Aging mechanisms of perfluorocarbon emulsions using image analysis

The aging mechanisms of perfluorocarbon emulsions were investigated using image analysis. Oil-in-water emulsions of two perfluorocarbons, n-perfluorohexane and perfluorodecalin, were prepared with three emulsifiers, Lecithin, Span 20, and Pluronic F-68. The effect of the temperature and the replacement of water by an aqueous phase consisting of a microbial culture medium were also studied. The emulsions were prepared by sonication and their stability was followed through analysis of the evolution of mean droplet size. The results indicate that the stability of perfluorocarbon in water emulsions depends on all the parameters investigated and that two aging mechanisms, coalescence and molecular diffusion, may take place. Analysis of the evolution of the mean droplet size during long time periods indicate that coalescence is more common than previously reported for these systems and seems to be favored by a temperature increase.     

Particle nucleation in emulsion polymerization. IV. Nucleation in monomer droplets

Nucleation in finely dispersed monomer emulsions in competition with homogeneous and micellar mechanism was studied. The emulsions were prepared with a high-pressure homogenizer under varying homogenizing conditions and made stable by the addition of hexadecane to the monomer. Sodium dodecyl sulfate was used as emulsifer. The number of particles in latexes polymerized with potassium persulfate and benzoyl peroxide initiators was measured and plotted as a function of the free emulsifier concentrations. With persulfate initiator the particle number achieved a minimum in the transition region between droplet and water phase–micellar nucleation mechanisms. With very fine emulsions Smith–Ewart case II kinetics with n = 0.5 applied. The reaction rate, which differed from conventional emulsion polymerizations, decreased with time up to the point at which n began to increase. In these runs the particle size distribution became nearly monodisperse.     

Thermo- and pH-Responsiveness of Emulsions Stabilized with Acidic Thermosentive Polymers

A temperature- and pH-responsive polymeric surfactant was prepared by copolymerizing N-isopropylacrylamide, methacrylic acid, and octadecylacrylate. Poly(N-isopropylacrylamide-co-methacrylic acid-co-octadecylacrylate) (P(NIPAM-MAA-ODA) was used as an emulsifier for the preparation of water-in-oil emulsions. The mean droplet size at room temperature was almost constant for 50 hours at pH 5.0, 7.0, and 9.0. However, the size markedly increased for 50 hours at pH 3.0, possibly because of the low hydrophilicity of the copolymer and the small interfacial area one molecule of the copolymer can stabilize at a low pH value. The droplet size markedly decreased from 4.7 to 1.8 µm, when the pH of medium increased from 5.0 to 9.0 with the temperature kept constant. This may be ascribed to that the hydrophilicity of the copolymer and the interfacial area one molecule of copolymer can stabilize will be higher at a higher pH value. When the temperature increased over 35°C with the pH kept constant, the droplet size significantly increased probably because the NIPAM segment of the copolymer becomes hydrophobic with increasing the temperature so the copolymer would poorly act as an emulsifier.     

Oil-in-water emulsions stabilized by whey protein aggregates: Effect of aggregate size,pH of aggregation and emulsion pH

Oil-in-water emulsions (60% oil (w/w)) were prepared using whey protein aggregates as the sole emulsifying agent. The effects of whey protein aggregate size (the diameter between 0.92 and 10.9?µm), the pH of emulsions (4–8.6) and storage time on physical properties, droplet size, and stability of emulsions were investigated. The results indicate that increment of whey protein aggregate size caused an increase in the firmness, droplet size, and viscosity of emulsions, and also a decrease in the emulsion creaming. The emulsion viscosity, firmness, and droplet size were reduced by increasing the emulsion pH; however, the creaming process was accelerated. Viscosity, creaming, and droplet size of emulsions were increased slightly during 21 days storage at 40°C.     

Effect of Emulsification Method on the Properties of Lecithin‐ and PGPR‐Stabilized Water‐in‐Oil‐Emulsions

Water‐in‐oil (w/o) emulsions were prepared with phosphatidylcholine‐depleted lecithin or polyglycerol polyricinoleate (PGPR) as emulsifying agents. The effect of different laboratory emulsification devices and the effect of sodium chloride on particle size distribution, coalescence stability, and water droplet sedimentation were investigated. The properties of lecithin‐stabilized w/o emulsions were found to depend more strongly on the emulsifying method than those prepared with PGPR. The rotor‐stator system was not suitable for preparing stable w/o emulsions with lecithin. Whereas the addition of salt was essential to achieve coalescence‐stable emulsions prepared with PGPR, the presence of NaCl favored the coalescence of water droplets and phase separation in emulsions containing lecithin.     

Amphiphilic polysaccharides: useful tools for the preparation of nanoparticles with controlled surface characteristics

Polymeric surfactants obtained by hydrophobic modification of dextran are used as stabilizers for oil-in-water emulsions. The kinetics of interfacial tension decrease is studied as a function of polymer structural characteristics (degree of hydrophobic substitution) and at various polymer concentrations. Several hydrocarbon oils, either aliphatic (octane, decane, dodecane, and hexadecane) or aromatic (styrene), are tested. Kinetics exhibits the same general trends no matter which oil or polymer is considered. The emulsifying properties of the polymeric surfactants are illustrated by the preparation of oil-in-water emulsions. The droplet size at the preparation is correlated to the amount of oil and to the polymer concentration in the aqueous phase. For low polymer/oil ratios, it is shown that the droplet size is limited by the initial amount of polymer. On the contrary, for high polymer/oil ratios, the droplet size seems to level down, indicating that other parameters become predominant. Emulsion aging occurs by Ostwald ripening, and it is demonstrated that the theoretical equation of Lifshitz, Slyozov, and Wagner (LSW) correctly describes the experimental results. The nature of the oil has important effects on emulsion aging, as described by the LSW equation. The aging of emulsions containing oil mixtures is quantitatively described on the basis of the results with pure oils. The influence of polymer chemical structure can be conveniently correlated to interfacial tension results through the LSW equation. On the contrary, the influence of oil volume fraction seems to be overestimated by the usual correction factor, k(phi). The effect of temperature on emulsion aging is finally examined. Miniemulsions stabilized with dextran derivatives are used for the radical polymerization of styrene. Following this procedure, polysaccharide-covered polystyrene nanoparticles are prepared and characterized (size and surface coverage). The size of the particles is directly correlated to that of the initial droplets for styrene volume fractions around 10%. On the contrary, for initial styrene volume fractions around 20%, particles exhibit a larger size than the initial droplets, indicating that coalescence processes take place during polymerization. The amount of dextran at the surface of the particles is determined and compared to the adsorbed amounts resulting from emulsion preparation.     

Influence of ionic calcium on stability of sodium caseinate emulsions

The stability of fine sodium caseinate emulsions (1 wt.% protein, 25 vol.% n-tetradecane, 20 mM imidazole, pH 7) containing various concentrations of calcium chloride has been investigated under perikinetic and orthokinetic conditions by measuring time-dependent changes in droplet-size distribution. Under quiescent storage conditions at 20°C, samples containing at least 10 mM ionic calcium added after emulsification were found to exhibit an increasing average droplet size with time and a developing bimodal droplet-size distribution. Under turbulent conditions of intense shearing, these same emulsions exhibited time-dependent flocculation and coalescence. This interpretation was confirmed by light microscopy. Emulsions prepared with up to 6 mM Ca²⁺ present during emulsification were stable in the presence or absence of flow, but satisfactory emulsions could not be prepared containing more than 6 mM ionic calcium. The results show that the emulsion stability is sensitive to whether the calcium ion content is adjusted before or after homogenization.     

A Videomicroscopic Investigation of Coupled Reversible Flocculation and Coalescence at Singlet-Doublet Equilibrium in an O/W Emulsion of Low Density Contrast

Video enhanced microscopy (VEM) enables direct investigation of dilute emulsions. A practical and effective preparative technique utilizes microslides, which are flat, rectangular microcapillaries made from borosilicate glass. Experimental difficulties due to droplet sedimentation and droplet-microslide wall interaction can be drastically reduced, even eliminated, by the use of low density contrast emulsions, i.e. emulsions where the densities of the dispersed and continuous phases are not very different. The dichlorodecane (DCD)-in-water emulsion is an example of such a system. This system.can as such be used for measurement of the time of the elementary act of coalescence, calculated from the evolution in the droplet size distribution. The developing distributions can be determined through automated VEM.

In this paper we discuss the perspective for elaboration of a standard method for the determination of an averaged time for the elementary act of coalescence. The experimental basis is automated measurement of the time dependence of the droplet size distribution, as applied to dilute DCD/w emulsions at singlet-doublet equilibrium.     

Influence of oil polarity on droplet growth in oil-in-water emulsions stabilized by a weakly adsorbing biopolymer or a nonionic surfactant

The influence of oil type (n-hexadecane, 1-decanol, n-decane), droplet composition (hexadecane:decanol), and emulsifier type (Tween 20, gum arabic) on droplet growth in oil-in-water emulsions was studied. Droplet size distributions of emulsions were measured over time (0-120 h) by laser diffraction and ultrasonic spectroscopy. Emulsions containing oil molecules of low polarity and low water solubility (hexadecane) were stable to droplet growth, irrespective of the emulsifier used to stabilize the droplets. Emulsions containing oil molecules of low polarity and relatively high water solubility (decane) were stable to coalescence, but unstable to Ostwald ripening, irrespective of emulsifier. Droplet growth in emulsions containing oil molecules of relatively high polarity and high water solubility (decanol) depended on emulsifier type. Decanol droplets stabilized by Tween 20 were stable to droplet growth in concentrated emulsions but unstable when the emulsions were diluted. Decanol droplets stabilized by gum arabic exhibited rapid and extensive droplet growth, probably due to a combination of Ostwald ripening and coalescence. We proposed that coalescence was caused by the relatively low interfacial tension at the decanol-water boundary, which meant that the gum arabic did not absorb strongly to the droplet surfaces and therefore did not prevent the droplets from coming into close proximity.     

Materials based on solid-stabilized emulsions

Solid-stabilized emulsions are obtained by shearing a mixture of oil, water, and solid colloidal particles. In this article, we present a large variety of materials, resulting from a limited coalescence process. Direct (o/w), inverse (w/o), and multiple (w/o/w) emulsions that are surfactant-free and monodisperse were produced in a very wide droplet size range, from micrometers to centimeters. These materials exhibit original properties compared with surfactant-stabilized emulsions: outstanding stability with respect to coalescence and unusual rheological behavior. For such systems, the elastic storage modulus G' is not controlled by interfacial tension but by the interfacial elasticity resulting from the strong adhesion between the solid particles adsorbed at the oil-water interface. Due to the wide accessible droplet size range, concentrated emulsions can be extremely fluid while emulsions with low droplet volume fraction can behave as solids.     

Influence of pH on the stability of oil-in-water emulsions stabilized by a splittable surfactant

A laboratory study was conducted to evaluate the effect of pH on the stability of oil-in-water emulsions stabilized by a commercial splittable surfactant Triton SP-190 by comparison with the results obtained by a common surfactant Triton X-100. The emulsion stability was explored by measuring the volume of oil phase separated and the size of the dispersed droplets. It was found that the addition of inorganic acids did not significantly affect the stability of emulsions stabilized by Triton X-100, but had a profound influence on the stability of emulsions stabilized by Triton SP-190. Moreover, the droplet size of a Triton X-100-stabilized emulsion and its dynamic interfacial activity were insensitive to acids. However, at lower pH the droplet size of the emulsions stabilized by Triton SP-190 was considerably increased. From the dynamic interfacial tension measurements the dynamic interfacial activity of Triton SP-190 at the oil/water interface was found to be strongly inhibited by the addition of acids, resulting in a slower decreasing rate of dynamic interfacial tension. The results demonstrate that the dramatic destabilization of Triton SP-190-stabilized emulsions could be realized by the use of acids, which evidently changed the interfacial properties of the surfactant and resulted in a higher coalescence rate of oil droplets.     

Process diagnosis of coalescence separation of oil-in-water emulsions-two case studies

Coalescence separation is a widely applied technology for oil/water emulsion separation. In this paper, we first review the existing coalescence theories regarding droplet capture, attachment and release. Two case studies are considered, dealing with the separation of oil-in-water emulsions using our recently developed coalescing filters. The first case (Case I) is associated with the separation of surfactant-stabilized hexadecane/water emulsions. The second case (Case II) addresses the separation of sulfonated kerosene/water emulsions in a continuous bench operation. In Case I, known wetting and collision theories were applied to understand the complex coalescence process occurring on the surface of the fibers. For this, the detrimental effect of surfactants on coalescence separation was taken into account. It was found that the best oil wetting coalescing material under water was not the most desired for coalescence, contradicting the existing theory. In addition, once the materials were pre-saturated with surfactant-containing emulsions, the oil wetting was enhanced significantly. However, the separation efficiency was maintained at the same level, unless the material adsorbed surfactant, resulting in minor reductions in the wetting angle. In Case II, based on the fiber properties and operation conditions, the droplet capture efficiency and released droplet size were calculated using the existing models. Fiber diameter and medium face velocity were found to affect not only the capture, but also drop release. Based on model predictions, the dominant capture mechanism was identified as interception followed by van der Waals forces. Overall, this work offers insights about the influencing parameters on oil/water emulsion separation for better designing coalescence systems.     

Bioemulsifier production in batch culture using glucose as carbon source by Candida lipolytica

The yeast Candida lipolytica IA 1055 produced an inducible extracellular emulsification activity while utilizing glucose at different concentrations as carbon source during batch fermentation at 27°C. In all glucose concentrations studied, maximum production of emulsification activity was detected in the stationary phase of growth, after pH reached minimal values. The bioemulsifier isolated was a complex biopolymer constituting proteins, carbohydrates, and lipids. The results obtained in this work show that the biosynthesis of a bioemulsifier is not simply a prerequisite for the degradation of extracellular hydrocarbon.     

Water‐in‐oil Emulsions Stabilized by Hydrophobized Microfibrillated Cellulose

The properties of water‐in‐toluene emulsions stabilized solely by hydrophobized microfibrillated cellulose (MFC) were investigated. By varying the degree of surface substitution (DSS), the wettability of the MFC was altered. All emulsions prepared with MFC displayed excellent stability to coalescence. The stability to gravity‐induced sedimentation increased with increasing MFC concentration, the highest stability being obtained with MFC of moderate hydrophobicity. Drop sizes increased with increasing DSS, with a corresponding decrease in stability to sedimentation. An increase in the toluene:water ratio at constant MFC concentration resulted in a decrease in the average drop size. For all emulsions, the polydispersity in drop size decreased with decreasing average drop diameter.     

Impact of Tween 60 on physicochemical properties and stability of Pistacia lentiscus fruit oil-in-water emulsion at a semi-low temperature

This study shows the effects of the Tween 60 emulsifier at different concentrations on the aqueous emulsion containing 5% of Pistacia lentiscus fruit oil. The rheological behavior and the droplet size distribution of cosmetic oil-in-water emulsions were investigated. This investigation was carried out by analyzing the shear flow and dynamic oscillatory followed by microscopic analysis and physical stability study for 24?hours and 4 months. During the period of 4 months, the emulsions were stored in a refrigerator at a semi-low temperature 12?°C. The physical stability test showed that the sample not emulsified yielded a creaming process after a short aging time. Flow curves of emulsions prepared with TW 60 exhibited a non-linear relationship between the shear stress σ and shear rate γ ?, which implies that the Herschel–Bulkley rheological model was the appropriate model for the shear flow. The increase of emulsifier quantities leading to an increase in the internal structure coherence, whereas the excess quantity affects the structure. Therefore, the optimal quantity proposed was 3.47%. Furthermore, the storage time at a semi-low temperature performed the stability and maintain the structure of emulsions.     

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.     

Optimizing organoclay stabilized Pickering emulsions

Oil-in-water emulsions were prepared using montmorillonite clay platelets, pre-treated with quaternary amine surfactants. In previous work, cetyl trimethylammonium bromide (CTAB) has been used. In this study, two more hydrophilic quaternary amine surfactants, Berol R648 and Ethoquad C/12, were used and formed Pickering emulsions, which were more stable than the emulsions prepared using CTAB coated clay. The droplets were also more mono-disperse. The most hydrophilic surfactant Berol R648 stabilizes the emulsions best. Salt also plays an important role in forming a stable emulsion. The droplet size decreases with surfactant concentration and relatively mono-disperse droplets can be obtained at moderate surfactant concentrations. The time evolution of the droplet size indicates a good stability to coalescence in the presence of Berol R648. Using polarizing microscopy, the clay platelets were found to be lying flat at the water oil interface. However, a significant fraction (about 90%) of clay stayed in the water phase and the clay particles at the water-oil interface formed stacks, each consisting of four clay platelets on average.     

Making Oil-in-Water Emulsions by Ultrasound and Stability Evaluation Using Taguchi Method

Oil-in-water emulsions containing 40% wt sunflower oil were prepared using ultrasound with the frequency of 30 kHz. The effect of sonication time, stabilizer concentration, NaCl, and pH of aqueous phase on the stability and particle size distribution of samples was investigated using Taguchi statistical method. The results showed that increasing sonication time decreased mean diameter of droplets and narrowed droplet size distribution curves. NaCl was found to have a positive effect on the stability of samples. More stable emulsions were prepared when using xanthan and pectin together at pH 4.     

An Electrorheological Study on the Behavior of Water‐in‐Crude Oil Emulsions Under Influence of a DC Electric Field and Different Flow Conditions

The influence of an applied DC electric field on viscosity and droplet size distribution of different water‐in‐crude oil emulsions was monitored in order to investigate the induction of coalescence of the water droplets. The effects caused by the voltage imposition were studied by rheological analysis and the validity of the obtained results was discussed, comparing with the features of real electrocoalcscer systems. A low field NMR technique (CPMG NMR) and digital video microscopy (DVM) were used to elucidate the behavior of the emulsions. Experiments performed at low shear rate with increasing electric field magnitude showed an increase in viscosity until a critical value. E_CRIT was reached. Thereafter coalescence occurred and viscosity decreased irreversibly below its initial value. The electrorheological behavior of the emulsions can be attributed to the organization (flocculation) of water droplets induced by the electric field, accompanied by an increase in viscosity. The structure breaks down as the shear rate is increased, leading to a decrease in viscosity. Experiments performed at high shear showed only a small decline in the viscosity. Although it was evident that coalescence took place, it did not involve the whole sample, because the electrodes were uncoated. As a direct consequence, the mean value of the droplet size within the emulsion did not change noticeably. Nonetheless this mean value was less recurrent and the formation of droplets of very large diameter occurred.     

Effects of pH and salt concentration on oil-in-water emulsions stabilized solely by nanocomposite microgel particles

Aqueous dispersions of lightly cross-linked poly(4-vinylpyridine)/silica nanocomposite microgel particles are used as a sole emulsifier of methyl myristate and water (1:1 by volume) at various pH values and salt concentrations at 20 degrees C. These particles become swollen at low pH with the hydrodynamic diameter increasing from 250 nm at pH 8.8 to 630 nm at pH 2.7. For batch emulsions prepared at pH 3.4, oil-in-water (o/w) emulsions are formed that are stable to coalescence but exhibit creaming. Below pH 3.3, however, these emulsions are very unstable to coalescence and rapid phase separation occurs just after homogenization (pH-dependent). The pH for 50% ionization of the pyridine groups in the particles in the bulk (pK(a)) was determined to be 3.4 by acid titration measurements of the aqueous dispersion. Thus, the charged swollen particles no longer adsorb at the oil-water interface. For continuous emulsions (prepared at high pH with the pH then decreased abruptly or progressively), demulsification takes place rapidly below pH 3.3, implying that particles adsorbed at the oil-water interface can become charged (protonated) and detached from the interface in situ (pH-responsive). Furthermore, at a fixed pH of 4.0, addition of sodium chloride to the aqueous dispersion increases the degree of ionization of the particles and batch emulsions are significantly unstable to coalescence at a salt concentration of 0.24 mol kg(-1). The degree of ionization of such microgel particles is a critical factor in controlling the coalescence stability of o/w emulsions stabilized by them.