Controlled production of monodisperse double emulsions by two-step droplet breakup in microfluidic devices

A microfluidic device having both hydrophobic and hydrophilic components is exploited for production of multiple-phase emulsions. For producing water-in-oil-in-water (W/O/W) dispersions, aqueous droplets ruptured at the upstream hydrophobic junction are enclosed within organic droplets formed at the downstream hydrophilic junction. Droplets produced at each junction could have narrow size distributions with coefficients of variation in diameter of less than 3%. Control of the flow conditions produces variations in internal/external droplet sizes and in the internal droplet number. Both W/O/W emulsions (with two types of internal droplets) and oil-in-water-in-oil emulsions were prepared by varying geometry and wettability in microchannels.     

Dielectric properties of emulsions

Summary Dielectric constants of O/W emulsions were measured over a wide range of concentration and at frequencies ranging from 20 cps. to 3 mc. No dielectric dispersion due to the interfacial polarization was observed in the experimental range of frequency, while the electrode polarization was observed below 100 kc. Experimental results were compared with theoretical values for spherical dispersions. It was concluded that the dielectric constants of O/W emulsions were expressed best byBruggeman's equation over the whole range of concentration.

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Zusammenfassung Die DK von ?l/Wasser-Emulsionen wurden über einen weiten Konzentrationsbereich und für Frequenzen zwischen 20 Hz und 3 MHz gemessen. Es war keine dielektrische Dispersion verursacht durch Oberfl?chenpolarisation innerhalb des experimentellen Frequenzbereiches zu beobachten. Dagegen wurde unterhalb 100 kHz Elektrodenpolarisation bemerkbar. Die experimentellen Ergebnisse wurden mit den theoretischen Darstellungen der Misch-DK für Dispersionen mit kugligen Teilchen verglichen. Der Verlauf der DK der ?l/Wasser-Emulsion wird am besten und über den ganzen Konzentrationsbereich durch die Gleichung vonBruggeman dargestellt.

     

Shell microparticles of morphology controlled and inner-modified hole from sequential inkjet-printed double emulsions

This article presents sequential inkjet-based method to produce double emulsions as templates to fabricate morphology-controlled and inner-modified hole-shell microparticles. This sequential printing strategy for producing double emulsions circumvents complex wettability modification of the microchannels in lithography-based microfluidic device and largely saves the reagent in comparison to the coaxial two-phase jet in glass capillary. The formation of hole-shell structures is attributed to the diffusion of solvent out of droplets into butanol at the interface between oil and extract phase. The change of hole size is controlled by different diffusion rate, which is determined by changing the volume ratio of butanol and alcohol in extract phase. This presented flexible method can fabricate some functionalized microparticles in our future work.     

Rheology of double emulsions

New equations for the viscosity of concentrated double emulsions of core-shell droplets are developed using a differential scheme. The equations developed in the paper predict the relative viscosity (eta(r)) of double emulsions to be a function of five variables: a/b (ratio of core drop radius to shell outer radius), lambda(21) (ratio of shell liquid viscosity to external continuous phase viscosity), lambda(32) (ratio of core liquid viscosity to shell liquid viscosity), phi(DE) (volume fraction of core-shell droplets in double emulsion), and phi(m)(DE) (the maximum packing volume fraction of un-deformed core-shell droplets in double emulsion). Two sets of experimental data are obtained on the rheology of O/W/O (oil-in-water-in-oil) double emulsions. The data are compared with the predictions of the proposed equations. The proposed equations describe the experimental viscosity data of double emulsions reasonably well.     

Synthesis and characterization of core-shell microspheres with double thermosensitivity

We have synthesized doubly thermosensitive core-shell microspheres composed of chemically cross-linked poly(N-n-propyl acrylamide-co-styrene) (P(nPA-co-S)) with different styrene contents as the core and linear poly(N,N-diethyl acrylamide) (PDEA), poly(N-isopropyl acrylamide) (PiPA), or poly(N-isopropyl methacrylamide) (PiPMA) as the shells. The morphologies and swelling properties of the core and the core-shell microspheres have been studied. The P(nPA-co-S) copolymers have a similar volume phase transition temperature regardless of the styrene content, indicating a two-layer structure in the microspheres with a PS-rich inner core and a PnPA-rich outer layer resulting from soap-free emulsion polymerization in water. Upon the addition of the second shell composed of linear thermosensitive polymers, the core-shell microspheres display a two-step shrinking behavior when heated. The P(nPA-co-S) core exhibits a volume phase transition temperature at 13-15 degrees C, while the shells of PDEA, PiPA, and PiPMA have volume phase transition temperatures at 28, 32, and 42 degrees C, respectively. The core-shell microspheres are composed of three layers and possess two volume phase transition temperatures.     

Small-angle x-ray analysis of latex particles with core-shell morphology

A small-angle x-ray scattering (SAXS) study of latex particles consisting of a polystyrene (PS) core and a polymethylmethacrylate (PMMA) shell in theq-range 0.037 nm^–1q1.5 nm^–1 (q=(4/) sin (/2); : scattering angle) is reported. The particle size distributions of the latices have been determined by ultracentrifugation and allow a quantitative comparison of the experimental scattering intensities with theoretical models. The data obtained for the PS/PMMA latex are shown to be consistent with the proposed core-shell morphology. Separate studies of the PS-core-latex demonstrate that the amount of surfactant being adsorbed on the surface of the particles can be monitored directly. All results show that SAXS is well-suited to study the structure of latex particles in great detail.     

Double emulsions with controlled morphology by microgel scaffolding

Double emulsions are valuable structures that consist of drops nested inside bigger drops; they can be formed with exquisite control through the use of droplet-based microfluidics, allowing their size, composition, and monodispersity to be tailored. However, only little control can be exerted on the morphology of double emulsions in their equilibrium state, because they are deformable and subject to thermal fluctuations. To introduce such control, we use droplet-based microfluidics to form oil-in-water-in-oil double emulsion drops and arrest their shape by loading them with monodisperse microgel particles. These particles push the inner oil drop to the edge of the aqueous shell drop such that the double emulsions adopt a uniform arrested, anisotropic shape. This approach circumvents the need for ultrafast polymerization or geometric confinement to lock such non-spherical and anisotropic droplet morphologies. To demonstrate the utility of this technique, we apply it to synthesize anisotropic and non-spherical polyacrylate-polyacrylamide microparticles with controlled size and shape.     

Ultrasonic attenuation spectroscopy of emulsions with droplet sizes greater than 10 microm

Ultrasonic attenuation measurement is a frequently used tool for non-destructive determination of dispersion characteristics. Useful information like particle or droplet size and their concentration can be obtained, if the relation between size and attenuation of the dispersion is known. In this work, the theoretical model by Faran for the intermediate sound wave regime (IWR) is presented in combination with experimental data. In the IWR, the acoustic behavior is governed by elastic scattering rather than by dissipative effects. Experiments with emulsion of droplet sizes greater than 10 mum were carried out. Silicone oil, sunflower oil and olive oil were selected for the disperse phase of the oil-in-water emulsions. First, emulsions having droplets in the micrometer range were created. Afterwords, attenuation measurements of different concentrated emulsion were carried out. Some adjustments reflecting concentration influence were performed to outline the agreement between calculations and measurements. The validity of the model can be confirmed, if the volume fraction of the disperse phase is considered as a variable. Finally, droplet size distributions from theoretical attenuation spectra could be calculated based on a log-normal distribution.     

Effect of confinement on droplet breakup in sheared emulsions

The breakup of Newtonian droplets in a Newtonian matrix during shear flow is investigated in a counterrotating parallel plate device. For bulk conditions, the critical capillary number for breakup is known to be only determined by the viscosity ratio. Here, we show that the critical capillary number is also affected by the degree of confinement: for low viscosity ratios, confinement suppresses breakup, whereas for high viscosity ratios, confinement promotes breakup. This way, above a critical value for the degree of confinement, even droplets with a viscosity ratio larger than 4, which are unbreakable by shear in a bulk situation, can be broken in a simple shear flow field.     

Structural evolution of polymer-stabilized double emulsions

Polymer-stabilized double emulsions are produced by a two-step process, high shear emulsification in the primary and membrane emulsification in the secondary. By repeated fractionation after each emulsification, we obtain monodisperse double emulsions with the size of the complex droplets ranging from submicrometer to a few micrometers. With osmotic pressure balance between the inner and outer phases, the polymer-stabilized double emulsions remain stable for a year at room temperature without structure deterioration. We generalize laser light scattering to probe the structure and internal dynamics of the complex system by including the effects of the amplitude fluctuations of the scattered fields. Both static light scattering (SLS) and dynamics light scattering (DLS) can resolve the inclusions inside the complex droplets. Water-soluble nonionic surfactants are used to induce destabilization of double emulsions. We find that a double emulsion turns into a simple emulsion within a minute at a surfactant concentration of less than 10(-)(3) mol/L. We demonstrate that DLS is a powerful technique to study the kinetics of destabilization of double emulsions. Coalescence between the internal droplets and the external continuous phase is identified as a major release pathway.     

Magnetic polystyrene nanocapsules with core-shell morphology obtained by emulsifier-free miniemulsion polymerization

Nanocapsules containing hexadecane and Fe₃O₄ magnetic nanoparticles as core materials and polystyrene as shell were produced in a new method through emulsifier-free miniemulsion polymerization using 2,2′-azobis(2-amidinopropane) dihydrochloride (V-50) as a water-soluble initiator. The effect of some parameters such as the amounts of Fe₃O₄ and initiator on morphology of resulting nanocapsules was studied. Transmission electron microscopy showed that the products had latex particles having a size range of about 300–1300 nanometer and both magnetic nanocapsules with core-shell morphology and solid particles. The phase transition temperature and phase transition heat of the produced capsules were determined by differential scanning calorimetric analyses. Thermal properties of the latex were compared with those of magneticparticles-free latex and with those of latex free of both magnetic particles and hexadecane. Thermogravimetric analysis was also used to confirm the encapsulation and to determine the amounts of hexadecane and Fe₃O₄ within the capsules.     

Investigation of droplet size distribution for liquid-liquid emulsions in Taylor-Couette flows

In this paper, we investigate oil-in-water emulsions in a Taylor-Couette flow. A high-speed camera was employed to record the formation of those emulsions, and image processing was used to obtain the diameter of the droplets. No surfactants were added in order to study the pure effect of the fluid dynamical forces on the droplets. The results for three different oil-in-water emulsions show that the Sauter mean diameter considerably depends on the local shear rate and the material properties and that the droplet size distribution follows a log-normal distribution. We, therefore, propose to express the Sauter mean diameter normalized by Prandtl mixing length in terms of a correlation, which is based on the Kolmogorov turbulence theory. This correlation subsequently depends on the local shear rate and the material properties such as viscosity, density, and interfacial tension. The predictions of the correlation show fairly good agreement with the experimental measurement the Sauter mean diameter. Finally, comparing the predictions of the correlation to the data presented by Eskin et al. [Chem. Eng. Sci. 161 36–47; 2017] shows excellent agreement in the case, where the droplets are larger than the Kolmogorov length scale.     

Design of double emulsions by osmotic pressure tailoring

A method was developed allowing in situ adjustment of water-in-oil-in-water double emulsion (W/O/W) morphologies by tailoring the osmotic pressure of the water phases. The control of internal droplet size is achieved by altering the chemical potential of the external and internal water phases by dissolving neutral linear polysaccharides of suitable molecular weights. As a consequence of the different chemical potentials in the two aqueous phases, transport of water takes place modifying the initial morphology of the double emulsion. Self-diffusion 1H nuclear magnetic resonance (1H NMR) was used to assess transport mechanisms of water in oil, while a numerical model was developed to predict the swelling/shrinking behavior of W/O/W double emulsions. The model was based on a two-step procedure in which the equilibrium size of a single internal water droplet was first predicted and then the results of the single droplet were extended to the entire double emulsion. The prediction of the equilibrium size of an internal droplet was derived by the equalization of the Laplace pressure with the osmotic pressure difference of the two aqueous phases, as modeled by mean-field theory. The double emulsion equilibrium morphologies were then predicted by upscaling the results of a single drop to the droplet size distribution of the internal W/O emulsion. Good agreement was found between the theoretical predictions and the measurement of double emulsion droplet size distribution. Therefore, the present model constitutes a valuable tool for in situ control of double emulsion morphology and enables new possible applications of these colloidal systems.     

Structure of multiresponsive "intelligent" core-shell microgels

A doubly temperature-sensitive core-shell microgel composed of two temperature-sensitive polymers with different lower critical solution temperatures (LCSTs) in the core and shell has been studied by small-angle neutron scattering (SANS). The application of a novel universal form factor model in the analysis of the SANS data reveals that the radial density profile at temperatures above the LCSTs of both polymers can be well described by a two-box profile with narrow interfaces. At temperatures between the LCSTs, the radial density profile reveals that the core in the core-shell microgel has larger dimensions than the naked core. Thus the swollen shell pulls the core apart. At temperatures below both LCSTs, however, the shell restricts the core swelling, and the core is found to be smaller than in its native state. This clearly demonstrates the mutual influence of core and shell swelling.     

Influence of iota-carrageenan on droplet flocculation of beta-lactoglobulin-stabilized oil-in-water emulsions during thermal processing

The influence of thermal processing on droplet flocculation in oil-in-water emulsions stabilized by either beta-lactoglobulin (primary emulsions) or beta-lactoglobulin-iota-carrageenan (secondary emulsions) at pH 6 has been investigated. In the absence of salt, the zeta-potential of the primary emulsion was less negative (-40 mV) than that of the secondary emulsion (-55 mV) due to adsorption of anionic iota-carrageenan to the anionic beta-Lg-coated droplet surfaces. The zeta-potential and mean diameter (d(43) approximately 0.3 microm) of droplets in primary and secondary emulsions did not change after storage at temperatures ranging from 30 to 90 degrees C. In the presence of 150 mM NaCl, the zeta-potential of the primary emulsion was much less negative (-27 mV) than that of the secondary emulsion (-50 mV), suggesting that the latter was less influenced by electrostatic screening effects. The zeta-potential of the primary emulsions did not change after storage at elevated temperatures (30-90 degrees C). The zeta-potential of the secondary emulsions became less negative, and the aqueous phase iota-carrageenan concentration increased at storage temperatures exceeding 50 degrees C, indicating iota-carrageenan desorbed from the beta-Lg-coated droplets. In the primary emulsions, appreciable droplet flocculation (d(43) approximately 8 microm) occurred at temperatures below the thermal denaturation temperature (T(m)) of the adsorbed proteins due to surface denaturation, while more extensive flocculation (d(43) > 20 microm) occurred above T(m) due to thermal denaturation. In the secondary emulsions, the extent of droplet flocculation below T(m) was reduced substantially (d(43) approximately 0.8 microm), which was attributed to the ability of adsorbed carrageenan to increase droplet-droplet repulsion. However, extensive droplet flocculation was observed above T(m) because carrageenan desorbed from the droplet surfaces. Differential scanning calorimetry showed that iota-carrageenan and beta-Lg interacted strongly in aqueous solutions containing 0 mM NaCl, but not in those containing 150 mM NaCl, presumably because salt weakened the electrostatic attraction between the molecules.