Spontaneous emulsification at oil–water interface by tetraalkylammonium chloride

Water droplets were formed spontaneously at the interface of the 2-nitrophenyloctyl ether and aqueous phases on the oil phase side when the oil contained tetraalkylammonium chloride without surfactants. The droplets, less than some micrometers in diameter, gathered at the interface. The number density of the droplets was proportional to the concentration of tetraethylammonium chloride, and hence this salt should be responsible for the formation of the droplets as a surfactant. When positive voltage was applied to the aqueous phase against the oil, the droplets departed from the interface toward the oil bulk. The droplets should be negatively charged by chloride. The adsorption model of the salt was suggested, in which chloride is immobilized at the interface on the aqueous side electrostatically with tetraethylammonium ion on the oil side.     

Spontaneous oil-in-water emulsification induced by charge-stabilized dispersions of various inorganic colloids

Charge-stabilized dispersions of inorganic colloids are shown to induce spontaneous emulsification of hydrophobic (TPM) molecules to stable oil-in-water emulsions, with monodisperse, mesoscopic oil droplet diameters in the range of 30-150 nm, irrespective of the polydispersity of the starting dispersions. The results for cobalt ferrite particles and commercial silica sols extend our first study (Sacanna, S.; Kegel, W. K.; Philipse, A. Phys. Rev. Lett. 2007, 98, 158301) on spontaneous emulsification induced by charged magnetite colloids and show that this type of self-assembly is quite generic with respect to the composition of the nanoparticles adsorbing at the oil-water interface. Moreover, we provide additional experimental evidence for the thermodynamic stability of these mesoemulsions, including spontaneous oil dispersal imaged by confocal microscopy and monitored in situ by time-resolved dynamic light scattering. We discuss the possibility that thermodynamic stability of the emulsions is provided by the negative tension of the three-phase line between oil, water, and adsorbed colloids.     

Faster multiple emulsification with drop splitting

Microfluidic devices can form emulsions in which the drops have an intricate, controlled structure; however, a challenge is that the droplets are produced slowly, typically only a few millilitres per hour. Here, we present a simple technique to increase the production rate. Using a large drop maker, we produce large drops at a fast volumetric rate; by splitting these drops several times in a splitting array, we create drops of the desired small size. The advantage of this over forming the small drops directly using a small drop maker is that the drops can be formed at much faster rates. This can be applied to the production of single and multiple emulsions.     

Porous microcapsule formation with microsieve emulsification

A simple route is presented to prepare core-shell Eudragit microcapsules through a solvent extraction method with the use of microsieve emulsification. Droplets from a solution of Eudragit FS 30D (a commercial copolymer of poly(methyl acrylate-co-methyl methacrylate-co-methacrylic acid) 7:3:1) and hexadecane in dichloromethane are dispersed into water, using a micro-engineered membrane with well-defined pores, in a cross-flow setting. The dichloromethane is extracted from the droplets, which induces demixing in the droplets, leading to a hexadecane-rich core, and an Eudragit-rich shell. The obtained microcapsules have a narrow size distribution due to the microsieve emulsification process. The capsules have a porous shell as shown by SEM and AFM measurements. Their porosity and pore size is dependent on the ratios of Eudragit and hexadecane in the dispersed phase. At pH 7.1 and above Eudragit (FS 30D) dissolves in water; this pH change is used to release the contents of the microcapsule.     

Visualization and characterization of SPG membrane emulsification

Shirasu-porous-glass (SPG) membrane emulsification is highly attractive for various fields of foods, cosmetics, and pharmaceuticals because this technique produces monodispersed emulsions. However, there are few reports on the observation of membrane emulsification at the membrane surface. In the present work, we aimed to visualize the membrane emulsification using a microscope high-speed camera system. The direct observation made it possible to measure the mean rate of droplet formation and the percentage of active pores. The mean rate of droplet formation ranged 0.3–12 s⁻¹ and the percentage of active pores ranged 0.3–0.5% under the dispersed-phase flux of 0.58×10⁻⁶–5.8×10⁻⁶ m³/(m² s). We also observed that the droplets were formed without continuous-phase flow and the droplets were also formed by shear force at the continuous-phase flow under different experimental conditions. The balance among the dispersed-phase flux and the continuous-phase flow velocity influenced droplet formation.     

Preparation of polyurea capsules using electrocapillary emulsification

Polyurea capsules have been prepared using the electrocapillary emulsification method in order to control the particle size within the submicron range. The polyurea capsules have been synthesized via the interfacial polycondensation between tetraethylenepentamine (TEP) dissolved in an aqueous phase and toluenediisocyanate (TDI) dissolved in a mixture of cyclohexane and chloroform. The oil phase contains a lipophilic nonionic surfactant (sorbitan sesquioleate, SO-15) as an emulsion stabilizer. Scanning electron microscope (SEM) observations reveal that the capsule size is decreased as (i) the amount of the aqueous phase injected into the oil phase is decreased and (ii) the dropping rate of the aqueous phase is decreased. Indeed, the mole ratio of the two monomers makes a significant impact on the capsule size. Under the best experimental condition examined in this study, we obtained polyurea capsules with a diameter of approximately 200 nm, which should be useful in developing bioreactors or carriers.     

Microchannel emulsification using gelatin and surfactant-free coacervate microencapsulation

In this study, we investigated the use of microchannel (MC) emulsifications in producing monodisperse gelatin/acacia complex coacervate microcapsules of soybean oil. This is considered to be a novel method for preparing monodisperse O/W and W/O emulsions. Generally, surfactants are necessary for MC emulsification, but they can also inhibit the coacervation process. In this study, we investigated a surfactant-free system. First, MC emulsification using gelatin was compared with that using decaglycerol monolaurate. The results demonstrated the potential use of gelatin for MC emulsification. MC emulsification experiments conducted over a range of conditions revealed that the pH of the continuous phase should be maintained above the isoelectric point of the gelatin. A high concentration of gelatin was found to inhibit the production of irregular-sized droplets. Low-bloom gelatin was found to be suitable for obtaining monodisperse emulsions. Finally, surfactant-free monodisperse droplets prepared by MC emulsification were microencapsulated with coacervate. The microcapsules produced by this technique were observed with a confocal laser scanning microscope. Average diameters of the inner cores and outer shells were 37.8 and 51.5 microm; their relative standard deviations were 4.9 and 8.4%.     

Phenomenological theory of the kinetics of ultrasonic emulsification

Summary A working model is given for the rate of ultrasonic emulsification, considering the dispersion at the interface (areaA) and the coagulations in the volumeV of the emulsion. A bimolecular coagulation leads to the equationc=c _∞tanhbt;c _∞=(Aα/Vβ)^1/2;b=(Aαβ/V)^1/2 while a monomolecular coagulation givesc=c _∞{1−exp (−at)};c _∞=Aα/Vβ;a=β. The experiments on the dependence of c_∞,a andb uponA andV favour the bimolecular coagulation. The results are satisfactorily explained on general theoretical grounds.

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Zusammenfassung Ein Arbeitsmodell für die Geschwindigkeit der Ultraschallemulgierung wird entwickelt, das Dispersion in der Grenzfl?che (Fl?cheA) und Koagulation im Volumen (V) der Emulsion annimmt. Eine bimolekulare Koagulation führt zu der Gleichung:c=c _∞ tanhbt;c _∞=(Aα/Vβ)^1/2;b=(Aαβ/V)^1/2, eine monomolekulare dagegen zu:c=c _∞{1−exp (at−)};c _∞=Aα/Vβ;α=β. Die Versuche über die Abh?ngigkeit vonc _∞,a undb vonA undV scheinen für bimolekulare Koagulation zu sprechen. Die Ergebnisse werden auf der Basis dieser einfachen theoretischen Grundlagen befriedigend erkl?rt.

     

Production of porous silica microparticles by membrane emulsification

A method for the production of near-monodispersed spherical silica particles with controllable porosity based on the formation of uniform emulsion droplets using membrane emulsification is described. A hydrophobic metal membrane with a 15 μm pore size and 200 μm pore spacing was used to produce near-monodispersed droplets, with a mean size that could be controlled between 65 and 240 μm containing acidified sodium silicate solution (with 4 and 6 wt % SiO(2)) in kerosene. After drying and shrinking, the final silica particles had a mean size in the range between 30 and 70 μm. The coefficient of variation for both the droplets and the particles did not exceed 35%. The most uniform particles had a mean diameter of 40 μm and coefficient of variation of 17%. By altering the pH of the sodium silicate solution and aging the gel particles in water or acetone, the internal structure of the silica particles was successfully modified, and both micro- and mesoporous near-monodispersed spherical particles were produced with an average internal pore size between 1 and 6 nm and an average surface area between 360 and 750 m(2) g(-1). A material balance and particle size analysis provided identical values for the internal voidage of the particles, when compared to the voidage as determined by BET analysis.     

特稠油乳化降黏机理研究

研究了胜利油田罗家高硫特稠油的黏度及其极性四组分、有机杂原子、金属元素的关联。结果表明,该稠油的高黏度主要与三个因素有关：（1） 含有高分子量的胶质和沥青质组分;（2） 硫的质量分数很高;（3） 金属元素V、Fe、Ni形成配位络合物增加了沥青质的内聚力。同时考察了所筛选的降黏剂的效果,降黏剂明显降低了油水界面张力,使得稠油的黏度降低。比较了添加降黏剂前后沥青质的电子探针照片的变化,推测降黏剂分子借助强的形成氢键的能力和渗透、分散作用进入沥青质片状分子之间,破坏了沥青质分子平面重叠的聚集体,使聚集结构变得疏松,表明聚集有序性降低是稠油降黏的主要机理。     

Influence of the deacetylation degree on chitosan emulsification properties

The emulsification of sunflower oil by chitosan solutions with deacetylation degrees (DD) between 73 and 95% was studied using different techniques. The droplet size distributions, conductivity, ageing behavior and viscosity of emulsions were studied as functions of the chitosan DD. All DD gave stable polydisperse water-in-oil-in-water emulsions with different viscosities. Two optimum DD values were found, 81 and 88%, giving complete emulsification without residual oil or sedimentation. Chitosans with intermediate DD were less effective emulsifiers. Chitosans with higher DD gave poor emulsification. Received: 11 January 1999 Accepted in revised form: 31 May 1999     

Manufacture of large uniform droplets using rotating membrane emulsification

A new rotating membrane emulsification system using a stainless steel membrane with 100 microm laser drilled pores was used to produce oil/water emulsions consisting of 2 wt% Tween 20 as emulsifier, paraffin wax as dispersed oil phase and 0.01-0.25 wt% Carbomer (Carbopol ETD 2050) as stabilizer. The membrane tube, 1 cm in diameter, was rotated inside a stationary glass cylinder, diameter of 3 cm, at a constant speed in the range 50-1500 rpm. The oil phase was introduced inside the membrane tube and permeated through the porous wall moving radially into the continuous phase in the form of individual droplets. Increasing the membrane rotational speed increased the wall shear stress which resulted in a smaller average droplet diameter being produced. For a constant rotational speed, the average droplet diameter increased as the stabilizer content in the continuous phase was lowered. The optimal conditions for producing uniform emulsion droplets were a Carbomer content of 0.1-0.25 wt% and a membrane rotational speed of 350 rpm, under which the average droplet diameter was 105-107 microm and very narrow coefficients of variation of 4.8-4.9%. A model describing the operation is presented and it is concluded that the methodology holds potential as a manufacturing protocol for both coarse and fine droplets and capsules.     

Surface activity and emulsification properties of hydrophobically modified dextrans

Neutral polymeric surfactants were synthesized by covalent attachment of hydrophobic groups (aromatic rings) onto a polysaccharide backbone (dextran). By changing the conditions of the modification reaction, the number of grafted hydrophobic groups per 100 glucopyranose units (substitution ratio) was varied between 7 and 22. In aqueous solution, these polymers behaved like classical associative polymers as demonstrated by viscometric measurements. The associative behavior was more pronounced when the substitution ratio increased. The surface-active properties of the modified dextrans were evidenced by surface tension (air/water) and interfacial tension (dodecane/water) measurements. In each case the surface or interfacial tension leveled down above a critical polymer concentration, which was attributed to the formation of a dense polymer layer at the liquid-air or liquid-liquid interface. Dodecane-in-water emulsions were prepared using the polymeric surfactants as stabilizers, with oil volume fractions ranging between 5 and 20%. The oil droplet size (measured by dynamic light scattering) was correlated to the amount of polymer in the aqueous phase and to the volume of emulsified oil. The thickness of the adsorbed polymer layer was estimated thanks to zeta potential measurements coupled with size measurements. This thickness increased with the amount of polymer available for adsorption at the interface. The dextran-based surfactants were also applied to emulsion polymerization of styrene and stable polystyrene particles were obtained with a permanent adsorbed dextran layer at their surface. The comparison with the use of an unmodified dextran indicated that the polymeric surfactants were densely packed at the surface of the particles. The colloidal stability of the suspensions of polystyrene particles as well as their protection against protein adsorption (bovine serum albumin, BSA, used as a test protein) were also examined.     

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.     

生物质腰果酚磺酸盐表面活性剂的合成及其乳化性能

采用发烟硫酸对生物质腰果酚进行磺化,得到腰果酚磺酸盐表面活性剂;利用红外光谱表征了产物的化学结构;分别采用悬滴法和小液滴法测定了腰果酚磺酸盐水溶液的表面张力和润湿性能,采用分水法测定了产物对液体石蜡的乳化性能,同时考察了氯化钠对乳化性能的影响.结果表明:所制备的腰果酚磺酸盐的临界胶束浓度(cmc)及γcmc分别为3.3...     

Micro-fabricated metal nozzle plates used for water-in-oil and oil-in-water emulsification

In this paper the fabrication and use of micro-structured metal nozzle plates as emulsification devices is investigated and discussed. These structured metal nozzle plates were fabricated via two distinct routes. Laser ablation, performed with a femtosecond laser, was used to drill micrometer-sized holes into stainless steel and aluminum foils. Also a conventional steel mesh with an average pore size of 2.4 μm fabricated by weaving and roll compaction of micrometer-sized steel wires was investigated. The perforated metal nozzle plates were used for oil-in-water and after hydrophobization with alkylchlorosilanes for water-in-oil emulsification as well. In both cases, two types of drop formation processes were observed. The first one is the shear-induced drop formation well known for cross-flow membrane emulsification. The second is the spontaneous drop formation known from microchannel emulsification.     

A new approach to anodic substitution reaction using acoustic emulsification

We have developed a novel electrolytic system for anodic substitution reactions using acoustic emulsification. This new system involves the generation of a carbocation by anodic oxidation of a substrate, and then its reaction with a nucleophile droplet formed by ultrasonication. In this system, even if the oxidation potential of the nucleophile is lower than that of the substrate, the substrate was predominantly oxidized to give the corresponding cation intermediate because the nucleophile phase, which was insoluble in the electrolytic medium, was electro-inactive. In addition, the overoxidation of the desired products was considerably suppressed by the extraction of products from the electrolyte solution into the nucleophile phase. As a result, the anodic substitution reaction of several carbamates with allyltrimethylsilane was carried out to provide the corresponding products in good to moderate yields.     

Efficient emulsification of viscous oils at high drop volume fraction

It is shown experimentally in this study that the increase of drop volume fraction can be used as an efficient tool for emulsification of viscous oils in turbulent flow. In a systematic series of experiments, the effects of drop volume fraction and viscosity of the dispersed phase on the mean, d(32), and maximum, d(V95), diameters of the drops, formed during emulsification, are quantified. The volume fraction, Φ, of the dispersed oily phase is varied between 1% and 90%, and oils with viscosity varying between 3 and 10,000 mPa.s are studied. All experiments are performed at sufficiently high surfactant concentration, as to avoid possible drop-drop coalescence during emulsification. The analysis of the experimental data shows that there is a threshold drop volume fraction, Φ(TR), at which a transition from inertial turbulent regime into viscous turbulent regime of emulsification occurs, due to the increased overall viscosity of the emulsion. At Φ < Φ(TR), d(32) and d(V95) depend weakly on Φ and are well described by known theoretical expression for emulsification in inertial turbulent regime (Davies, Chem. Eng. Sci. 1985, 40, 839), which accounts for the effects of oil viscosity and interfacial tension. At Φ > Φ(TR), both d(32) and polydispersity of the formed emulsions decrease very significantly with the increase of Φ (for the oils with η(D) > 10 mPa.s). Thus, very efficient emulsification of the viscous oils is realized. Very surprisingly, a third regime of emulsification is observed in the range of concentrated emulsions with Φ > 75%, where the mean drop size and emulsion polydispersity are found experimentally to be very similar for all oils and surfactants studied-an experimental fact that does not comply with any of the existing models of drop breakup during emulsification. Possible mechanistic explanations of this result are discussed. The experimental data for semiconcentrated and concentrated emulsions with Φ > Φ(TR) are described by a simple scaling expression, which accounts for the effects of all main factors studied.     

Status of cross-flow membrane emulsification and outlook for industrial application

Cross-flow membrane emulsification has great potential to produce monodisperse emulsions and emulsions with shear sensitive components. However, until now, only low disperse phase fluxes were obtained. A low flux may be a limiting factor for emulsion production on a commercial scale. Therefore, the effects of membrane parameters on the disperse phase flux are estimated. Besides, the effects of these parameters on the droplet size and droplet size distribution are qualitatively described. Wetting properties, pore size and porosity mainly determine the droplet size (distribution). Membrane morphology largely determines the disperse phase flux. As an example, industrial-scale production of culinary cream was chosen to evaluate the required membrane area of different types of membranes: an SPG membrane, an -Al₂O₃ membrane and a microsieve. Due to the totally different morphologies of these membranes, the fraction of active pores is 1 for a microsieve and is very low for the other membranes. The choice of the optimal membrane did not depend on the production strategy: either to produce large quantities or to produce monodisperse emulsions, the best suitable was a microsieve with an area requirement of around 1 m². In general, the total membrane resistance should be low to obtain a large disperse phase flux. In contrast, the membrane resistance should be high to obtain monodisperse emulsions when using membranes with a high porosity.