Tailoring the wetting response of silicon surfaces via fs laser structuring

Control over the wettability of solids and manufacturing of functional surfaces with special hydrophobic and self-cleaning properties has aroused great interest because of its significance for a vast range of applications in daily life, industry and agriculture. We report here a simple method for preparing stable superhydrophobic surfaces by irradiating silicon (Si) wafers with femtosecond (fs) laser pulses and subsequently coating them with chloroalkylsilane monolayers. It is possible, by varying the laser pulse fluence on the surface, to achieve control of the wetting properties through a systematic and reproducible variation of roughness at micro- and nano-scale which mimics both the topology of the “model” superhydrophobic surface—the natural lotus leaf—, as well as its wetting response. Water droplets can move along these irradiated superhydrophobic surfaces, under the action of small gravitational forces, and experience subsequent immobilization, induced by surface tension gradients. These results demonstrate the potential of manipulating liquid motion through selective laser patterning.     

Controlling the micro/nanostructure of self-cleaning polymer coating

Polypropylene bio-mimic self-cleaning surfaces with porous micro-nano-binary morphology structures were prepared by a simple casting method. The influence of the cooling process and solvent composition on water contact angle, sliding angles and self-cleaning properties has been investigated. Detailed SEM morphology studies revealed that the polymer used in this work is commercial-grade granular low-density polyethylene (LDPE) forms petal-like crystalline, which are of micrometer scale in length and nanometer scale in thickness. The nano-crystallines on the surface represent a porous three-dimensional micro-nano-binary structure. It was found that a compromise to the film porosity and crystal nano structure is essential for achieving a satisfied self-cleaning surface. Under optimum condition, a water contact angle of 152.2°, and a sliding angle of 1.7° can be obtained using this simple method.     

Lateral vibration of a water drop and its motion on a vibrating surface

The resonant modes of sessile water drops on a hydrophobic substrate subjected to a small-amplitude lateral vibration are investigated using computational fluid dynamic (CFD) modeling. As the substrate is vibrated laterally, its momentum diffuses within the Stokes layer of the drop. Above the Stokes layer, the competition between the inertial and Laplace forces causes the formation of capillary waves on the surface of the drop. In the first part of this paper, the resonant states of water drops are illustrated by investigating the velocity profile and the hydrostatic force using a 3d simulation of the Navier-Stokes equation. The simulation also allows an estimation of the contact angle variation on both sides of the drop. In the second part of the paper, we investigate the effect of vibration on a water drop in contact with a vertical plate. Here, as the plate vibrates parallel to gravity, the contact line oscillates. Each oscillation is, however, rectified by hysteresis, thus inducing a ratcheting motion to the water droplet vertically downward. Maximum rectification occurs at the resonant states of the drop. A comparison between the frequency-dependent motion of these drops and the variation of contact angles on their both sides is made. The paper ends with a discussion on the movements of the drops on a horizontal hydrophobic surface subjected to an asymmetric vibration.     

Magnetic movement of biological fluid droplets

Magnetic fields can be used to control the movement of aqueous drops on non-patterned, silicon nanowire superhydrophobic surfaces. Drops of aqueous and biological fluids are controlled by introducing magnetizable carbonyl iron microparticles into the liquid. Key elements of operations such as movement, coalescence, and splitting of water and biological fluid drops, as well as electrochemical measurement of an analyte are demonstrated. Superhydrophobic surfaces were prepared using vapor–liquid–solid (VLS) growth systems followed by coating with a perfluorinated hydrocarbon molecule. Drops were made from aqueous and biological fluid suspensions with magnetizable microparticle concentrations ranging from 0.1 to 10 wt%.     

纳米粒子构建表面的超疏水性能实验研究

采用疏水纳米粉体压片法和岩心吸附法构建了具有微纳米结构的表面,测试了这些表面的接触角,拍摄了水滴在吸附纳米粒子的岩石表面的滚动过程照片,采用扫描电子显微镜(scanning electron microscope,SEM)检测了表面的微结构.实验结果表明：无机纳米粒子经弱疏水性材料修饰后,其表面润湿性由强亲水变为强疏水;疏水纳米粒子吸附表面的接触角均大于120°,滚动角约7°,显示出超疏水特性;SEM照片显示,这些超疏水表面是具有不规则微纳米结构的气固复合面,符合Cassie-Baxter的复合表面模型. 关键词： 超疏水 纳米粒子 微纳米结构表面 接触角     

Directional motion of water drop on ratchet-like superhydrophobic surfaces

In this article, directional movements of drops on the ratchet-like superhydrophobic surfaces were observed. High-speed CCD images showed the caterpillar-like crawl of a drop on the inclined superhydrophobic surfaces as it rolled along the ridge of ratchet. In contrast, along the opposite direction, the movement of the drop only depended on the end of triple phase contact line while the front of contact line was pinned. The sliding angle (SA) measurements indicated that the ratchet-like superhydrophobic surfaces had directional drop retention traits. Moreover, the reduction of the rise angle ω₁, the height d of the ratchet's ridge and the volume V of the drop can greatly enhance the directional difference of drop retention on the ratchet-like superhydrophobic surfaces. Therefore, it was concluded that the superhydrophobicity and the periodic ratchet-like microstructures were the keys to the directional drop sliding at one-dimensional level. We believe that these findings would be helpful to better understand the ratchet-like effect on the superhydrophobic surfaces and guide some novel engineering applications.     

Superhydrophobic wind turbine blade surfaces obtained by a simple deposition of silica nanoparticles embedded in epoxy

Samples of wind turbine blade surface have been covered with a superhydrophobic coating made of silica nanoparticles embedded in commercial epoxy paint. The superhydrophobic surfaces have a water contact angle around 152°, a hysteresis less than 2° and a water drop sliding angle around 0.5°. These surfaces are water repellent so that water drops cannot remain motionless on the surface. Examination of coated and uncoated surfaces with scanning electron microscopy and atomic force microscopy, together with measurements of water contact angles, indicates that the air trapped in the cavity enhances the water repellency similarly to the lotus leaf effect. Moreover, this new coating is stable under UVC irradiation and water pouring. The production of this nanoscale coating film being simple and low cost, it can be considered as a suitable candidate for water protection of different outdoor structures.     

Wetting and superhydrophobic properties of PECVD grown hydrocarbon and fluorinated-hydrocarbon coatings

Wetting characteristics of micro-nanorough substrates of aluminum and smooth silicon substrates have been studied and compared by depositing hydrocarbon and fluorinated-hydrocarbon coatings via plasma enhanced chemical vapor deposition (PECVD) technique using a mixture of Ar, CH₄ and C₂F₆ gases. The water contact angles on the hydrocarbon and fluorinated-hydrocarbon coatings deposited on silicon substrates were found to be 72° and 105°, respectively. However, the micro-nanorough aluminum substrates demonstrated superhydrophobic properties upon coatings with fluorinated-hydrocarbon providing a water contact angle of ∼165° and contact angle hysteresis below 2° with water drops rolling off from those surfaces while the same substrates showed contact angle of 135° with water drops sticking on those surfaces. The superhydrophobic properties is due to the high fluorine content in the fluorinated-hydrocarbon coatings of ∼36 at.%, as investigated by X-ray photoelectron spectroscopy (XPS), by lowering the surface energy of the micro-nanorough aluminum substrates.     

Droplet transport and coalescence kinetics in emulsions subjected to acoustic fields

A method to aid the separation of the oil phase from aqueous emulsions using a low-intensity, resonant ultrasonic field has recently been developed. The density and compressibility difference between the dispersed and continuous phases within the emulsion results in a net force on the oil drops that pushes them toward the pressure antinodes of the standing-wave field, where coalescence subsequently occurs. A trajectory model is developed to predict the relative motion of drops subjected to the acoustic field. Such trajectories are sensitive to the physical properties and relative size of interacting drops, the initial configuration of the drops, and acoustic field parameters. Model predictions are validated by comparing experimentally observed trajectories with those predicted by the model. The modeling approach is then extended to determine the temporal evolution of the size of the region surrounding a target drop cleared by coalescence as a function of physical and acoustic field parameters. These results form the basis of a population balance model that attempts to track the size-evolution of a drop population coalescing under the influence of an acoustic field.     

Nucleation and growth on a superhydrophobic grooved surface

The growth dynamics of water drops condensed on a superhydrophobic geometrically patterned surface were studied. Drop size evolution at early and intermediate times is self-similar. Drop growth laws do not differ for a flat surface because of a reduction of both drop and substrate dimensionality. A striking observation is the instantaneous drying of the top surface of grooves at a point in time due to coalescence of the drops with a completely filled channel. At late times, only a few large drops grow connected to the channels, in a mixed Wenzel-penetration regime.     

Preparation of transparent BN films with superhydrophobic surface

A novel approach was investigated to obtain the superhydrophobicity on surfaces of boron nitride films. In this method boron nitride films were deposited firstly on Si(1 0 0) and quartz substrate using a radio frequency (RF) magnetron sputtering system, and then using CF₄ plasma treatment, the topmost surface area can be modified systematically. The results have shown that the water contact angle on such surfaces can be tuned from 67° to 159°. The films were observed to be uniform. The surfaces of films consist of micro-features, which were confirmed by Atomic Force Micrograph. The chemical bond states of the films were determined by Fourier Transform Infrared (FTIR) Spectroscopy, which indicate the dominance of B-N binding. According to the X-ray Photoelectron Spectroscopy analysis, the surface of film is mainly in BN phase. The micro-feature induced surface roughness is responsible for the observed superhydrophobic nature. The water contact angles measured on these surfaces can be modeled by the Cassie's formulation.     

Ultrasonic Vibration Suspends Large Pendant Drops

A stationary substrate can suspend only small pendant drops even with excellent wetting ability because of gravity. We report the suspension of large pendant water drops by a copper substrate that vibrates ultrasonically with a frequency of 22 kHz. The mass of the largest pendant drop suspended by the vibrating substrate reaches 1.1 g, which is 9 times that by the same stationary substrate. The pendant drop deforms drasticaJly and quickly at both the beginning and the end of the vibration procedure. As the vibration power increases, the contact area between the drop and substrate expands and the drop height shrinks accordingly. Theoretical analysis indicates that the Bernoulli pressure induced by ultrasonic vibration may contribute strongly to enhancing the suspensibility of pendant drops.     

Anti-icing performance of superhydrophobic surfaces

This article studies the anti-ice performance of several micro/nano-rough hydrophobic coatings with different surface chemistry and topography. The coatings were prepared by spin-coating or dip coating and used organosilane, fluoropolymer or silicone rubber as a top layer. Artificially created glaze ice, similar to the naturally accreted one, was deposited on the nanostructured surfaces by spraying supercooled water microdroplets (average size ∼80 μm) in a wind tunnel at subzero temperature (−10 °C). The ice adhesion strength was evaluated by spinning the samples in a centrifuge at constantly increasing speed until ice delamination occurred. The results show that the anti-icing properties of the tested materials deteriorate, as their surface asperities seem to be gradually broken during icing/de-icing cycles. Therefore, the durability of anti-icing properties appears to be an important point for further research. It is also shown that the anti-icing efficiency of the tested superhydrophobic surfaces is significantly lower in a humid atmosphere, as water condensation both on top and between surface asperities takes place, leading to high values of ice adhesion strength. This implies that superhydrophobic surfaces may not always be ice-phobic in the presence of humidity, which can limit their wide use as anti-icing materials.     

Tailoring the wettability of patterned silicon surfaces with dual-scale pillars: From hydrophilicity to superhydrophobicity

Wettability tailoring of patterned silicon surface has great potential in fields producing integrated circuits, solar cells, sensors, detectors, and micro/nano electromechanical systems. The present paper presents a convenient yet effective method of combining reactive ion etching and catalyzed etching to prepare silicon surface with micro-nano dual-scale pillars. The experimental results indicate that the hydrophilic surface transformed to a superhydrophobic surface when micro-nano dual-scale pillars were formed. The surface preserved superhydrophobicity even when the geometric parameters of the micropillars were changed. Overhangs of water drops on steep micro-nano dual-scale pillars result in superhydrophobicity. This method offers a new way for tailoring the wettability of patterned silicon surfaces.     

Casimir-Lifshitz quantum state of superhydrophobic black-silicon surfaces manufactured by a metal-assisted hierarchical nano-microtexturing process

We investigated superhydrophobic Si nanosurfaces similar to the lotus leaf by performing a hierarchical nanotexturing process on micropyramidal Si surfaces. The process was carried out using a metal-assisted chemical etching process based upon the deposition of Ag nanoparticles. The hierarchical micro-nanosurfaces showed a superhydrophobic character with contact angles of approximately 134～150°. The photon tunnelling also provides a strong light absorption as a black Si. The surface-light emission from broad and sharp photoluminescence was observed in the wavelength ranges of 414.7～440 and 509～516.2?nm. The field-induced tunnelling current on nanosurface shows the formation of quantum surface states. From the analyses of Casimir-Lifshitz quantum state of a photon in vacuum, the superhydrophobic behaviour of water droplet is closely related to the nanosurface and the nanoporous cavity shows the absorption of terahertz energy. Si nanosurface shows the broadband absorption in the spectral range of 800～900 cm^?1 corresponding to the energy range of 99.2～111.6?meV with 24～27 THz.     

A simple solution-immersion process for the fabrication of superhydrophobic cupric stearate surface with easy repairable property

The present work reports a simple and time-saving method to fabricate cupric stearate film on zinc substrate by a solution-immersion process. Superhydrophobic surfaces are conventionally prepared employing two steps: roughening a surface and lowering its surface energy. The fabrication of superhydrophobic cupric stearate surface is reported using a one-step process by immersing a zinc plate coated with copper into the stearic acid solution, simplifying the complexity of two different steps involved in the conventional methods. The surface of the zinc plate coated with copper is found to be covered with low surface energy cupric stearate film providing the water contact angle of 160 ± 1° with the rolling off properties. In addition, the damaged superhydrophobic surface can restore superhydrophobicity property by immersing the surface into the stearic acid solution again.     

Bouncing behaviors of suspension liquid drops on a superhydrophobic surface

Abstract  

This paper reveals three patterns of bouncing behaviors of suspension drops containing calcium carbonate (CaCO₃) powder on a superhydrophobic surface with the aid of a high-speed camera. In transmission electron microscopy (TEM) observation, the particles of CaCO₃ are shaped like sticks whose equivalent diameters are about 700 nm. Unlike a pure water drop, dense suspension drops cannot be pinched off at the bounce on the superhydrophobic surface due to a high effective viscosity, whereas the equilibrium contact angle appears to be almost identical in all kinds of droplets.     

Bio-inspired water repellent surfaces produced by ultrafast laser structuring of silicon

We report here an efficient method for preparing stable superhydrophobic and highly water repellent surfaces by irradiating silicon wafers with femtosecond laser pulses and subsequently coating them with chloroalkylsilane monolayers. By varying the laser pulse fluence on the surface one can successfully control its wetting properties via a systematic and reproducible variation of roughness at micro- and nano-scale, which mimics the topology of natural superhydrophobic surfaces. The self-cleaning and water repellent properties of these artificial surfaces are investigated. It is found that the processed surfaces are among the most water repellent surfaces ever reported. These results may pave the way for the implementation of laser surface microstructuring techniques for the fabrication of superhydrophobic and self-cleaning surfaces in different kinds of materials as well.     

Non-Axisymmetric Oscillation of Acoustically Levitated Water Drops at Specific Frequencies

A category of non-axisymmetric oscillations of acoustically levitated water drops was observed. These oscillations can be qualitatively described by superposing a sectorial oscillating term upon the initial oblate shape resulting from the effect of acoustic radiation pressure. The oscillation frequencies are around 25 Hz for the 2-lobed mode and exactly 50 Hz for the 3- and 4-1obed modes. These oscillations were excited by the disturbance from the power supply. For the same water drop, higher mode oscillations were observed with more oblate initial shape, indicating that the eigenfrequencies of these non-axisymmetric oscillations decrease with increasing initial distortion. The maximum velocity and acceleration within the oscillating drop can attain 0.3 m·s^-1 and 98.7 m·s^-2 respectively, resulting in strong fluid convection and enhanced heat and mass transfer.