Rapid fabrication of superhydrophobic surfaces on copper substrates by electrochemical machining

Hierarchical micrometer-nanometer-scale binary rough structures were fabricated on copper substrates by electrochemical machining in a neutral NaCl electrolyte. The rough structures are composed of the micrometer scale potato-like structures and the nanometer scale cube-like structures. After modified by the fluoroalkylsilane, the copper surfaces reached superhydrophobicity with a water contact angle of 164.3° and a water tilting angle less than 9°. This method has a high processing efficiency which can take just 3 s to fabricate the roughness required by the superhydrophobic surface. The effect of the processing time on wettability of the copper surfaces was investigated in this paper. The possible mechanism of the formation of the hierarchical roughness was also proposed, and the wettability of the copper surfaces was discussed on the basis of the Cassie-Baxter theory.     

The conversion of wettability in transparent conducting Al-doped ZnO thin film

We report on the systematic changes of surface wettability in one of the most promising transparent conducting oxide materials, Al-doped ZnO (AZO) thin films. It was revealed that the characteristic surface wettability, which would make a key role in adhesion with other layers of optoelectronic device, can be largely changed by Al concentrations and film growth temperature. Keeping the electrical conductivity constant, the water contact angle (WCA) of a 2 mol% AZO film was changed by about 50 ^°C depending on the surface roughness. In the samples grown at 300 ^°C, the roughness enhancement was large and a hydrophobic surface formed, whereas in the samples grown at 500 ^°C a hydrophilic surface formed. We attributed the variation in surface wettability with growth temperature to changes in surface morphology. This result suggests that 2 mol% Al doping concentration can be considered as a critical concentration in changing of surface morphology of AZO as well as in electrical properties.     

Macroporous fluoropolymeric films templated by silica colloidal assembly: A possible route to super-hydrophobic surfaces

A super-hydrophobic surface was obtained on a three-dimensional (3D) polyvinylidene fluoride (PVDF) macroporous film. The porous films were fabricated through self-assembled silica colloidal templates. The apparent water contact angle of the surface can be tuned from 106° to 153° through altering the sintering temperature and the diameter of the colloidal templates. A composite structure of micro-cavities and nanoholes on the PVDF surface was responsible for the super-hydrophobicity. The wettability of the porous surfaces was described by the use of the Cassie-Baxter model and Wenzel's equation.     

Preparation Principle of Super-Hydrophobic Surfaces by Phase Separation

The Flory–Huggins theory of polymer solutions combined with an evaporation process was employed to interpret the preparation mechanism of a super-hydrophobic surface by phase separation. The ternary phase diagram of a polymer/solvent/nonsolvent was calculated by using the solubility parameters of the components in the system. It indicated that with the increase of the nonsolvent fraction, the initial volume fraction of the polymer or the evaporation rate of the solvent, the evaporation time for phase separation would shorten and the phase separation rate would speed up. The polymer volume fraction in the dense phase would increase and the precipitating particles tended to collide and aggregate, resulting in a rough, super-hydrophobic surface. Experimental results were in agreement with this principle of phase separation for preparing super-hydrophobic surfaces. Membranes of acrylic resin and fluorinated acrylic resin with rough surfaces were successfully obtained by the phase separation method. Especially, the water contact angle of the fluorine-containing acrylic resin with the rough surface was greater than 150°, which satisfied the requirement of super-hydrophobicity.     

Preparation and properties of super-hydrophobic coating on magnesium alloy

The super-hydrophobic coating was successfully fabricated on the surface of magnesium alloy AZ31 by chemical etching and surface modification. The surface morphologies, compositions, wettability and corrosion resistance of the coating were investigated with SEM, XPS, contact angle measurement and electrochemical method, respectively. It shows that the rough and porous micro-nano-structure was presented on the surface of magnesium alloy, and the contact angle could reach up to 157.3 ± 0.5° with sliding angle smaller than 10°. The super-hydrophobic coating showed a long service life. The results of electrochemical measurements showed that anticorrosion property of magnesium alloy was improved. The super-hydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it finds that only about 10% of the water surface is contacted with the metal substrate and the rest 90% is contacted with the air cushion.     

Topological and chemical investigation on super-hydrophobicity of PTFE surface caused by ion irradiation

Super-hydrophobic PTFE surfaces were obtained by irradiation of 200 keV Xe⁺ ion with the fluence of 6.2×10¹³ ions/cm². The contact angle of water on such surface is as large as 161±3°. SEM and XPS were used to investigate how the topological and chemical changes affect the wettability of the irradiated surface. Needle like structures at nanometer scale caused by irradiation are considered to be the reason of the super-hydrophobicity. The formation of oxygen containing group and defluorination effect on the treated surface are inferred to have negative contribution to the hydrophobic optimization of PTFE surface.     

Control over the wettability of amorphous carbon films in a large range from hydrophilicity to super-hydrophobicity

Control of wettability is of significance in industry as well as our daily live. Amorphous carbon (a-C) films with nanostructured surface were deposited on silicon and glass substrates at different substrate temperatures through a magnetron sputtering technique. The microstructures of the a-C films were studied by SEM and XPS, which indicate that the surface of the a-C films deposited at room temperature are smooth due to their much dense sp³-bonded carbon, while they turn to be more porous graphite-like structure with elevated deposition temperature. The water contact angle (CA) measurements show that these pure carbon films exhibit different wettability, ranging from hydrophilicity with CA less than 40° to super-hydrophobicity with CA of 152°, which reveal that the surface wettability of a-C films can be controlled well by using nanostructures with various geometrical and carbon state features. The graphite-like carbon film deposited at 400 °C without any modification exhibits super-hydrophobic properties, due to the combining microstructures of spheres with nanostructures of protuberances and interstitials. It may have great significance on the study of wettability and relevant applications.     

基于热致相分离法和机械撕除技术的可再生超疏水表面构建

We report a simple preparation method of a renewable superhydrophobic surface by ther-mally induced phase separation (TIPS) and mechanical peeling. Porous polyvinylidene fluo-ride (PVDF) membranes with hierarchical structures were prepared by a TIPS process under different cooling conditions, which were confirmed by scanning electron microscopy and mer-cury intrusion porosimetry. After peeling off the top layer, rough structures with hundreds of nanometers to several microns were obtained. A digital microscopy determines that the surface roughness of peeled PVDF membranes is much higher than that of the original PVDF membrane, which is important to obtain the superhydrophobicity. Water contact angle and sliding angle measurements demonstrate that the peeled membrane surfaces display super-hydrophobicity with a high contact angle (152°) and a low sliding angle (7.2°). Moreover, the superhydrophobicity can be easily recovered for many times by a simple mechanical peel-ing, identical to the original superhydrophobicity. This simple preparation method is low cost, and suitable for large-scale industrialization, which may offer more opportunities for practical applications.     

Stable superhydrophobic surface with hierarchical mesh-porous structure fabricated by a femtosecond laser

Inspired by the lotus leaf, a new superhydrophobic surface with hierarchical mesh-porous structure is fabricated by femtosecond laser irradiation on silicon. The fabricated surface shows a superhydrophobic character with water contact angle being found to reach up to 158^°±1^° and sliding angle of 4^°±0.5^°. The superhydrophobicity is stable even if the PH of solution changes from 1 to 14. And the surface also exhibits excellent self-cleaning effect and bouncing behavior, implying that the adhesion of the surface is extremely low. This work will enhance further understanding of the wettability of a solid surface with special surface morphology.     

Super-hydrophobic transparent surface by femtosecond laser micro-patterned catalyst thin film for carbon nanotube cluster growth

In this work, super-hydrophobic surfaces were fabricated by femtosecond laser micro-machining and chemical vapor deposition to constitute hybrid scale micro/nano-structures formed by carbon nanotube (CNT) clusters. Nickel thin-film microstructures, functioning as CNT growth catalyst, precisely control the distribution of the CNT clusters. To obtain minimal heat-affected zones, femtosecond laser was used to trim the nickel thin-film coating. Plasma treatment was subsequently carried out to enhance the lotus-leaf effect. The wetting property of the CNT surface is improved from hydrophilicity to super-hydrophobicity at an advancing contact angle of 161 degrees. The dynamic water drop impacting test further confirms its enhanced water-repellent property. Meanwhile, this super-hydrophobic surface exhibits excellent transparency with quartz as the substrate. This hybrid fabrication technique can achieve super-hydrophobic surfaces over a large area, which has potential applications as self-cleaning windows for vehicles, solar cells and high-rise buildings.     

正癸烷纳米液滴润湿特性的分子动力学研究

流体液滴在固体表面的浸润性对其润滑性能至关重要.本文利用分子动力学方法研究了正癸烷纳米液滴在铜表面上的润湿特性.结果表明：在平坦光滑表面上,壁面的厚度和分子数目对润湿效果影响不大.随着壁面能量势阱参数εs 增大,接触角线性减小.随着温度升高,液滴的接触角减小.在沟槽粗糙表面上,随着粗糙度因子增大,对于疏液表面,接触角增大到一定值后基本保持不变,符合Cassie理论;中性和亲液表面接触角则会减小,为Wenzel润湿模式.当表面分数增大时,疏液与亲液表面接触角整体呈减小的趋势,对中性表面影响不大.当温度升高时,粗糙疏液表面接触角会增大,润湿效果更差,而粗糙中性和亲液表面液滴润湿性会更好.     

真实加工表面后向散射特性分析及表面参数反演

无合作目标激光绝对测距中,远距离、真实表面的后向散射特性机理不明朗,严重影响测距结果,是制约测距技术发展的重要瓶颈。以立铣、平铣、平磨等三种典型实际机械加工方式下的粗糙表面为研究对象,测量了在1 550 nm红外激光照射下形成的后向散射场,探究了不同加工方式下特殊后向散射场形成的原因,深入分析了表面纹理、入射方位角、入射角度、粗糙度对后向散射场分布的影响。实验结果分析表明,加工制造表面的后向散射光谱形态分布受加工方式的影响很大,且相互入射几何关系和粗糙度对每种加工方式下的实际粗糙表面均有规律性影响。为了能够获取足够的后向散射能量,对表面参数的识别反演显得十分重要。进一步构建了一种加工表面多维参数反演模型,采用另外一种加工方式(刨床)的样块数据进行验证,加工方式能够被准确区分,入射方位角和粗糙度反演的相对误差分别达到1.21%和1.03%,反演精度较高。经实验验证,通过表面参数的反演极大拓宽了无合作目标激光绝对测距的范围,有效降低了表面纹理、入射方位角、粗糙度等对测距范围的影响。这一研究结果还对具有纹理特征加工表面的后向散射光谱的研究和在其他领域的应用均具有一定的参考价值。     

Fabrication of superhydrophobic surfaces on zinc substrates and their application as effective corrosion barriers

Stable superhydrophobic surfaces have been effectively fabricated on the zinc substrates through one-step platinum replacement deposition process without the further modification or any other post processing procedures. The effect of reaction temperatures on the surface morphology and wettability was studied by using SEM and water contact angle (CA) analysis. Under room temperature, the composite structure formed on the zinc substrate was consisted of microscale hexagonal cavities, densely packed nanoparticles layer and micro/nanoscale structures like the flowers. The structure has exhibited great surface roughness and porosity contributing to the superhydrophobicity where the contact angle could reach an ultra high value of around 170°. Under reaction temperature of 80 °C, the composite structure, on the other hand, was hierarchical structure containing lots of nanoscale flowers and some large bushes and showed certain surface roughness (maximum CA value of about 150°). In addition, an optimal superhydrophobic platinum surface was able to provide an effective anticorrosive coating to the zinc substrate when it was immersed into an aqueous solution of sodium chloride (3% NaCl) for up to 20 days. The corrosion process was monitored through electrochemical means and the results are compared with those of unprotected zinc plates.     

Tailoring the wettability of nanocrystalline TiO2 films

The water contact angle (WCA) of nanocrystalline TiO₂ films was adjusted by fluoroalkylsilane (FAS) modification and photocatalytic lithography. FAS modification made the surface hydrophobic with the WCA up to ∼156°, while ultraviolet (UV) irradiation changed surface to hydrophilic with the WCA down to ∼0°. Both the hydrophobicity and hydrophilicity were enhanced by surface roughness. The wettability can be tailored by varying the concentration of FAS solution and soaking time, as well as the UV light intensity and irradiation time. Additionally, with the help of photomasks, hydrophobic-hydrophilic micropatterns can be fabricated and manifested via area-selective deposition of polystyrene particles.     

Transformation of a hydrophilic membrane into semi-super-hydrophobic based on self-assembly of stearic acid monolayer over induced nanostructures on the membrane surface

Both the chemical and structural properties of a surface determine the contact angle. For the formation of super-hydrophobic surfaces, modification of surface chemistry must be always combined with surface roughness enhancement. The used methods to make a super-hydrophobic surface are expensive and need very complicated equipments and cannot be scale up easily. In this study a simple and less expensive method was developed to transform a hydrophilic membrane into a semi-super-hydrophobic. In order to modify the membrane surface geometrically, the required needle-like rugosities were created by boiling the membrane in the water. The chemical modification of the roughened surface was created by the chemical adsorption and controlling the reaction time of stearic acid (STA) on the polymer of the membrane surface. Finally, by controlling the surface roughness, the concentration of the STA solution and duration of reaction time, a semi-super-hydrophobic membrane with the contact angle of 120° was prepared.     

The preparation of lotus-like super-hydrophobic copper surfaces by electroplating

The preparation of super-hydrophobic metal surfaces had to combine rough structures and the surface modifications with low surface energy materials. Although there were different views on it, no experiment was done to prove it yet. In this paper, the structure of natural lotus leaf was observed and the lotus-like surfaces on hydrophilic copper substrates were fabricated via electroplating in large current density. These surfaces were super-hydrophobic without any chemical modification. The hydrophobic mechanism was analyzed. It is believed that this was a meta-stable state in Cassie model. As long as the surface structure was suitable, hydrophobic surface, even super-hydrophobic surface, could be got on hydrophilic substrate.     

Preparation of porous super-hydrophobic and super-oleophilic polyvinyl chloride surface with corrosion resistance property

Porous super-hydrophobic polyvinyl chloride (PVC) surfaces were obtained via a facile solvent/non-solvent coating process without introducing compounds with low surface energy. The microstructure, wetting behavior, and corrosion resistance of resultant super-hydrophobic PVC coatings were investigated in relation to the effects of dosage of glacial acetic acid and the temperature of drying the mixed PVC solution spread over glass slide substrate. As-prepared PVC coatings had porous microstructure, and the one obtained at a glacial acetic acid to tetrahydrofuran volume ratio of 2.5:10.0 and under a drying temperature of 17 °C had a water contact angle of 150 ± 1.5°, showing super-hydrophobicity. In the meantime, it possessed very small contact angles for liquid paraffin and diiodomethane and good corrosion resistance against acid and alkali corrosive mediums, showing promising applications in self-cleaning, waterproof for outer wall of building, seawater resistant coating, and efficient separation of oil and water.     

Influence of surface roughness on water- and oil-repellent surfaces coated with nanoparticles

Various rough surfaces coated with titanium oxide nanoparticles and perfluoroalkyl methacrylic copolymer were conducted to explore the influence of surface roughness on the performance of water- and oil-repellence. Surface characteristics determined from nitrogen physisorption at −196 °C showed that the surface area and pore volume increased significantly with the extent of nanoparticle ratio, indicating an increase of surface roughness. Due to the surface nano-coating, the maximum contact angles of water and ethylene glycol (EG) droplets increased up to 56 and 48%, respectively, e.g. from 105° to 164° for water droplets and from 96° to 144° for EG droplets. The excellent water- and oil-repellence of the prepared surfaces was ascribed to this increase of surface roughness and fluorinated-contained surface. Compared with Wenzel model, the Cassie model yielded a fairly good fit to the simulation of contact angle with surface roughness. However, a derivation of 3°–10° at higher roughness still existed. This phenomenon was very likely due to the surface heterogeneity with different pore size distributions of the fractal surfaces. In this case, it was unfavorable for super repellency from rough surface with larger mesopore fraction because of its capillary condensation, reflecting that micropore provided more air resistance against wettability.     

Superior electrochemical performance of carbon cloth electrode-based supercapacitors through surface activation and nitrogen doping

A simple and low-cost strategy is developed to fabricate three-dimensional (3D) nitrogen-doped carbon cloth electrode through surface activation and nitrogen-doping process. The process can exfoliate the smooth surfaces of micro carbon fibers into nanostructures together with the doping of nitrogen-containing species. The as-fabricated carbon cloth electrode shows excellent areal capacitances of 882.36 and 706.68 mF cm^?2 at the current density of 1 and 60 mA cm^?2, respectively, exhibiting good rate performance. It also exhibits outstanding cycling stability with 98.7 % retention of its initial capacitance after 30,000 continuous charging/discharging tests. When the electrodes were assembled and tested as a symmetric supercapacitor, it also demonstrates superior electrochemical performance. It is believed that the 3D carbon structures with enlarged surface area, improved conductivity and electrode/electrolyte wettability, and enhanced pseudocapacitance by doping of nitrogen lead to the vast improvement of electrochemical performance.     

Synthesis and characterization of superhydrophobic functionalized Cu(OH)2 nanotube arrays on copper foil

Superhydrophobic functionalized cupric hydroxide (Cu(OH)₂) nanotube arrays were prepared on copper foils via a facile alkali assistant surface oxidation technique. Thus nanotube arrays of Cu(OH)₂ were directly fabricated on the surface of copper foil by immersing in an aqueous solution of NaOH and (NH₄)₂S₂O₈. The wettability of the surface was changed from surperhydrophilicity to superhydrophobicity by chemical modification with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS). The morphologies, microstructures, crystal structure, chemical compositions and states, and hydrophobicity of the films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. It was found that the rough structure of the surface helped to magnify the wettability. The static contact angle (CA) for water is larger than 160° and the contact angle hysteresis (CAH) is lower than 5° on the modified surface. The high roughness of the nanotube arrays along with the generated C-F chains by chemical modification contributed to the improved superhydrophobicity. The present research is expected to be significant in providing a new strategy for the preparation of novel multifunctional materials with potential industrial applications on copper substrates.