Emulsion electrospinning: composite fibers from drop breakup during electrospinning

We evaluate the feasibility of electrospinning oil‐in‐water type emulsions. The emulsions had an aqueous solution of polyethylene oxide (PEO) as the continuous phase, and either mineral oil or a polystyrene (PS) in toluene solution as the drop phase. The Taylor cones and electrified liquid jets were stable even when the emulsion drops were as large as a few‐ten microns in diameter. The resulting electrospun PEO fibers incorporated the dispersed phase of the emulsion in the form of drops (in case of mineral oil), or in the form of solid particles (in case of PS). Mineral oil drops appear to be completely encapsulated in the PEO fibers, whereas the PS particles are either incompletely encapsulated, or covered by only a very thin layer of PEO. Calculations show that in both cases, the initially large emulsion drops are broken during the electrospinning process. Copyright © 2007 John Wiley & Sons, Ltd.     

Effects of Applied Electric Fields on Drop—Interface and Drop—Drop Coalescence*

In this work, coalescence of a single organic or aqueous drop with its homophase at a horizontal liquid interface was investigated under applied electric fields. The coalescence time was found to decrease for aqueous drops as the applied voltage was increased, regardless of the polarity of the voltage. For organic drops, the coalescence time increased with increasing applied voltage of positive polarity and decreased with increasing applied voltage of negative polarity. Under an electric field, the coalescence time of aqueous drops decreases due to polarization of both the drop and the flat interface. The dependency of organic drop-interface coalescence on the polarity of the electric field may be a result of the negatively charged organic surface in the aqueous phase. Due to the formation of a double layer, organic drops are subjected to an electrostatic force under an electric field, which, depending on the field polarity, can be attractive or repulsive. Pair-drop coalescence of aqueous drops in the organic phase was also studied. Aqueous drop-drop coalescence is facilitated by polarization and drop deformation under applied electric fields. Without applied electric fields, drop deformation increases the drainage time of the liquid film between two approaching drops. Therefore, a decrease in the interfacial tension, which causes drop deformation, accelerates drop-drop coalescence under an electric field and inhibits drop coalescence in the absence of an electric field.     

分立式悬液四电极微液／液界面电解池的研制

本文研究了一种适用于液/液界面电化学研究的悬液电解池及其性能,它能产生3～20mm~2的球形界面和0.025mm~2的微盘界面。通过微量注射器调节,界面易更新,且液滴稳定时间长达1h。介绍了一种耐强极性有机溶剂接触的玻璃表面疏水处理方法,经处理后的电解池可连续使用14天。以典型的四乙基铵离子的转移特征来验证本电解池的性能,获得满意的结果。     

Drop formation in aqueous two-phase systems

Extraction using aqueous two-phase systems (ATPSs) is a versatile technique for the downstream processing of various proteins/enzymes. The study of drop formation deals with the fundamental understanding of the behavior of liquid drops under the influence of various external body as well as surface forces. These studies provide a basis for designing of the extractions in column contactors in which liquid drops play a major role. Most of the drop formation studies reported so far is restricted to aqueous-organic systems. ATPSs, differ from aqueous-organic systems in their physical properties. In view of this, an attempt was made to develop a model for drop formation in ATPSs adopting the information available on aqueous-organic systems. In order to validate the model, experiments were performed by using polyethylene glycol (PEG)/salt systems of different phase compositions at various flow rates. At low flow rates the single stage model and at high flow rates the two stage model are able to predict the drop volume during its formation from tip of capillary. The experimental results were found to agree reasonably well with those predicted by the model.     

Comment on "Two touching spherical drops in uniaxial extensional flow: analytic solution to the creeping flow problem"

From an analysis of tangent spherical drops in straining flow, Baldessari and Leal conclude that the drop-scale internal circulation, driven by the ambient flow, has a negligible influence on the drainage of the thin liquid film between drops under small-deformation conditions [F. Baldessari, L.G. Leal, J. Colloid Interface Sci. 289 (2005) 262]. However, their conclusion is incorrect as explained in this letter.     

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.     

Optofluidic encapsulation of crystalline colloidal arrays into spherical membrane

Double emulsion droplets encapsulating crystalline colloidal arrays (CCAs) with a narrow size distribution were produced using an optofluidic device. The shell phase of the double emulsion was a photocurable resin that was photopolymerized downstream of the fluidic channel within 1 s after drop generation. The present optofluidic synthesis scheme was very effective for fabricating highly monodisperse spherical CCAs that were made structurally stable by in situ photopolymerization of the encapsulating shells. The shell thickness and the number of core emulsion drops could be controlled by varying the flow rates of the three coflowing streams in the dripping regime. The spherical CCAs confined in the shell exhibited distinct diffraction patterns in the visible range, in contrast to conventional film-type CCAs. As a result of their structure, the spherical CCAs exhibited photonic band gaps for normal incident light independent of the position on the spherical surface. This property was induced by heterogeneous nucleation at the smooth wall of the spherical emulsion drop during crystallization into a face-centered cubic (fcc) structure. On the other hand, the solidified shells did not permit the penetration of ionic species, enabling the CCAs to maintain their structure in a continuous aqueous phase of high ionic strength for at least 1 month. In addition, the evaporation of water molecules inside the shell was slowed considerably when the core-shell microparticles were exposed to air: It took approximately 6 h for a suspension encapsulated in a thick shell to evaporate completely, which is approximately 1000 times longer than the evaporation time for water droplets with the same volume. Finally, the spherical CCAs additionally exhibited enhanced stability against external electric fields. The spherical geometry and high dielectric constant of the suspension contributed to reducing the electric field inside the shell, thereby inhibiting the electrophoretic movement of the charged particles.     

Solubilization of thermotropic liquid crystal compounds in aqueous surfactant solutions

We study the micellar solubilization of three thermotropic liquid crystal compounds by immersing single drops in aqueous solutions of the ionic surfactant tetradecyltrimethylammonium bromide. For both nematic and isotropic drops, we observe a linear decrease of the drop size with time as well as convective flows and self-propelled motions. The solubilization is accompanied by the appearance of small aqueous droplets within the nematic or isotropic drop. At low temperatures, nematic drops expell small nematic droplets into the aqueous environment. Smectic drops show the spontaneous formation of filament-like structures which resemble the myelin figures observed in lyotropic lamellar systems. In all cases, the liquid crystal drops become completely solubilized, provided the weight fraction of the liquid crystal in the system is not larger than a few percent. The solubilization of the liquid crystal drops is compared with earlier studies of the solubilization of alkanes in ionic surfactant solutions.     

Evaporation of pure liquid sessile and spherical suspended drops: a review

A sessile drop is an isolated drop which has been deposited on a solid substrate where the wetted area is limited by a contact line and characterized by contact angle, contact radius and drop height. Diffusion-controlled evaporation of a sessile drop in an ambient gas is an important topic of interest because it plays a crucial role in many scientific applications such as controlling the deposition of particles on solid surfaces, in ink-jet printing, spraying of pesticides, micro/nano material fabrication, thin film coatings, biochemical assays, drop wise cooling, deposition of DNA/RNA micro-arrays, and manufacture of novel optical and electronic materials in the last decades. This paper presents a review of the published articles for a period of approximately 120 years related to the evaporation of both sessile drops and nearly spherical droplets suspended from thin fibers. After presenting a brief history of the subject, we discuss the basic theory comprising evaporation of micrometer and millimeter sized spherical drops, self cooling on the drop surface and evaporation rate of sessile drops on solids. The effects of drop cooling, resultant lateral evaporative flux and Marangoni flows on evaporation rate are also discussed. This review also has some special topics such as drop evaporation on superhydrophobic surfaces, determination of the receding contact angle from drop evaporation, substrate thermal conductivity effect on drop evaporation and the rate evaporation of water in liquid marbles.     

Spreading, evaporation, and contact line dynamics of surfactant-laden microdrops

An optical technique based on the reflectivity measurements of a thin film was used to experimentally study the spreading, evaporation, contact line motion, and thin film characteristics of drops consisting of a water-surfactant (polyalkyleneoxide-modified heptamethyltrisiloxane, called superspreader) solution on a fused silica surface. On the basis of the experimental observations, we concluded that the surfactant adsorbs primarily at the solid-liquid and liquid-vapor interfaces near the contact line region. At equilibrium, the completely wetting corner meniscus was associated with a flat adsorbed film having a thickness of approximately 31 nm. The calculated Hamaker constant, A = -4.47 x 10(-)(20) J, shows that this thin film was stable under equilibrium conditions. During a subsequent evaporation/condensation phase-change process, the thin film of the surfactant solution was unstable, and it broke into microdrops having a finite contact angle. The thickness of the adsorbed film associated with the drops was lower than that of the equilibrium meniscus. The drop profiles were experimentally measured and analyzed during the phase-change process as the contact line advanced and receded. The apparent contact angle, the maximum concave curvature near the contact line region, and the convex curvature of the drop increased as the drop grew during condensation, whereas these quantities decreased during evaporation. The position of the maximum concave curvature of the drop moved toward the center of the drop during condensation, whereas it moved away from the center during evaporation. The contact line velocity was correlated to the observed experimental results and was compared with the results of the drops of a pure alcohol. The experimentally obtained thickness profiles, contact angle profiles, and curvature profiles of the drops explain how the surfactant adsorption affects the contact line motion. We found that there was an abrupt change in the velocity of the contact line when the adsorbed film of the surfactant solution was just hydrated or desiccated during the phase-change processes. This result shows the effect of vesicles and aggregates of the surfactant on the shape evolution of the drops. For these surfactant-laden water drops, we found that the apparent contact angle increased during condensation and decreased during evaporation. However, for the drop of a pure liquid (n-butanol and 2-propanol) the apparent contact angle remained constant at a constant velocity during condensation and evaporation. The contact line was pinned during the evaporation and spreading of the surfactant-laden water drops, but it was not pinned for a drop of a pure alcohol (self-similar shape evolution).     

Generation of core-shell microcapsules with three-dimensional focusing device for efficient formation of cell spheroid

We present a microfluidic device generating three-dimensional (3D) coaxial flow by the addition of a simple hillock to produce an alginate core-shell microcapsule for the efficient formation of a cell spheroid. A hillock tapered at downstream of the two-dimensional focusing channel enables outside flow to enclose the core flow. The aqueous solution in the core flow was focused and surrounded by 1.8% alginate solution to be solidified as a shell. The double-layered coaxial flow (aqueous phase) was broken up into a droplet by the shear flow of oleic acid (oil phase) containing calcium chloride for the polymerization of the alginate shell. The droplet generated from the laminar coaxial flow maintained a double-layer structure and gelation of the alginate solution made a core-shell microcapsule. The shell-thickness of the microcapsule was adjusted from 8-21 μm by the variation of two aqueous flow rates. The inner shape of the shell was almost spherical when the ratio of the water-glycol mixture in the core flow exceeded 20%. The microcapsule was used to form a spheroid of embryonic carcinoma cells (embryoid body; EB) by injecting a cell suspension into the core flow. The cells inside the microcapsule aggregated into an EB within 2 days and the EB formation rate was more than 80% with strong compaction. The microcapsule formed single spherical EBs without small satellite clusters or a bumpy shape as observed in solid microbeads. The microfluidic chip for encapsulation of cells could generate a number of EBs with high rate of EB formation when compared with the conventional hanging drop method. The core-shell microcapsule generated by 3D focusing in the microchannel was effective in forming large number of spherical cell clusters and the encapsulation of cells in the microcapsule is expected to be useful in the transplantation of islet cells or cancer stem cell enrichment.     

Spreading of liquid drops over saturated porous layers

Spreading of small liquid drops over thin porous layers saturated with the same liquid is investigated from both theoretical and experimental points of view. A theory is presented that shows that spreading is governed by the same power law as in the case of spreading over a dry solid substrate. The Brinkman's equations are used to model the liquid flow inside the porous substrate. An equation of the drop spreading is deduced, which shows that both an effective lubrication and the liquid exchange between the drop and the porous substrates are equally important. The presence of these two phenomena removes the well-known singularity at the moving three-phase contact line. Matching of the drop profile in the vicinity of the three-phase contact line with the main spherical part of the drop gives the possibility to calculate the pre-exponential factor in the spreading law via permeability and effective viscosity of the liquid in the porous layer. Unfortunately, the latter dependency turns out to be very weak. Spreading of silicone oils over different microfiltration membranes is carried out. Radii of spreading on time experimental dependencies confirm the theory predictions. Experimentally found coefficients agree with theoretical estimations.     

Characterization of pathogenic bacteria using ionic liquid via single drop microextraction combined with MALDI-TOF MS

The present research was based on the single drop microextraction (SDME) approach using an ionic liquid drop to extract bacteria from aqueous samples for characterization of pathogenic bacteria by MALDI-TOF MS. The SDME of bacteria from aqueous samples was successfully achieved by using platinum nanoparticles mixed in ionic liquid (IL, 1-butyl-3-methylimidazolium hexafluorophosphate) and IL alone as the extraction drops. The IL was used as liquid drops by SDME to obtain protein profiles from bacteria. Significant numbers of biomarker protein peaks of bacteria were identified from target biological samples. The IL also significantly improved the signal reproducibility of spectra using the SDME approach combined with MALDI-TOF MS. Thus, the present technique was successfully applied to detect pathogenic bacteria at low concentrations of 10(6) cfu mL(-1) from aqueous suspensions. The selected bacteria viz., Escherichia coli and Serratia marcescens were used as target biological sample.     

Double-emulsion drops with ultra-thin shells for capsule templates

We introduce an emulsification technique that creates monodisperse double-emulsion drops with a core-shell geometry having an ultra-thin wall as a middle layer. We create a biphasic flow in a microfluidic capillary device by forming a sheath flow consisting of a thin layer of a fluid with high affinity to the capillary wall flowing along the inner wall of the capillary, surrounding the innermost fluid. This creates double-emulsion drops, using a single-step emulsification, having a very thin fluid shell. If the shell is solidified, its thickness can be small as a hundred nanometres or even less. Despite the small thickness of this shell, these structures are nevertheless very stable, giving them great potential for encapsulation. We demonstrate this by creating biodegradable microcapsules of poly(lactic acid) with a shell thickness of a few tens of nanometres, which are potentially useful for encapsulation and delivery of drugs, cosmetics, and nutrients.     

Two touching spherical drops in uniaxial extensional flow: analytic solution to the creeping flow problem

We solve the problem of the creeping motion of a uniaxial extensional flow past two touching spherical drops when the line of centers is parallel to the axis of symmetry of the flow, using tangent sphere coordinates. We apply this solution to the case of two equal size drops. It provides an exact result for the equal and opposite force acting on each drop along the line of centers. We also use it to determine the magnitude of the internal recirculating flow in the vicinity of the rear stagnation point, which can be used to evaluate the importance of this flow on the film drainage process for two (nearly) touching drops in a coalescence process for the limiting case, Ca < 1.     

Replacing the solid needle by a liquid one when measuring static and advancing contact angles

In general, the optical determination of static and advancing contact angle is made on drops applied or extended, respectively, onto a substrate through the use of thin solid needles. Although this method is used extensively, this way of dosing can be time consuming, cumbersome and if not performed meticulously can lead to erroneous results. Herein, we present an alternative way of applying drops onto substrates using a liquid jet produced by a liquid pressure dosing system acting as a “liquid needle”. We performed a comparative static contact angle study on 14 different surfaces with two different liquids (water and diiodomethane) utilizing two different ways of dosing: the conventional solid and a novel liquid needle-based technique. We found, for all but one sample, that the obtained results on μl size drops were comparable within the experimental error bars provided the liquid needle is thin enough. Observed differences are explained by the special characteristics of either way of dosing. In addition, we demonstrate how the liquid pressure-based dosing system facilitates high-speed optical advancing contact angle measurement by expanding a drop from 0.1 to 22 μl within less than 1.2 s but yet providing constant contact angle versus drop base diameter curves. The obtained results were compared with data from tensiometric dynamic Wilhelmy contact angle measurements. These data, in conjunction with sequences of live images of the dosing process of the liquid pressure dosing system, illustrate how this system can replace the solid needle by a liquid needle.     

Salt precipitation and trapped liquid cavitation in micrometric capillary tubes

Laboratory evidence shows that the occurrence of solid salt in soil pores causes drastic changes in the topology of the porous spaces and possibly also in the properties of the occluded liquid. Observations were made on NaCl precipitation in micrometric cylindrical capillary tubes, filled with a 5.5 M NaCl aqueous solution and submitted to drying conditions. Solid plug-shaped NaCl (halite) commonly grows at the two liquid-air interfaces, isolating the inner liquid column. The initially homogeneous porosity of the capillary tube becomes heterogeneous because of these two NaCl plugs, apparently closing the micro-system on itself. After three months, we observed cavitation of a vapor bubble in the liquid behind the NaCl plugs. This event demonstrates that the occluded liquid underwent a metastable superheated state, controlled by the capillary state of thin capillary films persisting around the NaCl precipitates. These observations show, first, that salt precipitation can create a heterogeneous porous medium in an initially regular network, thus changing the transfer properties due to isolating significant micro-volumes of liquid. Second, our experiment illustrates that the secondary salt growth drastically modifies the thermo-chemical properties of the occluded liquid and thus its reactive behavior.     

Electrophoretic mobility of a liquid drop in a salt-free medium

A theory is proposed for the electrophoretic mobility mu of dilute spherical liquid drops of radius a in salt-free media containing only counterions (e.g., nonaqueous media). As in the case of the electrophoretic mobility of rigid particle in salt-free media, there is a certain critical value of the drop surface charge separating two cases, that is, the low-surface-charge case and the high-surface-charge case. For the low-surface-charge case, mu coincides with that of a drop in an electrolyte solution in the limit of very low electrolyte concentrations kappaa-->0 (Hückel's limit), where kappa is the Debye-Hückel parameter. For the high-surface-charge case, however, mu becomes constant independent of the drop surface charge, since the counterion condensation takes place near the drop surface.     

Large Ultrathin Shelled Drops Produced via Non‐Confined Microfluidics

We present a facile approach for producing large and monodisperse core–shell drops with ultrathin shells using a single‐step process. A biphasic compound jet is introduced into a quiescent third (outer) phase that ruptures to form core–shell drops. Ultrathin shelled drops could only be produced within a certain range of surfactant concentrations and flow rates, highlighting the effect of interfacial tension in engulfing the core in a thin shell. An increase in surfactant concentrations initially resulted in drops with thinner shells. However, the drops with thinnest shells were obtained at an optimum surfactant concentration, and a further increase in the surfactant concentrations increased the shell thickness. Highly monodisperse (coefficient of variation smaller than 3 %) core–shell drops with diameter of ～200 μm–2 mm with shell thickness as small as ～2 μm were produced. The resulting drops were stable enough to undergo polymerisation and produce ultrathin shelled capsules.