SANS and SAXS analysis of charged nanoparticle adsorption at oil-water interfaces

A systematic study of the adsorption of charged nanoparticles at dispersed oil-in-water emulsion interfaces is presented. The interaction potentials for negatively charged hexadecane droplets with anionic polystyrene latex particles or cationic gold particles are calculated using DLVO theory. Calculations demonstrate that increased ionic strength decreases the decay length of the electrostatic repulsion leading to enhanced particle adsorption. For the case of anionic PS latex particles, the energy barrier for particle adsorption is also reduced when the surface charge is neutralized through changes in pH. Complementary small-angle scattering experiments show that the highest particle adsorption for PS latex occurs at moderate ionic strength and low pH. For cationic gold particles, simple DLVO calculations also explain scattering results showing that the highest particle adsorption occurs at neutral pH due to the electrostatic attraction between oppositely charged surfaces. This work demonstrates that surface charges of particles and oil droplets are critical parameters to consider when engineering particle-stabilized emulsions.     

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.     

Influence of sodium dodecyl sulfate on the physicochemical properties of whey protein-stabilized emulsions

The influence of sodium dodecyl sulfate (SDS) on the flocculation of droplets in 20 wt.% soybean oil-in-water emulsions stabilized by whey protein isolate (WPI) was investigated by light scattering, rheology and creaming measurements. The SDS concentrations used were low enough to prevent depletion flocculation by surfactant micelles and extensive protein displacement. In the absence of SDS, emulsions were prone to droplet flocculation near the isoelectric point of the proteins (4<pH<6), but were stable at a higher and lower pH. Flocculation led to an increase in emulsion viscosity, pronounced shear thinning behavior and accelerated creaming. When the surfactant-to-protein molar ratio was increased from 0 to 10, the emulsion instability range shifted to lower pH values due to binding of the negatively charged SDS molecules to the droplets. Our results indicate that the physicochemical properties of protein-stabilized emulsions can be modified by utilizing surfactant–protein interactions.     

Characterization of fluorocarbon-in-water emulsions with added triglyceride

Fluorocarbon-in-water emulsions are being explored clinically as synthetic oxygen carriers in general surgery. Stabilizing fluorocarbon emulsions against coarsening is critical in maintaining the biocompatibility of the formulation following intravenous administration. It has been purported that the addition of a small percentage of long-chain triglyceride results in stabilization of fluorocarbon emulsions via formation of a three-phase emulsion. In a three-phase emulsion, the triglyceride forms a layer around the dispersed fluorocarbon, thereby improving the adhesion of the phospholipid surfactant to the dispersed phase. In the present study, we examined the effect of triglyceride addition on the physicochemical characteristics of the resulting complex dispersion. In particular, we examined the particle composition and stability of the dispersed particles using a method which first fractionates (classifies) the different particles prior to sizing (i.e., sedimentation field-flow fractionation). It was determined that the addition of a long-chain triglyceride (soybean oil) results in oil demixing and two distinct populations of emulsion droplets. The presence of the two types of emulsion droplets is not observed via light scattering techniques, since the triglyceride droplets dominate the scattering due to a large difference in the refractive index between the particles and the medium as compared to fluorocarbon droplets. The growth of the fractionated fluorocarbon emulsion droplets was followed over time, and it was found that there was no difference in growth rates with and without added triglyceride. In contrast, addition of medium-chain-triglyceride (MCT) oils results in a single population of emulsion droplets (i.e., a three-phase emulsion). These emulsions are not stable to droplet coalescence, however, as significant penetration of MCT into the phospholipid lipid interfacial layer results in a negative increment in the monolayer spontaneous curvature, thereby favoring water-in-oil emulsions and resulting in destabilization of the emulsion to the effects of terminal heat sterilization or mechanical stress.     

Spontaneous size selection in cholesteric and nematic emulsions

We study the spontaneous size selection in lyotropic cholesteric (W/O) and thermotropic nematic (O/W) liquid crystal emulsions. The droplet sizes have been characterized by dynamic light scattering, which indicates a narrow monomodal distribution of droplets achieved spontaneously even without emulsion filtration. Anchoring of the director, provided by the chosen surfactant on the interface, may generate a topological defect inside the droplet. Below the critical radius R = K/W, determined by the ratio of Frank elastic and the surface anchoring constants, the effective anchoring strength is weak and droplets are not topologically charged; this allows them to coalesce freely, depleting the size distribution in this range. Large droplets possess a topological charge of +1 and present a high elastic energy barrier for pair coalescence; the resulting size distribution is skewed, with R > R, and effectively frozen.     

Preparation of positively charged oil/water nano-emulsions with a sub-PIT method

The phase inversion temperature (PIT) method is generally used to prepare nonionic surfactant stabilized nano-emulsions because of its low energy and surfactant consumption. The emulsion droplets are usually negatively charged because of the selective adsorption of OH(-) onto the droplet surfaces. In this work, positively charged oil/water nano-emulsions were prepared by adding a cationic surfactant to the system. The cationic molecules change the spontaneous curvature of the surfactant layers and raise the PIT above 100 °C. The PIT can be depressed by addition of NaBr, as shown by conductivity measurements and equilibrium phase behavior. Therefore, these nano-emulsions can be prepared by the PIT method. We found that the formation of the nano-emulsions did not require a cross-PIT cycle. The mechanism of the emulsification is the formation of mixed swollen micelles that can solubilize all the oil above a "clearing boundary", followed by a stir-quench to a temperature where these droplets become metastable emulsions. The zeta potential of the emulsion droplets can be easily tuned by varying the cationic surfactant concentrations. Due to electrosteric stabilization, the resulting nano-emulsions are highly stable, thus could find significant applications in areas such as pharmaceuticals, cosmetics and food industries.     

Characteristics of spontaneously formed nanoemulsions in octane/AOT/brine systems

Nanoemulsions were formed spontaneously by diluting water-in-oil (W/O) or brine-in-oil (B/O) microemulsions of a hydrocarbon (octane), anionic surfactant (Aerosol-OT or AOT) and water or NaCl brine in varying levels of excess brine. The water-continuous nanoemulsions were characterized by interfacial tension, dynamic light scattering, electrophoresis, optical microscopy and phase-behavior studies. The mechanism of emulsification was local supersaturation and resulting nucleation of oil during inversion. For nanoemulsions formed at low salinities with Winsor I phase behavior, octane drops grew from initial diameters of 150-250nm to 480-1000nm over 24h, depending on salinity. Growth was caused by mass transfer but seemed to approach the asymptotic stage of Ostwald ripening described by the Lifshitz-Slyozov-Wagner (LSW) theory only for dilution with salt-free water. Near the higher cross-over salinity (Winsor III), the nanoemulsions showed much slower growth with droplet size consistently remaining below 200nm over 24h and reaching 250nm after 1week. Birefringence indicated the presence of liquid crystal for these conditions, which could have contributed to the slow growth rate. At even higher salinity levels in the Winsor II domain, W/O/W multiple emulsions having drops greater than 1μm in diameter were consistently recorded for the first 5-7h, after which size decreased to values below 1μm. The number and size of internal water droplets in multiple emulsion drops was found to decrease over time, suggesting coalescence of internal droplets with the continuous water phase and mass transfer of water from internal droplets to continuous phase as possible mechanisms of the observed drop shrinkage. Electrophoresis studies showed the nanoemulsions to be highly negatively charged (zeta potentials of -60mV to -120mV). The high charge on octane droplets helped assure stability to flocculation and coalescence, thereby allowing mass transfer to control growth in the Winsor I and III regions.     

Preparation characteristics of water-in-oil-in-water multiple emulsions using microchannel emulsification

Microchannel (MC) emulsification is a novel technique for preparing monodispersed emulsions. This study demonstrates preparing water-in-oil-in-water (W/O/W) emulsions using MC emulsification. The W/O/W emulsions were prepared by a two-step emulsification process employing MC emulsification as the second step. We investigated the behavior of internal water droplets penetrating the MCs. Using decane, ethyl oleate, and medium-chain triglyceride (MCT) as oil phases, we observed successful MC emulsification and prepared monodispersed oil droplets that contained small water droplets. MC emulsification was possible using triolein as the oil phase, but polydispersed oil droplets were formed from some of the channels. No leakage of the internal water phase was observed during the MC emulsification process. The internal water droplets penetrated the MC without disruption, even though the internal water droplets were larger than the resulting W/O/W emulsion droplets. The W/O/W emulsion entrapment yield was measured fluorometrically and found to be 91%. The mild action of droplet formation based on spontaneous transformation led to a high entrapment yield during MC emulsification.     

Effect of Ionic Strength of Dispersed Phase on Ostwald Ripening in Water-in-Oil Emulsions

Water-in-oil emulsions with a low electrolyte content in the internal phase are unstable with respect to Ostwald ripening. The main components of the total pressure acting on the surface of internal phase droplets are considered. The equilibrium values of the diameters of dispersed phase droplets are calculated. The dependences of the difference in the osmotic and Laplace pressures on the droplet size and electrolyte concentration in the droplets are obtained. It is shown that, at the electrolyte concentration below the critical value, the number of droplets in emulsion decreases. If the concentration is above the critical value, water diffuses from small to large droplets, but their number remains unchanged. The change in NaCl concentration in the droplets of internal phase of polydisperse emulsion during the Ostwald ripening is calculated. The results of calculations correlate with the experimental data on the stability of emulsions with respect to coalescence and sedimentation.     

Self-diffusion and collective diffusion of charged colloids studied by dynamic light scattering

A microemulsion of decane droplets stabilized by a nonionic surfactant film is progressively charged by substitution of a nonionic surfactant molecule by a cationic surfactant. We check that the microemulsion droplets remain identical within the explored range of volume fraction (0.02-0.18) and of the number of charges per droplet (0-40). We probe the dynamics of these microemulsions by dynamic light scattering. Despite the similar structures of the uncharged and charged microemulsions, the dynamics are very different. In the neutral microemulsion, the fluctuations of polarization relax, as is well-known, via the collective diffusion of the droplets. In the charged microemulsions, two modes of relaxation are observed. The fast one is ascribed classically to the collective diffusion of the charged droplets coupled to the diffusion of the counterions. The slow one has, to our knowledge, not been observed previously neither in similar microemulsions nor in charged spherical colloids. We show that the slow mode is also diffusive and suggest that its possible origin is the relaxation of local charge fluctuations via the local exchange of droplets bearing different numbers of charges. The diffusion coefficient associated with this mode is then the self-diffusion coefficient of the droplets.     

Emulsion liquid membranes: Role of internal droplet size distribution on toluene/n-heptane separation

Using oil/water/oil-type emulsion liquid membranes, batch wise extraction experiments are carried out to separate toluene from a mixture of toluene and n-heptane. In the separation process using emulsion liquid membranes, the internal phase polydispersity affects mass transport of a solute because under steady operating conditions, internal droplet size and size distribution are proportional to the interfacial area. The present study aims to assess the polydispersity character of the internal droplets of emulsion globules. In this paper, the important variables affecting dispersed drop sizes as well as internal droplets mean diameter and size distribution of the emulsion globule, including impeller speed during emulsification, surfactant concentration, volume ratio of surfactant solution, carrier concentration and composition of feed phase are systematically investigated.     

纳米SiO2/十二烷基氨基丙酸钠协同稳定的pH响应性Pickering乳状液

用纳米SiO₂颗粒与微量氨基酸型两性表面活性剂十二烷基氨基丙酸钠作复合乳化剂, 以正癸烷为油相, 制备了pH响应性O/W型Pickering乳状液. 室温下该乳状液在pH≤4.0 时稳定, 在pH≥6.0时不稳定, 因此, 可以通过改变水相的pH值使乳状液在稳定和破乳之间多次循环. 在酸性水介质中, 氨基酸型两性表面活性剂分子呈阳离子状态, 可通过静电作用吸附到带负电荷的SiO₂颗粒表面, 产生原位疏水化作用, 使其转变为表面活性颗粒; 而在中性和碱性水介质中, 氨基酸型两性表面活性剂呈两性或阴离子状态, 不能产生原位疏水化作用, 因而导致乳状液破乳. 相关作用机理通过吸附量、 Zeta电位及接触角等实验数据得以论证. 该刺激-响应性Pickering乳状液在乳液聚合、 油品输送以及燃料生产等领域具有重要的应用价值.     

Separation of copper (II) ions from humic complexes with oxine-impregnated emulsion globules

A water-in-oil type emulsion containing oxine has been used for the discrimination of copper(II) ions and copper-humic complexes in aqueous solutions. A toluene solution containing oxine and nonionic surfactant (Span-80) was vigorously mixed with 1 mol/L HCl by ultrasonic irradiation. The resulting emulsion was added to water and dispersed by stirring as numerous small globules. Copper(II) ions were quantitatively permeated across the oil layer and incorporated in the tiny droplets of HCl, whereas copper-humic complexes remained in the sample solution. After collecting the dispersed emulsion globules, they were destroyed by heating to segregate the aqueous (HCl) and organic (toluene) phases. The copper in the aqueous phase was determined by graphite-furnace atomic absorption spectrometry (GFAAS). The analytical results agreed with those obtained by the adsorption method, where negatively charged humic complexes were selectively collected on a macroreticular anion exchanger Sephadex A-25 column. The conventional liquid-liquid extraction did not offer a chemical speciation because copper(II) ions and humic complexes were simultaneously extracted into the organic phase. The proposed emulsion method was successfully applied to the analysis of river water samples.     

Fractional crystallization of oil droplets in O/W emulsions dispersed by Synperonic F127

The aim of this works is to study an oil-in-water emulsion stabilized with a triblock copolymer Synperonic F127 which presents a double size distribution of oil droplets. The emulsions were studied experimentally by means of differential scanning calorimetry (DSC) and dynamic light scattering (DLS). The DSC analysis was carried out focusing on the cooling behavior of the emulsion. The cooling thermograms of the oil-in-water emulsion revealed two crystallization peaks with Gaussian profile; the interesting characteristic is that both peaks are separated in temperature. In accordance to previous works for a single oil dispersed within an aqueous phase, the DSC technique must show a single Gaussian peak of crystallization attributable to a size distribution of droplets. In the present case of emulsions stabilized with 1 g/L of Synperonic F127, the aggregation behavior of triblock as a function of temperature allows to produce an emulsion with a double size droplet distribution. Comparison with emulsions stabilized with 2 and 4 wt% of non-ionic Tween 20 are also presented.     

Patterning amyloid peptide fibrils by AFM charge writing

Surface charge patterns generated by atomic force microscopy-based charge writing were used to pattern amyloid-like peptide fibrils on a solid substrate. Fibrils of the short peptide TTR105-115 were encapsulated inside water droplets of a water-in-perfluorocarbon oil emulsion and retained their rod morphology. They were observed to deposit selectively with a lateral resolution of approximately 1 microm onto negatively charged patterns on a polymethyl-methacrylate substrate.     

Separation of copper (II) ions from humic complexes with oxine-impregnated emulsion globules

A water-in-oil type emulsion containing oxine has been used for the discrimination of copper(II) ions and copper-humic complexes in aqueous solutions. A toluene solution containing oxine and nonionic surfactant (Span-80) was vigorously mixed with 1 mol/L HCl by ultrasonic irradiation. The resulting emulsion was added to water and dispersed by stirring as numerous small globules. Copper(II) ions were quantitatively permeated across the oil layer and incorporated in the tiny droplets of HCl, whereas copper-humic complexes remained in the sample solution. After collecting the dispersed emulsion globules, they were destroyed by heating to segregate the aqueous (HCl) and organic (toluene) phases. The copper in the aqueous phase was determined by graphite-furnace atomic absorption spectrometry (GFAAS). The analytical results agreed with those obtained by the adsorption method, where negatively charged humic complexes were selectively collected on a macroreticular anion exchanger Sephadex A-25 column. The conventional liquid-liquid extraction did not offer a chemical speciation because copper(II) ions and humic complexes were simultaneously extracted into the organic phase. The proposed emulsion method was successfully applied to the analysis of river water samples. Received: 14 April 1998 / Revised: 22 July 1998 / Accepted: 27 July 1998     

Preparation and size control of monodispersed surface charged polystyrene nanoparticles by reversible addition fragmentation transfer reaction

Highly monodispersed polystyrene (PS) nanoparticles were prepared via reversible addition fragmentation transfer (RAFT) living radical emulsion polymerization technique. Two types of novel sur-iniferters with different hydrophilic lipophilic balance (HLB) values, 4-diethythiocarbonylsulfanylmethyl-benzoic acid and 4-(2-hydroxyethyl)piperazine-1-carbodithioicacid benylether, were synthesized for the PS RAFT reaction and their chemical synthesis was identified using nuclear magnetic resonance spectroscopy. Scanning electron microscope and dynamic light scattering experiments showed that the size distribution of the particles prepared was highly monodispersed. The average particle size was affected by the type and concentration of sur-iniferters. It increased with decreasing sur-iniferter concentrations, and the use of sur-iniferters with higher HLB values led to increases of particle sizes, as the particles were growing from, initially, much larger monomer droplets. The surfaces of the nano particles prepared were ionically charged. The surface charge measured was −50 mV, which enabled particles to be stably dispersed in aqueous medium.     

Electrostatic stabilization of colloids in carbon dioxide: electrophoresis and dielectrophoresis

Over the past decade, steric stabilization has been achieved for a variety of inorganic and organic colloids in supercritical fluid carbon dioxide (scCO2). Herein we demonstrate that colloids may also be stabilized in CO2 by electrostatic forces, despite the ultralow dielectric constant of 1.5. Zeta potentials of micrometer-sized water droplets, measured in a microelectrophoresis cell, reached -70 mV corresponding to a few elementary charges per square micrometer of droplet surface. This degree of charge was sufficient to stabilize water/CO2 emulsions for an hour, even with water volume fractions of 5%. Hydrogen ions partition preferentially, relative to bicarbonate ions, from the emulsion droplets to the cores of surfactant micelles in the diffuse double layer surrounding the droplets. The micelles, formed with a low molecular weight branched hydrocarbon surfactant, prevent ion pairing of the hydrogen counterions to the negatively charged emulsion droplets. Dielectrophoresis of the water droplets at a frequency of 60 Hz leads to chains containing a dozen droplets with lengths of 50 mum. The ability to form electrostatically stabilized colloids in carbon dioxide is particularly useful in practical applications, because steric stabilization in CO2 is often limited by the poor solvation of the stabilizers.     

Stabilization of Water‐Soluble Antioxidant in Water‐in‐Oil‐in‐Water Double Emulsions

Abstract

In this study, we are introducing a method that can effectively stabilize antioxidants in water‐in‐oil‐in‐water (W/O/W) double emulsions. Preliminarily, stable W/O/W double emulsions were produced by manipulating the characteristics of internal aqueous phase via two‐stage emulsification, resulting consequently in the formation of fine internal water droplets in the dispersed oil droplets. From conductivity measurements that can determine the elution amount of internal aqueous phase, it was confirmed that the double emulsion stability could be improved by treating the internal aqueous phase with a hydroxypropyl‐beta‐cyclodextrin. In this study, kojic acid, 5‐hydroxy‐2‐(hydroxymethyl)‐4‐pyrone was selected as a model antioxidant. The stabilization of kojic acid was attempted by locating it in the internal water droplets of the stable W/O/W double emulsions. The stability of kojic acid in the double emulsion system could be maintained at 90% for 10 weeks at high temperature. We believe that these stable W/O/W double emulsions could be used meaningfully as a carrier for many unstable antioxidants.     

Interfacial layers of stimuli-responsive poly-(N-isopropylacrylamide-co-methacrylicacid) (PNIPAM-co-MAA) microgels characterized by interfacial rheology and compression isotherms

Stimuli-sensitive emulsions stabilized by microgel particles consisting of poly-(N-isopropylacrylamide-co-methacrylicacid) (PNIPAM-co-MAA) and being responsive to both pH and temperature have been investigated with respect to the visco-elastic properties of the interfacial layer. Properties of the interfacial layer were probed by means of shear and dilatational rheology as well as by compression isotherms and are related to the microgel packing at the interface as visualized by cryogenic scanning electron microscopy. The corresponding pH dependent emulsion stability is strongly correlated with the visco-elastic properties of the microgel covered oil-water interface. At high pH when the microgels are charged, a structure of partially interconnected microgels is found that provides elastic, soft gel-like interfaces. At low pH, however, the uncharged microgels are densely packed and the interface is rather brittle. Obviously, these pH dependent visco-elastic properties of the microgel layer at the oil-water interface play a determining role in the stability of emulsion droplets and allow us to prepare very stable emulsions when the microgels are charged and to break the emulsion by changing the pH.