Synthesis of monodisperse fluorinated silica nanoparticles and their superhydrophobic thin films

Monodispersive silica nanoparticles have been synthesized via the Sto?ber process and further functionalized by adding fluorinated groups using fluoroalkylsilane in an ethanolic solution. In this process, six different sizes of fluorinated silica nanoparticles of varying diameter from 40 to 300 nm are prepared and used to deposit thin films on aluminum alloy surfaces using spin coating processes. The functionalization of silica nanoparticles by fluorinated group has been confirmed by the presence C-F bonds along with Si-O-Si bonds in the thin films as analyzed by Fourier transform infrared spectroscopy (FTIR). The surface roughnesses as well as the water contact angles of the fluorinated silica nanoparticle containing thin films are found to be increased with the increase of the diameter of the synthesized fluorinated silica nanoparticles. The thin films prepared using the fluorinated silica nanoparticles having a critical size of 119 ± 12 nm provide a surface roughness of ～0.697 μm rendering the surfaces superhydrophobic with a water contact angle of 151 ± 4°. The roughness as well as the water contact angle increases on the superhydrophobic thin films with further increase in the size of the fluorinated silica nanoparticles in the films.     

Morphologies and Superhydrophobicity of Hybrid Film Surfaces Based on Silica and Fluoropolymer

Fluoropolymer and different kinds of silica particles were used for controlling surface chemistry and morphology, respectively. A superhydrophobic surface originated from strawberry-like or quincunx-shaped composite silica particles was obtained. The dual size particles are obtained by utilizing the graft of different modified silica particles with epoxy functional group and amine functional group, This makes the surface of film form a composite interface to have irregular binary structure which plays an essential role in trapping air between the substrate surface and the liquid droplets to be necessary for high contact angle and low contact angle hysteresis. The maximum contact angle for water on the hybrid film is about 174±2° and the contact angle hysteresis is less than 2°. The surface morphologies, roughness and the wettability on the surface of films containing different structural silica particles were compared. It was shown that the hierarchical irregularly structure with a low roughness factor and high air-trapped ratio is indispensable for superhydrophobic surface. Although this structural surfaces based on composite silica particles play a vital role in governing the surface wettability, it is necessary to combine with a low surface energy to make the surface superhydrophobic.     

Wettability control of ZnO nanoparticles for universal applications

Herein, a facile approach for the fabrication of a superhydrophobic nanocoating through a simple spin-coating and chemical modification is demonstrated. The resulting coated surface displayed a static water contact angle of 158° and contact angle hysteresis of 1°, showing excellent superhydrophobicity. The surface wettability could be modulated by the number of ZnO nanoparticle coating cycles, which in turn affected surface roughness. Because of its surface-independent characteristics, this method could be applicable to a wide range of substrates including metals, semiconductors, papers, cotton fabrics, and even flexible polymer substrates. This superhydrophobic surface showed high stability in thermal and dynamic conditions, which are essential elements for practical applications. Furthermore, the reversible switching of wetting behaviors from the superhydrophilic state to the superhydrophobic state was demonstrated using repeated chemical modification/heat treatment cycles of the coating films.     

碱式硫酸镁晶须复合SiO2纳米粒子制备高/低黏附性超疏水涂层

超疏水材料因性能独特,应用前景广阔而被广泛关注。本文采用碱式硫酸镁晶须(MOSWs)与二氧化硅纳米粒子制备超疏水涂层,首先对MOSWs及50 nm、500 nm SiO₂进行表面改性以降低表面能,然后基于混料实验将三者按比例混合以构造表面粗糙度,以接触角、滚动角及平均粗糙度R_a为响应变量建立回归模型,分析了混合分量的形貌、尺寸与混合比例对响应变量的影响,并探讨了超疏水涂层微观结构对水滴黏附性的影响以及粗糙度与超疏水性能之间的关系。结果表明：MOSWs复合SiO₂纳米粒子可制备具有不同黏附性的超疏水涂层,单独使用MOSWs可制备高黏附性超疏水涂层,其接触角达152.59°,涂层水平倒置水滴不滴落;而MOSWs与50 nm SiO₂以相同质量分数混合,可制备低黏附性超疏水涂层,其接触角达163.25°,滚动角可趋近0°。所制备涂层的平均粗糙度R_a值位于5～10μm之间时,接触角较大,滚动角较小,超疏水性能较佳。     

仿生超疏水棉织物的制备与表面分析

以荷叶表面微/纳米结构为参考模型,先用硅溶胶处理天然棉织物,再用N-β-氨乙基-γ-氨丙基聚二甲基硅氧烷(ASO-1)对其进行修饰,获得了微/纳米二元粗糙的超疏水织物,水滴在该织物表面接触角可达160.5°。场发射扫描电子显微镜(FE-SEM)观察发现超疏水纤维表面存在大量均匀分布的纳米微凸体。接触角分析表明织物织造过程中形成的微米级粗糙度和ASO-1膜的存在是织物疏水的主要原因,纳米微凸体能减少纤维与水的接触面积,提高水在纤维表面的接触角,使织物由疏水转变为超疏水。最后用X射线光电子能谱仪(XPS)证实了纤维表面SiO2粒子和ASO-1膜的存在。     

Superhydrophobic surfaces on cotton textiles by complex coating of silica nanoparticles and hydrophobization

By the complex coating of amino- and epoxy-functionalized silica nanoparticles on epoxy-functionalized cotton textiles to generate a dual-size surface roughness, followed by hydrophobization with stearic acid, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, or their combination, superhydrophobic surfaces were prepared. The static water contact angle of the most superhydrophobic sample as prepared reaches 170° for a 5 μL droplet. The wettability and morphology were investigated by contact angle measurement and scanning electron microscopy. Characterizations by Fourier transformation infrared spectroscopy, and thermal gravimetric analysis were also conducted.     

铝合金表面超疏水涂层的火焰喷雾热解法制备及其耐蚀性能

采用火焰喷雾热解与表面修饰相结合的方法在铝合金表面制备了具有一定耐蚀性能的超疏水表面。以六甲基二硅氧烷溶液为前驱液,通过火焰喷雾热解方法,首先在铝合金表面沉积SiO2纳米颗粒构建粗糙结构,再以氟硅烷溶液进行表面修饰,获得了具有154.9°静态接触角,滚动角<2°的超疏水表面。通过电化学测试,对比了构筑超疏水表面前后的铝合金样品的耐蚀性能。结果表明沉积层与低表面能物质协同作用,通过对腐蚀性离子的有效隔离,提高了铝合金基体的耐蚀性能。     

Fabrication of raspberry-like superhydrophobic hollow silica particles

Raspberry-like superhydrophobic hollow silica particles were prepared through a sacrificial polymer template method. The Stöber method was adopted to coat silica onto the surface of cationic polymethylmethacrylate(PMMA) particles by electrostatic interaction. The surface of the PMMA-silica composite particles exhibited raspberry-like morphology with high surface roughness. Hollow silica particles were then obtained by calcination to selectively remove the PMMA core. Subsequent modification with nonafluorohexyltriethoxysilane (NFH-silane) conferred superhydrophobicity on the hollow silica particles. The surface property of this particles were investigated by measuring their water contact angle, and the results showed that such perfluorinated raspberry-like hollow particles had unique superhydrophobic.     

纳米微结构涂层的制备及其超疏水性研究

通过简便的纳米粒子填充法制备超疏水表面,将SiO2纳米粒子与含氟丙烯酸酯聚合物按不同比例混溶制备出具有不同微结构的表面,并探讨了表面微结构对润湿性能的影响.接触角测试表明,随着SiO2纳米粒子含量的增加,涂层与水接触角逐渐增大,并且当SiO2与聚合物质量比＞1.2时发生突跃,显示出超疏水性质.采用X射线光电子能谱分析了涂层表面化学环境,通过扫描电子显微镜、原子力显微镜、孔结构分析等方法观察和分析了不同SiO2纳米粒子含量时涂层表面微结构.研究结果表明,涂层表面润湿特性的变化主要归因于其表面微结构的不同.并通过粗糙表面润湿理论的Wenzel模型和Cassie模型解释了表面微结构对润湿性的影响及接触角的突跃现象.     

Hierarchically structured superhydrophobic coatings fabricated by successive Langmuir-Blodgett deposition of micro-/nano-sized particles and surface silanization

The present study demonstrates the creation of a stable, superhydrophobic surface by coupling of successive Langmuir-Blodgett (LB) depositions of micro-?and nano-sized (1.5?μm/50?nm, 1.0?μm/50?nm, and 0.5?μm/50?nm) silica particles on a glass substrate with the formation of a self-assembled monolayer of dodecyltrichlorosilane on the surface of the particulate film. Particulate films, in which one layer of 50?nm particles was deposited over one to five sublayers of larger micro-sized particles, with hierarchical surface roughness and superhydrophobicity, were successfully fabricated. Furthermore, the present 'two-scale' (micro-?and nano-sized particles) approach is superior to the previous 'one-scale' (micro-sized particles) approach in that both higher advancing contact angle and lower contact angle hysteresis can be realized. Experimental results revealed that the superhydrophobicity exhibited by as-fabricated particulate films with different sublayer particle diameters increases in the order of 0.5?μm>1.0?μm>1.5?μm. However, no clear trend between sublayer number and surface superhydrophobicity could be discerned. An explanation of superhydrophobicity based on the surface roughness introduced by two-scale particles is also proposed.     

Facile preparation of superhydrophobic surface with high adhesive forces based carbon/silica composite films

Glass substrates modified by carbon/silica composites are fabricated through a two-step process for the preparation of a superhydrophobic surface (water contact angle ≥ 150°). Carbon nanoparticles were first prepared through a deposition process on glass using a hydrothermal synthesis route, then the glass was modified by SiO₂ using the hydrolysis reaction of tetraethylorthosilicate at room temperature. It is not only a facile method to create a superhydrophobic surface, but also helps to form a multi-functional surface with high adhesive forces.     

Large-scale assembly of colloidal nanoparticles and fabrication of periodic subwavelength structures

This paper reports a simple and scalable spin-coating technique for assembling 70?nm silica nanoparticles into non-close-packed colloidal crystals over a large area. The thickness of the shear-aligned colloidal crystals can be controlled from hundreds of layers to a single monolayer by adjusting the spin-coating conditions. We further demonstrate that the spin-coated colloidal monolayers can be used as structural templates to pattern sub-100?nm pillar arrays directly on silicon substrates. The resulting subwavelength-structured pillar arrays exhibit excellent broadband antireflective and superhydrophobic properties, which are promising for developing self-cleaning antireflection coatings for crystalline silicon solar cells. This bottom-up approach enables large-scale production of periodic nanostructures with resolution beyond the optical diffraction limit that have important technological applications ranging from high-density data storage and optoelectronics to biological sensing and subwavelength optics.     

A non-fluorinated mechanochemically robust volumetric superhydrophobic nanocomposite

The widespread use of water-repellent superhydrophobic surfaces is limited by the inherent fragility of their micro-and nanoscale roughness, which is prone to damage and degradation. Here, we report a non-fluorinated volumetric superhydrophobic nanocomposites that demonstrate mechanochemical robustness. The nanocomposites are produced through the addition of microscale diatomaceous earth and nanoscale fumed silica particles to high-temperature vulcanized silicone rubber. The water-repellency of the surface and bulk of nanocomposites having 120 phr of filler was determined based on the water contact angle and contact angle hysteresis. We compared the water-repellency of nanocomposites of differing diatomaceous earth to fumed silica mass ratios. Increasing the amount of diatomaceous earth enhanced the water-repellency of the nanocomposite surface, whereas an increased amount of fumed silica improved the water-repellency of the bulk material. Moreover, increasing the diatomaceous earth/fumed silica mass ratio improved the cross-linking density and hardness values of the nanocomposite.Despite being subjected to a range of mechanical durability tests, including sandpaper abrasion,knife scratching, tape peeling, water jet impact, and sandblasting, the nanocomposite maintained a water contact angle of 163. and contact angle hysteresis of 2°. When the water-repellency of the prepared nanocomposites eventually deteriorated, we restored their superhydrophobicity by removing the upper surface of the nanocomposite. This extraordinary robustness stems from the embedded low surface energy micro/nanostructures distributed throughout the nanocomposite. We also demonstrated the chemical stability, UV resistance, and self-cleaning abilities of the nanocomposite to illustrate the potential for real-life applications of this material.     

Transforming an intrinsically hydrophilic polymer to a robust self-cleaning superhydrophobic coating via carbon nanotube surface embedding

A single-step method, including surface embedding of nanoparticles into a polymer matrix, was employed to fabricate superhydrophobic thermoplastic polyurethane (TPU)/carbon nanotube (CNT) nanocomposite coatings. The main aim was to prove that surface roughness plays a more important role in designing superhydrophobic surfaces as compared with the surface energy. Therefore, TPU was used as the model hydrophilic polymer and CNTs were employed as non-hydrophobic nanoparticles. It was found that, at a certain pressing time, CNTs form an efficient hair-like morphology which is able to highly enclose air within its as-formed pores leading to superhydrophobic behavior. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and confocal microscopy were utilized for characterization of samples. SEM and confocal microscopy results proved that surface roughness played the key role in the final wettability behavior. Based on XPS results, it was also found that a very long pressing time led to partial migration of TPU macromolecules into the CNTs' pores, and hence, superhydrophobicity was reduced. The effects of mechanical abrasion and nanoparticle type on wettability behavior of samples were evaluated as well. In conclusion, it is suggested that surface roughness factor should be highly considered in designing superhydrophobic nanocomposite coatings rather than surface energy.     

One-pot preparation of fluorinated mesoporous silica nanoparticles for liquid marble formation and superhydrophobic surfaces

One-pot synthesis of fluorinated mesoporous silica nanoparticles (FMSNs) is reported. Uniform mesoporous nanoparticles are prepared by condensation of tetraethyl orthosilicate (TEOS) and fluoroalkyl containing organotriethoxy silane monomers, respectively. The method enables selective deposition of fluorine atoms on the surface of the particles. FMSNs are used to prepare stable liquid marbles with water. An organo-modified silica sol is used with FMSNs to prepare mechanically stable superhydrophobic surfaces (water contact angle of 161°). The mechanical stability of the surface is investigated with water dripping and adhesive tape tests. The prepared FMSNs are promising building blocks for robust, large-area, and multifunctional self-cleaning surfaces.     

Al2O3微滤膜的超疏水改性研究

采用多层自组装技术在Al₂O₃微滤膜表面制备TiO₂纳米涂层, 并利用1H,1H,2H,2H-全氟辛基乙基三乙氧基硅烷(PFDS)对其表面进行氟化处理, 获得超疏水改性膜。通过X射线衍射仪, 傅立叶变换红外光谱仪, 原子力显微镜, 水接触角测试仪和扫描电子显微镜对改性膜进行表征。分析了TiO₂纳米涂层的晶型结构, 探讨了TiO₂沉积时间与改性膜表面粗糙度和疏水性之间的关系, 研究了PFDS改性次数对膜表面形貌和疏水性能的影响规律。结果表明: 在600℃退火1 h后, 获得锐钛矿结构的TiO₂纳米涂层。随TiO₂沉积时间的延长, 膜表面粗糙度增大, 水滴在膜表面的接触由Wenzel状态转变为Cassie状态; 当TiO₂沉积时间为50?min, PFDS改性3次时, 获得理想的微纳米二级超疏水表面形貌, 水接触角达到174.5°。     

Scalable Fabrication of Superhydrophobic Coating with Rough Coral Reef-Like Structures for Efficient Self-Cleaning and Oil-Water Separation: An Experimental and Molecular Dynamics Simulation Study

Superhydrophobic coating has a great application prospect in self-cleaning and oil-water separation but remains challenging for large-scale preparation of robust and weather-resistant superhydrophobic coatings via facile approaches. Herein, this work reports a scalable fabrication of weather-resistant superhydrophobic coating with multiscale rough coral reef-like structures by spraying the suspension containing superhydrophobic silica nanoparticles and industrial coating varnish on various substrates. The coral reef-like structures effectively improves the surface roughness and abrasion resistance. Rapid aging experiments (3000 h) and the outdoor building project application (3000 m²) show that the sprayed superhydrophobic coating exhibits excellent self-cleaning properties, weather resistance, and environmental adaptability. Moreover, the combined silica-coating varnish-polyurethane (CSCP) superhydrophobic sponge exhibits exceptional oil-water separation capabilities, selectively absorbing the oils from water up to 39 times of its own weight. Furthermore, the molecular dynamics (MD) simulation reveals that the combined effect of higher surface roughness, smaller diffusion coefficient of water molecules, and weaker electrostatic interactions between water and the surface jointly determines the superhydrophobicity of the prepared coating. This work deepens the understanding of the anti-wetting mechanism of superhydrophobic surfaces from the perspective of energetic and kinetic properties, thereby paving the way for the rational design of superhydrophobic materials and their large-scale applications.     

Highly Stretchable Superhydrophobic Composite Coating Based on Self‐Adaptive Deformation of Hierarchical Structures

With the rapid development of stretchable electronics, functional textiles, and flexible sensors, water‐proof protection materials are required to be built on various highly flexible substrates. However, maintaining the antiwetting of superhydrophobic surface under stretching is still a big challenge since the hierarchical structures at hybridized micro‐nanoscales are easily damaged following large deformation of the substrates. This study reports a highly stretchable and mechanically stable superhydrophobic surface prepared by a facile spray coating of carbon black/polybutadiene elastomeric composite on a rubber substrate followed by thermal curing. The resulting composite coating can maintain its superhydrophobic property (water contact angle ≈170° and sliding angle <4°) at an extremely large stretching strain of up to 1000% and can withstand 1000 stretching–releasing cycles without losing its superhydrophobic property. Furthermore, the experimental observation and modeling analysis reveal that the stable superhydrophobic properties of the composite coating are attributed to the unique self‐adaptive deformation ability of 3D hierarchical roughness of the composite coating, which delays the Cassie–Wenzel transition of surface wetting. In addition, it is first observed that the damaged coating can automatically recover its superhydrophobicity via a simple stretching treatment without incorporating additional hydrophobic materials.     

Nanosilica-decorated sponges for efficient oil/water separation: role of nanoparticle’s type and concentration

Oil absorption by porous materials is currently regarded as a very efficient method for water purification and oil spill cleanup. Simultaneous induction of superhydrophobic and superoleophilic properties into porous materials was conducted in this study via surface decoration of sponges by nanosilica. The main aim was to investigate the effects of nanosilica concentration on the final wetting behavior of the sponges. To this end, the sponges were treated with both modified and unmodified nanosilica particles through a simple dipping process. It was found that only a moderate concentration of nanoparticles (2 vol%) causes the sponges surface to be uniformly decorated with silica. Based on X-ray photoelectron spectroscopy results, it was postulated that surface energy of the sponges was a more influential factor in the final wetting behavior as compared with the surface roughness. The values of oil absorption capacity were varied in the range of 51–72 g/g (gram of oil per gram of sponge) for the superhydrophobic sample using four different oils and organic liquids. It was concluded that the prepared sponges definitely possess promising potential in the separation of oil/water mixtures provided that an optimum concentration of nanosilica with proper surface modification is used.     

Vi-PDMS/S-SiO2超疏水聚酯纤维织物的制备及性能研究

目的 基于普通织物材料防水性较差的问题,制备一种具有超疏水涂层的聚酯纤维织物,并对其性能进行研究。方法 以聚酯纤维织物为基材,基于紫外光固化技术通过浸涂法,使用商用气相纳米SiO₂颗粒(S-SiO₂)、端乙烯基聚二甲基硅氧烷(Vi-PDMS)在织物表面构筑微纳粗糙结构,获得超疏水的织物。采用扫描电子显微镜、水接触角测量仪对其微观结构和疏水性能进行表征,并通过机械摩擦实验对其超疏水稳定性进行考察。结果 当Vi-PDMS和S-SiO₂质量比为1∶4时,选择交联剂为三羟甲基丙烷三丙烯酸酯(TMPTA)制备的聚酯纤维织物表面的水接触角可达到151°,滚动角可达9°;且经过40次循环摩擦后,其表面水接触角仍大于140°,具有一定的耐磨性。结论 基于紫外光固化技术,采用操作简便的浸涂法制备的聚酯纤维织物具有优异的超疏水性能和一定的耐磨性,为织物超疏水性能研究提供参考,有望应用于超疏水聚酯纤维织物领域。