Long-ranged electrostatic repulsion and crystallization of emulsion droplets in an ultralow dielectric medium supercritical carbon dioxide

Electrostatic repulsion stabilizes micrometer-sized water droplets with spacings greater than 10 microm in an ultralow dielectric medium, CO2 (epsilon = 1.5), at elevated pressures. The morphology of the water/CO2 emulsion is characterized by optical microscopy and laser diffraction as a function of height. The counterions, stabilized with a nonionic, highly branched, stubby hydrocarbon surfactant, form an extremely thick double layer with a Debye screening length of 8.9 microm. As a result of the balance between electrostatic repulsion and the downward force due to gravity, the droplets formed a hexagonal crystalline lattice at the bottom of the high-pressure cell with spacings of over 10 microm. The osmotic pressure, calculated by solving the Poisson-Boltzmann equation in the framework of the Wigner-Seitz cell model, is in good agreement with that determined from the sedimentation profile measured by laser diffraction. Thus, the long-ranged stabilization of the emulsion may be attributed to electrostatic stabilization. The ability to form new types of colloids in CO2 with electrostatic stabilization is beneficial because steric stabilization is often unsatisfactory because of poor solvation of the stabilizers.     

Investigation of the interactions in emulsions stabilized by a polymeric surfactant and its mixtures with an anionic surfactant

 The interaction of a nonionic polymeric surfactant with an anionic surfactant at the oil–water interface has been studied by its effects on the droplet size, stability and rheology of emulsions. Oil-in-water (o/w) emulsions were prepared using isoparaffinic oil and mixtures of a nonionic polymeric surfactant with an anionic surfactant. The macro-molecular surfactant was a graft copolymer with a backbone of polymethyl methacrylate and grafted polyethylene oxide (a graft copolymer with PEO chains of MW=750). The anionic surfactant was sodium dodecyl sulfate (SDS). The stabiliza-tion of the emulsion droplets was found to be different when using one or the other surfactant. The mechanism of stabilization of emulsion droplets by the macro-molecular surfactant is of the steric type while the stabilization by anionic surfactant is of the electrostatic repulsion type. Emulsions stabilized with mixtures present both types of stabilization. Other effects on the preparation and stabilization of emulsions were found to be dependent on properties associated with the surfactant molecular weight such as the Marangoni effect and Gibbs elasticity. The initial droplet size of the emulsions showed a synergistic effect of the surfactant combination, showing a minimum for the mixtures compared to the pure components. Emulsion stability also shows a synergistic interaction of both surfactants. Rheological measurements allow for the estimation of the interparticle interaction when measured as a function of volume fraction. Most of the effects observed can be attributed to the differences in interfacial tension and droplet radius produced by both surfactants and their mixtures. The elastic moduli are well explained on the basis of droplet deformation. Ionic versus steric stabilization produce little difference in the observed rheology, the only important differences observed concerned the extent of the linear viscoelasticity region. Received: 22 November 1996 Accepted: 24 March 1997     

Self-assembled reverse micelles in supercritical CO2 entrap protein in native state

Molecular dynamics simulations of random quaternary mixtures of protein-water-CO2-fluorosurfactants show the self-assembly of reverse micelles in supercritical carbon dioxide where the protein becomes entrapped inside the aqueous pool. Analyses show that the protein native state remains intact in the water pool. This is because of the bulk nature of the enclosed water that provides a suitable environment for the extracted protein. Results from ab initio calculations imply that the existing fluorosurfactants can be made more effective in stabilizing water-in-CO2 microemulsions by a partial hydrogenation in their tails. A Lewis acid-Lewis base interaction among CO2 and the surfactant tails enhances the stability of the aqueous droplets substantially. The study can help accelerate the search for surfactant process for environmentally benign applications in dense CO2.     

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.     

Carbon dioxide-in-water microemulsions

Liquid and supercritical carbon dioxide swell potassium carboxylate perfluoropolyether (PFPE-K) cylindrical micelles in water to produce novel CO(2)-in-water (C/W) microemulsions. The swelling elongates the micelles significantly from 20 to 80 nm as the molar ratio of CO(2) in the micelles to surfactant (R(CO2)) reaches approximately 8. As the micelles swell to form microemulsions, the solubility of pyrene increases by a factor of ca. 10. Fluorescence spectra suggest that pyrene resides primarily in the low-polarity micelle core rather than in the palisade region. The results illustrate the ability of C/W microemulsions to solubilize both lipophilic and fluorophilic substances simultaneously.     

Steric Stabilization of Colloids by Poly(dimethylsiloxane) in Carbon Dioxide: Effect of Cosolvents

Steric stabilization and flocculation of colloids with surface-grafted poly(dimethylsiloxane) (PDMS) chains are examined in liquid and supercritical carbon dioxide with and without hexane as a cosolvent. Neither poly(methyl methacrylate) (PMMA) nor silica particles with grafted 10,000 g/mol PDMS could be stabilized in pure CO(2) at pressures up to 345 bar at 25 degrees C and 517 bar at 65 degrees C without stirring. The addition of 15 wt% hexane to CO(2) led to stable dispersions with sedimentation velocities of 0.2 mm/min for 1-2 μm PMMA particles. The critical flocculation pressure of the colloids in the hexane/CO(2) mixture, determined from turbidity versus time measurements, was found to be the same for silica and PMMA particles and was well above the upper critical solution pressure for the PDMS-CO(2) system. The addition of a nonreactive cosolvent, hexane, eliminates flocculation of PMMA particles synthesized through dispersion polymerization in CO(2) with PDMS-based surfactants. Copyright 2000 Academic Press.     

Molecular dynamics simulation of a reverse micelle self assembly in supercritical CO2

In this communication we report on molecular dynamics computer simulations of self-assembly of reverse micelles in supercritical carbon dioxide. The reverse micelles contain perfluoropolyether ammonium carboxylate surfactants and an aqueous core. We observed a quick self-assembly of these micelles over time periods of approximately 5 ns, irrespective of initial conditions. In most cases, the self-assembled perfluorinated reverse micelles have a nice spherical shape and properties consistent with experiments. When the fluorinated surfactant is replaced by its hydrogenated analogue, the assembled aggregate contains a region of direct contact between water and carbon dioxide, indicating that hydrogenated surfactant is not a good agent for creation of microemulsions in water/carbon dioxide mixtures.     

Acidification of reverse micellar nanodroplets by atmospheric pressure CO2

Water absorption of atmospheric carbon dioxide lowers the solution pH due to carbonic acid formation. Bulk water acidification by CO(2) is well documented, but significantly less is known about its effect on water in confined spaces. Considering its prominence as a greenhouse gas, the importance of aerosols in acid rain, and CO(2)-buffering in cellular systems, surprisingly little information exists about the absorption of CO(2) by nanosized water droplets. The fundamental interactions of CO(2) with water, particularly in nanosized structures, may influence a wide range of processes in our technological society. Here results from experiments investigating the uptake of gaseous CO(2) by water pools in reverse micelles are presented. Despite the small number of water molecules in each droplet, changes in vanadium probes within the water pools, measured using vanadium-51 NMR spectroscopy, indicate a significant drop in pH after CO(2) introduction. Collectively, the pH-dependent vanadium probes show CO(2) dissolves in the nanowater droplets, causing the reverse micelle acidity to increase.     

Light and neutron scattering study of PEG-oleate and its use in emulsion polymerization

Steric stabilization of colloids forms a robust mechanism to obtain colloids that are stable in a variety of environments, and that can be used to study the phase behavior of hard or soft spheres. We report the synthesis of sterically stabilized colloids in an aqueous environment using readily dissolvable surfactants, with an unsaturated hydrophobic tail. We synthesized a new surfactant by esterification of a poly(ethylene glycol) (PEG) chain of 4.1 kg/mol with oleic acid, called PEG4OA. The micellization of PEG4OA was characterized by light and neutron scattering, which yielded values for the aggregation number and the overall size that are in excellent agreement with a comparable surfactant with a saturated octadecane chain, Brij 700. We successfully used PEG4OA in the emulsion polymerization of polystyrene colloids. In comparison with the smaller surfactant Tween 80, PEG4OA yielded smaller colloids with radii around 50 nm, and the addition of 1-dodecanethiol reduced the formation of aggregates during the synthesis. A contrast variation study with small angle neutron scattering (SANS) showed that a dense PEG layer was grafted to the colloid surface.     

Lattice Monte Carlo simulations of phase separation and micellization in supercritical CO2/surfactant systems: effect of CO2 density

Lattice Monte Carlo simulations are used to study the effect of nonionic surfactant concentration and CO2 density on the micellization and phase equilibria of supercritical CO2/surfactant systems. The interaction parameter for carbon dioxide is obtained by matching the critical temperature of the model fluid with the experimental critical temperature. Various properties such as the critical micelle concentration and the size, shape, and structure ofmicelles are calculated, and the phase diagram in the surfactant concentration-CO2 density space is constructed. On increasing the CO2 density, we find an increase in the critical micelle concentration and a decrease in the micellar size; this is consistent with existing experimental results. The variation of the micellar shape and structure with CO2 density shows that the micelles are spherical and that the extension of the micellar core increases with increasing micellar size, while the extension of the micellar corona increases with increasing CO2 density. The predicted phase diagram is in qualitative agreement with experimental phase diagrams for nonionic surfactants in carbon dioxide.     

Emulsification through surfactant hydration: the PIC process revisited

We have performed sudden composition changes on a (surfactant + oil + water) system by adding water to a (surfactant + oil) solution. This composition change quenches the system into a metastable oil-in-water emulsion with a population in the 100 nm range. The conditions for a successful quench are as follows: the initial water content should be below a boundary called the "clearing boundary" (CB), the final water content should be sufficiently beyond CB, and the quench should be fast. We have used high purity components to avoid the complex phase separation patterns that occur with low purity ingredients: the surfactant is octaethylenehexadecyl ether (C(16)E(8)) and the oil is hexadecane (C(16)). Under these conditions, we show that the pathway for this type of quench proceeds through the swelling of the reverse micellar phase by the added water and the formation of a sponge phase. Then, further water addition causes the nucleation of oil droplets in this sponge phase, with a size that matches the spontaneous curvature of the sponge phase. Part of the surfactant remains adsorbed on these droplets, and the rest is expelled as micelles that coexist with the droplets. It is concluded that a PIC emulsification will always lead to a bimodal size distribution with surfactant "wasted" in small micelles. This is in contrast with the more efficient PIT emulsification.     

Electrostatic and steric interactions in oil-in-water emulsion films from Pluronic surfactants

Stabilization of oil-in-water emulsion films from PEO-PPO-PEO triblock copolymers is described in terms of interaction surface forces. Results on emulsion films from four Pluronic surfactants, namely F108, F68, P104 and P65 obtained with the Thin Film Pressure Balance Technique are summarized. It is found that film stabilization is due to DLVO (electrostatic) and non-DLVO (steric in origin) repulsive forces. The charging of the oil/water film interfaces is related to preferential adsorption of OH(-) ions. This is confirmed by pH-dependent measurements of the equivalent film thickness (h(w)) at both constant capillary pressure and ionic strength. With reducing pH in the acidic region, a critical value (pH(cr,st)) corresponding to an isoelectric state of the oil/water film surfaces is found where the electrostatic interaction in the films is eliminated. At pH≤pH(cr,st), the emulsion films are stabilized only by steric forces due to interaction between the polymer adsorption layers. Disjoining pressure (Π) isotherms measured for emulsion films from all the four Pluronic surfactants used at pH相似文献   

Monitoring the simultaneous ostwald ripening and solubilization of emulsions

The simultaneous Ostwald ripening of an emulsion and the solubilization of its oil droplets by added micellar surfactant solutions are monitored by measurements of time-averaged scattered intensities. A simple computer simulation model for the interpretation of the measurements is presented. Experimental data are analyzed with this model using one single parameter: an effective ratio of oil to surfactant molecules involved in the withdrawal of oil from the Ostwald ripening process by the added micelles. The fitted value of this parameter appears to be more than twice the one that can be predicted from the equilibrium solubilization of oil by the surfactant micelles, indicating that more oil is involved in the nonequilibrium exchange of oil and surfactant between micelles and droplets.     

Water Transport by Nanodispersion Droplets in a Water-in-Oil Emulsion

The mechanisms of water transport through an organic dispersion medium are considered for an emulsion during Ostwald ripening and for a three-phase system upon a contact of a water-in-oil emulsion with an external aqueous phase. Electron microscopy shows a formation of nanodispersion droplets during the diffusion of water through the organic phase of water-in-oil emulsions. The experimental water diffusion coefficient during Ostwald ripening in emulsions is 40 times smaller than the calculated molecular diffusion coefficient. The experimental diffusion coefficients are determined for rhodamine C, which solubilizes in the surfactant micelles, and for ethyl alcohol, a cosurfactant, which reduces the interfacial tension in the emulsion and promotes the formation of nanodispersion droplets. The experimental diffusion coefficients of rhodamine C and ethanol are three orders of magnitude smaller than the calculated values. The ratio between the numbers of rhodamine C and water molecules diffusing through the organic phase is 1 : 10000. The nanodispersion droplets are shown to make the main contribution to the water transport in the organic dispersion medium of the emulsions. Water can also be transported by single surfactant molecules, but this mechanism is not the predominant one.     

Enhanced stabilization of reverse micelles by compressed CO2

The effect of compressed CO2 on the solubilization capacity of water in reverse micelles of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in longer chain n-alkanes was studied at different temperatures and pressures. It was found that the amount of solubilized water is increased considerably by CO2 in a suitable pressure range. The suitable CO2 pressure range in which the solubilization capacity of water could be enhanced decreased with increasing W0 (water-to-AOT molar ratio). The microenvironments in the CO2-stabilized reverse micelles were investigated by UV/Vis adsorption spectroscopy with methyl orange (MO) as probe. The mechanism by which the reverse micelles are stabilized by CO2 is discussed in detail. The main reason is likely to be that CO2 has a much smaller molecular volume than the n-alkane solvents studied in this work. Therefore, it can penetrate the interfacial film of the reverse micelles and stabilize them by increasing the rigidity of the micellar interface and thus reducing the attractive interaction between the droplets. However, if the CO2 pressure is too high, the solvent strength of the solvents is reduced markedly, and this induces phase separation in the micellar solution.     

Enhancement of Ostwald ripening by depletion flocculation

The time dependence of the dynamic mobility and the ultrasonic attenuation of octane and decane oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) was measured. The emulsions grew to larger droplets due to Ostwald ripening. The growth rate measured by attenuation depends on the surfactant concentration and the polydispersity of the emulsion. At surfactant concentrations below the critical micelle concentration (cmc) of SDS, the growth was linear with time and the rate was dependent on the polydispersity of the drops; the rate was several times faster than that predicted on the basis of a diffusion growth mechanism. Above the cmc, however, as the droplets grew in size there was a point at which the rate of growth increased, which corresponds to the droplet size at which depletion forces due to the surfactant micelles become significant. Under these conditions both the electroacoustic dynamic mobility and the acoustic attenuation spectra displayed characteristics of flocs: a large decrease in the phase lag at higher frequencies in the dynamic mobility spectrum and a decrease in the attenuation coefficient at low-megahertz frequencies with an increase at higher frequencies. This depletion flocculation enhancement in ripening rates in the presence of SDS micelles provides another, alternative, and self-consistent mechanism for the effect of surfactant micelles on Ostwald ripening.     

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.     

Electrostatically stabilized metal oxide particle dispersions in carbon dioxide

We report electrostatic stabilization of micrometer-sized TiO(2) particles at long range (several micrometers) in liquid and supercritical CO(2) despite the ultralow dielectric constant, as low as 1.5. The counterions were solubilized in dry reverse micelles, formed with a low-molecular weight cationic perfluoropolyether trimethylammonium acetate surfactant, to prevent ion pairing with the particle surface. Dynamic light scattering and settling velocities indicate a particle diameter of 620-740 nm. The electrophoretic mobility of -2.3 x 10(-8) m(2)/V s indicated a particle charge on the order of -1.7 x 10(-17) C, or 105 elementary negative charges per particle. The balance of particle compression by an electric field versus electrostatic repulsion generated an amorphous arrangement of particles with 5-9 mum spacing, indicating Debye lengths greater than 1 mum. Scattering patterns also indicate that chains of particles may be achieved in CO(2) by dielectrophoresis with alternating fields. The electrostatic stabilization has been achieved by solubilizing a small concentration of counterions in only a small fraction of the reverse micelles in the double layer. Whereas many low-molecular weight surfactants have been shown to form reverse micelles in CO(2), very few polymers are able to stabilize micrometer-sized colloids sterically. Thus, electrostatic stabilization has the potential to expand markedly the domain of colloid science in apolar supercritical fluids.     

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.