The dynamics of impacting water droplets on alkanethiol self-assembled monolayers with co-adsorbed CH3 and CO2H terminal groups

The impact of water droplets (diameter 3.6 mm) at a fixed Weber number of 59 on solid surfaces with precisely tailored surface wettabilities was studied experimentally using a high-speed imaging camera at 2500 frames per second. Solid surface wettability was varied using four fractional mixtures of self-assembled monolayers of 1-octadecanethiol and 16-mercaptohexadecanoic acid. The surfaces so obtained are characterized for contact angle and chemical functionality using the axisymmetric drop shape analysis profile (ADSA-P) technique and Fourier transform infrared spectroscopy (FT-IR). Our results correlate the wetting effects of the impacting droplets with the surface energy and contact angle measurements of the tailored surfaces. Literature models for the maximum spreading diameter are employed and compared with those from our experiments. An equation is also proposed for the maximum spreading diameter which makes use of the correct contact angles and results in the least error among the models considered. As a consequence of Young's equation, the correct contact angles to be used for droplet impact dynamics should be the corresponding advancing angles on a smooth substrate of interest. We also conclude that accurate examination of literature models requires careful experimentation on impact dynamic data on well-prepared and characterized surfaces such as those presented here.     

Liquid–paper interactions during liquid drop impact and recoil on paper surfaces

The spreading and recoiling of water drops on several flat and macroscopically smooth model surfaces and on sized paper surfaces were studied over a range of drop impaction velocities using a high-speed CCD camera. The water drop spreading and recoiling results on several model hydrophobic and hydrophilic surfaces were found to be in agreement with observations reported in the literature. The maximum drop spreading diameter for those model surfaces at impact was found to be dependent upon the initial drop kinetic energy and the degree of hydrophobicity/hydrophilicity of the surface. The extent of the maximum drop recoiling was found to be much weaker for hydrophilic substrates than for hydrophobic substrates. Sized papers, however, showed an interesting switch of behaviour in the process of water drop impaction. They behave like a hydrophobic substrate when a water drop impacts on it, but like a hydrophilic substrate when water drop recoils. Although the contact angle between water and hydrophilic or hydrophobic non-porous surfaces changes from advancing to receding as reported in literature, the change of contact angle during water impact on paper surface is unique in that the level of sizing was found to have a smaller than expected influence on the degree of recoil. Atomic force microscopy (AFM) was used to probe fibres on a sized filter paper surface under water. The AFM data showed that water interacted strongly with the fibre even though the paper was heavily sized. Implications of this phenomenon were discussed in the context of inkjet print quality and of the surface conditions of sized papers. Results of this study are very useful in the understanding of inkjet ink droplet impaction on paper surfaces which sets the initial condition for ink penetration into paper after impaction.     

Generation of picoliter droplets of liquid for electrospray ionization with piezoelectric inkjet

We report the association of inkjet and electrospray ionization MS to detect picoliter droplet, where the liquid volume and its position onto the tip can be precisely controlled to form ultrafine droplets for successive ionization of the analyte. Single rectangle pulse was applied to piezoelectric device on inkjet microchip for the ejection of each picoliter droplet, and it was controlled by a computer. The voltage and width of driving pulse for the inkjet were optimized to make reproducible ejection of the solvent with low viscosity. The volume of each droplet was about 600 pl, and a trigger of 10 droplets was selected as the best inlet mode taking relative standard derivation of the droplets into consideration. The target substrate used with high voltage to form ionization was graphite, after several attempts with some materials. High‐speed camera was used to capture the breaking‐up process of a droplet. The distance between the inkjet nozzle and the tip was set at 2 cm to avoid short circuit. The influences on the mass intensity of the diameter of the tip, the volume and the concentration of the sample were examined. The tip with a small diameter performed greater intensity, and the limit of detection decreased, whereas the small volume of liquid played high ionization efficiency. Linear regression in the range between 1 and 200 ppm for caffeine was conducted, where internal standard theobromine was used. Some real samples were also detected with the instrument. Copyright © 2013 John Wiley & Sons, Ltd.     

Statics of polymer droplets on deformable surfaces

The equilibrium properties of polymer droplets on a soft deformable surface are investigated by molecular dynamics simulations of a bead-spring model. The surface consists of a polymer brush with irreversibly end-tethered linear homopolymer chains onto a flat solid substrate. We tune the softness of the surface by varying the grafting density. Droplets are comprised of bead-spring polymers of various chain lengths. First, both systems, brush and polymer liquid, are studied independently in order to determine their static and dynamic properties. In particular, using a numerical implementation of an AFM experiment, we measure the shear modulus of the brush surface and compare the results to theoretical predictions. Then, we study the wetting behavior of polymer droplets with different surface/drop compatibility and on substrates that differ in softness. Density profiles reveal, under certain conditions, the formation of a wetting ridge beneath the three-phase contact line. Cap-shaped droplets and cylindrical droplets are also compared to estimate the effect of the line tension with respect to the droplet size. Finally, the results of the simulations are compared to a phenomenological free-energy calculation that accounts for the surface tensions and the compliance of the soft substrate. Depending on the surface/drop compatibility, surface softness, and drop size, a transition between two regimes is observed: from one where the drop surface energy balances the adhesion with the surface, which is the classical Young-Dupre? wetting regime, to another one where a coupling occurs between adhesion, droplet and surface elastic energies.     

Spreading of Surfactant Solutions over Hydrophobic Substrates

The spreading of surfactant solutions over hydrophobic surfaces is considered from both theoretical and experimental points of view. Water droplets do not wet a virgin solid hydrophobic substrate. It is shown that the transfer of surfactant molecules from the water droplet onto the hydrophobic surface changes the wetting characteristics in front of the drop on the three-phase contact line. The surfactant molecules increase the solid-vapor interfacial tension and hydrophilize the initially hydrophobic solid substrate just in front of the spreading drop. This process causes water drops to spread over time. The time of evolution of the spreading of a water droplet is predicted and compared with experimental observations. The assumption that surfactant transfer from the drop surface onto the solid hydrophobic substrate controls the rate of spreading is confirmed by our experimental observations. Copyright 2000 Academic Press.     

On the solidification of a supercooled liquid droplet lying on a surface

We model the solidification and subsequent cooling of a supercooled liquid droplet that is lying on a cold solid substrate after impact. It is assumed that solidification occurs for a given fixed droplet shape. The shapes used by the model are a sphere, truncated spheres, and an experimentally registered droplet shape. The freezing process is conduction-dominant and is modeled as a one-phase Stefan problem. This moving boundary problem is reformulated with the enthalpy method and then solved numerically with an implicit finite-difference technique. The numerical results for the simple case of a spherical droplet touching a surface are similar to those of a freely freezing spherical droplet and are well confirmed by the 1D asymptotic analytical model of Feuillebois et al. (J. Colloid Interface Sci. 169 (1995) 90). A freezing water droplet is considered as an example. The numerical results for full freezing time, subsequent cooling time, and last freezing point coordinate for the various droplets shapes are fitted by analytical functions depending on supercooling, thermal resistance of the target surface (expressed by Biot number), and spreading parameter. These functions are proposed for direct application, thus avoiding the need to solve the full freezing and cooling problem.     

Droplet on a liquid substrate: Wetting,dewetting, dynamics,instabilities

Droplets on a liquid substrate (‘liquid lenses’) play an important role in various branches of engineering, including microfluidics, chemical engineering, environment protection, etc. In the present paper, we discuss basic phenomena characteristic for liquid lenses. We recall classical results on the shape of an equilibrium droplet and the kinds of droplet wetting. We overview briefly the main theoretical approaches used for the analysis of droplet dynamics, discuss the phenomena accompanying a droplet impact, physical effects used for droplet manipulations, and the factors that determine the interaction between droplets. We describe the main types of droplet instabilities leading to oscillations, self-propulsion, and disintegration of droplets. Some promising directions of further research are listed.     

Induced detachment of coalescing droplets on superhydrophobic surfaces

Coalescence of a falling droplet with a stationary sessile droplet on a superhydrophobic surface is investigated by a combined experimental and numerical study. In the experiments, the droplet diameter, the impact velocity, and the distance between the impacting droplets were controlled. The evolution of surface shape during the coalescence of two droplets on the superhydrophobic surface is captured using high speed imaging and compared with numerical results. A two-phase volume of fluid (VOF) method is used to determine the dynamics of droplet coalescence, shape evaluation, and contact line movement. The spread length of two coalesced droplets along their original center is also predicted by the model and compared well with the experimental results. The effect of different parameters such as impact velocity, center to center distance, and droplet size on contact time and restitution coefficient are studied and compared to the experimental results. Finally, the wetting and the self-cleaning properties of superhydrophobic surfaces have been investigated. It has been found that impinging water drops with very small amount of kinetic impact energy were able to thoroughly clean these surfaces.     

Liquid nanodroplets spreading on chemically patterned surfaces

Controlling the spatial distribution of liquid droplets on surfaces via surface energy patterning can be used to deliver material to specified regions via selective liquid/solid wetting. Although studies of the equilibrium shape of liquid droplets on heterogeneous substrates exist, much less is known about the corresponding wetting kinetics. Here we present large-scale atomistic simulations of liquid nanodroplets spreading on chemically patterned surfaces. Results are presented for lines of polymer liquid (droplets) on substrates consisting of alternating strips of wetting (equilibrium contact angle theta0 = 0 degrees) and nonwetting (theta0 approximately 90 degrees) material. Droplet spreading is compared for different wavelength lambda of the pattern and strength of surface interaction on the wetting strips. For small lambda, droplets partially spread on both the wetting and nonwetting regions of the substrate to attain a finite contact angle less than 90 degrees. In this case, the extent of spreading depends on the interaction strength in the wetting regions. A transition is observed such that, for large lambda, the droplet spreads only on the wetting region of the substrate by pulling material from nonwetting regions. In most cases, a precursor film spreads on the wetting portion of the substrate at a rate strongly dependent on the width of the wetting region.     

水滴在超疏水植物叶片上的沉积方法和机理研究进展

自然界中有很多超疏水植物叶片, 水滴撞击在这些表面时极易产生溅射和反弹, 造成农用化学品喷雾施药时药物的大量损失, 利用率低下, 从而重复喷洒施药. 农用化学品过度使用将造成食品安全、 农药残留、 水资源浪费及环境生态污染等问题. 因此, 增加水滴在超疏水植物叶片表面的沉积效率对提高农药利用率尤为重要. 本文从分析水滴在超疏水表面的撞击动力学特征开始, 结合添加助剂后液滴的物理化学性质, 系统阐述了水滴在超疏水植物叶片上的沉积方法和机理, 并提出筛选助剂和研究机理不仅要考虑助剂性质还要结合基底结构、 撞击动力学特征等因素, 而且还要考虑单水滴尺寸大小、 基底运动和弹性及环境因素等对沉积的影响. 本文对农药喷洒及生物医学、 机械工程、 涂料喷涂和油墨打印等领域均有指导意义和应用价值.     

Isothermal noncoalescence of liquid droplets at the air-liquid interface

The mechanism of the generation and sustainability of noncoalescent droplets (NCDs) was investigated at the liquid-air interface of the same liquids in the context of inkjet printing. The Weber number (We) was used to correlate and predict the generation of NCDs in a falling-drop experiment. This study found that NCDs can be generated for We higher than 130. We values of this magnitude are relevant to inkjet printing. The formation of NCD can reduce the print quality because the NCD droplets roll away uncontrollably from the print target, thus reducing print resolution. This study also used a simple experiment to demonstrate the physical origin of the NCD, which is the existence of a gaseous cushion between the liquid drop and the liquid-air interface that supports the drop. The gaseous cushion has a thickness greater than the van der Waals attraction range (around 10 nm).     

Wetting in the nanoscale: a continuum mechanics approach

A continuum mechanics model has been developed to study the equilibrium shape of nanometric droplets on a planar solid substrate and how, in this scale, the contact angle depends on the drop size. The drop is modeled as a liquid volume enclosed in an inextensible membrane, subject to an isotropic tension (the surface tension) and to a field of surface forces including, in the proximity of the solid, the liquid-to-solid interactions, envisaged as a generic potential force per unit surface directed normally to the solid surface (i.e. vertically). The only conditions required to solve the problem are those of mechanical and thermodynamic equilibrium. The predictions of the model are discussed in comparison with data on nanodrops retrieved by a special AFM device for a number of different liquid–solid systems.     

Molecular-dynamic simulation of nanosized droplet spreading over a continual solid surface

Molecular dynamics methods are employed for a comparative study of the spread of nanosized simple fluid droplets and nanodroplets composed of model chains that reflect molecules of normal alkanes over a solid substrate. The effects of the droplet size, the energy of the molecule-substrate interactions, temperature, and degree of chain rigidity on the spreading kinetics are investigated. The substrate is described in terms of the continual Lennard-Jones model.     

Deformation of water droplets on solid surface in electric field

The purpose of this paper is to analyze the deformation of water droplets on a solid surface under electric stress. A mathematical model making it possible to simulate the axisymmetric as well as non-axisymmetric deformations of droplets is developed. According to this model, the droplet deformation depends on several parameters such as the volume and the number of droplets, the conductivity and the permittivity of droplets, their proximity to one another, the surface of the solid material, and the location of each droplet on the dielectric surface. The results of the simulation show the disturbance of the background field through the presence of a single or multiple droplets. An experimental study is also achieved by considering one to three droplets aligned simultaneously on a dielectric smooth surface between two electrodes subjected to AC voltages. The influence of the background field and the droplet location regarding the electrodes on the deformation of water droplets are evidenced.     

Impact of a superhydrophobic sphere onto water

When a water drop hits a superhydrophobic solid surface, it bounces off the substrate like an elastic ball. Here we show that when a tiny superhydrophobic solid sphere impacts with water, it can bounce off the free surface just as it impacts with an elastic membrane. The motion of a sinking sphere is analytically calculated by solving a potential flow whose free boundary is determined by the Young-Laplace equation. To find conditions under which the solid sphere should sink, bounce off, or oscillate upon impact with water, we construct simple scaling laws which are shown to agree well with experimentally found boundaries between the distinct impact behaviors in a regime map based on dimensionless parameters.     

Modeling of wetting: a study of nanowetting at rough and heterogeneous surfaces

Molecular dynamics simulations were performed to study the behavior of nanoscale water droplets at solid surfaces. Simulations of droplets on heterogeneous patterned surfaces show that the relative sizes of the domains and the droplets play an important role as do the interactions between the solid and the liquid, particularly when the domain width is comparable to the droplet radius. For pillar surfaces, a transition is observed between the Wenzel and the Cassie and Baxter regimes with increasing pillar height. The effects of pillar width and the gap between the pillars were also examined. The simulations show clearly the importance of the detailed topography and composition of the solid surface.     

Analysis on wetting and local dynamic properties of single water droplet on a polarized solid surface: a molecular dynamics study

Molecular dynamics simulations of single water droplets on a solid surface were carried out in order to investigate the effects that the Coulomb interaction between liquid and solid molecules has on wetting behavior by appending vertical electric polarization on a solid surface. The water droplet became more wettable both on upward and downward polarized surfaces, although structures of the adsorption layer appearing near the solid surface were clearly different, and the relation between droplet contact angle and surface polarization was also different for upward and downward polarization directions. The probability density distribution of molecular orientation around the adsorption layer indicated that preferable water molecule orientations varied largely by the surface polarization, and the rotational mobility around the preferable orientations was also affected. The dynamic property due to this rotational mobility was clearly captured by means of distribution of rotational diffusion coefficient, which potentially corresponded to local viscosity distribution.     

New Pickering emulsions stabilized by bacterial cellulose nanocrystals

We studied oil in water Pickering emulsions stabilized by cellulose nanocrystals obtained by hydrochloric acid hydrolysis of bacterial cellulose. The resulting solid particles, called bacterial cellulose nanocrystals (BCNs), present an elongated shape and low surface charge density, forming a colloidal suspension in water. The BCNs produced proved to stabilize the hexadecane/water interface, promoting monodispersed oil in water droplets around 4 μm in diameter stable for several months. We characterized the emulsion and visualized the particles at the surface of the droplets by scanning electron microscopy (SEM) and calculated the droplet coverage by varying the BCN concentration in the aqueous phase. A 60% coverage limit has been defined, above which very stable, deformable droplets are obtained. The high stability of the more covered droplets was attributed to the particle irreversible adsorption associated with the formation of a 2D network. Due to the sustainability and low environmental impact of cellulose, the BCN based emulsions open opportunities for the development of environmentally friendly new materials.