Relationship between sliding acceleration of water droplets and dynamic contact angles on hydrophobic surfaces

This study measured sliding acceleration of water droplets on hydrophobic solid surfaces and used expanding and contracting method to compare that value with dynamic contact angles. Sliding action of the droplet was classified into three motion categories: constant accelerated motion, constant velocity and stasis. Differences exist in the dependencies of contact radius and the injection-suction rate in dynamic contact angle hysteresis according to these categories. This method is an effective indicator of water droplets’ sliding acceleration.     

Sliding behavior of water droplets on line-patterned hydrophobic surfaces

We prepared line-patterned hydrophobic surfaces using fluoroalkylsilane (FAS) and octadecyltrimethoxysilane (ODS) then investigated the effect of line direction on sliding behavior of water droplets by direct observation of the actual droplet motion during sliding. Water droplets slide down with a periodic large deformation of the contact line and sliding velocity fluctuation that occurred when they crossed over the 500-μm ODS line regions in FAS regions on a Si surface tilted at 35°. These behaviors are less marked for motion on a 100-μm line surface, or on lines oriented parallel to the slope direction. Smaller droplets slide down with greater displacement in the line direction on 500-μm line patterning when the lines were rotated at 13° in-plane for the slope direction. This sliding behavior depended on the droplet size and rotation angle, and is accountable by the balance between gravitational and retentive forces.     

Study on the hydrophobic surfaces prepared by two-step sol-gel process

In this study, the two-step sol-gel process was used to prepare hydrophobic coating films on the glass substrates. The first step was to add hydrogen chloride into TEOS (tetraethoxysilane) solution, and then the second step was to add ammonia into the above reacted solution. We adopted different amount of hydrogen chloride and ammonia to control the sol-gel reaction and observed the change of the viscosity, gelatin period of the solution and contact angles of the coating films. By this method, we created a surface with roughness and then the hydroxyl groups were terminated by adding trimethylchlorosilane (TMCS) to produce a hydrophobic coating layer. The amount of the acid, base and water added in the solution influenced the reaction rate and resulted in the aggregation and condensation of the particles to form rough surfaces. Consequently, the rough surfaces made by aggregation and condensation of the large particles, which were modified by TMCS resulted in higher contact angles (>140°). In this study, a surface with contact angle 150° was obtained.     

Wetting mode transition of nanoliter scale water droplets during evaporation on superhydrophobic surfaces with random roughness structure

During evaporation, shape changes of nanoliter-scale (80-100 nL) water droplets were evaluated on two superhydrophobic surfaces with different random roughness (nm-coating, μm-coating). The square of the contact radius and the square of the droplet height decreased linearly with evaporation time. However, trend changes were observed at around 170 s (nm-coating) and around 150 s (μm-coating) suggesting a wetting mode transition. The calculated droplet radii for the wetting mode transition from the average roughness distance and the average roughness height of these surface structures were approximately equal to the experimental values at these trend changes. A certain level of correlation between the roughness size and droplet radius at the wetting mode transition was confirmed on surfaces with random roughness.     

Deformation and motion by gravity and magnetic field of a droplet of water-based magnetic fluid on a hydrophobic surface

Motion and deformation of a water-based magnetic fluid on a hydrophobic surface were investigated under gravity and a magnetic field. Surface energy and the resultant contact angle of the magnetic fluid depend on the surfactant concentration. The fluid viscosity is governed mainly by magnetite concentration. The front edge of the droplet moved under a weak external field. The rear edge required a higher external field for movement. The forces of gravity and the magnetic field for moving of the front edge are almost equal. However, those of the rear edge are different. The motion of magnetic fluids by an external field depends on concentrations of surfactants and magnetic particles, the external field, and experimental assembly.     

Sliding behavior of oil droplets on nanosphere stacking layers with different surface textures

Two facile coating techniques, gravitational sediment and spin coating, were applied for the creation of silica sphere stacking layers with different textures onto glass substrates that display various sliding abilities toward liquid drops with different surface tensions, ranged from 25.6 to 72.3 mN/m. The resulting silica surface exhibits oil repellency, long-period durability > 30 days, and oil sliding capability. The two-tier texture offers a better roll-off ability toward liquid drops with a wide range of γ_L, ranged from 30.2 to 72.3 mN/m, i.e., when the sliding angle (SA) < 15°, the oil droplet start to roll off the surface. This improvement of sliding ability can be ascribed to the fact that the two-tier texture allows for air pockets (i.e., referred to as the Cassie state), thus favoring the self-cleaning ability. Taking Young-Duprè equation into account, a linearity relationship between sine SA and work of adhesion (W_ad) appears to describe the sliding behavior within the W_ad region: 2.20-3.03 mN/m. The smaller W_ad, the easier drop sliding (i.e., the smaller SA value) takes place on the surfaces. The W_ad value ∼3.03 mN/m shows a critical kinetic barrier for drop sliding on the silica surfaces from stationary to movement states. This work proposes a mathematical model to simulate the sliding behavior of oil drops on a nanosphere stacking layer, confirming the anti-oil contamination capability.     

Anisotropically microstructured and micro/nanostructured polypropylene surfaces

Anisotropically microstructured and hierarchically micro/nanostructured surfaces were fabricated on polypropylene by injection moulding. Microstructured mould inserts were obtained by structuring electropolished aluminium foils with a micro-working robot, and hierarchically structured mould inserts by anodizing the microstructured aluminium foils. On both types of inserts, the microstructures were anisotropic, consisting of alternating smooth and microstructured zones. Anisotropy, and other properties of microstructures, can be controlled by adjusting the parameters of the micro-working robot. The mould inserts were used to prepare micro- and hierarchically structured polypropylene discs by injection moulding. Replication accuracy at both structure levels can be controlled through the moulding conditions. The behaviour of water on the structures was characterized by measuring the contact and sliding angles parallel and perpendicular to the microstructured zones. Surfaces with microstructures alone were highly hydrophobic, where water droplets adopted the Wenzel state and had clearly different parallel and perpendicular contact angles. Surfaces with dual structures had contact angles near 170° and sliding angles near 0°, and again the angles in parallel and perpendicular directions differed. Superhydrophobic, anisotropic Cassie-Baxter state was achieved.     

Electrical energy harvesting from water droplets passing a hydrophobic polymer with a metal film on its back side

Recent research has demonstrated that electrical energy can be harvested when water droplets move over a hydrophobic polymer covered by a single electrode on its back-side. Here we study the charge dynamics as water droplets pass the polymer. We also investigate how the charging of an external capacitor changes with water flow volume rate, and present a model to understand the results.     

Improvement of water and oil repellency on wood substrates by using fluorinated silica nanocoating

We have investigated a one-step fabrication of fluoro-containing silica coating on wooden substrates, showing multi-functions including super repellency toward water and sunflower oil, low sliding angles, good durability, and low adsorption capacity of moisture. The repellent slurry, consisting of well-mixing silica nanospheres and perfluoroalkyl methacrylic copolymer, is simply prepared and subsequently sprayed over wooden substrates with good adhesion. It has shown that the decoration of silica nanospheres on microscaled wooden texture acts as a crucial role in improving the repellency toward water and sunflower oil droplets. The maximal contact angles can reach as high as 168.3° and 153.6° for water and sunflower oil drops, respectively. These analyses of wetted fraction and work of adhesion also demonstrate the improved repellency due to the addition of silica. This improvement of the repellencies is ascribed to the fact that the drops partially sit on F-coated silica spheres, leaving a layer of air underneath the droplet (i.e., Cassie state). On the basis of the results, the multi-functional coating on wooden substrates delivers a promising commercial feasibility on a variety of woodworks.     

Sliding acceleration of water droplets on a surface coated with fluoroalkylsilane and octadecyltrimethoxysilane

Both fluoroalkylsilane (FAS) and octadecyltrimethoxysilane (ODS) were coated on oxidized silicon wafers using soaking and CVD method. Smooth coatings with Ra values of less than 1 nm were attained. The slope of the sliding acceleration against the inverse of the droplet mass showed an inflection point. That point shifted to the direction of smaller droplets with decreasing FAS ratio to ODS. The water droplets’ length was increased when the sliding velocity was increased. Fluoroalkylsilane addition to ODS increases the interaction between water and the hydrophobic surface. Results showed that the sliding acceleration of a water droplet depends strongly on the surface ratio of these silanes.     

用晶格玻尔兹曼方法研究微结构表面的疏水性能

将固体表面分别近似为具有简单的周期性矩形、三角形和半圆形微粗糙结构表面,建立了两相流的晶格玻尔兹曼模型.通过测量不同微粗糙结构表面上液滴的接触角,探讨微结构形状和尺寸的改变对固体材料表面疏水性能的影响.最后,由流体在各种糙壁管中的速度滑移,验证了结论的正确性.     

Field dependent shape variation of magnetic fluid droplets on magnetic dots

The morphology of magnetic fluid droplets on magnetic thin film dots is studied experimentally, including the aspect ratio and the contact angle variation of the droplets. Under a uniform external magnetic field, the droplet's aspect ratio increases with the external field and with the diameter of the magnetic dot due to the concentrated magnetic flux inside the magnetic fluid droplet. Similar to the electrical wetting phenomenon, the induced magnetic dipoles in the magnetic film and in the magnetic fluid near the solid–liquid interface change the solid–liquid interfacial tension, and in consequence reduce the apparent contact angle of the magnetic fluid droplet.     

Facile fabrication of a lotus-effect composite coating via wrapping silica with polyurethane

A lotus-effect coating was fabricated by wrapping micro-silica and nano-silica with polyurethane (PU) and subsequent spraying. The coating shows the similar self-cleaning property as lotus leaves: the contact angle is as large as 168° and the sliding angle is as low as 0.5°. Surface morphology of the coating was studied with scanning electron microscopy and atomic force microscopy. The composite coating shows the similar structure as lotus leaves.     

TMOS based water repellent silica thin films by co-precursor method using TMES as a hydrophobic agent

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings on glass substrates using trimethylethoxysilane (TMES) as a co-precursor. Silica sol was prepared by keeping the molar ratio of tetramethoxysilane (TMOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:29.27:2.09 respectively, with 0.5 M NH₄OH throughout the experiments and the TMES/TMOS molar ratio (M) was varied from 0 to 3.8. It was found that with an increase in M value, the roughness and hydrophobicity of the films increased, however the optical transmission decreased from 93% to 57% in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 250 °C and above this temperature the films became hydrophilic. The hydrophobic silica thin films were characterized by taking into consideration the surface roughness studies, Fourier transform infrared (FT-IR) spectroscopy, percentage of optical transmission, scanning electron microscopy (SEM) and contact angle measurements.     

Electric-field-induced oscillations of water droplets deposited on insulating surfaces

The 3-D oscillations of a water droplet under the effect of external fields, such as gravity and sinusoidal electric field, were investigated numerically. The time variation of the shape of a perfectly conducting droplet demonstrates that a water droplet vibrates strongly at certain frequencies. It was found that the resonance frequency and the magnitude of the deformation strongly depend on the surface properties and the value of contact angle. A comparison of the numerical results with the known experimental data shows satisfactory agreement with respect to the shape of the droplet and the resonant frequencies.     

Study on hydrophilicity of polymer surfaces improved by plasma treatment

Surface properties of polycarbonate (PC), polypropylene (PP), polyethylene terephthalate (PET) samples treated by microwave-induced argon plasma have been studied with contact angle measurement, X-ray photoelectron spectroscopy (XPS) and scanned electron microscopy (SEM). It is found that plasma treatment modified the surfaces both in composition and roughness. Modification of composition makes polymer surfaces tend to be highly hydrophilic, which mainly depended on the increase of ratio of oxygen-containing group as same as other papers reported. And this experiment further revealed that CO bond is the key factor to the improvement of the hydrophilicity of polymer surfaces. Our SEM observation on PET shown that the roughness of the surface has also been improved in micron scale and it has influence on the surface hydrophilicity.     

Adsorption of bovine serum albumin on amorphous carbon surfaces studied with dip pen nanolithography

This article reports the use of dip pen nanolithography (DPN) for the study of adsorption of bovine serum albumin (BSA) proteins on amorphous carbon surfaces; tetrahedral amorphous carbon (t-aC) and silicon doped hydrogenated amorphous carbon (a-C:H:Si). Contact angle study shows that the BSA proteins reduce the contact angle on both carbon materials. We also noticed that the drop volume dependence is consistent with a negative line tension, i.e. due to an attractive protein/surface interaction. The DPN technique was used to write short-spaced (100 nm) BSA line patterns on both samples. We found a line merging effect, stronger in the case of the a-C:H:Si material. We discuss possible contributions from tip blunting, scratching, cross-talk between lever torsion and bending and nano-shaving of the patterns. We conclude that the observed effect is caused in large measure by the diffusion of BSA proteins on the amorphous carbon surfaces. This interpretation of the result is consistent with the contact angle data and AFM force curve analysis indicating larger tip/surface adhesion and spreading for the a-C:H:Si material. We conclude by discussing the advantages and limitations of DPN lithography to study biomolecular adsorption in nanoscale wetting environments.     

In situ investigation of ice formation on surfaces with representative wettability

In this work, we have prepared a series of samples with five representative surface wettabilities: i.e. superhydrophilic, hydrophilic, critical, hydrophobic and superhydrophobic. These samples were in situ observed the freezing process of water droplets on clean and artificially contaminated surfaces to investigate the relationship between surface wettability and ice formation. Ice accretion was also tested by spraying supercooled water to samples at different horizontal inclination angles (HIA). Surface topography was proved to be essential to the icing through heterogeneous nucleation. However, the correlation between surface wettability and ice formation was not observed. Finally, we found that the superhydrophobic surface clearly exhibited reduced ice accumulation in the initial stage of ice formation associated with the lower sliding angle (SA) of water droplets.     

Hot embossing of PTFE: Towards superhydrophobic surfaces

Three types of reusable stamps with features in the form of 2D arrays of pits having lateral dimensions in the range of 2-80 μm and heights of 1.5-15 μm were successfully employed for the hot embossing of PTFE at temperatures up to 50 °C above the glass transition temperature of PTFE amorphous phase. Due to the softening of PTFE at the temperatures used in this study, we were able to decrease imprint pressure significantly when comparing with the imprint conditions reported by other authors. Impact of the imprint temperature, pressure and time on the fidelity of pattern transfer as well as on water repellency was tested. The best results of embossing were achieved by applying pressure of 10 kg/cm² for 2 min at 170 °C. In this case, flattening of a natural PTFE roughness and pretty accurate deep replicas of the stamp patterns were observable on the whole imprinted area. Improvement in water repellency was largest for the samples imprinted by Ni stamp patterned with a 2D array of 2 μm square pits spaced by the same dimension and having a depth of 1.5 μm. Cassie-Baxter wetting regime was observed for the deepest imprints with water contact angles up to the superhydrophobic limit.     

Fabrication of durable hydrophobic surfaces through surface texturing

Low surface energy polymer thin-films can be applied to surfaces to increase hydrophobicity and reduce friction for a variety of applications. However, wear of these thin films, resulting from repetitive rubbing against another surface, is of great concern. In this study, we show that highly hydrophobic surfaces with persistent abrasion resistance can be fabricated by depositing fluorinated carbon thin films on sandblasted glass surfaces. In our study, fluorinated carbon thin films were deposited on sandblasted and as-received smooth glass using deep reactive ion etching equipment by only activating the passivation step. The surfaces of the samples were then rubbed with FibrMet abrasive papers in a reciprocating motion using an automatic friction abrasion analyzer. During the rubbing, the static and kinetic friction forces were also measured. The surface wetting properties were then characterized using a video-based contact angle measuring system to determine the changes in water contact angle as a result of rubbing. Assessment of the wear properties of the thin films was based on the changes in the water contact angles of the coated surfaces after repetitive rubbing. It was found that, for sandblasted glass coated with fluorinated carbon film, the water contact angle remained constant throughout the entire rubbing process, contrary to the smooth glass coated with fluorinated carbon film which showed a drastic decrease in water contact angle with the increasing number of rubbing cycles. In addition, the static and kinetic friction coefficients of the sandblasted glass were also much lower than those of the smooth glass.