Two-dimensional fluidics based on differential lyophobicity and gravity

We have prepared planar fluidics devices using binary chemical patterns consisting of hydrophobic "roads" on which water droplets slide easily and more hydrophobic "curbs" that direct droplet motion. Contact angle and contact angle hysteresis both control the motion of liquid droplets on surfaces. The difference between the advancing contact angles of the two regions prevents the liquid from crossing the interface between them. The low hysteresis of the roads allows facile movement. Gravity (slight tilting of samples) forces droplets to move effortlessly in defined pathways even though the difference in contact angles is not large and both regions are hydrophobic.     

Electrowetting-based droplet mixers for microfluidic systems

Mixing of analytes and reagents is a critical step in realizing a lab-on-a-chip. However, mixing of liquids is very difficult in continuous flow microfluidics due to laminar flow conditions. An alternative mixing strategy is presented based on the discretization of liquids into droplets and further manipulation of those droplets by electrowetting. The interfacial tensions of the droplets are controlled with the application of voltage. The droplets act as virtual mixing chambers, and mixing occurs by transporting the droplet across an electrode array. We also present an improved method for visualization of mixing where the top and side views of mixing are simultaneously observed. Microliters of liquid droplets are mixed in less than five seconds, which is an order of magnitude improvement in reported mixing times of droplets. Flow reversibility hinders the process of mixing during linear droplet motion. This mixing process is not physically confined and can be dynamically reconfigured to any location on the chip to improve the throughput of the lab-on-a-chip.     

Stability of the jet flow of charged particles in a gaseous medium

The dynamics of the unidimensional straight-line motion of charged liquid droplets has been considered. Stability criterion has been derived for the jet motion of liquid droplets in a space bounded by two electrodes. The motion of an ensemble of charged droplets in a constant electric field and in a nonuniform field between a needle-like electrode and a plane has been calculated by the molecular dynamics method. Experimental data have been presented on the motion of micron and submicron charged particles formed by the electrostatic spraying of different liquids. The experimental data have been compared with the theoretical calculations and numerical simulation results.     

Spontaneous emulsification at oil–water interface by tetraalkylammonium chloride

Water droplets were formed spontaneously at the interface of the 2-nitrophenyloctyl ether and aqueous phases on the oil phase side when the oil contained tetraalkylammonium chloride without surfactants. The droplets, less than some micrometers in diameter, gathered at the interface. The number density of the droplets was proportional to the concentration of tetraethylammonium chloride, and hence this salt should be responsible for the formation of the droplets as a surfactant. When positive voltage was applied to the aqueous phase against the oil, the droplets departed from the interface toward the oil bulk. The droplets should be negatively charged by chloride. The adsorption model of the salt was suggested, in which chloride is immobilized at the interface on the aqueous side electrostatically with tetraethylammonium ion on the oil side.     

Step Morphology of Liquid Phase Epitaxial GaAs Determined by Atomic Force Microscopy

Single, double and triple growth spirals were observed on liquid phase epitaxy(LPE) grown layers using atomic force microscopy (AFM). Spiral growth arises from the motion of growth steps in a spiral fashion. The LPE grown GaAs Layers show quite a different step morphology as compared with cleaved GaAs crystals. The step treads are atomically flat planes in the cleaved crystals. but are generally not atomically flat planes and rather bow upwards in the LPE layers. The mechanism arousing this difference is unclear.     

NMR and SANS studies of aggregation and microemulsion formation by phosphorus fluorosurfactants in liquid and supercritical carbon dioxide

(1)H NMR relaxation and diffusion studies were performed on water-in-CO(2) (W/C) microemulsion systems formed with phosphorus fluorosurfactants of bis[2-(F-hexyl)ethyl] phosphate salts (DiF(8)), having different counterions (Na(+), NH(4)(+), N(CH(3))(4)(+)) by means of high-pressure in situ NMR. Water has a low solubility in CO(2) and is mainly solubilized by the microemulsion droplets formed with surfactants added to CO(2) and water mixtures. There is rapid exchange of water between the bulk CO(2) and the microemulsion droplets; however, NMR relaxation measurements show that the entrapped water has restricted motion, and there is little "free" water in the core. Counterions entrapped by the droplets are mostly associated with the surfactant headgroups: diffusion measurements show that counterions and the surfactant molecules move together with a diffusion coefficient that is associated with the droplet. The outer shell of the microemulsion droplets consists of the surfactant tails with some associated CO(2). For W/C microemulsions formed with the phosphate-based surfactant having the ammonia counterion (A-DiF(8)), the (1)H NMR signal for NH(4)(+) shows a much larger diffusion coefficient than that of the surfactant tails. This apparent paradox is explained on the basis of proton exchange between water and the ammonium ion. The observed dependence of the relaxation time (T(2)) on W(0) (mole ratio of water to surfactant in the droplets) for water and NH(4)(+) can also be explained by this exchange model. The average hydrodynamic radius of A-DiF(8) microemulsion droplets estimated from NMR diffusion measurements (25 degrees C, 206 bar, W(0) = 5) was R(h) = 2.0 nm. Assuming the theoretical ratio of R(g)/R(h) = 0.775 for a solid sphere, where R(g) is the radius of gyration, the equivalent hydrodynamic radius from SANS is R(h) = 1.87 nm. The radii measured by the two techniques are in reasonable agreement, as the two techniques are weighted to measure somewhat different parts of the micelle structure.     

Numerical and theoretical study on the mechanism of biopolymer translocation process through a nano-pore

We conducted a numerical study on the translocation of a biopolymer from the cis side to the trans side of a membrane through a synthetic nano-pore driven by an external electric field in the presence of hydrodynamic interactions (HIs). The motion of the polymer is simulated by 3D Langevin dynamics technique using a worm-like chain model of N identical beads, while HI between the polymer and fluid are incorporated by the lattice Boltzmann equation. The translocation process is induced by electrophoretic force, which sequentially straightens out the folds of the initial random configuration of the polymer chain on the cis side. Our simulation results on translocation time and velocity are in good quantitative agreement with the corresponding experimental ones when the surface charge on the nano-pore and the HI effect are considered explicitly. We found that the translocation velocity of each bead inside the nano-pore mainly depends upon the length of the straightened portion of the polymer in forced motion near the pore. We confirmed this by a theoretical formula. After performing simulations with different pore lengths, we observed that translocation velocity mainly depends upon the applied potential difference rather than upon the electric field inside the nano-pore.     

Advancing and receding motion of droplets on ultrahydrophobic post surfaces

We have fabricated a range of silicon post surfaces where post width and spacing have been systematically varied. As one subset, we have generated surfaces where the post spacings in x and y assume different values. On these surfaces, the dynamic contact angles become anisotropic. A fluoropolymer monolayer is photochemically attached to the microstructured silicon, leading to the appearance of ultrahydrophobic properties. On one side, the advancing contact angles on these surfaces are not affected by variations in the geometric parameters. This furthers the conclusion that, during the advancing motion, a true contact angle of 180 degrees is reached. On the other side, the receding angles are strongly influenced by the post size and spacing. We quantitatively analyze this dependence and relate variations in the receding angle to the shape and movement of the three-phase contact line. It is suggested that during the receding motion the meniscus successively dewets from one post at a time, with a step function running along the contact line until it has receded from a row of posts over its entire length.     

Molecular dynamics simulation on influence of temperature effect on electro-coalescence behavior of nano-droplets

In electric dehydration of crude oil, the dewatering efficiency can be improved by raising emulsion temperature properly which reduces the viscosity of crude oil. However, it should be noticed that the emulsion temperature does not only affect the emulsion viscosity but also nano-droplets dynamics behavior which impacts the coalescence efficiency either. Therefore the influence of temperature effect on the electro-coalescence of nano-droplets is studied by a molecular dynamics method. The results show that the temperature presents an active or negative effect, depending on the competitive relation between electrostatic interaction and thermal motion. Two stages are distinguished according to the dominant mechanism. During stage I, governed by the electrostatic interaction, lower temperature promotes the polarization and leads to an acceleration of the droplets coalescence, but higher temperature restrains the coalescence process due to molecules thermal motion breaking the polarization process. During stage II, governed by the thermal motion, lower temperature improves the coalescence because of a diffusion effect, but higher temperature deteriorates electro-coalescence because of a violent molecular thermal motion. Additionally, hydrogen bond and radial distribution functions are obtained by statistics to describe droplets micromorphology, which explains the reason why the droplet forms longer chain structure at the critical electric field.     

Temperature stability of the interfacial structure between a sulfonated crystalline alkyl side-chain polymer and a soft adhesive

The fracture toughness of interfaces between a sulfonated alkyl side-chain graft copolymer and a soft acrylic random copolymer containing acrylic acid monomers was investigated with a probe test method. Interfaces between a thin (100 nm) layer of the block copolymer and a thick (100 microm) layer of the acrylic copolymer were prepared at room temperature and subsequently annealed for 7 h at different temperatures. After the annealing step, the interface was quenched to room temperature and tested, a strategy that provides the advantage of keeping constant the mechanical properties of the materials on both sides of the interface so that any major difference in adhesive behavior can only be attributed to a change in the interfacial structure. For annealing temperatures below the crystalline to liquid crystalline transition temperature (86 degrees C), the adhesion energy remained very low and failure occurred by interfacial crack propagation. However when the interface was annealed above that temperature, a much higher adhesion energy was observed at room temperature because of the formation of a fibrillar structure upon debonding. The results indicate that the crystalline order at low temperature is very stable presumably because of the strong interactions between the sulfone groups in the side chains. However, when these interactions weaken and the side chains become liquid crystalline, the surface reconstruction mechanism cannot be prevented and strong interactions formed between the polar parts of the copolymer and the acrylic acid. These strong interactions remain during the cooling step, and a mechanism of surface reconstruction is proposed.     

Transformation of isotactic polypropylene droplets from the mesophase into the α‐phase

The structural transformation of homogeneously nucleated metastable mesophase of polypropylene (PP) particles was investigated in this study. We demonstrated the formation of heterogeneity‐free mesophase by slow cooling of the droplets unlike mesophase formation by quenching of the PP melt, which contained large number of bulk nuclei. Submicron size PP droplets were produced by thermal break up of PP and polystyrene layered film assembly. When cooled from melt, the PP droplets crystallized into mesophase at 44 °C revealing granular morphology. Subsequent heating thermogram of the PP particles showed a broad exotherm, which was attributed to the transformation of mesophase into α‐phase. This transformation was investigated during heating by annealing the PP particles at different temperatures. Annealed PP particles were analyzed by means of thermal, morphological and structural properties measurements. Results revealed a two step process for the transformation process. In the first step, the internal rearrangement of PP chains, as against melting and recrystallization of the mesophase, was observed. Since granular morphology was not affected significantly up to 120 °C, it was suggested that translational and rotational motions of PP helices produced ordered α‐phase. In the second step, increment in grain size distribution was observed, when the droplets were annealed at 140 °C. The results were attributed to enhanced chain mobility and merging of the grain boundaries. Annealing at 160 °C revealed the formation of short lamellar structures. Crystal thickening, melting and recrystallization of α‐phase were suggested at high temperature annealing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Droplet Motion Induced by Diffusion of Soluble Surfactant to the External Medium: Experiment

Experimental examinations were performed for the motion of liquid droplets suspended under the condition of neutral buoyancy (Plateau technique) in the second liquid in the presence of surfactant transfer from droplets to the surrounding liquid or surfactant transfer to the droplet from the external medium. It was shown that, at a certain initial surfactant concentration, spontaneous droplet motion arises, which has the oscillation character. When the initial concentration exceeds a certain critical value, almost steady-state translational droplet motion occurs in addition to oscillation displacements. In the case of surfactant transfer from the surrounding liquid to the droplet, only oscillation displacements of a droplet with larger amplitude take place.     

Laser photophoretic migration with periodic expansion-contraction motion of photo-absorbing microemulsion droplets in water

When the water-in-oil (w/o) microemulsion droplets including the Co(III)-pyridylazo complex as the photo-absorber were irradiated with a continuous-wave Ar(+) ion laser (514.5 nm), we have observed unexpected phenomenon that photo-absorbing microemulsion droplets in water repeated the expansion and the sudden contraction during the laser photophoretic migration. The period of the expansion-contraction cycle was inversely proportional to both the concentration of the complex and the irradiated laser power and was independent of the initial size of the droplet. The mechanism of the periodic motion of the droplet was investigated by local temperature measurement and Raman microscope spectroscopy. It was suggested that the first step was the phase separation of the bicontinuous microemulsion droplet into the normal w/o microemulsion outer phase and the aqueous inner phase in the droplet, which was caused by the laser-induced temperature gradient inside the droplet. Subsequently, an expansion of the inner aqueous phase was induced by the percolation of the external water by thermo-osmosis, which was caused by the laser-induced temperature gradient between the inside and the outside of the microemulsion liquid membrane of the droplet. When the liquid membrane became thinner to a critical thickness, the inner aqueous phase was released and the droplet shrank into the original size. The proposed mechanism can give an account of the unique cyclical motion.     

Nucleation on cylindrical plates: sharp transitions and double barriers

We apply methods of density-functional theory in statistical mechanics to study the properties of droplets and bubbles formed on a single cylindrical plate or between two such disks immersed in a metastable fluid. Our approach allows us to analyze the properties of different types of aggregates and investigate the effect of disk size, disk separation, and solid-fluid interactions on the dynamics of a liquid-vapor phase transition. The finite size of disks induces nucleation phenomena that are not observed in the cases of either a planar wall or a slit pore. Heterogeneous nucleation on a single disk is characterized by the existence of two distinct types of critical nuclei that control the phase-transition dynamics at different supersaturations. Asymmetric droplets or bubbles formed on one side of the disk are the preferred nucleation path at high supersaturations. However, these types of aggregates become unstable close to the binodal, where they abruptly collapse into nuclei that engulf the cylindrical plates. Droplet or bubble nucleation in between two disks may occur through a free-energy barrier with one or two maxima depending on the value of the system parameters and the supersaturation. Metastable droplets or bubbles corresponding to local minima of the free energy are observed forming between two plates only after density fluctuations in the system achieve a critical size. These types of aggregates only exist for cylindrical plates larger than a minimum size given a fixed distance between the disks. The stability of these droplets and bubbles decreases when the plates are separated.     

体系pH值、乳化温度和电解质离子对异丙甲草胺水乳剂稳定性的影响

通过测定药物液滴的平均粒径和Zeta电位研究了体系pH值、 乳化温度和电解质离子对乳化剂三苯乙烯基苯酚聚氧乙烯醚磷酸酯三乙醇胺盐(SCP)稳定的异丙甲草胺水乳剂稳定性的影响. 结果发现, 体系的pH值影响SCP分子在水中的电离能力, 当pH=9时, SCP完全电离, 能为液滴提供较大的静电稳定作用, 水乳剂稳定性最好; 乳化温度低时, SCP分子向液滴界面扩散慢, 且舒展不完全, 液滴所带负电荷较少, 水乳剂稳定性差; 温度升高后, 水相黏度减小, 布朗运动加剧, 液滴碰撞合并几率增大, 且SCP分子热运动增强, 易从界面逃逸, 液滴间静电斥力减弱, 同时SCP亲水性下降, 水乳剂稳定性变差; 电解质离子会压缩界面双电层, 降低Zeta电位, 液滴带电量减少而聚结, 离子浓度越大, 电荷数越大, 水乳剂稳定性越差. 在相同的离子浓度下, 水合半径小的Ca²⁺压缩双电层能力强于Mg²⁺, 添加Ca²⁺后水乳剂稳定性更差.     

Delayed coalescence behavior of droplets with completely miscible liquids

Because of capillary forces, sessile droplets usually fuse instantaneously after contact. We find however a delay of the droplet fusion by many seconds if the droplets consist of different but completely miscible liquids. After the initial contact, the main bodies of the droplets remain separated, connected only through a shallow conduit with a flow from the low to the high surface tension liquid. Sporadically, this connecting film can thicken with turbulent or pulsating flows. The droplets will finally fuse when the flow has sufficiently reduced the difference in composition and surface tension. We present calculations which explain this delayed droplet fusion with the compensation of the fusion-promoting capillary pressure by a droplet-separating dynamic pressure caused by the flow between the droplets. Droplets with high contact angles fuse instantaneously. In this case, no separation-stabilizing dynamic pressure can build up because the interdroplet flow becomes turbulent.     

Molecular dynamics simulations of water droplets on polymer surfaces

Molecular dynamics simulations were used to study the wetting of polymer surfaces with water. Contact angles of water droplets on crystalline and two amorphous polyethylene (PE) and poly(vinyl chloride) (PVC) surfaces were extracted from atomistic simulations. Crystalline surfaces were produced by duplicating the unit cell of an experimental crystal structure, and amorphous surfaces by pressing the bulk polymer step by step at elevated temperature between two repulsive grid surfaces to a target density. Different-sized water droplets on the crystalline PE surface revealed a slightly positive line tension on the order of 10(-12)-10(-11) N, whereas droplets on crystalline PVC did not yield a definite line tension. Microscopic contact angles produced by the simple point charge (SPC) water model were mostly a few degrees smaller than those produced by the extended SPC model, which, as the model with lowest bulk energy, presents an upper boundary for contact angles. The macroscopic contact angle for the SPC model was 94 degrees on crystalline PVC and 113 degrees on crystalline PE. Amorphicity of the surface increased the water contact angle on PE but decreased it on PVC, for both water models. If the simulated contact angles on crystalline and amorphous surfaces are combined in proportion to the crystallinity of the polymer in question, simulated values in relatively good agreement with measured values are obtained.     

CTAB/n-C5H11OH/H2O体系对青霉素G钾盐水解的抑制作用

微乳液是由表面活性剂、助表面活性剂、水、油等组成的各向同性、低粘度的热力学体系［１］,在生物、环境及其相关领域有着十分重要的应用［２］．近年来,以微乳液为微反应器进行化学反应已引起重视［３－１０］青霉素是一种很重要的抗生素药物,它在阴暗干燥的空气中较...     

Elasticity-driven droplet movement on a microbeam with gradient stiffness: a biomimetic self-propelling mechanism

Directional movement of liquid droplets is of significance not only for certain physiological processes in nature but also for design of some microfluidic devices. In this study, we report a novel way to drive directional movement of liquid droplets on a microbeam with a varying or gradient stiffness. We use the energy method to theoretically analyze the interaction between a droplet and the elastic microbeam. The system tends to have the minimum potential energy when the droplet moves to the softer end of the beam. Therefore, a gradient change of the bending stiffness may be utilized to help the directional motion of droplets. Similarly, one can also drive droplets to move in a designed direction by varying the cross sectional geometry of the beam. Finally, some possible applications of this self-propelling mechanism are suggested.