Nanodroplets on rough hydrophilic and hydrophobic surfaces

We present results of Molecular Dynamics (MD) calculations on the behavior of liquid nanodroplets on rough hydrophobic and hydrophilic solid surfaces. On hydrophobic surfaces, the contact angle for nanodroplets depends strongly on the root-mean-square roughness amplitude, but it is nearly independent of the fractal dimension of the surface. Since increasing the fractal dimension increases the short-wavelength roughness, while the long-wavelength roughness is almost unchanged, we conclude that for hydrophobic interactions the short-wavelength (atomistic) roughness is not very important. We show that the nanodroplet is in a Cassie-like state. For rough hydrophobic surfaces, there is no contact angle hysteresis due to strong thermal fluctuations, which occur at the liquid-solid interface on the nanoscale. On hydrophilic surfaces, however, there is strong contact angle hysteresis due to higher energy barrier. These findings may be very important for the development of artificially biomimetic superhydrophobic surfaces.     

Drop impact on superheated surfaces

At the impact of a liquid droplet on a smooth surface heated above the liquid's boiling point, the droplet either immediately boils when it contacts the surface ("contact boiling"), or without any surface contact forms a Leidenfrost vapor layer towards the hot surface and bounces back ("gentle film boiling"), or both forms the Leidenfrost layer and ejects tiny droplets upward ("spraying film boiling"). We experimentally determine conditions under which impact behaviors in each regime can be realized. We show that the dimensionless maximum spreading γ of impacting droplets on the heated surfaces in both gentle and spraying film boiling regimes shows a universal scaling with the Weber number We (γ~We(2/5)), which is much steeper than for the impact on nonheated (hydrophilic or hydrophobic) surfaces (γ~We(1/4)). We also interferometrically measure the vapor thickness under the droplet.     

液滴在润湿梯度表面运动的分子动力学模拟

本文进行了液滴在不同润湿梯度表面运动的分子动力学模拟,通过改变Lennard-Jones(LJ)势参数来实现表面的不同润湿性。模拟结果表明在润湿梯度差为10°的界面上,疏水表面的液滴运动更快,达到最终界面所需时间最短,并且液滴运动方向距离最远。当润湿梯度差为20°和30°时,液滴在疏水表面工况的运动速度与从疏水跨越到亲水的工况之间的差距越来越小,并且液滴在从疏水跨越到亲水的工况达到了最远的运动距离。同时,润湿梯度差的增加也引起了液滴运动速度的增大。     

受限胶体液滴蒸发过程中胶体颗粒沉积过程观察

亲水玻璃基片在掩模板的保护下, 通过喷涂超疏水层, 得到了被疏水层包围的圆形亲水区域. 胶体液滴在这一区域被很好地限制, 并且液滴体积可以在较大范围内变化, 体积的变化可以改变液滴与基片的表观接触角. 通过显微观察手段原位观察了表观接触角为疏水的受限胶体液滴蒸发过程中粒子沉积行为. 在整个蒸发过程中, 受限液滴边界被钉扎在亲疏水交界处. 粒子沉积过程中, 驱动粒子的液滴内部流动会发生变化. 粒子沉积图案形成过程由三种流体行为控制, 最初, Marangoni效应占主导作用, 驱动粒子在液滴表面聚集, 随之沉积到液滴边缘; 随着蒸发进行, 当接触角变小(<60°)时, 由于边界蒸发速度更快导致的毛细补偿流使得粒子直接向边界沉积. 在干燥的最后阶段, 亲水区域内的液层变得很薄, 只有一单层粒子存在于这一薄液层中, 蒸发继续进行时, 薄液层发生失稳使得粒子迅速聚集而形成网络化图案, 由于粒子间距变小, 球间的液桥毛细力也会参与到这一聚集过程中.     

超亲水-超疏水组合壁面冷凝性能研究

本文通过水热法,结合气相沉积法和掩膜紫外光刻法,在玻璃基底上成功地制备了一种具有多尺度结构的超亲水-超疏水组合壁面,并对制备的具有不同润湿差异的组合壁面的冷凝效率进行了测试。结果表明壁面的冷凝效率取决于亲疏水区域的宽度和润湿性差异,其中当亲水区域宽度为0.80 mm,接触角约为0°,疏水区域宽度为0.95 mm,接触角为158°时,其冷凝效率相比光滑铜片的冷凝效率可以提高39%。进一步分析表明,液滴在极端润湿模式的组合表面的润湿分界线处具有较高的体积传输速率,且在超亲水区形成的连续微流通道加快了冷凝液滴快速排放,提高了整体表面的自更新能力。本文的研究,将为复杂润湿界面滴状冷凝的优化提供方向。     

表面能梯度驱动下纳米水滴在不同微结构表面上的运动

近年来, 微观尺度下水滴在能量梯度表面上的运动情况受到了广泛关注, 然而通过实验进行研究尚存在困难. 本文利用分子动力学方法研究了不同微结构表面上纳米水滴在表面能梯度驱动下的运动情况. 结果表明: 槽状和柱状微结构可以明显提升纳米水滴在微结构表面上的运动效率, 钉状微结构会降低纳米水滴的运动效率, 尽管它具有稳定的疏水性; 结合槽状和钉状结构的混合状微结构兼具二者的优点, 不但可以有效地提高纳米水滴在粗糙表面上的运动效率, 而且具有比较高的疏水稳定性. 此外, 表面能的微小改变会明显影响水滴的运动效率.     

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.     

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.     

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.     

Performing chemical reactions in virtual capillary of surface tension-confined microfluidic devices

In this paper we report a new method of fabrication of surface tensionconfined microfluidic devices on glass. We have also successfully carried out some well-known chemical reactions in these fluidic channels to demonstrate the usefulness of these wall-less microchannels. The confined flow path of liquid was achieved on the basis of extreme differences in hydrophobic and hydrophilic characters of the surface. The flow paths were fabricated by making parallel lines using permanent marker pen ink or other polymer on glass surfaces. Two mirror image patterned glass plates were then sandwiched one on top of the other, separated by a thin gap-created using a spacer. The aqueous liquid moves between the surfaces by capillary forces, confined to the hydrophilic areas without wetting the hydrophobic lines, achieving liquid confinement without physical side-walls. We have shown that the microfluidic devices designed in such a way can be very useful due to their simplicity and low fabrication cost. More importantly, we have also demonstrated that the minimum requirement of such a working device is a hydrophilic line surrounded by hydrophobic environment, two walls of which are constituted of air and the rest is made of a hydrophobic surface.     

Long term hydrophilic coating on poly(dimethylsiloxane) substrates for microfluidic applications

Poly(dimethylsiloxane) (PDMS) has been used extensively for microfluidic components and as substrates for biological applications. Since the native nature of PDMS is hydrophobic it requires a functionalization step for use in conjunction with aqueous media. Commonly, oxygen plasma treatment is used for the formation of hydrophilic groups on the surface. However, the hydrophilic nature of these surfaces is short lived and the surfaces quickly revert back to their original hydrophobic state. In this work, branched-polyethylenimine (b-PEI) was used for long term modification of plasma treated PDMS surface. Contact angle, X-ray photoelectron spectroscopy (XPS) and Atomic force microscopy (AFM) were used for characterization of the modified surfaces and their stability with time was studied. The results obtained demonstrate that comparatively higher stability, hydrophilic, positively charged surfaces can be obtained after b-PEI treatment. These b-PEI treated PDMS surfaces can be used as fluidic channels for the separation of molecules as well as a substrate for the adherence of bio-molecules or biological cells.     

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,借此对模型进行了误差分析和修正.研究表明:1)共振时,液滴高度变化率即比振幅随体积增大而增大,随阶数增大而减小;2)各模式区间的起止频率首尾相接,其范围随体积增大而减小;3)液滴体积越大,共振频率越小,随着阶数增大,共振频率f与体积V的关系趋于f-V^–0.4,不同于一般性疏水表面上的f-V^–0.5;4)直接应用Noblin模型计算共振频率会产生较大误差,主要原因在于液滴表面波波段数量统计存在较大偏差,而修正后的模型可以准确计算超疏水表面大体积液滴的共振频率.     

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.     

Dynamics of non-Newtonian droplets

We study the impact and subsequent retraction dynamics of aqueous liquid droplets upon high-speed impact on hydrophobic surfaces. Often a spectacular "rebound" of the droplet can be observed: after the impact and expansion, the drop retracts rapidly, leading to ejection of part of the material from the surface. We show how non-Newtonian flow properties can be used to slow down the retraction sufficiently to completely inhibit rebound. The slowing down is due to non-Newtonian normal stresses generated near the moving contact line of the droplet. We provide a quantitative theory for the slowing down, and show that the non-Newtonian effects profoundly change the contact line dynamics.     

Surface wetting of liquid nanodroplets: droplet-size effects

The spreading of liquid nanodroplets of different initial radii R0 is studied using molecular dynamics simulation. Results for two distinct systems, Pb on Cu(111), which is nonwetting, and a coarse-grained polymer model, which wets the surface, are presented for Pb droplets ranging in size from approximately 55,000 to 220,000 atoms and polymer droplets ranging in size from approximately 200,000 to 780 000 monomers. In both cases, a precursor foot precedes the spreading of the main droplet. This precursor foot spreads as r(2)(f)(t) = 2D(eff)t with an effective diffusion constant that exhibits a droplet-size dependence D(eff) approximately R(1/2)(0). The radius of the main droplet r(b)(t) approximately R(4/5)(0) is in agreement with kinetic models for the cylindrical geometry studied.     

A new model for the formation of contact angle and contact angle hysteresis

The formation mechanism of the contact angle and the sliding angle for a liquid drop on a solid surface plays an important role in producing hydrophobic surfaces. A new half soakage model is established in this paper as a substitute for Wenzel (complete soakage) and Cassie (no soakage) models. The model is suited to many solid surfaces, whether they are hydrophilic or hydrophobic, or even superhydrophobic. Based on the half soakage model, we analyse two surfaces resembling lotus, i.e. taper-like surface and corona-like surface. Furthermore, this new model is used to establish a quantitative relationship between the sliding angle and the parameters of surface morphology.     

Desolvation of polymers by ultrafast heating: Influence of hydrophilicity

Using molecular-dynamics simulation, we investigate the consequences of ultrafast laser-induced heating of a small water droplet containing a solvated polymer. Two polymers are studied: polyethylene as an example of a hydrophobic, and polyketone as an example of a hydrophilic polymer. In both cases, when the droplet is heated below the critical temperature of water, strong water evaporation is started, but the polymer remains in contact with a central water cluster. However, upon heating beyond the critical temperature, the hydrophilic polyethylene becomes completely desolvated, while polyketone still remains solvated. We analyze this behavior in terms of the intermolecular interactions and of the expansion dynamics of the heated droplet.     

亲水性微观粗糙表面润湿状态转变性能研究

以亲水性微观粗糙表面上不同几何形貌及分布的微柱阵列为对象, 讨论了液滴在亲水性粗糙表面上的润湿过程以及润湿状态的转变阶段. 从能量角度分别考察了微观粗糙结构几何形貌及分布、微柱几何参数、固体表面亲水性、接触角滞后作用等因素对液滴润湿状态转变的影响规律. 研究发现: 在亲水粗糙表面, 正方形微柱呈正六边形阵列分布时, 液滴更容易形成稳定的Cassie状态, 或者液滴仅发生Cassie状态向中间浸润状态的转变; 与此同时, 减小微柱间距、增大方柱宽度或圆柱直径、增大微柱高度、增强固体表面的亲水性将有利于液滴处于稳定的Cassie状态, 或阻止润湿状态向伪-Wenzel或Wenzel状态转变; 然而, 当液滴处于Cassie状态时, 较小的固-液界面面积分数或减弱固体表面亲水性能均有利于增大液滴的表观接触角, 因此在亲水表面设计粗糙结构时应综合考虑润湿状态稳定性和较大表观接触角两方面因素; 此外, 接触角滞后作用对于液滴状态的稳定性以及疏水性能的实现具有相反作用的影响. 研究结果为液滴在亲水表面获得稳定Cassie状态的粗糙结构设计方法提供了理论依据. 关键词： 亲水表面 微观粗糙结构 表面自由能 润湿状态转变     

Nanofluidics in the Debye layer at hydrophilic and hydrophobic surfaces

By using evanescent waves, we study equilibrium and dynamical properties of liquid-solid interfaces in the Debye layer for hydrophilic and hydrophobic surfaces. We measure velocity profiles and nanotracer concentration and diffusion profiles between 20 and 300 nm from the walls in pressure-driven and electro-osmotic flows. We extract electrostatic and zeta potentials and determine hydrodynamic slip lengths with 10 nm accuracy. The spectacular amplification of the zeta potential resulting from hydrodynamic slippage allows us to clarify for the first time the dynamic origin of the zeta potential.     

Predicting initial nucleation events occurred in a metastable nanodroplet during acoustic droplet vaporization

Acoustic droplet vaporization (ADV) capable of converting liquid perfluorocarbon (PFC) micro/nanodroplets into gaseous microbubbles has gained much attention due to its medical potentials. However, its physical mechanisms for nanodroplets have not been well understood due to the disappeared superharmonic focusing effect and the prominent Laplace pressure compared to microdroplets, especially for the initial ADV nucleation occurring in a metastable PFC nanodroplet. The classical nucleation theory (CNT) was modified to describe the ADV nucleation via combining the phase-change thermodynamics of perfluoropentane (PFP) and the Laplace pressure effect on PFP nanodroplets. The thermodynamics was exactly predicted by the Redlich–Kwong equation of state (EoS) rather than the van der Waals EoS, based on which the surface tension of the vapor nucleus as a crucial parameter in the CNT was successfully obtained to modify the CNT. Compared to the CNT, the modified CNT eliminated the intrinsic limitations of the CNT, and it predicted a larger nucleation rate and a lower ADV nucleation threshold, which agree much better with experimental results. Furthermore, it indicated that the nanodroplet properties exert very strong influences on the nucleation threshold instead of the acoustic parameters, providing a potential strategy with an appropriate droplet design to reduce the ADV nucleation threshold. This study may contribute to further understanding the ADV mechanism for PFC nanodroplets and promoting its potential theranostic applications in clinical practice.