稳定超疏水性表面的理论进展

自然界中很多动植物都具有稳定的超疏水性, 它们既拥有高接触角, 又拥有低滚动角, 且能长期稳定存在.通过对它们的研究, 发现表面的润湿性与表面的化学成分、表面的几何形貌有关, 并且表面几何结构的影响更为显著, 甚至可以实现由亲水性表面向超疏水转变. 虽然目前在这个领域已经有大量的实验验证了表面粗糙结构的重要作用, 但是对于表面微纳米结构对表面疏水性机理的理论研究还并不完善. 本文详细介绍了超疏水表面的基本理论及其适用性、 接触角滞后现象, 分别从经典理论和能量的观点探讨了润湿状态转化发生的条件, 重点介绍了通过仿生理念对表面几何形貌的优化设计, 包括单尺度和多尺度表面结构对于设计稳定超疏水表面的作用. 最后, 对超疏水理论的不足和未来发展进行了展望. 关键词： 超疏水 仿生 接触角 滞后     

纳米结构超疏水表面冷凝现象的三维格子玻尔兹曼方法模拟

采用三维多相流格子玻尔兹曼方法 (lattice Boltzmann method, LBM),对纳米结构超疏水表面液滴的冷凝行为进行模拟研究.通过Laplace定律和光滑表面的本征接触角理论对三维LBM模型进行定量验证.模拟分析了超疏水表面纳米阵列的几何尺寸和润湿性的局部不均匀性对冷凝液滴形核位置和最终润湿状态的影响规律.结果表明,较高的纳米阵列使液滴在纳米结构间隙的上部侧面和底部优先形核长大,通过采用上下不均匀的间隙可避免液滴在底部形核长大,而在上部侧面形核的冷凝液滴在生长过程中向上运动,其润湿状态由Wenzel态转变为Cassie态;较低的纳米阵列使液滴在纳米结构底部优先形核长大,液滴的最终润湿状态为Wenzel态;润湿性不均匀的纳米结构表面使液滴在阵列顶端亲水位置处优先形核长大,成为Cassie态.冷凝液滴在不同几何尺寸的纳米结构表面上的最终润湿状态的模拟结果与文献报道的实验结果符合良好.通过模拟还发现,冷凝液滴在生长过程中的运动行为与液滴统计平均作用力的变化有关.本文的LBM模拟再现了三维空间中液滴的形核、长大和润湿状态转变等物理现象.     

微液滴在超疏水表面的受迫振动及其接触线的固着-移动转变

利用高速摄影技术对超疏水表面液滴振动的动态行为进行观测,研究液滴在不同频率下的振动特性. 实验发现,液滴的共振频率满足Rayleigh方程,微液滴在超疏水表面具有自由液滴的振动性质. 在80–200 Hz的驱动频率范围内,接触线出现了明显的固着-移动现象,液滴的振动频率是驱动频率的一半,液滴振动时的形变较大. 当驱动频率大于200 Hz时,接触线基本固着,液滴的振动频率近似等于驱动频率,液滴共振时的形态边缘始终有节点存在. 分析表明,液滴对外界驱动的不同响应与接触线的振荡行为和变形程度密切相关 关键词： 超疏水表面 受迫振动 共振 接触线     

Fabrication of superhydrophilic or superhydrophobic self-cleaning metal surfaces using picosecond laser pulses and chemical fluorination

Bioinspired superhydrophilic/phobic self-cleaning surfaces have recently drawn a lot of interest in both fundamental and applied research. A hybrid method to produce the self-cleaning property of micro/nanostructured surface using ultra-fast laser pulses followed by chemical fluorination is proposed. The typical micro/nanocomposite structures that form from microporous arrays and microgroove groups have been processed by picosecond laser on titanium alloy surface. The surface hydrophilic/phobic and self-cleaning properties of micro/nanostructures before and after fluorination with fluoroalkyl-silane were investigated using surface contact angle measurements. The results indicate that surface properties change from hydrophilic to hydrophobic after fluorination, and the micro/nanostructured surface with increased roughness contributes to the improvement of surface hydrophobicity. The micro/nanomodification can make the original hydrophilic titanium alloy surface more hydrophilic or superhydrophilic. It also can make an originally hydrophobic fluorinated titanium alloy surface more hydrophobic or superhydrophobic. The produced micro/nanostructured titanium alloy surfaces show excellent self-cleaning properties regardless of the fluorination treatment, although the fluorinated surfaces have slightly better self-cleaning properties. It is found that surface treatment using ultra-fast laser pulses and subsequent chemical fluorination is an effective way to manipulate surface wettability and obtain self-cleaning properties.     

Simulation solution for micro droplet impingementon a flat dry surface

This paper presents a computational fluid dynamics approach for micro droplet impacting on a flat dry surface. A two-phase flow approach is employed using FLUENT VOF multiphase model to calculate the flow distributions upon impact. The contact line velocity is tracked to calculate the dynamic contact angle through user defined function program. The study showed that the treatment of contact line velocity is crucial for the accurate prediction of droplet impacting on poor wettability surfaces. On the other hand, it has much less influence on the simulation of droplet impacting on good wettability surfaces. Good fit between simulation results and experimental data is obtained using this model.     

Fabrication of superhydrophobic surfaces on zinc substrates

Stable superhydrophobic surfaces were fabricated on the zinc substrates through simple silver replacement deposition process with the modification of octadecyl mercaptan. The effects of reaction conditions on the surface morphology and wettability of the prepared surfaces were carefully studied. The results show that the fabrication of a best superhydrophobic surface depends largely on the moderate reactant concentration. When the concentration of AgNO₃ solution was 2 mmol/L, the zinc substrate was covered by a dendritic outline structure. Aggregated silver nanoparticles were formed on the substrate in accordance with some certain laws, exhibiting great surface roughness. The typical hierarchical micro-nanostructures, flower-like structures and porous structures also could be found from the SEM images. The maximal water contact angle (CA) value of about 161 ± 2°, and the minimal sliding angle (SA) of about 2° were obtained under the same reaction condition.     

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.     

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     

液滴在梯度微结构表面上的铺展动力学分析

本文通过改变肋柱宽度和间距, 构造了二级和多级梯度微结构表面, 采用格子-Boltzmann方法对液滴在两种梯度表面上的铺展过程进行了研究, 探析液滴运动的机理和调控方法. 结果表明, 在改变肋柱间距的二级梯度表面上, 当液滴处于Cassie态时, 接触角滞后大小与粗糙度梯度成正比关系; 当液滴从Cassie态转换为Wenzel态或介于两者之间的不稳定态时, 这一正比关系不再遵循. 在改变肋柱宽度的二级梯度表面上, 接触角滞后大小与粗糙度梯度始终成正比关系. 在多级梯度表面上, 随液滴初始半径增大, 接触角滞后减小, 但液滴平衡位置相较于初始位置偏离增大. 对梯度微结构表面上液滴运动和接触角滞后的定量分析, 可为实现梯度微结构表面液滴运动调控提供理论依据.     

超疏水表面液滴的振动特性及其与液滴体积的关系

超疏水表面液滴的振动特性与接触线的移动、液滴体积、基底振幅等因素密切相关.本文在基底振幅较小且恒定的条件下,研究了超疏水表面液滴的共振振幅、模式区间、共振频率等振动特性及其与液滴体积(20—500μL)的关系.此外,将基于一般性疏水表面建立的Noblin共振频率计算模型应用于超疏水表面,并提出虚驻点的概念,借此对模...     

剪切变稀液滴撞击不同浸润性壁面的数值模拟研究

基于有限元法,采用水平集方法捕捉相界面的移动,构建了液滴撞击固体壁面的数值模型.通过修正的幂律模型描述流体的非牛顿剪切变稀特性,探讨了剪切变稀特性对液滴撞击固体壁面后铺展行为的影响,分析了撞击不同浸润性壁面时剪切变稀特性对液滴撞击壁面行为的影响差异.研究结果表明:随着幂律指数m的减小,液滴撞击过程中的黏性耗散减小,液滴的形貌变化及无量纲参数变化更为显著.接触角为55°的情况下:当m降低至0.85时,液滴铺展过程中开始出现显著区别于牛顿流体液滴的振荡现象;当m降低至0.80时,液滴在回缩过程中会出现中心液膜断裂的情况.接触角为100°时,剪切变稀液滴均会出现振荡行为,振荡幅度随着m的减小而增大.接触角为160°时,牛顿流体液滴与剪切变稀液滴均会在回缩过程中弹起,但剪切变稀液滴的弹起速度更快.此外,基于数值计算结果,本文提出了接触角为55°情况下剪切变稀液滴撞击壁面后的最大无量纲铺展直径预测模型.     

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.     

A comparative study of droplet impact dynamics on a dual-scaled superhydrophobic surface and lotus leaf

The impact dynamics of water droplets on an artificial dual-scaled superhydrophobic surface was studied and compared with that of a lotus leaf with impact velocity V up to 3 m/s. The lower critical impact velocity for the bouncing of droplets was about 0.08 m/s on both surfaces. At relatively low impact velocities, regular rebound of droplets and air bubble trapping and flow jetting on both surfaces were observed as V was increased. For intermediate V, partial pinning and rebound of droplets were found on the artificial dual-scaled surface due to the penetration of the droplets into the micro- and nano-scale roughness. On the lotus leaf, however, the droplets bounced off with intensive vibrations instead of being partially pinned on the surface because of the irregular distribution of microbumps on the leaf. As the impact velocity was sufficiently high, droplet splashing occurred on both surfaces. The contact time and restitution coefficient of the impinging droplets were also measured and discussed.     

实验观测液滴撞击倾斜表面液膜的特殊现象

采用高速摄像仪以10000帧/s 的拍摄速度对液滴撞击倾斜表面液膜的过程进行了实验观测, 分析了液滴撞击倾斜表面液膜后的铺展、水花形成以及飞溅等现象, 考察了撞击角对液滴震荡变形过程的影响; 在此基础上, 定量讨论了液滴铺展速度随时间的变化规律, 揭示了液滴撞击速度和撞击角对前、后铺展因子及初始铺展速度的影响.观测发现, 在撞击角为28.0°–74.7°范围内, 随着撞击角的减小, 液滴在液膜表面的震荡变形程度增大; 前铺展因子随撞击速度的增大而增大, 随撞击角的减小而增大; 后铺展因子随撞击速度的增大几乎不发生变化, 但是随撞击角的增大而增大; 液滴初始铺展速度随撞击速度和撞击角的升高而增大. 关键词： 液滴撞击 倾斜液膜 铺展因子 铺展速度     

Numerical modeling of condensate droplet on superhydrophobic nanoarrays using the lattice Boltzmann method

In the present study,the process of droplet condensation on superhydrophobic nanoarrays is simulated using a multicomponent multi-phase lattice Boltzmann model.The results indicate that three typical nucleation modes of condensate droplets are produced by changing the geometrical parameters of nanoarrays.Droplets nucleated at the top(top-nucleation mode),or in the upside interpillar space of nanoarrays(side-nucleation mode),generate the non-wetting Cassie state,whereas the ones nucleated at the bottom corners between the nanoarrays(bottom-nucleation mode) present the wetting Wenzel state.Time evolutions of droplet pressures at the upside and downside of the liquid phase are analyzed to understand the wetting behaviors of the droplets condensed from different nucleation modes.The phenomena of droplet condensation on nanoarrays patterned with different hydrophilic and hydrophobic regions are simulated,indicating that the nucleation mode of condensate droplets can also be manipulated by modifying the local intrinsic wettability of nanoarray surface.The simulation results are compared well with the experimental observations reported in the literature.     

液滴撞击等温固体平壁的数值模拟

建立了液滴撞击等温固体平壁的物理和数学模型,数值模拟了撞击后液滴的变形和反弹过程,将模拟结果与文献中的实验结果做了比较,两者吻合较好,表明所采用的模型可以模拟液滴在水平壁面上的运动形态.通过比较不同条件下铺展因素随时间的变化规律,分析了液滴碰撞速度、初始接触角对变形过程的影响.     

Water contact angles on charged surfaces in aerosols

Interactions between water and solid substrates are of fundamental importance to various processes in nature and industry. Electric control is widely used to modify interfacial water, where the influence of surface charges is inevitable. Here we obtain positively and negatively charged surfaces using LiTaO₃ crystals and observe that a large net surface charge up to 0.1 C/m² can nominally change the contact angles of pure water droplets comparing to the same uncharged surface. However, even a small amount of surface charge can efficiently increase the water contact angle in the presence of aerosols. Our results indicate that such surface charges can hardly affect the structure of interfacial water molecular layers and the morphology of the macroscopic droplet, while adsorption of a small amount of organic contaminants from aerosols with the help of Coulomb attraction can notably decrease the wettability of solid surface. Our results not only provide a fundamental understanding of the interactions between charged surfaces and water, but also help to develop new techniques on electric control of wettability and microfluidics in real aerosol environments.     

液滴撞击加热壁面传热实验研究

本文采用高速摄像仪对水滴和乙醇液滴撞击加热壁面后的蒸发过程进行了实验观测, 分析了液滴撞击加热壁面后的蒸发特性参数. 实验中, 两种液体初始温度均为20 ℃, 不锈钢壁面初始温度范围为68-126℃. 水滴初始直径为2.07 mm, 撞击壁面时Weber 数为2-44; 乙醇液滴初始直径为1.64 mm, Weber数为3-88. 结果表明, 液滴受到重力、表面张力及流动性的影响, 在蒸发过程的大部分时间内, 水滴高度持续降低而接触直径几乎不变; 蒸发后期, 液滴发生回缩, 水滴的接触直径、高度和接触角出现振荡现象. 乙醇液滴的接触角随时间的增加呈现先减小随后保持不变的趋势, 而接触直径和高度则持续减小, 直到液滴完全蒸发. 液滴蒸发总时长与液体物性和壁面温度有关, 随壁面温度的升高而减小, 与液滴撞击壁面时的Weber 数无关. 同时, 随着壁面温度的升高, 液滴显热部分占总换热量的比重增大, 显热部分能量不可忽略, 本文实验条件下得到水滴的平均热流密度为0.014-0.110 W·mm^-2.     

Fabrication of superhydrophobic surfaces based on ZnO-PDMS nanocomposite coatings and study of its wetting behaviour

Superhydrophobic surfaces based on ZnO-PDMS nanocomposite coatings are demonstrated by a simple, facile, time-saving, wet chemical route. ZnO nanopowders with average particle size of 14 nm were synthesized by a low temperature solution combustion method. Powder X-ray diffraction results confirm that the nanopowders exhibit hexagonal wurtzite structure and belong to space group P63mc. Field emission scanning electron micrographs reveal that the nanoparticles are connected to each other to make large network systems consisting of hierarchical structure. The as formed ZnO coating exhibits wetting behaviour with Water Contact Angle (WCA) of ∼108°, however on modification with polydimethylsiloxane (PDMS), it transforms to superhydrophobic surface with measured contact and sliding angles for water at 155° and less than 5° respectively. The surface properties such as surface free energy (γ_p), interfacial free energy (γ_pw), and the adhesive work (W_pw) were evaluated. Electron paramagnetic resonance (EPR) studies on superhydrophobic coatings revealed that the surface defects play a major role on the wetting behaviour. Advantages of the present method include the cheap and fluorine-free raw materials, environmentally benign solvents, and feasibility for applying on large area of different substrates.