on rough microtextured superhydrophobic surfaces has demonstrated evidence of high heat transfer enhancement compared to smooth hydrophobic surfaces. In this study, we experimentally investigate the use of microporous sintered copper powder on copper substrates coated with a thiol-based self-assembled monolayer to attain enhanced DWC for steam in a custom condensation chamber. Although microtextured superhydrophobic surfaces have shown advantageous droplet growth dynamics, precise heat transfer measurements are underdeveloped at high heat flux. Sintered copper powder diameters from 4 μm to 119 μm were used to investigate particle size effects on heat transfer. As powder diameter decreased, competing physical factors led to improved thermal performance. At consistent operating conditions, we experimentally demonstrated a 23% improvement in the local condensation heat transfer coefficient for a superhydrophobic 4 μm diameter microporous copper powder surface compared to a smooth hydrophobic copper surface. For the smallest powders observed, this improvement is primarily attributed to the reduction in contact angle hysteresis as evidenced by the decrease in departing droplet size. Interestingly, the contact angle hysteresis of sessile water droplets measured in air is in contradiction with the departing droplet size observations made during condensation of saturated steam. It is evident that the specific design of textured superhydrophobic surfaces has profound implications for enhanced condensation in high heat flux applications.

Ultimate Stable Underwater Superhydrophobic State.

Underwater metastability hinders the durable application of superhydrophobic surfaces. In this work, through thermodynamic analysis, we theoretically demonstrate the existence of an ultimate stable state on underwater superhydrophobic surfaces. Such a state is achieved by the synergy of mechanical balance and chemical diffusion equilibrium across the entrapped liquid-air interfaces. By using confocal microscopy, we insitu examine the ultimate stable states on structured hydrophobic surfaces patterned with cylindrical micropores in different pressure and flow conditions. The equilibrium morphology of the meniscus is tuned by the dissolved gas saturation degree within a critical range at a given liquid pressure. Moreover, with fresh lotus leaves, we prove that the ultimate stable state can also be realized on randomly rough superhydrophobic surfaces. The finding here paves the way for applying superhydrophobic surfaces in environments with different liquid pressure and flow conditions.

Delayed lubricant depletion on liquid-infused randomly rough surfaces

In this study, pressure drops on liquid-infused superhydrophobic surfaces were measured through a microchannel. A number of different superhydrophobic surfaces were prepared and tested. These surfaces included several PDMS surfaces containing precisely patterned microposts and microridges as well as a number of PTFE surfaces with random surface roughness created by sanding the PTFE with different sandpapers. Silicone oil was selected as the lubricant fluid and infused into the microstructures of the superhydrophobic surfaces. Several aqueous glycerin solutions with different viscosities were used as working fluids so that the viscosity ratio between the lubricant and the working fluid could be varied. The lubricant layer trapped within the precisely patterned superhydrophobic PDMS surfaces was found to be easily depleted over a short period of time even in limit of low flow rates and capillary numbers. On the other hand, the randomly rough superhydrophobic PTFE surfaces tested were found to maintain the layer of lubricant oil even at moderately high capillary numbers resulting in drag reduction that was found to increase with increasing viscosity ratio. The pressure drops on the liquid-infused PTFE surfaces were measured over time to determine the longevity of the lubricant layer. The pressure drops for the randomly rough PTFE surfaces were found to initially diminish with time before reaching a short-time plateau which is equivalent to maximum drag reduction. This minimum pressure drop was maintained for at least three hours in all cases regardless of feature size. However, as the depletion of the oil from the lubricant layer was initiated, the pressure drop was observed to grow slowly before reaching a second long-time asymptote which was equivalent to a Wenzel state.

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.

Three-tier rough superhydrophobic surfaces

A three-tier rough superhydrophobic surface was fabricated by growing hydrophobic modified (fluorinated silane) zinc oxide (ZnO)/copper oxide (CuO) hetero-hierarchical structures on silicon (Si) micro-pillar arrays. Compared with the other three control samples with a less rough tier, the three-tier surface exhibits the best water repellency with the largest contact angle 161° and the lowest sliding angle 0.5°. It also shows a robust Cassie state which enables the water to flow with a speed over 2 m s−1. In addition, it could prevent itself from being wetted by the droplet with low surface tension (mixed water and ethanol 1:1 in volume) which reveals a flow speed of 0.6 m s−1 (dropped from the height of 2 cm). All these features prove that adding another rough tier on a two-tier rough surface could futher improve its water-repellent properties.

Does liquid slippage within a rough channel always increase the flow rate?

Slippage of liquid over rough superhydrophobic surfaces that induce the Cassie-Baxter state decreases frictional force on the flow. This may easily lead to a hasty conclusion that liquid slip enhances the flow rate in rough channels. Here, we show that flow rates can be rather reduced by roughening and hydrophobizing microchannel walls to support liquid slippage, depending on the topography of the roughness. We consider theoretical models that predict liquid flow rates in channels of different roughness and wetting conditions, to construct criteria for the surface structure that determine whether slip or no-slip would be advantageous in enhancing flow rates. It is shown that liquid slips are advantageous only in channels with highly hydrophobic, short, sparsely distributed protrusions. We corroborate our theoretical predictions with microchannels decorated with micropillars of varying wettabilities.

Colloids in external electric and magnetic fields: Colloidal crystals, pinning, chain formation, and electrokinetics

The motion of dilute and concentrated dispersions of colloids by external electric or magnetic fields is discussed. Electrokinetics is studied for colloids in confinement, where the confining walls can be flat or rough. As an example for a rough wall superhydrophobic surfaces are chosen. It is shown that the reduced friction at the water-air interface is insufficient to enhance electro-osmosis. Magnetic particles are pulled through a crystalline matrix formed by nonmagnetic colloids to investigate local melting and recrystallization of a crystalline matrix. The average strain field is calculated and the reorganization processes are compared to those induced by shear fields. Using single domain, magnetically blocked particles of different shape and surface characteristics, the interplay between particles, their environment and an external field is investigated.

Superhydrophobic poly(L-lactic acid) surface as potential bacterial colonization substrate

Hydrophobicity is a very important surface property and there is a growing interest in the production and characterization of superhydrophobic surfaces. Accordingly, it was recently shown how to obtain a superhydrophobic surface using a simple and cost-effective method on a polymer named poly(L-lactic acid) (PLLA). To evaluate the ability of such material as a substrate for bacterial colonization, this work assessed the capability of different bacteria to colonize a biomimetic rough superhydrophobic (SH) PLLA surface and also a smooth hydrophobic (H) one. The interaction between these surfaces and bacteria with different morphologies and cell walls was studied using one strain of Staphylococcus aureus and one of Pseudomonas aeruginosa. Results showed that both bacterial strains colonized the surfaces tested, although significantly higher numbers of S. aureus cells were found on SH surfaces comparing to H ones. Moreover, scanning electron microscopy images showed an extracellular matrix produced by P. aeruginosa on SH PLLA surfaces, indicating that this bacterium is able to form a biofilm on such substratum. Bacterial removal through lotus leaf effect was also tested, being more efficient on H coupons than on SH PLLA ones. Overall, the results showed that SH PLLA surfaces can be used as a substrate for bacterial colonization and, thus, have an exceptional potential for biotechnology applications.

Contact line dynamics of a superhydrophobic surface: application for immersion lithography

The dynamic contact line behavior of water on nanotextured rough hydrophobic and superhydrophobic surfaces is studied and contrasted to smooth hydrophobic surfaces for application in immersion lithography. Liquid loss occurs at the receding meniscus when the smooth substrate is accelerated beyond a critical velocity of approximately 1 m/s. Nanotexturing the surface with average roughness values even below 10 nm results in critical velocity larger than 2.5 m/s, the upper limit of the apparatus. This unexpected increase in critical velocity is observed for both sticky hydrophobic and slippery superhydrophobic surfaces. The authors attribute this large increase in critical velocity both in increased receding contact angle and in increased slip length for such nanotextured surfaces.