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.     

Temperature-induced three-phase equilibrium of medium-chain-length poly-3-hydroxyalkanoates-incorporated emulsion system for production of polymeric nanoparticle

The study investigated the effects of temperature on the phase behavior of medium-chain-length poly-3-hydroxyalkanoates (mcl-PHA)-incorporated emulsion system. It is suggested that the three-phase equilibrium consisting of lamellar liquid crystalline (L_a), bi-continuous microemulsion (D), and oil-swollen micelle phases formed in the vicinity of optimal formulation when the combination of phase inversion composition (PIC) and phase inversion temperature (PIT) methods was applied. The interaction effects between two parameters, viz. temperature and mcl-PHA molecular weight, influenced the lamellar/bi-continuous microemulsion formation within the mcl-PHA-incorporated emulsion. It is suggested that the lamellar/bi-continuous microemulsion phase of mcl-PHA-incorporated emulsion can be thermally induced from multiple emulsion system proximately before EIP, and its hypothetical formation mechanism is elucidated in this study.     

Polyurea nanocapsules obtained from nano‐emulsions prepared by the phase inversion temperature method

We describe here a new and simple method for preparation of polyurea nanocapsules from nanodroplets that were obtained by the phase inversion temperature (PIT) method. In the first stage, a nano‐emulsion was prepared, by a heating–cooling cycle, in which the oil phase contained an oil soluble monomer (toluene 2 , 4 ‐diisocyanate (TDI)). In the second stage, a water‐soluble monomer and crosslinker (diethylenetriamine (DETA)) was added, leading to formation of a polymeric shell by an interfacial polycondensation reaction. The new method was demonstrated for obtaining nanocapsules of about 100 nm, in which hexadecane, dodecane, or decane were the core materials, without using any special equipment. The morphology and structure of the nanocapsules were evaluated by attenuated total reflection Fourier transform infrared (ATR‐FTIR) measurements and electron microscopy. The thermal behavior of the nanocapsules containing hexadecane was studied by Differential Scanning Calorimetry (DSC) measurements, indicating that such nanocapsules can be utilized in thermal energy storage. Copyright © 2010 John Wiley & Sons, Ltd.     

卵磷脂类液晶乳液的性能

以卵磷脂为主乳化剂制备了一款液晶乳液。 该乳液在皮肤上具有良好的稳定性能,在皮肤表层停留6 h仍能保持完整的液晶结构,克服了一般液晶乳液中液晶织构无法在皮肤上长时间停留的问题。 液晶结构在皮肤温度范围内具有较高的稳定性,可为液晶乳液其他性能的发挥提供条件。 基于此,我们采用体外称重法研究了液晶乳液的锁水性,发现液晶乳液锁水性能明显优于传统乳液,实验7 h后仍能保持原有水分总质量的50%;体外透析实验证实,液晶乳液表现出显著的缓释性能且能释放完全,7 h后目标分子(水杨酸钠)释放率可达96%;耐温性能研究表明,液晶乳液耐高温性能及低温冻融性能优良,且温度对乳液中层状液晶的影响是可恢复的;采用离心法、高低温循环和高低温长时间(3个月)放置的方法探究了乳液储运稳定性,结果表明,液晶乳液产品储运稳定性极佳,便于实际的应用和储运。 该研究不仅可为开发多效的高端化妆品提供必要信息和参考数据,而且有望拓展卵磷脂类液晶乳化剂体系的应用范畴。     

The effect of concentration of surfactant and electrolyte on the pit and droplet sizes nanoemulsions of <Emphasis Type="Italic">n</Emphasis>-dodecane in water

Nanoemulsions are transparent or semi-transparent systems mostly covering the size range of 50–200 nm. In the research, the production of nanoemulsion of n-dodecane in water was studied by phase inversion temperature method (PIT), and the effect of the changes in NaCl and surfactant concentration on PIT and droplet size of n-dodecane was studied. The changes in conductivity with temperature were measured for emulsions containing 20 wt % dodecane, 4 and 8 wt % Brij30, and NaCl of various concentrations in aqueous phase. The results showed a decrease in PIT with a rise in concentration of NaCl and also Brij30. There was a linear model fitted to the data. Analysis of variance (ANOVA) shows that, the significance value (p-value) is less than 0.05, and the effect of the changes in concentration of surfactant Brij30 on the decrease in PIT and droplet size was the more than that in concentration of NaCl in aqueous phase. The lowest mean droplet diameters were in the range of 8.6–14 nm.     

Factors Affecting the Phase-Inversion Temperature of Fatty Alcohol Ethoxylates

Factors that affect the phase-inversion temperature (PIT) based on nonionic surfactant fatty alcohol ethoxylates were investigated. Phase-inversion process was continuously monitored by determining changes in conductivity with temperature. The influences of oil-to-water ratio, emulsifier concentration, emulsifier mixing ratio, sodium chloride, and oil types on the PIT of emulsions were investigated. Results showed that the PIT of the emulsions declined with increased oil-to-water ratio. Emulsifier concentration significantly affected the PIT temperature. High sodium chloride content suppressed phase inversion. A lower Brij72-to-Brij721 ratio corresponded to higher PIT. Different oils required different HLB numbers in the phase-inversion process.     

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.     

Water transfer in emulsified liquid membrane processes

Water transfer through the organic phase of a water-in-oil emulsion (liquid membrane) is investigated as a function of emulsion composition, water activity, temperature and agitation in a two-compartment cell. It is shown that the rate of transfer increases with the difference of water activities in the two aqueous phases and depends on the nature and the concentration of the surfactant. A decrease of the organic phase viscosity and an increase in temperature increase the transfer rate. A mathematical model is proposed which is based on the assumption of water—surfactant associations and carrier-mediated water transport. This model qualitatively explains the experimental results.     

Determination of the Phase Inversion Temperature of Orange Oil/Water Emulsions by Rheology and Microcalorimetry

Abstract

In low-energy emulsification processes, phase inversion occurs when the phases of a dispersion exchange, because of changes in the medium's properties. This paper reports experiments to determine the phase inversion temperature (PIT) of orange oil/water emulsions stabilized by nonionic surfactants. Two techniques were employed: rheology, which is already commonly used to obtain the PIT, and microcalorimetry, which has been proposed as a new technique. Continuous monitoring of the emulsions' viscosity permitted identifying different phenomena that occur while the temperature varies. For all the dispersions prepared, the rheological curves obtained showed two peaks, one attributed to the phase separation process and the other to the phase inversion phenomenon. The microcalorimetry technique showed two endothermic transitions as the dispersion's temperature increased. The initial temperatures were comparable to those obtained by rheology. The influence of the surfactant concentration and the hydrophilic-lipophilic balance (HLB) of the mixture of surfactants and the reduction in volume of the phases at the phase inversion temperature were also evaluated. In general, both methods used to evaluate the phase inversion of the orange oil/water systems (rheology and microcalorimetry) presented concordant results, both for the phase separation process and the phase inversion temperature.     

Study on thermal induced phase inversion of concentratedO/W emulsions stabilized by various tween emulsifiers

Summary Thermal induced phase inversion of concentrated oil-in-water emulsions stabilized by various fatty acid polyoxyethylene esters of sorbitan (Tween 21, Tween 61, Tween 65, Tween 80 and Tween 81) has been studied. Phase inversion temperature (PIT) was determined by differential thermal analysis and the changes in internal structure of emulsions caused by heating were followed microscopically. The PITS obtained were dependent on the kind of Tween. When the emulsions were stabilized by Tween 65, the PIT also depended on whether the emulsifier was dissolved in water or in oil phase or in the both. Microscopic examination of the emulsions during heating showed that the appearance of water droplets within the oil drops, i.e. the development of a multiphase (W/O/W) emulsion structure precedes phase inversion.

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Zusammenfassung Die thermische Phaseninversion konzentrierter Öl-in-Wasser-Emulsionen (durch verschiedene Emulgatoren des Tween-Typs stabilisiert) wurde untersucht und die Phasen-inversionstemperatur durch Differentialthermoanalyse bestimmt.Die Phaseninversionstemperatur hängt von der Tweenart ab. Mit Tween 65 ist die Phaseninversionstemperatur auch davon abhängig, ob der Emulgator in Wasser, in Öl oder in beiden Phasen gelöst wird. Mikroskopische Untersuchungen haben gezeigt, daß Wassertröpfchen innerhalb der Öltropfen entstehen, d. h., daß die Entwicklung einer mehrphasigen Wasser-Ö1-Wasser-Struktur der Phaseninversion vorangeht.

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With 5 figures     

A Novel Synthetic Method and Potential Application of a Sulfanilic Acid-Based Surfactant

A novel synthetic method was developed to prepare a difunctional surfactant using sulfanilic acid and dodecyl bromide. In the first step, sulfanilic acid was protected by acetic anhydride. Then, Friedel–Crafts alkylation of the synthesized acetanilide with dodecyl bromide was performed in the presence of aluminum chloride. The protecting group (amide) was removed easily by acid hydrolysis. The formation of surfactant was confirmed with Fourier transform infrared and proton nuclear magnetic resonance spectroscopy. The demulsification property of this surfactant was studied using brine-fuel oil emulsion, and its result was compared with a commercially available demulsifier. The results showed that 52% of water was separated from emulsion at room temperature, but at elevated temperature 98% of water was separated from brine-fuel oil emulsion.     

Phase transitions in O/W lauryl acrylate emulsions during phase inversion,studied by light microscopy and cryo-TEM

Phase changes during the preparation of nano-emulsions containing polymerizable monomer as the oil phase, by the phase inversion temperature technique (PIT), were investigated using light microscopy, cryo-TEM and viscosity measurements. The nano-emulsions were prepared using a poly(oxyethylene) nonionic surfactant and a polymerizable acrylic monomer (lauryl acrylate) as the oil phase. Inversion of the emulsion, followed by rapid cooling, resulted in emulsions having an average droplet size as low as 25 nm. Cryo-TEM was used to observe the structures that are present above and below the phase transition temperature, and gave, for the first time, visual indication of the presence of a microemulsion and a locally ordered structure in the process. At high surfactant concentrations, the inversion–cooling process yields emulsions with unique structures, in which the oil phase is present as worm-like structures.     

Effect of oil phase transition on freeze/thaw-induced demulsification of water-in-oil emulsions

Recently, there has been an increasing interest in the breakage of water-in-oil (W/O) emulsions by the freeze/thaw method. Most of the previous works focused on the phase transition of the water droplet phase. This paper emphasizes the effect of continuous oil phase transition. A series of oils with different freezing points were used as oil phases to produce model emulsions, which were then frozen and thawed. The emulsion whose oil phase froze before the water droplet phase did (OFBW) on cooling was readily demulsified with a dewatering ratio as high as over 80%, but the emulsion whose oil phase did not freeze when the water droplet phase did (NOFBW) was relatively hard to break. The difference in demulsification performance between them resulted from the distinction between their demulsification mechanisms via the analyses of the emulsion stability, emulsion crystallization/melting behaviors, oil phase physical properties, and wettability of the frozen oil phase, etc. For the OFBW emulsion, the first-frozen oil phase was ruptured by the volume expansion of the subsequently frozen droplet phase, and meanwhile, some liquid droplet phase was drawn into the fine gaps/crevices of the frozen oil phase to bridge droplets, which were considered to be essential to the emulsion breakage, whereas for the NOFBW emulsion, the demulsification was attributed to the collision mechanism proposed in our previous work. The findings may provide some criteria for selecting a proper oil phase in the emulsion liquid membrane (ELM) process and then offer an alternative approach to recycle the oil phase for continuous operation. This work may also be useful for emulsion stability against temperature cycling.     

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.     

Highly Concentrated Emulsions: Physicochemical Principles of Formulation

This review deals with the preparation, stability, rheology and different applications of highly concentrated emulsions. These emulsions, which are known as high internal phase ratio emulsions (HIPRE), gel-emulsions, biliquid foams, etc., containing over 90% internal phase by volume, have a swollen micellar (L₁ or L₂) solution of nonionic or ionic surfactants as a continuous phase. These emulsions have the structure of biliquid foams and behave as gels since they present viscoelastic and plastic properties. The functional macroscopic properties of gel-emulsions are dependent on the structural parameters of the microemulsion continuous phase as well as of the interfacial properties (interfacial tension, bending modules, spontaneous curvature) of surfactant monolayers. The depletion interaction between emulsion droplets due to the non-compensated osmotic pressure of micelles is revealed as a main factor, along with surface forces, which determine the aggregative stability and the rheological properties of these emulsions. The effect of electrolyte and surfactant concentration, temperature, as well as other physicochemical parameters on the fiocculation threshold, stability, and yielding properties of highly concentrated emulsions is explained by the effect of these parameters on the critical micelle concentration (CMC) and the aggregation number of surfactants, and, consequently, on the depletion interaction. The thermodynamic theory of adhesion of fluid droplets in micellar solution and the suggested model of elasticity of gel-emulsions permit to explain the effect of mentioned physicochemical parameters on the elasticity modulus, the plastic strength and the linear deformation of these emulsions. A novel mechanism for the spontaneous formation of gel-emulsions by the phase inversion temperature (PIT) route is suggested, allows the selection of ternary systems able to yield these emulsions, and explains how the droplet size can be controlled during the PIT process. An original model for liquid film rupture is also suggested, and allows the prediction of the effect of structural parameters of micellar solutions and the interfacial properties of surfactant monolayers on the stability of gel-emulsions.     

Effect of Experimental Variables on the Combustion Characteristics of Water-in-Diesel Emulsion Fuels

Water-in-diesel (W/D) emulsion fuels were prepared through an ultrasonic processor by using high energy emulsification method. Accordingly, the physical and chemical properties were analyzed. A decrease in viscosity was found in the emulsion fuel in contrast to the neat diesel which signifies the enhanced fluidity of the fuel. The emulsion fuel was then used to carry combustion tests in an internal combustion engine. A decrease in exhaust temperature was observed when a high surfactant to water ratio was used, which lead to minimal heat loss. As water is emulsified with diesel, effectiveness of combustion is improved rather than neat diesel fuel. It was also explored that the addition of water-in-diesel is influential in terms of reduction in exhaust gas emission such as carbon dioxide, carbon monoxide, ammonia from the internal combustion engine. Therefore, this type of emulsion fuel would be a useful contribution in the fuel economy, but also in making it environmentally friendly since diesel fuel is now considered one of the leading fuels causing ecological contamination.     

Oil/water droplet formation by temperature change in the water/c(16)e(6)/mineral oil system

Droplet sizes of oil/water (O/W) nanoemulsions prepared by the phase inversion temperature (PIT) method, in the water/C16E6/mineral oil system, have been compared with those given by a theoretical droplet model, which predicts a minimum droplet size. The results show that, when the phase inversion was started from either a single-phase microemulsion (D) or a two-phase W+D equilibrium, the resulting droplet sizes were close to those predicted by the model, whereas, when emulsification was started from W+D+O or from W+D+Lalpha (Lalpha = lamellar liquid crystal) equilibria, the difference between the measured and predicted values was much higher. The structural changes produced during the phase inversion process have been investigated by the 1H-PFGSE-NMR technique, monitoring the self-diffusion coefficients for each component as a function of temperature. The results have confirmed the transition from a bicontinuous D microemulsion at the hydrophile-lipophile balance (HLB) temperature to oil nanodroplet dispersion in water when it is cooled to lower temperatures.     

Black Gold: Plasmonic Colloidosomes with Broadband Absorption Self‐Assembled from Monodispersed Gold Nanospheres by Using a Reverse Emulsion System

A facile approach for the fabrication of novel black plasmonic colloidosomes assembled from Au nanospheres is developed by an emulsion‐templating strategy. This self‐assembly process is based on a new reverse water‐in‐1‐butanol emulsion system, in which the water emulsion droplets can dissolve into 1‐butanol (oil) phase at an appropriate rate. These Au colloidosomes possess hexagonal close‐packed multilayer shells and show a low reflectivity and intense broadband absorption owing to the strong interparticle plasmonic coupling, which is further investigated by a finite‐difference time‐domain method. This method is universal and is suitable for self‐assembly of different noble‐metal nanoparticles into different colloidosomes. These colloidosomes have important applications in photothermal therapy, biosensors, and drug delivery.     

Study of phase transitions in lyotropic liquid-crystal emulsion systems tetraethylene glycol monododecyl ether,water, and vaseline oil by the wetting angle method

Phase behavior of emulsion liquid-crystal systems constituted by tetraethylene glycol monododecyl ether, water, and Vaseline oil was studied by a set of methods. The type of the mesophase and the temperature range of its existence were determined. It is shown that the wetting method is applicable to identification of phase transitions in the given lyotropic liquid-crystal emulsion systems.     

Copolymerization of styrene and methacrylic acid in concentrated emulsions

Copolymerization of styrene and methacrylic acid was carried out by the concentrated emulsion polymerization method, using sodium dodecylsulfate and AIBN as emulsifier and initiator, respectively. Compared to conventional emulsion polymerization, a much smaller amount of water (5–25 vol %) is employed as the continuous phase and thus the loss of methacrylic acid, which is very soluble in water, is minimized. The concentrated emulsion, which has the appearance of a gel, was prepared at room temperature, and was polymerized at 40°C. The size of copolymer latexes is affected by the internal phase ratio, and was in the range of 0.2–0.3 μm in diameter. Potentiometric titration was used to determine the surface density of the carboxylic groups of the copolymer latexes and its dependence on the feed molar ratio of methyacrylic acid to styrene. NMR and IR spectroscopies have been employed to determined the composition of the copolymer latexes.