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.     

Effects of electrolyte concentration and pH on the coalescence stability of beta-lactoglobulin emulsions: experiment and interpretation

Experimental results are presented about the effects of ionic strength and pH on the mean drop-size after emulsification and on the coalescence stability of emulsions, stabilized by a globular protein beta-lactoglobulin (BLG). The mean drop-size is determined by optical microscopy, whereas the coalescence stability is characterized by centrifugation. In parallel experiments, the zeta-potential and protein adsorption on drop surface are determined. The experiments are performed at two different BLG concentrations, 0.02 and 0.1 wt%. The electrolyte concentration in the aqueous phase, C(EL), is varied between 1.5 mM and 1 M, and pH is varied between 4.0 and 7.0. The experiments show that the mean drop-size after emulsification depends slightly on C(EL), at fixed protein concentration and natural pH = 6.2. When pH is varied, the mean drop-size passes through a maximum at fixed protein and electrolyte concentrations. A monolayer protein adsorption is registered in the studied ranges of C(EL) and pH at low BLG concentration of 0.02 wt%. In contrast, a protein multilayer is formed at higher BLG concentration, 0.1 wt%, above a certain electrolyte concentration (C(EL) > 100 mM, natural pH). The experimental results for the emulsion coalescence stability are analyzed by considering the surface forces acting between the emulsion drops. The electrostatic, van der Waals, and steric interactions are taken into account to calculate the barriers in the disjoining pressure isotherm at the various experimental conditions studied. The comparison of the theoretically calculated and the experimentally determined coalescence barriers shows that three qualitatively different cases can be distinguished. (1) Electrostatically stabilized emulsions, with monolayer protein adsorption, whose stability can be described by the DLVO theory. (2) Sterically stabilized emulsions, in which the drop-drop repulsion is created mainly by overlapping protein adsorption multilayers. A simple theoretical model is shown to describe emulsion stability in these systems. (3) Sterically stabilized emulsions with a monolayer adsorption on drop surface.     

Synergistic stabilization of emulsions by a mixture of surface-active nanoparticles and surfactant

The stability and rheology of tricaprylin oil-in-water emulsions containing a mixture of surface-active hydrophilic silica nanoparticles and pure nonionic surfactant molecules are reported and compared with those of emulsions stabilized by each emulsifier alone. The importance of the preparation protocol is highlighted. Addition of particles to a surfactant-stabilized emulsion results in the appearance of a small population of large drops due to coalescence, possibly by bridging of adsorbed particles. Addition of surfactant to a particle-stabilized emulsion surprisingly led to increased coalescence too, although the resistance to creaming increased mainly due to an increase in viscosity. Simultaneous emulsification of particles and surfactant led to synergistic stabilization at intermediate concentrations of surfactant; emulsions completely stable to both creaming and coalescence exist at low overall emulsifier concentration. Using the adsorption isotherm of surfactant on particles and the viscosity and optical density of aqueous particle dispersions, we show that the most stable emulsions are formed from dispersions of flocculated, partially hydrophobic particles. From equilibrium contact angle and oil-water interfacial tension measurements, the calculated free energy of adsorption E of a silica particle to the oil-water interface passes through a maximum with respect to surfactant concentration, in line with the emulsion stability optimum. This results from a competition between the influence of particle hydrophobicity and interfacial tension on the magnitude of E.     

Effect of Emulsifier Type on the Characterization of O/W Emulsions Using a Spectroscopy Technique

The droplet size distribution (DSD) of emulsions is the result of two competitive effects that take place during emulsification process, i.e., drop breakup and drop coalescence, and it is influenced by the formulation and composition variables, i.e., nature and amount of emulsifier, mixing characteristics, and emulsion preparation, all of which affect the emulsion stability. The aim of this study is to characterize oil-in-water (O/W) emulsions (droplet size and stability) in terms of surfactant concentration and surfactant composition (sodium dodecyl benzene sulphonate (SDBS)/Tween 80 mixture). Ultraviolet-visible (UV-vis) transmission spectroscopy has been applied to obtain droplet size and stability of the emulsions and the verification of emulsion stability with the relative cleared volume technique (time required for a certain amount of emulsion to separate as a cleared phase). It is demonstrated that the DSD of the emulsions is a function of the oil concentration and the surfactant composition with higher stability for emulsions prepared with higher SDBS ratio and lower relative cleared volume with the time. Results also show that smaller oil droplets are generated with increasing Tween 80 ratio and emulsifier concentration.     

Emulsification properties of a star-shaped anionic surfactant in oil-based drilling fluid

A novel star-shaped sulfonate surfactant, synthesized with triethanolamine, was identified as a hydrophilic emulsifier which could form a stable water-in-oil emulsion. The interfacial film strength was measured by suspension drop method. The emulsification properties of emulsions were obtained by the emulsification rate experiment and demulsification voltage measurement. The emulsion shows an excellent emulsification effect when the addition of star-shaped anionic surfactant into oil-based drilling fluid was 2.0?wt%. In addition, the properties of surfactant in drilling fluid with different adding amounts were studied by rheological properties, thermal stability analysis and filtration experiments. The results show that star-shaped anionic surfactant used as emulsifier can improve the performance in oil-based drilling fluid, which maybe provides a new idea for this type of surfactant.     

Emulsification in turbulent flow 1. Mean and maximum drop diameters in inertial and viscous regimes

Systematic experimental study of the effects of several factors on the mean and maximum drop sizes during emulsification in turbulent flow is performed. These factors include: (1) rate of energy dissipation, epsilon; (2) interfacial tension, sigma; (3) viscosity of the oil phase, eta(D); (4) viscosity of the aqueous phase, eta(C); and (5) oil volume fraction, Phi. The emulsions are prepared by using the so-called "narrow-gap homogenizer" working in turbulent regime of emulsification. The experiments are performed at high surfactant concentration to avoid the effect of drop-drop coalescence. For emulsions prepared in the inertial turbulent regime, the mean and the maximum drop sizes increase with the increase of eta(D) and sigma, and with the decrease of epsilon. In contrast, Phi and eta(C) affect only slightly the mean and the maximum drop sizes in this regime of emulsification. These results are described very well by a theoretical expression proposed by Davies [Chem. Eng. Sci. 40 (1985) 839], which accounts for the effects of the drop capillary pressure and the viscous dissipation inside the breaking drops. The polydispersity of the emulsions prepared in the inertial regime of emulsification does not depend significantly on sigma and epsilon. However, the emulsion polydispersity increases significantly with the increase of oil viscosity, eta(D). The experiments showed also that the inertial turbulent regime is inappropriate for emulsification of oils with viscosity above ca. 500 mPa s, if drops of micrometer size are to be obtained. The transition from inertial to viscous turbulent regime of emulsification was accomplished by a moderate increase of the viscosity of the aqueous phase (above 5 mPa s in the studied systems) and/or by increase of the oil volume fraction, Phi>0.6. Remarkably, emulsions with drops of micrometer size are easily formed in the viscous turbulent regime of emulsification, even for oils with viscosity as high as 10,000 mPa s. In this regime, the mean drop size rapidly decreases with the increase of eta(C) and Phi (along with the effects of epsilon, sigma, and eta(D), which are qualitatively similar in the inertial and viscous regimes of emulsification). The experimental results are theoretically described and discussed by using expressions from the literature and their modifications (proposed in the current study).     

Influence of droplet characteristics on the formation of oil-in-water emulsions stabilized by surfactant-chitosan layers

The objective of this study was to establish the optimum conditions for preparing stable oil-in-water emulsions containing droplets surrounded by surfactant-chitosan layers. A primary emulsion containing small droplets (d32 approximately = 0.3 microm) was prepared by homogenizing 20 wt% corn oil with 80 wt% emulsifier solution (20 mM SDS, 100 mM acetate buffer, pH 3) using a high-pressure valve homogenizer. The primary emulsion was diluted with chitosan solutions to produce secondary emulsions with a range of oil and chitosan concentrations (0.5-10 wt% corn oil, 0-1 wt% chitosan, pH 3). The secondary emulsions were sonicated to help disrupt any droplet aggregates formed during the mixing process. The electrical charge, particle size, and amount of free chitosan in the emulsions were then measured. The droplet charge changed from negative to positive as the amount of chitosan in the emulsions was increased, reaching a relatively constant value (approximately +50 mV) above a critical chitosan concentration (C(Sat)), which indicated that saturation of the droplet surfaces with chitosan occurred. Extremely large droplet aggregates were formed at chitosan concentrations below C(Sat), but stable emulsions could be formed above C(Sat) provided the droplet concentration was not high enough for depletion flocculation to occur. Interestingly, we found that stable multilayer emulsions could also be formed by mixing chitosan with an emulsion stabilized by a nonionic surfactant (Tween 20) due to the fact the initial droplets had some negative charge. The information obtained from this study is useful for preparing emulsions stabilized by multilayer interfacial layers.     

Latex-particle-stabilized emulsions of anti-Bancroft type

Here, we investigate water-in-oil (W/O) emulsions that are stabilized by polystyrene latex particles with sulfate surface groups. The particles, which play the role of emulsifier, are initially contained in the disperse (water) phase. The existence of such emulsions formally contradicts the empirical Bancroft rule. Theoretical considerations predict that the drop diameter has to be inversely proportional to the particle concentration, but should be independent of the volume fraction of water. In addition, there should be a second emulsification regime, in which the drop diameter is determined by the input mechanical energy during the homogenization. The existence of these two regimes has been experimentally confirmed, and the obtained data agree well with the theoretical model. Stable W/O emulsions have been produced with hexadecane and tetradecane, while, in the case of more viscous and polar oils (soybean and silicone oil), the particles enter into the oily phase, and Pickering emulsions cannot be obtained. The formation of stable emulsions demands the presence of a relatively high concentration of electrolyte that lowers the electrostatic barrier to particle adsorption at the oil-water interface. Because the attachment of particles at the drop surfaces represents a kind of coagulation, it turns out that the Schulze-Hardy rule for the critical concentration of coagulation is applicable also to emulsification, which has been confirmed with suspensions containing Na(+), Mg(2+), and Al(3+) counterions. The increase of the particle and electrolyte concentrations and the decrease of the volume fraction of water are other factors that facilitate emulsification in the investigated system. To quantify the combined action of these factors, an experimental stability-instability diagram has been obtained.     

Non-Newtonian behavior of concentrated emulsions stabilized with globular protein in the presence of nonionic surfactant

Changes in the rheological properties of a model concentrated oil-in-water emulsion stabilized with globular protein (bovine serum albumin) upon the addition of nonionic surfactant polyoxyethylene (20) sorbitan monooleate (Tween 80) are studied. Non-Newtonian behavior is typical of the emulsions in question; moreover, they are characterized by the existence of yield stress. At stresses above the yield stress, the viscosity drops not immediately but after the intermediate Newtonian region at the flow curve. For all systems studied, the total flow curve is exhibited with the minimum Newtonian viscosity that is adequately described by the Cross formula. An increase in the Tween 80 concentration leads to a decrease in the viscosity of emulsion. Two threshold phenomena on the concentration dependences of rheological properties are revealed: at low concentration of added nonionic surfactant, the yield stress drops abruptly, whereas the viscosity lowers considerably with an increase in surfactant concentration to 1 × 10^?3 mol/l and the emulsion becomes unstable. The effects observed can be explained by the gradual displacement of high-molecular-weight stabilizer from interfacial layers and its replacement by nonionic surfactant.     

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.     

Discussion of the Drop Rest Phenomenon at Millimeter Scale and Coalescence of Droplets at Micrometer Scale

Adsorption of surfactants at water-oil interfaces is of great importance in the coalescence of drops and stability of emulsions. In this work, we have studied the adsorption of nonionic surfactants Span 80 at water-oil interfaces and its influence on the drop rest phenomenon and W/O emulsion stability in a pulsed DC electrical field. The variation of interfacial tension with the concentration of surfactant was studied and the data were fitted using a surface equation of state derived from the Langmuir adsorption isotherm. A stochastic model for coalescence was used to fit the coalescence time distributions. The significance of the model parameters was discussed. The stability of the emulsion was evaluated by conductivity methods. The researches in this article indicated that both of the rest time distribution of the drops at the interface and stability of the emulsion in the electrical field was significantly affected by surfactant concentration.     

The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

Silica particle-stabilized emulsions of silicone oil and water: aspects of emulsification

A study of the emulsification of silicone oil and water in the presence of partially hydrophobic, monodisperse silica nanoparticles is described. Emulsification involves the fragmentation of bulk liquids and the resulting large drops and the coalescence of some of those drops. The influence of particle concentration, oil/water ratio, and emulsification time on the relative extents of fragmentation and coalescence during the formation of emulsions, prepared using either batch or continuous methods, has been investigated. For batch emulsions, the average drop diameter decreases with increasing particle concentration as the extent of limited coalescence is reduced. Increasing the oil volume fraction in the emulsion at fixed aqueous particle concentration results in an increase in the average drop diameter together with a dramatic lowering of the uniformity of the drop size distribution as coalescence becomes increasingly significant until catastrophic phase inversion occurs. For low oil volume fractions (phi(o)), fragmentation dominates during emulsification since the mean drop size decreases with emulsification time. For higher phi(o) close to conditions of phase inversion, coalescence becomes more prevalent and the drop size increases with time with stable multiple emulsions forming as a result.     

Coalescence during emulsification. 3. Effect of gelatin on rupture and coalescence

An oil-soluble fluorescent probe, undecyl pyrene (UDP), is used to measure the amount of coalescence that occurs during the emulsification of tri-2-ethylhexyl phosphate using a high-pressure homogenizer. From these measurements, the roles of anionic surfactant (SDS) and gelatin in stabilizing drops against coalescence and promoting drop rupture during emulsification are deduced. It is found that gelatin aids in reducing coalescence, whereas SDS aids in rupture of drops. The effect of variables such as gelatin MW, surfactant type, and pH on coalescence and final drop size is investigated.     

FORMATION OF O/W EMULSIONS BY SURFACTANT PHASE EMULSIFICATION AND THE SOLUTION BEHAVIOR OF NONIONIC SURFACTANT SYSTEM IN THE EMULSIFICATION PROCESS

Surfactant-Phase Emulsification is a very useful method to produce oil-in-water emulsions having fine and uniform droplets. The mechanism of this emulsification method and the effect of hydrophile-lipophile balance (HLB) of the surfactants on the process of this emuisification were investigated by using phase diagrams of nonionic surfactant/hexadecane/water/1,3-butanediol four component systems.

It was shown that the process of this emulsification begins with the formation of isotropic surfactant solution, followed by formation of oil-in-surfactant clear gel emulsion, and finally by formation of oil-in-water emulsion. By using this emulsification technique, fine oil-in-water emulsions were formed without a need for adjusting of HLB.     

Application of the fractional factorial design in multiple W/O/W emulsions

In presented research, multiple W/O/W emulsions were developed by using experimental design method. A 24-1 fractional factorial design was performed by varying the following input parameters: primary polymeric emulsifier (PEG 30-dipolyhydroxystearate) concentration (0.8% and 2.4%), secondary polymeric emulsifier (Poloxamer 407) concentration (0.8% and 1.2%), electrolyte magnesium sulfate heptahydrate (0.08% and 0.4%) and electrolyte sodium chloride (0.08% and 0.4%). Multiple emulsions were prepared by a two-step emulsification process. Obtained emulsions were characterized with rheological measurements, conductivity and centrifugation tests. Factorial analysis revealed that the concentration of the primary emulsifier was the predominant factor influencing the phase separation, conductivity and maximal apparent viscosity. Additionally, electrolyte magnesium sulfate heptahydrate was more efficient in stabilizing these systems, compared to sodium chloride. The applied fractional factorial design method enabled determination of the optimal concentrations of the primary and secondary emulsifier, as well as the concentration of electrolytes, in order to obtain W/O/W emulsions with desired maximal apparent viscosities, low values of conductivity and without phase separation after centrifugation.     

Effect of thermal treatment, ionic strength, and pH on the short-term and long-term coalescence stability of beta-lactoglobulin emulsions

We present experimental results about the effects of thermal treatment, ionic strength, and pH on the protein adsorption and coalescence stability of freshly prepared (2 h after emulsification) and 6-day-stored emulsions, stabilized by the globular protein beta-lactoglobulin (BLG). In all emulsions studied, the volume fraction of the dispersed soybean oil is 30% and the mean drop diameter is d(32) approximately 40 microm. The protein concentration, C(BLG), is varied between 0.02 and 0.1 wt %, the electrolyte concentration, C(EL), between 1.5 mM and 1 M, and pH between 4.0 and 7.0. The emulsion heating is performed at 85 degrees C, which is above the denaturing temperature of BLG. The results show that, at C(BLG) > or = 0.04 wt %, C(EL) > or = 150 mM, and pH > or = 6.2, the heating leads to higher protein adsorption and to irreversible attachment of the adsorbed molecules, which results in enhanced steric repulsion between the protein adsorption multilayers and to higher emulsion stability. At low electrolyte concentration, C(EL) < or = 10 mM, the emulsion stability is determined by electrostatic interactions and is not affected significantly by the emulsion heating. The latter result is explained by electrostatic repulsion between the adsorbed protein molecules, which keeps them separated from each other and thus precludes the formation of disulfide covalent bonds in the protein adsorption layer. The coalescence stability of heated and nonheated emulsions is practically the same and does not depend on C(EL), when pH is around the isoelectric point (IEP) of the protein molecules. This is explained with the adsorption of uncharged BLG molecules, in compact conformation, which stores the reactive sulfhydryl groups hidden inside the molecule interior, thus preventing the formation of covalent intermolecular bonds upon heating. We studied also the effect of storage time on the stability of heated and nonheated emulsions. The stability of nonheated emulsions (C(BLG) = 0.1 wt %, C(EL) > or = 150 mM, and pH = 6.2) significantly decreases after 1 day of storage (aging effect). In contrast, no aging effect is observed after emulsion heating. FTIR spectra of heated and nonheated, fresh and aged emulsions suggest that the aging effect is caused by slow conformational changes of the protein molecules in the adsorption layer, accompanied with partial loss of the ordered secondary structure of the protein and with the formation of lateral noncovalent bonds (H-bonds and hydrophobic interactions) between the adsorbed molecules. After thermal treatment of the BLG emulsions, the molecules preserve their original secondary structure upon storage, which eliminates the aging effect.     

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     

Role of the Surfactant Structure in the Behavior of Hydrophobic Ionic Liquids within Aqueous Micellar Solutions

The behavior of an ionic liquid (IL) within aqueous micellar solutions is governed by its unique property to act as both an electrolyte and a cosolvent. The influence of the surfactant structure on the properties of aqueous micellar solutions of zwitterionic SB‐12, nonionic Brij‐35 and TX‐100, and anionic sodium dodecyl sulfate (SDS) in the presence of the “hydrophobic” IL 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]) is assessed along with the possibility of forming oil‐in‐water microemulsions in which the IL acts as the “oil” phase. The solubility of [bmim][PF₆] within aqueous micellar solutions increases with increasing surfactant concentration. In contrast to anionic SDS, the zwitterionic and nonionic surfactant solutions solubilize more [bmim][PF₆] at higher concentrations and the average aggregate size remains almost unchanged. The formation of IL‐in‐water microemulsions when the concentration of [bmim][PF₆] is above its aqueous solubility is suggested for nonionic Brij‐35 and TX‐100 aqueous surfactant solutions.