A Three-Step Model for Submicron W/O Emulsion Formation in a Transitional-Phase Inversion Process

A three-step model of the transitional phase inversion (TPI) process for the formation of water-in-oil (W/O) emulsions is presented. Three types of emulsions exist in an emulsification process at different oil–water ratios and hydrophilic–lipophilic balance (HLB). A stable W/O emulsion was obtained using Sorbitan oleate (Span 80) and polyoxyethylenesorbitan monooleate (Tween 80) with a specified HLB and oil volume fraction. Oil was added into water, which contained the water-soluble surfactant, to dissolve the oil-soluble surfactant. This route allowed TPI to occur, and an interesting emulsification process was observed by varying the HLB, which corresponded to the change in the oil–water ratio. Two types of emulsions in the emulsification process were found: transition emulsion 1 (W/O/W high internal phase emulsion) and target emulsion 2 (W/O emulsion with low viscosity). This study describes the changes that occurred in the emulsification process.     

Relationship between rheological properties and one-step W/O/W multiple emulsion formation

Formation of a normal (not temporary) W/O/W multiple emulsion via the one-step method as a result of the simultaneous occurrence of catastrophic and transitional phase inversion processes has been recently reported. Critical features of this process include the emulsification temperature (corresponding to the ultralow surface tension point), the use of a specific nonionic surfactant blend and the surfactant blend/oil phase ratio, and the addition of the surfactant blend to the oil phase. The purpose of this study was to investigate physicochemical properties in an effort to gain a mechanistic understanding of the formation of these emulsions. Bulk, surface, and interfacial rheological properties of adsorbed nonionic surfactant (CremophorRH40 and Span80) films were investigated under conditions known to affect W/O/W emulsion formation. Bulk viscosity results demonstrated that CremophorRH40 has a higher mobility in oil compared than in water, explaining the significance of the solvent phase. In addition, the bulk viscosity profile of aqueous solutions containing CremophorRH40 indicated a phase transition at around 78 ± 2 °C, which is in agreement with cubic phase formation in the Winsor III region. The similarity in the interfacial elasticity values of CremophorRH40 and Span80 indicated that canola oil has a major effect on surface activity, showing the significance of vegetable oil. The highest interfacial shear elasticity and viscosity were observed when both surfactants were added to the oil phase, indicating the importance of the microstructural arrangement. CremophorRH40/Span80 complexes tended to desorb from the solution/solution interface with increasing temperature, indicating surfactant phase formation as is theoretically predicted in the Winsor III region. Together these interfacial and bulk rheology data demonstrate that one-step W/O/W emulsions form as a result of the simultaneous occurrence of phase-transition processes in the Winsor III region and explain the critical formulation and processing parameters necessary to achieve the formation of these normal W/O/W emulsions.     

Novel thermo-responsive coloring phenomena in water/surfactant/oil emulsions

Emulsions comprising a dual-surfactant system of a long-chain amidoamine derivative and a quaternary ammonium salt developed an iridescent color at a specific temperature region. The emulsions underwent phase inversion on heating from an O/W emulsion to a W/O emulsion, passing through a periodical lamellar structure which developed a characteristic interference color. Interestingly, the color and the coloring temperature can be independently controlled by adjusting the concentration of surfactants, respectively.     

One-step formation of w/o/w multiple emulsions stabilized by single amphiphilic block copolymers

Multiple emulsions are complex polydispersed systems in which both oil-in-water (O/W) and water-in-oil (W/O) emulsion exists simultaneously. They are often prepared accroding to a two-step process and commonly stabilized using a combination of hydrophilic and hydrophobic surfactants. Recently, some reports have shown that multiple emulsions can also be produced through one-step method with simultaneous occurrence of catastrophic and transitional phase inversions. However, these reported multiple emulsions need surfactant blends and are usually described as transitory or temporary systems. Herein, we report a one-step phase inversion process to produce water-in-oil-in-water (W/O/W) multiple emulsions stabilized solely by a synthetic diblock copolymer. Unlike the use of small molecule surfactant combinations, block copolymer stabilized multiple emulsions are remarkably stable and show the ability to separately encapsulate both polar and nonpolar cargos. The importance of the conformation of the copolymer surfactant at the interfaces with regards to the stability of the multiple emulsions using the one-step method is discussed.     

Multiple emulsion stability: pressure balance and interfacial film strength

The objective of this study was to investigate the significance of inner and outer phase pressure, as well as interfacial film strength on W/O/W multiple emulsion stability using microscopy and long-term stability tests. It was observed that immediately upon applying a coverslip to samples the multiple droplets deformed and there was coalescence of the inner aqueous droplets. Under certain conditions (such as lipophilic surfactant concentration and internal phase osmotic pressure) the destabilized multiple emulsions formed unique metastable structures that had a "dimpled" appearance. The formation of these metastable structures correlated with the real-time instability of the W/O/W multiple emulsions investigated. Multiple emulsion stability also correlated with the interfacial film strength (measured by interfacial elasticity) of the hydrophobic surfactant at the mineral oil/external continuous aqueous phase interface. The formation of the metastable dimpled structures and the long-term stability of the multiple emulsions were dependent on the osmotic pressure of the inner droplets and the Laplace curvature pressure as described by the Walstra Equation (P. Walstra, "Encyclopedia of Emulsion Technology" (P. Becher, Ed.), Vol. 4. Dekker, New York, 1996). It appears that the effect of coverslip pressure on multiple emulsions may be useful as an accelerated stability testing method or for initial formulation screening.     

纳米SiO2与阳离子表面活性剂的相互作用及其诱导的正辛烷-水乳状液的双重相转变

研究了3种不同结构的水溶性阳离子表面活性剂对纳米二氧化硅颗粒的原位表面活性化作用, 它们分别是单头单尾的十六烷基三甲基溴化铵(CTAB)、单头双尾的双十二烷基二甲基溴化铵(di-C12DMAB)和双头双尾的Gemini型阳离子三亚甲基-二(十四酰氧乙基溴化铵)(II-14-3), 并通过测定Zeta电位、吸附等温线及接触角等参数对相关机理进行了阐述. 结果表明, 阳离子表面活性剂吸附到颗粒/水界面形成以疏水基朝向水的单分子层, 从而增强了颗粒表面的疏水性是原位表面活性化的基础. 通过吸附CTAB和II-14-3, 颗粒的疏水性适当增强, 能吸附到正辛烷/水界面稳定O/W(1)型乳状液; 而通过吸附di-C12DMAB所形成的单分子层更加致密, 颗粒的疏水性进一步增强, 进而使乳状液从O/W(1)型转变为W/O型; 当表面活性剂浓度较高时, 由于链-链相互作用, 表面活性剂分子将在颗粒/水界面形成双层吸附, 使颗粒表面变得亲水而失去活性, 但此时体系中游离表面活性剂的浓度已增加到足以单独稳定O/W(2)型乳状液的程度. 因此当采用纳米二氧化硅和di-C12DMAB的混合物作乳化剂时, 通过增加di-C12DMAB的浓度即可诱导乳状液发生O/W(1)→W/O→O/W(2)双重相转变.     

Phase inversion of the Pickering emulsions stabilized by plate-shaped clay particles

We investigated the phase inversion of Pickering emulsions stabilized by plate-shaped clay particles. Addition of water induced a phase inversion from a water-in-oil (W/O) emulsion to an oil-in-water (O/W) emulsion when the amount of the oil phase exceeded a limiting amount of oil absorption to solid particles. On the other hand, a phase inversion from a powdery state to an O/W emulsion state through an oil-separated state is observed when the amount of an oil phase is less than the limiting amount of the oil absorption. Interestingly, the oil separated is re-dispersed as emulsion droplets into the O/W emulsion phase. This type of phase inversion, which is a feature of the Pickering emulsions stabilized by the clay particles, is caused by a change in the aggregate structures of particles.     

High internal phase emulsions: catastrophic phase inversion, stability, and triggered destabilization

We have investigated the formation, drop sizes, and stability of emulsions prepared by hand shaking in a closed vessel in which the emulsion is in contact with a single type of surface during its formation. The emulsions undergo catastrophic phase inversion from oil-in-water (o/w) to water-in-oil (w/o) as the oil volume fraction is increased. We find that the oil volume fraction required for catastrophic inversion exhibits a linear correlation with the oil-water-solid surface contact angle. W/o high internal phase emulsions (HIPEs) prepared in this way contain water drops of diameters in the range 10-100 μm; emulsion drop size depends on the surfactant concentration and method of preparation. W/o HIPEs with large water drops show water separation but w/o HIPEs with small water drops are stable with respect to water separation for more than 100 days. The destabilization of the w/o HIPEs can be triggered by either evaporation of the oil continuous phase or by contact the emulsion with a solid surface of the "wrong" wettability.     

A one-step process for oil-in-water-in-oil double emulsion formation using a single surfactant

A one-step double emulsification protocol using one surfactant was developed for oil-in-water-in-oil (O(1)/W/O(2)) double emulsions. Two n-alkane oils and three different surfactants were studied, with focus placed on a formulation containing mineral oil, glycerol monoleate (GMO) and deionized water. Phenomenologically, double emulsion formation and stability originate from the combined actions of phase inversion and interfacial charging of the oil/water interface during high shear homogenization. Based on the extent of double emulsion formation and stability, a critical emulsification zone dependent on the weight ratios of GMO to water was identified. Within this critical zone, enhanced O(1)/W/O(2) emulsion formation occurred at higher pH and lower salt concentrations, demonstrating the key role of interfacial charging on double emulsification. Overall, this novel approach provides a novel platform for the development of double emulsions with simple compositions and processing requirements.     

MINIEMULSION FORMATION BY TRANSITIONAL INVERSION

Very fine emulsions with droplet size in the sub-micron range, often called miniemulsions, are prepared by the moderate (magnetic) stirring of a system undergoing a dynamic transitional inversion driven by a continuous change in physicochemical formulation (here temperature). Near optimum formulation for three-phase systems, the ultralow interfacial tension favors the drop breaking rate, and fine emulsions can be made. However, this region is also known for its rapid coalescence rate. Thus, a high enough stability can be attained only by shifting the formulation away from optimum as soon as the emulsion is made. Moreover, a rapid change in formulation through the three-phase region also results in a separation phenomenon that can be harnessed to produce ultra fine droplets.

The phase behavior of surfactant-oil-water systems and emulsion properties (type, droplet size and stability) are studied as a function of surfactant concentration (2 wt.% and 6 wt.%), for two different nonionic surfactants (polyoxyethylene tri-terbutyl ethers and sorbitan derivatives) with HLB ranging from 4 to 16. Kerosene and paraffin oil are used as oil phases. The transitional inversion form W/O to O/W is induced by a rapid cooling of the stirred systems from above to below the optimum temperature for three-phase behavior.

Miniemulsions are attained when the surfactant concentration is high enough, and when the temperature quenching span covers an appropriate range related to phase behavior.     

Behavior and Stability of Naphthenic Acid/Naphthenate Stabilized Emulsions. Mixed C80-Tetraacid and Stearic Acid Stabilization

Previous studies have focused on monomeric naphthenic acids and their ability to stabilize emulsions, but little has been reported on C80-tetraacids and their ability to function as an emulsifier. In this article, we report on the chemistry of the C80-tetraacids as an emulsion stabilizer and also on the role this acid has in mixed monoacid-tetraacid systems. The study focuses on the type of emulsion formed and the stability of these emulsions with respect to water cut, pH, salinity of the water phase, and type of counterion. Interfacial behavior and the electrostatic properties of the emulsion were studied in order to determine which of the acids were present at the interface and which of the acids gave the largest contribution to the emulsion stability. It was found that C80-tetraacids form only O/W emulsion under the conditions studied. Addition of monoacid to the system did not change the type of emulsion formed. Highest stability was seen for emulsions containing both monoacid and tetraacids. When adding NaCl a phase inversion from O/W to W/O emulsion appeared around a concentration of 2 wt% of NaCl.     

Changes in two-phase emulsion morphology in temperature-amphiphile concentration or fish diagram for ternary amphiphile/oil/water systems

We examined the morphologies of two-phase emulsions in the ternary 2-butoxyethanol/n-decane/water system at various temperatures and water-to-oil ratios (WORs). The two-phase emulsion morphologies depended on temperature, WOR, and amphiphile concentration, and the results are presented in a temperature-amphiphile concentration coordinate system or a "fish" diagram. The observations made in this work contradict the predictions by the phase-inversion-temperature (PIT) concept. At WOR<1, a vertical inversion line was observed at TT(uc) (upper critical endpoint temperature) and at low amphiphile concentrations, only B/T emulsions appeared, irrespective of temperature. At WOR>1, the situation was reversed; T/B emulsions at TT(uc), and T/B emulsions at low amphiphile concentrations, irrespective of temperature. At WOR=1, two horizontal inversion lines, one each at TT(uc), were observed. The morphologies of the two-phase emulsions were B/T or T/B emulsions at low amphiphile concentrations, and at higher amphiphile concentrations T/B at TT(uc). All these findings along with three-phase emulsion data result in complete emulsion morphology diagrams in the temperature-amphiphile concentration space or fish diagram.     

Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization

Poly(styrene-co-methacrylic acid) (PS-co-MAA) particles were synthesized via surfactant-free emulsion polymerization and then used as particulate emulsifiers for preparation of Pickering emulsions. Our results showed that adjusting the solution pH can tune the wettability of PS-co-MAA particles to stabilize either water-in-oil (W/O) or oil-in-water (O/W) Pickering emulsions. Stable W/O emulsions were obtained with PS-co-MAA particles at low pH values due to their better affinity to the dispersed oil phase. In contrast, increasing the pH value significantly changed the stabilizing behavior of the PS-co-MAA particles, leading to the phase inversion and formation of stable O/W emulsions. We found that the oil/water ratio had a significant influence on pH value of the phase inversion. It decreased with decreasing the oil/water ratio, and no phase inversion occurred when the styrene volume fraction reduced to 10 %. Additionally, macroporous polystyrene (PS) foam and PS microspheres were obtained via polymerization of Pickering high internal phase emulsion (Pickering HIPE) and O/W Pickering emulsion, respectively.     

Catastrophic phase inversion of abnormal emulsions in the vicinity of the locus of transitional inversion

This paper deals with the phase behaviour of model abnormal emulsions of cyclohexane/water/polyethoxylated surfactant in the vicinity of the locus of transitional inversion (optimum formulation). Abnormal emulsions are formed under dynamic conditions if the phase containing the soluble surfactant becomes the dispersed phase. Phase maps have been suggested in the literature that define the boundaries of emulsion morphologies. On these maps, only one transformation can be observed for any formulation scan. Furthermore, the morphology of emulsions in the vicinity of the locus of transitional inversion is rather vague. One might assume that by changing the HLB of the surfactant used in an abnormal emulsion to favour the continuous phase, that abnormal emulsion will gradually transform to a normal emulsion of the same type. A new experimental procedure was adopted in which emulsification was started with abnormal emulsions. To transform the abnormal emulsions to the normal emulsion of the same type, they were exposed to variations in temperature, the surfactant HLB, or water–oil phase ratio. As the optimum formulation was approached, the abnormal emulsions became so unstable that could not exist anymore in the un-favoured morphology and inverted to the normal emulsion of the opposite type. Further variation in the formulation along the route led to a transitional inversion to the normal emulsion of the original type. The result indicates an important finding that the transformation of abnormal emulsions to normal ones of the same type occurred via two successive inversions of catastrophic and transitional nature. It appears that the boundaries of catastrophic inversion correspond to the emulsions with the finest drop size. A modification to the phase behaviour maps, to include the locus of catastrophic phase inversion in the vicinity of the transitional inversion, was thus suggested.     

Simultaneous conductivity and viscosity measurements as a technique to track emulsion inversion by the phase-inversion-temperature method

Two kinds of transitions can occur when an emulsified water-oil-ethoxylated nonionic surfactant system is cooled under constant stirring. At a water-oil ratio close to unity, a transitional inversion takes place from a water-in-oil (W/O) to an oil-in-water (O/W) morphology according to the so-called phase-inversion-temperature method. At a high water content, a multiple w/O/W emulsion changes to a simple O/W emulsion. The continuous monitoring of both the emulsion conductivity and viscosity allows the identification of several phenomena that take place during the temperature decrease. In all cases, a viscosity maximum is found on each side of the three-phase behavior temperature interval and correlates with the attainment of extremely fine emulsions, where the best compromise between a low-tension and a not-too-unstable emulsion is reached. The studied system contains Polysorbate 85, a light alkane cut oil, and a sodium chloride brine. All transitions are interpreted in the framework of the formulation-composition bidimensional map.     

Role of liquid crystal in the emulsification of a gel emulsion with high internal phase fraction

A gel emulsion with high internal oil phase volume fraction was formed via an inversion process induced by a water–oil ratio change. The process involved the formation of intermediate multiple emulsions prior to inversion. The multiple emulsions contain a liquid crystal formed by the surfactant with water; this was both predicted by the equilibrium phase diagram as well as observed using polarization microscopy. These multiple emulsions were more stable compared to alternative multiple emulsions prepared in the same way with a surfactant that does not form liquid crystals. While the formation of a stable intermediate multiple emulsion may not be a necessary condition for the inversion to occur, the transitional presence of a liquid crystal proved to be a significant factor in the stabilization of the intermediate multiple emulsions. The resulting gel emulsion contained a small fraction of the liquid crystal according to the phase diagram, and it exhibited excellent stability.     

Interface composition of multiple emulsions: rheology as a probe

We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W1/O/W2) consist of water droplets (W1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W1 in oil globules) and the inverse emulsion (oil globules in W2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.     

Phase transitions and microstructure of emulsion systems prepared with acylglycerols/zinc stearate emulsifier

The emulsification processes, during which acylglycerols/zinc stearate emulsifier, water, and oil phase formed ternary systems, such as water-in-oil (W/O) emulsions, oil-in-water (O/W) dispersions, and unstable oil-water mixtures, were investigated in order to characterize the progressive transformations of the dispersed systems. The type, structure, and phase transitions of the systems were found to be determined by temperature and water phase content. Crystallization of the emulsifier caused the destabilization and subsequent phase inversion of the emulsions studied, at a temperature of 60-61 degrees C. The observed destabilization was temporary and led, at lower temperature, to W/O emulsions, "O/W + O" systems, or O/W dispersions, depending on the water content. Simultaneous emulsification and cooling of 20-50 wt % water systems resulted in the formation of stable W/O emulsions that contained a number of large water droplets with dispersed oil globules inside them ("W/O + O/W/O"). In water-rich systems (60-80 wt % of water), crystallization of the emulsifier was found to influence the formation of crystalline vesicle structures that coexisted, in the external water phase, with globules of crystallized oil phase. Results of calorimetric, rheological, and light scattering experiments, for the O/W dispersions obtained, indicate the possible transition of a monostearoylglycerol-based alpha-crystalline gel phase to a coagel state, in these multicomponent systems.     

Emulsifying potency of new amino acid-type surfactant (II): stable water-in-oil (W/O) emulsions containing 85 wt% inner water phase

The ternary phase diagram for N-[3-lauryloxy-2-hydroxypropyl]-L-arginine L-glutamate (C12HEA-Glu), a new amino acid-type surfactant, /oleic acid (OA)/water system was established. The liquid crystal and gel complex formations between C12HEA-Glu and OA were applied to a preparation of water-in-oil (W/O) emulsions. Stable W/O emulsions containing liquid paraffin (LP) as the oil and a mixture of C12HEA-Glu and OA as the emulsifier were formed. The preparation of stable W/O emulsions containing 85 wt% water phase was also possible, in which water droplets would be polygonally transformed and closely packed, since the maximum percentage of inner phase is 74% assuming uniformly spherical droplets. Water droplets would be taken into the liquid crystalline phase (or the gel complex) and the immovable water droplets would stabilize the W/O emulsion system. The viscosity of emulsions abruptly increased above the 75 wt% water phase (dispersed phase). The stability of W/O emulsions with a lower weight ratio of OA to C12HEA-Glu and a higher ratio of water phase was greater. This unusual phenomenon may be related to the formation of a liquid crystalline phase between C12HEA-Glu and OA, and the stability of the liquid crystal at a lower ratio of oil (continuous phase). W/O and oil-in-water (O/W) emulsions containing LP were selectively prepared using a mixture of C12HEA-Glu and OA since the desirable hydrophile-lipophile balance (HLB) number for the emulsification was obtainable by mixing the two emulsifiers.     

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.