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.     

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.     

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     

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.     

液滴在粗糙固体表面上的铺展特性

本文建立了粗糙固体表面上液滴铺展过程的理论模型并采用了格子Boltzmann方法进行数值模拟,研究了粗糙与光滑表面上液滴铺展过程的形貌变化。研究结果表明,无论表面光滑还是粗糙,液滴都沿着半径方向逐渐铺展,整体首先呈帽形,随着时间的推移,液滴在表面铺展成一平面。粗糙表面与光滑表面铺展特性间的差异主要在于粗糙表面液滴受到粗糙元干扰,其铺展形状随时间推移由圆形向八边形过渡.粗糙元间隙的增大导致液滴润湿半径增大,液滴厚度沿半径方向变化梯度降低。     

基于异形微结构表面的低表面能工质液滴润湿特性研究

尺寸效应是探索异形微结构表面液滴润湿特性的研究基础。本文以单凹角异形微结构和双凹角异形微结构为研究对象,通过数值模拟,得到了微结构的几何参数尺寸与低表面能液滴润湿特性间的变化规律。对于单凹角异形微结构,临界本征接触角随着悬臂长度减小呈指数增加,微结构间的间距直接影响着表观接触角的大小,悬臂高度的增加不利于疏液状态的实现。对于双凹角异形微结构,悬臂长度和悬臂高度不是影响液滴润湿的主要因素,微结构间的间距和支柱高度共同作用下决定了液滴润湿状态。     

微纳复合结构表面稳定润湿状态及转型过程的热力学分析

自然界中的微纳复合结构超疏水表面由于其独特的润湿性质引起了人们的广泛关注, 大量实验研究表明了仿生人工微纳复合结构表面润湿性能的优越性, 然而液滴在微纳复合结构表面的润湿状态和转型过程的理论研究还并不完善. 本文首先用热力学方法分析了液滴在微纳复合结构表面可能存在的所有状态(四种稳定润湿状态和五种亚稳态到稳定态转型中的过渡态), 推导出了相应的能量表达式及表观接触角方程; 基于最小能量原理, 确定液滴在微纳复合结构表面的稳定状态, 较以往模型相比, 能够更好的预测已有的实验结果; 其次研究了微纳结构尺寸对稳定润湿状态和亚稳态到稳定态转型过程的影响; 最后提出了微纳复合结构表面设计原则, 即确定“超疏水稳定区”尺寸范围, 为超疏水表面的制备提供理论依据.     

液滴撞击微尺度矩形沟槽表面的数值研究

采用CLSVOF方法建立了液滴撞击微尺度矩形沟槽表面的三维数值模型,对撞击过程中的动态特性及传热特性进行了数值研究。分析了液滴在微尺度矩形沟槽表面的润湿状态,给出了液滴润湿状态转变的临界速度。研究了表面接触角及撞击速度对液滴铺展特性的影响。数值研究结果表明:微尺度沟梢结构会使液滴在撞击后产生横纵差异。液滴的最大铺展因子随着撞击表面接触角的增大而减小,随着撞击速度的增大而增大。液滴撞击微尺度矩形沟槽表面后,撞击表面的热流量先增大后减小。撞击表面的最大热流量受到表面接触角与沟槽深度的耦合作用,撞击表面的最大热流量随着表面接触角的增大而减小。     

SiC表面圆环槽边缘效应实验研究

基于固体边缘效应,对碳化硅(SiC)表面激光加工圆环形沟槽的润湿特性进行实验研究,通过分析去离子水在圆环槽上的润湿性能及其在边缘处的铺展行为,获得了环槽深度与环槽宽度对液滴在边缘处最大表观接触角的影响规律.结果表明,SiC圆环槽阻碍液滴铺展,光滑基体表面上接触角为70°,激光加工圆环槽深度为290μm,宽度为1 mm时,接触角可达138.5°.随槽深的增大,接触角呈现先增大后趋于稳定的趋势,临界槽深为80μm.当槽深小于该极值时,接触角随槽深的增大而线性增大;当槽深大于该极值时,液滴处于稳定钉扎状态,接触角趋于稳定,其稳定值符合Gibbs不等式.环槽宽度存在一临界值40μm.当槽宽低于该值时,液滴接触环槽外缘后越过沟槽继续在平面上铺展;当槽宽大于该值时,接触角趋于稳定,液滴沿边缘铺展.     

纳秒激光加工微孔阵列铝膜的润湿性的实验及模拟

润湿性与固体材料表面的微观几何结构和表面化学组成密切相关,是固体材料表面的一个重要特性体现。文章用实验和仿真的方式研究了双面超亲水和双面超疏水表面的润湿特性。首先采用纳秒激光钻孔技术在厚度为35μm的铝箔上加工微孔阵列,得到了双面超亲水铝膜表面;然后将铝膜在十七氟癸基三乙氧基硅烷(PFDTES)浸泡20h,铝膜从双面超亲水表面改性为双面超疏水表面;研究了改性前后铝膜的液滴渗透情况。用COMSOL Multiphysics中的两相流分析模块研究了基于双面超亲水和双面超疏水状态下的微孔通道内的水渗透过程,仿真结果和实验结果基本一致,对实验起指导作用。     

The apparent state of droplets on a rough surface

The factors influencing the state and wetting transition of droplets on a rough surface are both complex and obscure. The change in wetting is directly reflected by changes under the contact condition of the droplets with the surface. The recent study about the wettability of the superhydrophobic surface under the condensing condition arouses the new understanding about the apparent state of droplets on a rough surface. In this work, to validate the existence of droplets in an intermediate state, a microscale pillar topological polydimethylsiloxane (PDMS) surface was manufactured and its wettability under various conditions was studied. According to the experimental data, it is proposed that the wetting state of a rough surface may be embodied using the contact area ratio of a solid/liquid/gas droplet with the projective plane. A general calculation model for the apparent contact angle of droplets is given and expressed diagrammatically. It is found that the measured apparent contact angles of droplets at different states on the surface falls within the range predicted by our proposed equation. Supported by the National Natural Science Foundation of China (Grant No. 50606025)     

微矩形凹槽表面液滴各向异性浸润行为的研究

受自然界启发,仿生微结构被广泛用于调控固-液界面的性质.研究显示,液滴在微结构表面的各向异性浸润行为可用于实现微流动方向和速度的控制,且其各向异性浸润与微结构的尺寸和分布等密切相关.本文研究了微矩形凹槽尺寸对液滴各向异性浸润行为的影响规律.结果显示,液滴沿平行沟槽的方向具有较小的运动阻力、易铺展,因此具有较小接触角;而垂直于沟槽方向,由于沟槽的阻隔作用具有较大运动阻力,因而具有较大接触角,并且在垂直方向液滴的浸润过程是三相线一系列钉扎和跳跃行为.在微矩形凹槽表面,液滴沿平行方向接触角θ//与肋板宽度R和凹槽宽度G密切相关,其值与表面固体面积比成反比;而垂直于沟槽方向的接触角θ⊥随肋板宽度R和凹槽宽度G变化基本保持不变.同时各向异性液滴的变形比L/W、特征方向接触角比值θ⊥/θ//与表面固体面积比成正比.研究结果有助于加深理解微结构表面浸润行为的机制,并为微矩形凹槽在微流动控制方向的应用提供技术支持.     

The debate on the dependence of apparent contact angles on drop contact area or three-phase contact line: A review

A sessile drop is an isolated drop which has been deposited on a solid substrate where the wetted area is limited by the three-phase contact line and characterized by contact angle, contact radius and drop height. Although, wetting has been studied using contact angles of drops on solids for more than 200 years, the question remains unanswered: Is wetting of a rough and chemically heterogeneous surface controlled by the interactions within the solid/liquid contact area beneath the droplet or only at the three-phase contact line? After the publications of Pease in 1945, Extrand in 1997, 2003 and Gao and McCarthy in 2007 and 2009, it was proposed that advancing, receding contact angles, and contact angle hysteresis of rough and chemically heterogeneous surfaces are determined by interactions of the liquid and the solid at the three-phase contact line alone and the interfacial area within the contact perimeter is irrelevant. As a consequence of this statement, the well-known Wenzel (1934) and Cassie (1945) equations which were derived using the contact area approach are proposed to be invalid and should be abandoned. A hot debate started in the field of surface science after 2007, between the three-phase contact line and interfacial contact area approach defenders. This paper presents a review of the published articles on contact angles and summarizes the views of the both sides. After presenting a brief history of the contact angles and their measurement methods, we discussed the basic contact angle theory and applications of contact angles on the characterization of flat, rough and micropatterned superhydrophobic surfaces. The weak and strong sides of both three-phase contact line and contact area approaches were discussed in detail and some practical conclusions were drawn.     

Phase field modeling of hysteresis in sessile drops

We propose a novel approach to describe wetting of plane solid surfaces by liquid drops. A two-dimensional nonconserved phase field variable is employed to distinguish between wetted and nonwetted regions on the surface. The imbalance in the Young's force provides for the exchange of relative stability of the two phases. The three-phase contact line tension arises from the gradient energy and contact angle hysteresis from the kinetic coefficient. Using this theory, we discuss contact angle hysteresis on chemically heterogeneous surfaces. We show significant departure from the classical Cassie theory, which is attributed to defect pinning of the continuous triple line.     

Experimental and theoretical evaluation of wettability on micro/nano hierarchically engineered surfaces based on robust micro-post-arrayed- and highly ordered nano-rippled-structures

This paper reports a simple approach for demonstrating a micro/nano hierarchical surface, ensuring both geometrical regularity and mechanical stability, for improving the hydrophobicity. The proposed dual-scale hierarchical surfaces were realized simply by combining the highly self-ordered ripple-like nano patterns with the robust micro-post arrays, based on the cost-effective nonlithographic chemical oxidation process and well-established microfabrication technologies. The wettability of the proposed nano-scale mono- and micro/nano dual-roughened surfaces was evaluated by measuring the apparent contact angles (ACAs), and analyzed theoretically with analytic models based on the Wenzel, Cassie, and combined wetting theories. Through experimental and theoretical observations, it was found that the proposed micro/nano hierarchical structures can improve the wetting property and the superhydrophobic robustness of high- and low-density micro-post arrayed surfaces, respectively.     

微液滴在不同能量表面上润湿状态的分子动力学模拟

微小液滴在不同能量表面上的润湿状态对于准确预测非均相核化速率和揭示界面效应影响液滴增长微观机理具有重要意义. 通过分子动力学模拟, 研究了纳米级液滴在不同能量表面上的铺展过程和润湿形态. 结果表明, 固液界面自由能随固液作用强度增加而增加, 并呈现不同液滴铺展速率和润湿特性. 固液作用强度小于1.6的低能表面呈现疏水特征, 继续增强固液作用强度时表面变为亲水, 而固液作用强度大于3.5的高能表面上液体呈完全润湿特征. 受微尺度条件下非连续、非对称作用力影响, 微液滴气液界面存在明显波动, 呈现与宏观液滴不同的界面特征. 统计意义下, 微小液滴在不同能量表面上铺展后仍可以形成特定接触角, 该接触角随固液作用强度增加而线性减小, 模拟结果与经典润湿理论计算获得的结果呈现相似变化趋势. 模拟结果从分子尺度为核化理论中的毛细假设提供了理论支持, 揭示了液滴气液界面和接触角的波动现象, 为核化速率理论预测结果和实验测定结果之间的差异提供了定性解释.     

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.