Water-in-oil-in-water double nanoemulsion induced by CO(2)

The cetyltrimethylammonium bromide (CTAB)/water/heptane emulsion system with different CO(2) pressure has been studied. The phase behavior investigation shows the nanoemulsion can be formed at suitable pressure range. The generalized indirect Fourier transformation (GIFT) analysis of the small-angle X-ray scattering (SAXS) data has drawn a clear picture of the structural information of the nanoemulsion, which reveals that the droplet of emulsion has a double structure with both the outer and inner droplet size in nanometre range. Furthermore, the investigation of the heptane/CTAB/water/CO(2) emulsion system by using electrical conductivity confirms the emulsion type transforms from O/W to W/O/W. In addition, the effect of different CTAB concentration on the nanoemulsion formation has been studied. It is found that enough CTAB concentration is necessary for the inclusion of continuous water into oil droplets. We also explored the application of the W/O/W double nanoemulsion in material synthesis. Interestingly, the hollow silica spheres with double shells were obtained in this CO(2)-induced double nanoemulsion.     

Nanoemulsions prepared by a two-step low-energy process

A simple low-energy two-step dilution process has been applied in oil/surfactant/water systems with pentaoxyethylene lauryl ether (C12E5), dodecyldimethylammonium bromide, sodium bis(2-ethylhexyl)sulfosuccinate, sodium n-dodecyl sulfate-pentanol, and hexadecyltrimethylammonium bromide-pentanol. Appropriate formulations were chosen for the concentrate to be diluted with water to generate oil-in-water (O/W) emulsions or nanoemulsions. For the system of decane/C12E5/water, bluish, transparent nanoemulsions having droplet radii of the order of 15 nm were formed, only when the initial concentrate was a bicontinuous microemulsion, whereas opaque emulsions were generated if the concentrate began in an emulsion-phase region. Nanoemulsions generated in the system decane/C12E5/water have been investigated both by dynamic light scattering (DLS) and contrast-variation small-angle neutron scattering (SANS). The SANS profiles show that nanodroplets exist as spherical core-shell (decane-C12E5) particles, which suffer essentially no structural change on dilution with water, at least for volume fractions phi down to 0.060. These results suggest that the nanoemulsion droplet structure is mainly controlled by the phase behavior of the initial concentrate and is largely independent of dilution. A discrepancy between apparent nanoemulsion droplet sizes was observed by comparing DLS and SANS data, which is consistent with long-range droplet interactions occurring outside of the SANS sensitivity range. These combined phase behavior, SANS, and DLS results suggest a different reason for the stability/instability of nanoemulsions compared with earlier studies, and here it is proposed that a general mechanism for nanoemulsion formation is homogeneous nucleation of oil droplets during the emulsification.     

Structure of concentrated nanoemulsions

We use extreme shear to create a dispersion of nanoscale droplets of silicone oil in an immiscible water phase containing an anionic surfactant sodium dodecylsulfate. Using centrifugal size fractionation, we obtain nanoemulsions having a well-defined average radius of a=75 nm. We measure the structure of concentrated nanoemulsions over a wide range of volume fractions, 0相似文献   

Characteristics of pickering emulsion gels formed by droplet bridging

We experimentally characterize the microstructure and rheology of a carefully designed mixture of immiscible fluids and near-neutral-wetting colloidal particles. Particle bridging across two fluid interfaces provides a route to highly stable gel-like emulsions at volume fractions of the dispersed phase well below the random close-packing limit for spheres. We investigate the microstructural origins of this behavior by confocal microscopy and reveal a percolating network of colloidal particles that serves as a cohesive scaffold, bridging together droplets of the dispersed phase. Remarkably, the mixture's salient rheological characteristics are governed predominantly by the solids loading and can be tailored irrespective of the droplet volume fraction. The identification of this rheological hallmark could provide a means toward the improved design of modern products that utilize solid-stabilized interfaces.     

A simple model for the disintegration of highly charged solvent droplets during electrospray ionization

This work uses a minimalist model for deciphering the opposing effects of Coulomb repulsion and surface tension on the stability of electrosprayed droplets. Guided by previous observations, it is assumed that progeny droplets are ejected from the tip of liquid filaments that are formed as protrusions of an initially spherical parent. Nonspherical shapes are approximated as assemblies of multiple closely spaced beads. This strategy greatly facilitates the calculation of electrostatic and surface energies. For a droplet at the Rayleigh limit the model predicts that growth of a very thin filament is a spontaneous process with a negligible activation barrier. In contrast, significant barriers are encountered for the formation of larger diameter filaments. These different barrier heights favor highly asymmetric droplet fission because the dimensions of the filament determine those of the ejected droplet(s). Substantial charge accumulation occurs at the filament termini. This allows each progeny droplet to carry a significant fraction of charge, despite its very small volume. In the absence of a long connecting filament, relieving electrostatic stress through progeny droplet emission would be ineffective. The model predicts the prevalence of fission events leading to the formation of several progeny droplets, instead of just a single one. Ejection bursts are followed by collapse back to a spherical shape. The resulting charge depleted system is incapable of producing additional progeny droplets until solvent evaporation returns it to the Rayleigh limit. Despite the very simple nature of the model used here, all of these predictions agree with experimental data.     

Optically probing nanoemulsion compositions

Many types of colloids, including nanoemulsions, which contain sub-100 nm droplets, are dispersed in molecular and micellar solutions, especially surfactant solutions that confer stability. Since it would be desirable to measure the droplet volume fraction ? and surfactant concentration C of a nanoemulsion non-destructively, and since the droplet and surfactant structures are significantly smaller than the shortest wavelengths of visible light, optical refractometry could provide a simple and potentially useful approach. By diluting a silicone oil-in-water nanoemulsion having an unknown ? and C with pure water, measuring its refractive index n(?,C) using an Abbé refractometer, and fitting the result using a prediction for n that treats the nanoemulsion as an effective medium, we show that ? and C can be deduced accurately over a relatively wide range of compositions. Moreover, we generalize this approach to other types of nanoemulsions in which a molecular constituent partitions in varying degrees between the dispersed and the continuous phases.     

Boundary-element calculations for dielectric relaxation of water-in-oil-in-water emulsions consisting of spherical droplets with a spheroidal core

Using the boundary-element method, theoretical calculations were made for the complex permittivity of water-in-oil-in-water emulsions consisting of spherical droplets. A spheroidal inner phase was placed at the center of the droplet. To examine the effects of the shape of the inner phase, the axial ratio of the inner phase was changed by keeping its volume unchanged. The results showed that the dielectric relaxation of the emulsions was markedly affected by the shape of the inner phase. As a detailed analysis, effects of external electric fields directed in the mirror plane and those along the rotation axis of the droplets were examined separately. This showed that the relaxation consisted of two kinds of relaxation terms. The first related to the structure of the droplet parallel to the external field and had similar character to the low-frequency relaxation of emulsions of shelled spheres. The second, found in restricted cases, related to the structure perpendicular to the external field, having character similar to the high-frequency relaxation for the shelled spheres. Received: 8 May 2001 Accepted: 29 August 2001     

A new droplet breakup phenomenon in electrokinetic flow through a microchannel constriction

A completely new droplet breakup phenomenon is reported for droplets passing through a constriction in an electrokinetic flow. The breakup occurs during the droplet shape recovery process past the constriction throat by the interplay of the dielectrophoretic stress release and the interface energy for droplets with smaller permittivity than that of the ambient fluid. There are conditions for constriction ratios and droplet size that the droplet breakup occurs. The numerical predictions provided here require experimental verification, and then can give rise to a novel microfluidic device design with novel droplet manipulations.     

Sphere,honeycomb, regularly spaced droplet and fiber structures of polyion complexes of chitosan and gellan

Different characteristic surface structures such as true and hemi spheres, honeycomb, regularly spaced droplets and fibers are created by electrostatic polysaccharide interaction between chitosan and gellan gum via polyion complex formation. Spherical droplet capsules of varying diameters form in solution. Strong fibers can be spun by gravity and by wet spinning in ethanol. These fibers possess a counter ion pairing structure, and exhibit a ‘nervation/veining’ pattern.     

Displacement of liquid droplets on a surface by a shearing air flow

The motion of droplets on surfaces is crucial to the performance of a wide range of processes; this study examines the initiation of droplet motion through a shearing mechanism generated here by a controlled air flow. Systematic experiments are carried out for a range of fluids and well defined surfaces. A model is postulated that balances surface tension forces at the contact line and the drag force due to the air motion. Experiments reveal that the critical velocity at which droplet motion is initiated depends on the contact angle and the droplet size. Visualizations highlight three modes of motion: (I) the droplet retains a footprint similar to that at the point of motion; (II) a tail exists at the rear of the droplet; (III) a trail remains behind the droplet (that can shed smaller droplets). The predictions of droplet initiation velocity are good for type I motion, in accordance with the assumptions inherent within the model. This model confirms the dominant physics associated with the initiation of droplet motion and provides a useful predictive expression.     

Viscosity based droplet size controlling in negative pressure driven droplets generator for large‐scale particle synthesis

The poor control and regulation of droplets limit the applications of negative pressure driven droplet generator (NPDDG). Here, we present a simple method to control droplet size in NPDDG via varying the oil viscosity. Depending on the infinite intersolubility of high viscous mineral oil and low viscous hexadecane, we obtain a series of oils with kinematic viscosities linearly varied from 4.2 to 194.6 mm²/s. By using these oils as continuous phases, monodisperse droplets are fabricated with controllable size in NPDDG. This viscosity‐based droplet regulation method is effective, reliable, and compatible with scale‐up processes. Compared with droplet generator driven by positive pressure, the presented method can fabricate hydrogel particles massively, without complicated multilayer chip structure and complex fluid controlling, which may extend the potential of NPDDG in droplets based high‐throughput assay or large‐scale materials synthesis.     

Shape‐Tunable Colloids from Structured Liquid Droplet Templates

Shaping colloidal building units is of paramount importance for their self‐assembly into complex objects. Continuous tuning of colloidal shapes is highly desired for understanding self‐assembly, but it still remains a challenge. Herein, we report a new template strategy for the shape‐tunable synthesis of anisotropic colloids with shapes that can be continuously tuned from discs (oblate spheroids) to spheres to theta shapes to dumbbells. This was realized by creating structured shape‐tunable droplets from patchy colloidal discs and using these droplets as templates. In particular, we found that a controlled dumbbell‐to‐eyeball droplet transformation can be used for the synthesis of eyeball‐shaped colloids. We also demonstrated the droplet transformation pathways and applied the method to the synthesis of colloidal molecules. These colloids provide possibilities for exploring their ordered packing structures, and the method based on the use of structured droplets can be adapted for the synthesis of other functional colloidal particles.     

Structure of microemulsion-ABA triblock copolymer networks

Structural equilibrium properties of transient networks formed by microemulsion droplets and ABA triblock copolymers in solution have been studied by Monte Carlo simulation. The droplets were represented by soft spheres, and the polymers were represented by junctions connected by harmonic bonds with an angular potential regulating the intrinsic chain stiffness. The interaction parameters were selected such that the end A-blocks were localized inside the droplets and the middle B-block in the continuous phase. The influence of (i) the polymer concentration, (ii) the polymer stiffness, and (iii) the contour length of the middle B-block on the formation and the structure of the microemulsion-polymer network were investigated using polymer end-to-end separation probability distribution functions, droplet radial distribution functions, droplet-droplet nearest-neighbor probability distribution functions, and network connectivity indicators. An increase of the polymer-droplet number ratio had a strong impact on the network formation. Under typical conditions and at an intermediate polymer-droplet number ratio, (i) the fraction of polymers forming bridges between droplets increased from essentially zero to unity and (ii) the fraction of polymers that were forming loops decreased as the ratio of the polymer end-to-end separation and the surface-to-surface separation between neighboring droplets for a hypothetical homogeneous droplet distribution was increased from 0.5 to 2. For long and flexible polymers, a mesoscopic segregation triggered by a depletion attraction between droplets appeared, and, furthermore, for sufficiently stiff chains, only bridge conformations occurred. The percolation probability could be represented as a function of the average droplet cluster size only, across all systems.     

Dynamics of field-induced droplet ionization: time-resolved studies of distortion, jetting, and progeny formation from charged and neutral methanol droplets exposed to strong electric fields

We recently reported that strong electric fields may be employed to directly extract positive and negative ions for mass analysis, including intact proteins, from neutral droplets. The present study investigates the dynamics of this process using switched high electric fields to enable time-resolved studies of droplet distortion, Taylor cone formation, and charged progeny droplet extraction from neutral and charged 225 microm methanol droplets. After a specific time in the field, a flashlamp is triggered to record droplet distortions using shadow photography. At a critical field strength E(c)0 corresponding to the Taylor limit, neutral droplets exhibit a prolate elongation along the field axis forming symmetric cone-jets of positive and negatively charged progeny droplets, approximately 10 microm in diameter. This process is termed field-induced droplet ionization (FIDI). Because the time scale of FIDI is related to the frequency of shape oscillations that occur below the Taylor limit, models of field-dependent oscillation become an important predictor of the time scale for progeny jet formation. Droplets with a net charge q distort into asymmetric tear shapes and emit a single charged jet of progeny at a critical field E(c)(q) that is less than E(c)0. The measured decrease in droplet stream charge indicates that total charge loss can be greater than the original charge on the droplet, resulting in oppositely charged droplets. Interestingly, above E(c)0, charged droplets sequentially emit a jet of the same polarity as the net charge followed by a jet of reverse polarity emitted in the opposite direction. For both neutral and charged droplets, increasing the electric field decreases the time to form jets and the combination of net charge and higher-than-critical fields has a compound effect in accelerating progeny formation. The implications of our results for using switched fields in FIDI-mass spectrometry for on-demand ion sampling from neutral and charged droplets are discussed.     

How to prepare and stabilize very small nanoemulsions

Practical and theoretical considerations that apply when aiming to formulate by ultrasonication very small nanoemulsions (particle diameter up to 150 nm) with very high stability are presented and discussed. The droplet size evolution during sonication can be described by a monoexponential function of the sonication time, the characteristic time scale depending essentially on the applied power. A unique master curve is obtained when plotting the mean diameter size evolution as a function of sonication energy. We then show that Ostwald ripening remains the main destabilization mechanism whereas coalescence can be easily prevented due to the nanometric size of droplets. The incorporation of "trapped species" within the droplet interior is able to counteract Ostwald ripening, and this concept can be extended to the membrane compartment. We finally clarify that nanoemulsions are not thermodynamically stable systems, even in the case where their composition lies very close to the demixing line of a thermodynamically stable microemulsion domain. However, as exemplified in the present work, nanoemulsion systems can present very long-term kinetic stability.     

Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity

Aerosol optical tweezers are used to simultaneously characterize and compare the hygroscopic properties of two aerosol droplets, one containing inorganic and organic solutes and the second, referred to as the control droplet, containing a single inorganic salt. The inorganic solute is either sodium chloride or ammonium sulfate and the organic component is glutaric acid. The time variation in the size of each droplet (3-7 microm in radius) is recorded with 1 s time resolution and with nanometre accuracy. The size of the control droplet is used to estimate the relative humidity with an accuracy of better than +/-0.09%. Thus, the Kohler curve of the multicomponent inorganic/organic droplet, which characterizes the variation in equilibrium droplet size with relative humidity, can be determined directly. The measurements presented here focus on high relative humidities, above 97%, in the limit of dilute solutes. The experimental data are compared with theoretical treatments that, while ignoring the interactions between the inorganic and organic components, are based upon accurate representations of the activity-concentration relationships of aqueous solutions of the individual salts. The organic component is treated by a parametrized fit to experimental data or by the UNIFAC model and the water activity of the equilibrium solution droplet is calculated using the approach suggested by Clegg, Seinfeld and Brimblecombe or the Zdanovskii-Stokes-Robinson approximation. It is shown that such an experimental strategy, comparing directly droplets of different composition, enables highly accurate measurements of the hygroscopic properties, allowing the theoretical treatments to be rigorously tested. Typical deviations of the experimental measurements from theoretical predictions are shown to be around 1% in equilibrium size, comparable to the variation between the theoretical frameworks considered.     

Statistical Characteristics of the Process of Homogeneous Nucleation in the Vapor–Gas Medium during Free Molecular Regime of the Growth of Forming Droplets

Statistical approach to the study of the process of homogeneous nucleation of droplets in the vapor–gas medium in the presence of originally generated growing droplet at free molecular regime of droplet growth after the instantaneous creation of initial vapor supersaturation is proposed. The probability density of the creation of a new droplet in the vicinity of originally generated droplet is found. The mean distance between two neighboring droplets and the relative scatter of this distance are determined. The mean expectation time for the appearance of neighboring droplet estimating the duration of the droplet nucleation stage is found. The average number of droplets in a unit volume of the vapor–gas medium by the end of the droplet nucleation stage is estimated. The results obtained are compared with the predictions of the theory based on the assumption of the homogeneity of metastable phase.     

Effect of the surface-stimulated mode on the kinetics of homogeneous crystal nucleation in droplets

The thermodynamics of surface-stimulated crystal nucleation demonstrates that if at least one of the facets of the crystal is only partially wettable by its melt, then it is thermodynamically more favorable for the nucleus to form with that facet at the droplet surface rather than within the droplet. So far, however, the kinetic aspects of this phenomenon had not been studied at all. In the present paper, a kinetic theory of homogenous crystal nucleation in unary droplets is proposed by taking into account that a crystal nucleus can form not only in the volume-based mode (with all its facets within the droplet) but also in the surface-stimulated one (with one of its facets at the droplet surface). The theory advocates that even in the surface-stimulated mode crystal nuclei initially emerge (as subcritical clusters) homogeneously in the subsurface layer, not "pseudo-heterogeneously" at the surface. A homogeneously emerged subcritical crystal can become a surface-stimulated nucleus due to density and structure fluctuations. This effect contributes to the total rate of crystal nucleation (as the volume-based mode does). An explicit expression for the total per-particle rate of crystal nucleation is derived. Numerical evaluations for water droplets suggest that the surface-stimulated mode can significantly enhance the per-particle rate of crystal nucleation in droplets as large as 10 microm in radius. Possible experimental verification of the proposed theory is discussed.     

Polymer particles with various shapes and morphologies produced in continuous microfluidic reactors

We report a novel approach to continuous and scalable production of core-shell droplets and polymer capsules in microfluidic devices. The described method is also useful in the synthesis of polymer particles with nonspherical shapes. We used capillary instability-driven break-up of a liquid jet formed by two immiscible fluids. Precise control of emulsification of each liquid allowed for the production of highly monodisperse core-shell droplets with a predetermined diameter of cores and thickness of shells. We also achieved control over the number of cores per droplet and the location of cores in the droplet. We carried out fast throughput photopolymerization of the monomeric shells and obtained polymer particles with various shapes and morphologies, including spheres, truncated spheres and, hemispheres, and single and multicore capsules.