Drop Size Distribution of O/W Emulsions by Drop Immobilization with Agarose

ABSTRACT

A method for the determination of the drop size distribution of oil-in-water (O/W) emulsions is presented. Water-based coolant emulsions used in rolling mill operations were studied. The emulsions were gelled in agarose so that the oil droplets were immobilized and samples of these gels were measured by confocal laser scanning microscopy (CLSM) and image processing. The influence of the addition of CaCl₂ as an emulsion destabilizer on the size distributions was also studied. The experimental data obtained were compared to those obtained using photon correlation spectroscopy (PCS).     

Study of Bimodal Drop Size Distributions of Emulsion

In order to increase the present understanding of bimodal emulsion drop size distributions, systematic series of experiments have been carried out to investigate the effects of formulation variables on bimodal drop size distributions, and probability distribution functions were proposed to analyze the distribution. The results show that, the span of the drop size and Sauter mean diameter become larger when the dispersed phase volume fraction becomes higher and rotor speed becomes lower; the Frechet function represents the experimental data satisfactorily. The prediction model of Sauter mean diameter established by combining the prediction theory of the maximum stable drop diameter and experimental analysis results can fit the experimental data well.     

Effect of Aqueous Phase Composition on the Properties of a Silica-Stabilized W/O Emulsion

A high volume fraction silica stabilized w/o emulsion with small droplet size ( approximately 3 μm) has been prepared using a commercially available hydrophobic silica. Addition of hydroxypropyl cellulose to the dispersed aqueous phase was found to improve the monodispersity of the emulsion by suppressing the production of larger droplets. The droplet size distribution showed complex behavior as the silica concentration was varied, which was explained using a simple kinetic argument. The effect of varying the acidity and ionic strength of the internal water phase was investigated. It was found that the presence of strong acid or strong alkali in the internal aqueous phase increased the gelation of the emulsions by promoting flocculation. This could be explained by acid- and alkali-catalyzed cleavage of surface siloxane groups increasing the number of surface silanol groups. If emulsions of strong acid and strong alkali were mixed, substantial additional gelation (again caused by flocculation) occurred. A possible explanation, preferred by the author, was an electrostatic one involving the interaction of dipoles in close proximity in the flocculated emulsion. Copyright 1999 Academic Press.     

The Relation Between Phase Behavior and Formation of Narrow Size Distribution W/O Emulsions

Water-in-oil (W/O) emulsions of the water/C₁₂E₅/isooctanol/isooctane system have been prepared at 25° C. Phase behavior studies of the system with constant (2.5 and 6 wt.%) isooctanol concentration showed that the surfactant becomes more lipophilic with the increase in the alkanol concentration. Emulsification was carried out using four low-energy emulsification methods using the slow addition of one or various components to the rest of them, with gentle agitation. Emulsions with low-polydis-persity were obtained when the emulsification process started with a single lamellar liquid crystalline phase. If in addition to a lamellar liquid crystalline phase, other phases, such as excess water phase, were initially present, emulsions with intermediate polydispersity were produced. When a lamellar liquid crystalline phase was not involved and the spontaneous natural curvature of the surfactant was not changed during emulsification, highly polydisperse emulsions were obtained.     

W/O Emulsion Destabilization and Release of a Polysaccharide Entrapped in the Droplets

This study was conducted as part of European project VEGEPHY to develop a product for the crop protection purposes. It concerns first the destabilization of a W/O emulsion containing water droplets in which the polysaccharide carboxymethylcellulose (CMC) is trapped, the droplets being dispersed in a vegetable oil made of rapeseed methyl ester. Polyglycerolpolyricinoleate (PGPR) is used as surfactant and glycerol is added to enhance the dispersion of the CMC. The second part is dealing with the study of the release and dilution of the CMC obtained by dilution of the destabilized emulsion in water in order to obtain the required final amount of CMC for practical purposes. The destabilization of the emulsion by the demulsifier (cynthiorex PMH 1125) has been followed by differential scanning calorimetry (DSC) that permits by studying the freezing of the dispersed water to detect the presence of bulk water. The release and dilution in water of the CMC versus time was followed and quantified by measuring the conductivity of the sample. The release kinetic was modeled using a first-order empirical model. The results showed that the release process of the W/O emulsion depends on the concentration of the demulsifier, on the stirring rate, and on the temperature. The optimum amount of the non-ionic surfactant was found to be 10% and the full release of the CMC has been obtained in 600 seconds.     

A Study of Drop Size Distribution in Multistage Bubble Extractor

Results obtained in determining experimentally the mean volume-surface drop diameter of the dispersed phase in a multistage bubble extractor are presented.     

Surfactant-Oil-Water Systems Near the Affinity Inversion. XII. Emulsion Drop Size Versus Formulation and Composition

Emulsion drop size depends on the both formulation and composition of the surfactant-oil-water system, as well as on the stirring conditions prevailing during emulsification. General trends versus formulation or composition changes are presented. However, it is shown that the effects are not independent and that a proper combination of these parameters allows the attainment of very small drop size, even at low stirring energy. An overall phenomenology is presented on a two-dimensional formulation-composition map from which it is easy to select the best emulsification conditions.     

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.     

烷基硫酸钠中碳链长度分布对MMA种子乳液聚合粒径分布影响的研究

氯磺酸法合成了C8－10、C12和C14－16烷基硫酸钠，精制后表征了碳链分布组成，在C12为30％－80％范围内研究了烷基硫酸钠中高碳同系物和低碳同系物的比例对甲基丙烯酸甲酯种子乳液聚合生成的聚合物粒径大小和分布的影响，并讨论了成核模式。研究结果表明：高碳同系物比例的增加，聚合物平均粒径增大，低碳同系物比例的增加，胶束数目增多，由胶束成核（包括均相成核）而形成的聚合物粒径分布变宽，而对在种子上增长的聚合物粒径分布无影响。     

W／O／W乳液的渗透溶胀与夹带溶胀

研究了W/O/W乳液的溶胀,实验结果表明,渗透溶胀随内外相溶液间的渗透压差、表面活性剂及载体浓度的增大而增加,但随膜粘度的增加而降低,渗透压差较高时,水渗透的影响大于夹带的影响;膜相中含氧化合物对溶胀的影响大于含氮化合物,采用Span 80作乳化剂时,比采用E 644渗透溶胀约高6倍,夹带溶胀也较高;重复聚结再分散使夹带溶胀急剧增加,因而多级混合澄清槽对液膜操作似不适用。     

乙酸对阳离子型PVAc乳液粒径的影响

以醋酸乙烯酯(VAc)和甲基丙烯酰氧基乙基三甲基氯化铵为主单体,Gemini超支化双子型阳离子表面活性剂和OP-10为复合乳化剂,通过乳液聚合制得一系列阳离子型聚醋酸乙烯酯乳液(1n),考察了VAc的主要杂质乙酸对1n粒径的影响.研究结果表明,乙酸含量增多时,Gemini超支化阳离子表面活性剂的临界胶束浓度和表面张力都...     

Highly Efficient Nano-Structured Polymer-Based Membrane/Sorbent for Oil Adsorption from O/W Emulsion Conducted of Petroleum Wastewater

Wastewater disposal has been an important issue from an environmental perspective in terms of the serious damages and harms its contaminants may cause. Treatment of the wastewater, through the pollutants removal, either before disposal or for the reuse in certain industrial or agricultural purposes, is an essential process. In response to this environmental claim, a novel nano-structured, macro-porous, polymer-based membrane/sorbent was prepared, in terms of its highly open and porous structure with nano-structured sorbent interconnecting walls and based on high internal phase emulsion polymerization. This sorbent was used to remove the oil from polluted wastewater in a laboratory-scale through the application of a new method called flotation–nano-filtration. In order to avoid the water flux decline and simultaneously enhance the oil removal efficiency from the wastewater, the polymeric material, after being prepared and used in sheet form (membrane), was ultimately introduced to the wastewater system as small pieces, as with the intention of physically increasing the area of surface for the oil removal. The material performance studies applied several variables, namely, the physical sectioning of the material surface area, sorbent concentration, mixing speed, and mixing time. An efficiency of 99.75% for the oil removal from the polluted water was successfully achieved at 75 minutes mixing time, a sorbent concentration of 0.158 g/200 mL (each piece with dimensions of 2 mm × 3 mm × 1 mm), and 300 rpm mixing speed. The sorbent structure before and after the oil removal process was examined using scanning electron microscope and x-ray diffraction analysis.     

Population Balance Model for Emulsion Polymerisation Under Pseudo-Bulk Conditions: Combined Particle Size Distribution and Molecular Weight Distribution

A comprehensive model for emulsion polymerisation is presented, accounting for particle size distribution (PSD) and molecular weight distribution (MWD). The PSD information is incorporated through a population balance framework. A mechanistic formulation is adopted in modelling the average number of radicals/particle under pseudo-bulk compartmentalisation conditions. The method of moments is adopted to simplify the MWD equations over each discrete size class. The impact of the pseudo-bulk assumption on the PSD and MWD results is assessed. An identification of potential manipulated variables for control of PSD and MWD is done through sensitivity analysis.     

Effect of Fenton's reagent on O/W emulsions stabilized by black liquor

The effect of Fenton's reagent (FR) on surface and dispersion properties of black liquor (BL) was investigated. These properties were compared to those of indulin C (IC), a commercial lignin, and egg lecithin (Le). FR was applied at two different bulk concentrations of H2O2 (160 and 320 mM). At pH 8, a minimum in surface tension for the Fenton treated BL was observed. The dispersant ability of BL, IC and Le in oil-in-water (O/W) emulsions was studied by measuring emulsion stability and drop size. It was found that the surface activity and emulsifying capability of BL were higher than those of IC. The emulsifying capability of Le was improved by the FR treatment at low H2O2 concentration.     

Transfer and distribution of L-tryptophan between W/O and O/W, and between W/O and bicontinuous microemulsions through the study of interphase electric properties

The influence of L-tryptophan (L-Trp) on the interphase electric properties of sodium dodecyl sulfate (SDS)/n-pentanol (n-C(5)H(11)OH)/water (H(2)O) system was studied by the method of AC impedance, and the distribution of L-Trp between the microemulsion phases with different structures in SDS/n-C(5)H(11)OH/H(2)O system was determined by UV-vis spectroscopy. The results show that L-Trp transfers from the lower phase (O/W or bicontinuous) to the upper phase (W/O), and that a small amount of SDS transfers from the upper phase to the lower phase correspondingly with the increase of the total SDS content at a constant weight ratio of n-C(5)H(11)OH/H(2)O=50/50 and a total L-Trp concentration of 1.0 x 10(-4) mol/L. In addition, the concentrations of L-Trp in both the upper and lower phases increase, but the SDS content decreases slightly in the upper phase and increases appreciably in the lower phase with the increase of the total L-Trp concentration at a constant total content of SDS. The interphase capacitance and the interphase charge-transfer current of the system increase, but the interphase resistivity decreases.     

Controllable preparation of monodisperse O/W and W/O emulsions in the same microfluidic device

This letter presents a simple way to prepare monodisperse O/W and W/O emulsions in the same T-junction microfluidic device just by changing the wetting properties of the microchannel wall with different surfactants. Highly uniform droplets ranging from 50 to 400 mum with a polydispersity index (sigma) value of less than 2% were successfully prepared. With the change in surfactants and surfactant concentrations, the interfacial tension and the wetting properties varied, and disordered or ordered two-phase flow patterns could be controllable. Monodisperse O/W and W/O emulsions were prepared under the action of a cross-flowing shear force or a perpendicular shear force by using an oil solution with 0.1-2.0 wt % Span 80 and an aqueous solution with 0.1-2.0 wt % Tween 20 as a continuous-phase flow, respectively. It gives a controllable method of preparing O/W and W/O emulsions in the same microfluidic device.     

STATISTICAL MECHANICAL MODEL THEORY OF THE STABILITY OF O/W AND W/O MICROEMULSIONS

A theoretical model to clarify the molecular origin of the mechanical and thermal stabilities of O/W or W/O microemulsion is proposed in which the low concentration of surfactants (emulsifiers) is limited. We assume only a short range interaction between surfactants and a bending stiffness energy which expresses the deformation energy from a preferable monolayer membrane curvature. We have found an interrelation among the interfacial pressure, Δp, of the monolayer due to the adsorption of surfactants in the microemulsion interface, interfacial tensions of oil-water interface and of the microemulsion, and the bending stiffness energy. We conclude that the interfacial tension and the stable form of the microemulsions (O/W type or W/O type) are infuenced largely by the effect of the bending stiffness energy. The interrelationship between the therraodynamical and mechanical stabilities of microemulsions is clarified by the use of our assumption.     

Preparation and characterization of W/O/W double emulsions containing MgCl2

The aim of present study is to design food-grade W/O/W double emulsions encapsulating Mg²⁺ and investigate their stability and release properties. Prepared emulsions were characterized in terms of global stability, particle size, rheological properties, and interfacial tension. The double emulsions were sensitive to the presence of magnesium salt. The mean droplet size and viscosity of emulsions was positively correlated to MgCl₂ concentration. The microscopic pictures confirmed that the water transfer between two aqueous phases caused the reduced stability of double emulsions. It was suggested that swelling breakdown was the main mechanism in controlling the release of encapsulated Mg²⁺.     

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.     

Encapsulation and Prolonged Release Behaviour of W/O/W Type Multiple Emulsions

W/O/W type multiple emulsions were prepared by two step emulsification procedures using an oily lymphographic agent, lipiodol, as an inner oil phase and Pluronic F-68 as a hydrophilic emulsifier contained in the outer aqueous phase. Span 80, Pluronic L-64 and HCO-60 were used as emulsifiers incorporating them into the inner oil phase. The phase volume of the inner and outer aqueous phases and the yield of the w/o/w type multiple emulsions were studied. The dissolution behaviour of the w/o/w type multiple emulsions were determined by a dialysis method employing cellulose tubing. The effect of emulsifier type and the amount of HCO-60 on the stability and prolonged release behavior of the w/o/w type multiple emulsions with or without lecithin, was also examined. The results indicate the HCO-60 is a better emulsifier than Span 80 or Pluronic L-64. Its use improves the stability and the prolonged release behavior of w/o/w type multiple emulsions.