超疏水表面微纳二级结构对冷凝液滴最终状态的影响

从超疏水表面(SHS)上初始冷凝液核长大、合并、形成初始液斑开始,分析计算了冷凝液斑变形成为Wenzel或Cassie液滴过程中界面能量的变化,并以界面能曲线降低、是否取最小值为判据,确定冷凝液滴的最终稳定状态.计算结果表明:在只有微米尺度的粗糙结构表面上,冷凝液滴的界面能曲线一般都是先降低再升高,呈现Wenzel状态;而当表面具有微纳米二级粗糙结构,且纳米结构的表面空气面积分率较高时,冷凝液滴的能量曲线持续降低,直至界面能最小的Cassie状态,因此可以自发地形成Cassie液滴.还计算了文献中具有不同结构参数的SHS上冷凝液滴的状态和接触角,并与实验结果进行了比较,结果表明,计算的冷凝液滴状态与实验观察结果完全吻合.因此,微纳二级结构是保持冷凝液滴在SHS上呈现Cassie状态的重要因素.     

Superhydrophobicity of biological and technical surfaces under moisture condensation: stability in relation to surface structure

The stability of superhydrophobic properties of eight plants and four technical surfaces in respect to water condensation has been compared. Contact and sliding angles were measured after application of water drops of ambient temperature (20 degrees C) onto cooled surfaces. Water evaporating from the drops condensed, due to the temperature difference between the drops and the surface, on the cooled samples, forming "satellite droplets" in the vicinity of the drops. Surface cooling to 15, 10, and 5 degrees C showed a gradual decrease of superhydrophobicity. The decrease was dependent on the specific surface architecture of the sample. The least decrease was found on hierarchically structured surfaces with a combination of a coarse microstructure and submicrometer-sized structures, similar to that of the Lotus leaf. Control experiments with glycerol droplets, which show no evaporation, and thus no condensation, were carried out to verify that the effects with water were caused by condensation from the drop (secondary condensation). Furthermore, the superhydrophobic properties after condensation on cooled surfaces from a humid environment for 10 min were examined. After this period, the surfaces were covered with spherical water droplets, but most samples retained their superhydrophobicity. Again, the best stability of the water-repellent properties was found on hierarchically structured surfaces similar to that of the Lotus leaf.     

Wetting and absorption of water drops on Nafion films

Water drops on Nafion films caused the surface to switch from being hydrophobic to being hydrophilic. Contact angle hysteresis of >70 degrees between advancing and receding values were obtained by the Wilhelmy plate technique. Sessile drop measurements were consistent with the advancing contact angle; the sessile drop contact angle was 108 degrees . Water drop adhesion, as measured by the detachment angle on an inclined plane, showed much stronger water adhesion on Nafion than Teflon. Sessile water and methanol drops caused dry Nafion films to deflect. The flexure went through a maximum with time. Flexure increased with contact area of the drop, but was insensitive to the film thickness. Methanol drops spread more on Nafion and caused larger film flexure than water. The results suggest that the Nafion surface was initially hydrophobic but water and methanol drops caused hydrophilic sulfonic acid domains to be drawn to the Nafion surface. Local swelling of the film beneath the water drop caused the film to buckle. The maximum flexure is suggested to result from motion of a water swelling front through the Nafion film.     

Contact angle measurements by confocal microscopy for non-destructive microscale surface characterization

Contact angle measurements are of great importance in surface characterization but the practical use has often been limited to macroscopic dimensions (millimeters). Therefore, we have developed a confocal microscopy method that allows non-destructive measurements of both low (<30 degrees ) and high (30 degrees -90 degrees ) contact angles. Low contact angles were measured by reconstructing the drop profile from the interference patterns in droplets condensed from atmospheric humidity. At higher contact angles water droplets with a small amount of fluorescein were sprayed onto the surfaces and 3D-image stacks were recorded and used to extract the contact angle. Suitable drop sizes were between a few up to about 50 mum radius, using a 40x magnification objective. Using drops >10 micrometers radius for microcontact angle measurements a good correlation was obtained between measured micro- and macrocontact angles. After microcontact angle measurements the surfaces were rinsed and heavy meromyosin motor fragments were adsorbed to the surface. Importantly, the sensitive actin propelling function of these motor proteins was not affected by the previous contact angle measurements using fluorescent droplets. This suggests that the methodology should be suitable for non-destructive characterization of different parts of micropatterned surfaces being developed for biological assays.     

Fog deposition and accumulation on smooth and textured hydrophobic surfaces

We investigated the deposition and accumulation of droplets on both smooth substrates and substrates textured with square pillars, which were tens of micrometers in size. After being coated with a hydrophobic monolayer, substrates were placed in an air flow with a sedimenting suspension of micrometer-sized water droplets (i.e., fog). We imaged the accumulation of water and measured the evolution of the mean drop size. On smooth substrates, the deposition process was qualitatively similar to condensation, but differences in length scale revealed a transient regime not reported in condensation experiments. Based on previous simulation results, we defined a time-scale characterizing the transition to steady-state behavior. On textured substrates, square pillars promoted spatial ordering of accumulated drops. Furthermore, texture regulated drop growth: first enhancing coalescence when the mean drop size was smaller than the pillar, and then inhibiting coalescence when drops were comparable to the pillar size. This inhibition led to a monodisperse drop regime, in which drop sizes varied by less than 5%. When these monodisperse drops grew sufficiently large, they coalesced and could either remain suspended on pillars (i.e., Cassie-Baxter state) or wet the substrate (i.e., Wenzel state).     

Non-aqueous phase liquid drop formation within a water saturated fracture

This work focuses on the mechanisms of non-aqueous phase liquid (NAPL) drop formation within a single fracture fed from a NAPL reservoir by way of a circular orifice, such as a pore. The fracture is assumed to be fully saturated, the relative wettability of the system is assumed water-wet, and the water velocity profile within the fracture is described by a Poiseuille flow. The size of the NAPL drops is investigated for various water flow velocities and NAPL entrance diameters. A force balancing method was used to determine the radii of detached drops. The drop sizes calculated from the model developed here are shown to be in agreement with available experimental drop size data. It is shown that at low Reynolds numbers the buoyancy force is the dominant force acting on the drop during the formation process and at high Reynolds numbers the viscous forces dominate. A simplified expression relating the geometry of the fractured system to the drop radii is developed from the model equations, and it is shown to predict drop radii that match well with both the model simulations and the available experimental data.     

Studies of the rate of water evaporation through adsorption layers using drop shape analysis tensiometry

With modified measuring procedure and measuring cell design in the drop profile tensiometer PAT, it became possible to study the rate of water evaporation through adsorbed or spread surface layers. This method was employed to measure the rate of water evaporation from drops covered by adsorbed layers of some proteins and surfactants, in particular n-dodecanol. It was shown that the formation of dense (double or condensed) adsorbed layers of protein and the formation of 2D-condensed n-dodecanol layer decrease the water evaporation rate by 20-25% as compared with pure water. At the same time, the adsorbed layers of ordinary surfactants (sodium dodecyl sulfate and nonionic ethoxylated surfactant C(14)EO(8)) do not affect the water evaporation rate remarkably.     

Adsorption of paraffin vapor on oxidized molybdenum substrates at nano- and micro-scales

Sputtered oxidized molybdenum surfaces were exposed at room temperature for different times to paraffin vapors obtained at 150 degrees C. Scanning polarization force microscopy (SPFM), optical and confocal microscopy were used to characterize the surfaces. The condensed morphologies are complex and strongly dependent upon the quantity of vapor molecules deposited on the substrate surface. A thin paraffin film is initially formed and quite uniform nano-height drops are nucleated randomly over it within 10-20 s time exposures. Their average contact angle ranged between 1 degrees -2.5 degrees . Further vapor deposition led to a more complex regime where nano-height drops do not show a clear interface with the film, while micro-sized drops do. The tangent approximation method adopted by Salmeron and Xu for the nano-drop regimes was extended to the micro-sized drop regime obtaining an averaged effective contact angle equal to 4 degrees -5 degrees . Both nano-height and micro-sized drops shape and effective contact angles have been discussed taking into account their interactions between the film and the drops.     

High internal phase emulsions: catastrophic phase inversion, stability, and triggered destabilization

We have investigated the formation, drop sizes, and stability of emulsions prepared by hand shaking in a closed vessel in which the emulsion is in contact with a single type of surface during its formation. The emulsions undergo catastrophic phase inversion from oil-in-water (o/w) to water-in-oil (w/o) as the oil volume fraction is increased. We find that the oil volume fraction required for catastrophic inversion exhibits a linear correlation with the oil-water-solid surface contact angle. W/o high internal phase emulsions (HIPEs) prepared in this way contain water drops of diameters in the range 10-100 μm; emulsion drop size depends on the surfactant concentration and method of preparation. W/o HIPEs with large water drops show water separation but w/o HIPEs with small water drops are stable with respect to water separation for more than 100 days. The destabilization of the w/o HIPEs can be triggered by either evaporation of the oil continuous phase or by contact the emulsion with a solid surface of the "wrong" wettability.     

Emulsification in turbulent flow 2. Breakage rate constants

Systematic experimental study of the effects of several factors on the breakage rate constant, k(BR), during emulsification in turbulent flow is performed. These factors are the drop size, interfacial tension, viscosity of the oil phase, and rate of energy dissipation in the flow. As starting oil-water premixes we use emulsions containing monodisperse oil drops, which have been generated by the method of membrane emulsification. By passing these premixes through a narrow-gap homogenizer, working in turbulent regime of emulsification, we study the evolution of the number concentration of the drops with given diameter, as a function of the emulsification time. The experimental data are analyzed by a kinetic scheme, which takes into account the generation of drops of a given size (as a result of breakage of larger drops) and their disappearance (as a result of their own breakage process). The experimental results for k(BR) are compared with theoretical expressions from the literature and their modifications. The results for all systems could be described reasonably well by an explicit expression, which is a product of: (a) the frequency of collisions between drops and turbulent eddies of similar size, and (b) the efficiency of drop breakage, which depends on the energy required for drop deformation. The drop deformation energy contains two contributions, originating from the drop surface extension and from the viscous dissipation inside the breaking drop. In the related subsequent paper, the size distribution of the daughter drops formed in the process of drop breakage is analyzed for the same experimental systems.     

A Growing Drop Technique for Measuring Dynamic Interfacial Tension

A novel, growing drop technique is described for measuring dynamic interfacial tension due to sorption of surface-active solutes. The proposed method relates the instantaneous pressure and size of expanding liquid drops to the interfacial tension and is useful for measuring both liquid/gas and liquid/liquid tensions over a wide range of time scales, currently from 10 ms to several hours. Growing drop measurements on surfactant-free water/ air and water/octanol interfaces yield constant tensions equal to their known literature values. For surfactant-laden, liquid drops, the growing drop technique captures the actual transient tension evolution of a single interface, rather than interval times as with the classic maximum-drop-pressure and drop-volume tension measurements. Dynamic tensions measured for 0.25 mM aqueous 1-decanol solution/air and 0.02 kg/m³ aqueous Triton X-100 solution/dodecane interfaces show nonmonotonic behavior, indicating slow surfactant transport relative to the imposed rates of interfacial dilatation. The dynamic tension of a purified and fresh 6 mM aqueous sodium dodecyl sulfate (SDS) solution/air interface shows only a monotonic decrease, indicating rapid surfactant transport relative to the imposed rates of dilatation. Conversely, an aged SDS solution, naturally containing trace dodecanol impurities, exhibits dynamic tensions which reflect a superposition of the rapidly equilibrating SDS and the slowly adsorbing dodecanol.     

Assessing the accuracy of contact angle measurements for sessile drops on liquid-repellent surfaces

Gravity-induced sagging can amplify variations in goniometric measurements of the contact angles of sessile drops on super-liquid-repellent surfaces. The very large value of the effective contact angle leads to increased optical noise in the drop profile near the solid-liquid free surface and the progressive failure of simple geometric approximations. We demonstrate a systematic approach to determining the effective contact angle of drops on super-repellent surfaces. We use a perturbation solution of the Bashforth-Adams equation to estimate the contact angles of sessile drops of water, ethylene glycol, and diiodomethane on an omniphobic surface using direct measurements of the maximum drop width and height. The results and analysis can be represented in terms of a dimensionless Bond number that depends on the maximum drop width and the capillary length of the liquid to quantify the extent of gravity-induced sagging. Finally, we illustrate the inherent sensitivity of goniometric contact angle measurement techniques to drop dimensions as the apparent contact angle approaches 180°.     

利用Breath Figures法制备具有蜂窝状结构的 PMMA/TBT复合膜

以聚甲基丙烯酸甲酯(PMMA)和钛酸四丁酯(TBT)的氯仿溶液为铸膜溶液,采用Breath Figures法制备了蜂窝状结构的PMMA/TBT多孔阵列薄膜,采用SEM、JR、XRD对制备的多孔膜进行了表征,探讨了聚合物浓度、PMMA/TBT配比以及水解抑制剂对膜蜂窝状结构的影响.实验结果表明,起始溶液浓度为20～30m...     

纳米结构表面上冷凝液滴的生长模式及部分润湿液滴的形成机制

分析并计算了纳米结构表面上冷凝液滴按照不同途径长大的过程中液滴能量的增加速率, 并以能量增加最小为判据来确定液滴的生长途径. 结果表明, 纳米结构内形成的冷凝液斑在初期按接触角(CA)增加的模式生长时, 其能量增加速率远低于其它模式, 于是, 初始液斑先按增大接触角、并保持底面积不变的模式生长, 直至液滴达到前进角状态. 此后, 沿接触角增加的模式长大所导致的能量增加速率开始远高于其它生长模式, 于是液滴三相线开始移动, 底面积开始增加, 但接触角保持不变. 液滴所增加的底面积可以呈润湿或复合两种状态, 分别形成Wenzel 液滴及部分润湿液滴, 前者的表观接触角一般小于160°, 而后者则明显大于160°. 液滴的生长模式及其润湿状态均与纳米结构参数密切相关, 仅当纳米柱具有一定高度、且间距较小时, 冷凝液滴才能呈现部分润湿状态. 最后, 本模型对纳米结构表面上冷凝液滴润湿状态的计算结果与绝大部分实测结果相一致, 准确率达到91.9%, 明显高于已有公式的计算准确率.     

Coalescence during emulsification. 3. Effect of gelatin on rupture and coalescence

An oil-soluble fluorescent probe, undecyl pyrene (UDP), is used to measure the amount of coalescence that occurs during the emulsification of tri-2-ethylhexyl phosphate using a high-pressure homogenizer. From these measurements, the roles of anionic surfactant (SDS) and gelatin in stabilizing drops against coalescence and promoting drop rupture during emulsification are deduced. It is found that gelatin aids in reducing coalescence, whereas SDS aids in rupture of drops. The effect of variables such as gelatin MW, surfactant type, and pH on coalescence and final drop size is investigated.     

Measurement of the Mass Transfer into Single Drops in the System of Water/Supercritical Carbon Dioxide

This paper presents a new method for the measurement of mass transfer in isolated water drops. The transport of a component in the water drop can be detected by a change in electrical conductivity. Measurements were performed using a new type of sensor design. In particular the transfer of CO(2) from a continuous fluid phase into the water drop was investigated. CO(2) leads to an increased conductivity in water because of the carbonic acid equilibrium. Experimental conditions ranged from 298 to 323 K in temperature and from 2.5 up to 30.7 MPa in pressure. The mass transfer coefficients obtained give insight into the transfer process and its physical mechanisms. Increasing temperature and density of the surrounding carbon dioxide lead to faster mass transfer processes. The effects of drop geometry and internal turbulences on the mass transfer velocity are discussed. Copyright 2000 Academic Press.     

The drop size in membrane emulsification determined from the balance of capillary and hydrodynamic forces

Here, we investigate experimentally and theoretically the factors that determine the size of the emulsion droplets produced by membrane emulsification in "batch regime" (without applied crossflow). Hydrophilic glass membranes of pore diameters between 1 and 10 mum have been used to obtain oil-in-water emulsions. The working surfactant concentrations are high enough to prevent drop coalescence. Under such conditions, the size of the formed drops does not depend on the surfactant type and concentration, on the interfacial tension, or on the increase of viscosity of the inner (oil) phase. The drops are monodisperse when the working transmembrane pressure is slightly above the critical pressure for drop breakup. At higher pressures, the size distribution becomes bimodal: a superposition of a "normal" peak of monodisperse drops and an "anomalous" peak of polydisperse drops is observed. The theoretical model assumes that, at the moment of breakup, the hydrodynamic ejection force acting on the drop is equal to the critical capillary force that corresponds to the stability-instability transition in the drop shape. The derived equations are applied to predict the mean size of the obtained drops in regimes of constant flow rate and constant transmembrane pressure. Agreement between theory and experiment is established for the latter regime, which corresponds to our experimental conditions. The transition from unimodal to bimodal drop size distribution upon increase of the transmembrane pressure can be interpreted in terms of the transition from "dripping" to "jetting" mechanisms of drop detachment.     

Silica particle-stabilized emulsions of silicone oil and water: aspects of emulsification

A study of the emulsification of silicone oil and water in the presence of partially hydrophobic, monodisperse silica nanoparticles is described. Emulsification involves the fragmentation of bulk liquids and the resulting large drops and the coalescence of some of those drops. The influence of particle concentration, oil/water ratio, and emulsification time on the relative extents of fragmentation and coalescence during the formation of emulsions, prepared using either batch or continuous methods, has been investigated. For batch emulsions, the average drop diameter decreases with increasing particle concentration as the extent of limited coalescence is reduced. Increasing the oil volume fraction in the emulsion at fixed aqueous particle concentration results in an increase in the average drop diameter together with a dramatic lowering of the uniformity of the drop size distribution as coalescence becomes increasingly significant until catastrophic phase inversion occurs. For low oil volume fractions (phi(o)), fragmentation dominates during emulsification since the mean drop size decreases with emulsification time. For higher phi(o) close to conditions of phase inversion, coalescence becomes more prevalent and the drop size increases with time with stable multiple emulsions forming as a result.