Effect of silica particles on stability of highly concentrated water-in-oil emulsions with non-ionic surfactant

Water-in-oil, high internal phase emulsion made of super-cooled aqueous solution containing a mixture of inorganic salts and stabilized with non-ionic surfactant (sorbitan monooleate) alone was investigated. It was not possible to produce a highly concentrated emulsion (with aqueous phase fraction = 94 wt %), stabilized with surface-treated silica, solely: we were able to form an emulsion with a maximal aqueous phase mass fraction of 85 wt % (emulsion inverts/breaks above this concentration). The inversion point is dependent on the silica particle concentration, presence of salt in the aqueous phase, and does not depend on the pH of the dispersed phase. All emulsions stabilized by the nanoparticles solely were unstable to shear. So, the rheological properties and stability of the emulsions containing super-cooled dispersed phase, with regards to crystallization, were determined for an emulsion stabilized by non-ionic surfactant only. The results were compared to the properties obtained for emulsions stabilized by surface treated (relatively hydrophobic) silica nanoparticles as a co-surfactant to sorbitan monooleate. The influence of the particle concentration, type of silica surface treatment, particle/surfactant ratio on emulsification and emulsion rheological properties was studied. The presence of the particles as a co-stabilizer increases the stability of all emulsions. Also, it was found that the particle/surfactant ratio is important since the most stable emulsions are those where particles dominate over the surfactant, when the surfactant’s role is to create bridging flocculation of the particles. The combination of the two types of hydrophobic silica particles as co-surfactants is: one that resides at the water/oil interface and provides a steric boundary and another that remains in the oil phase creating a 3D-network throughout the oil phase, which is even more beneficiary in terms of the emulsion stability.     

Surface activity and redox behavior of a non-ionic surfactant containing a phenothiazine group

A novel non-ionic surfactant, -(phenothiazinylhexyl)-ω-hydroxy-oligo(ethylene oxide) (PCPEG) containing phenothiazine as an electro-active group has been synthesized. Fundamental interfacial behavior of the surfactant at the air/water interface has been investigated by means of surface tensiometry to provide an insight into the relationship between the structure of the hydrophobic moiety and the surfactant properties. A comparison of diffusivity of PCPEG in the aqueous phase with that in the acetonitrile solution at high PCPEG concentrations shows that micellization has a pronounced effect on the redox behavior of PCPEG. The electrochemical responses for PCPEG aqueous solutions at the interface of a glassy carbon electrode are fairly dependent on the concentration of PCPEG. Above CMC, PCPEG molecules self-associate to form micellar aggregates and the formation and disruption of micelles can be reversibly controlled by change in the redox state of the phenothiazine group. The cyclic voltammetric responses for PCPEG aqueous solutions have been correlated with the dissolved states to explain the distinctive feature of the surfactant.     

The influence of surfactant on the alkali-thickening of acrylic emulsions

Colloid and Polymer Science -     

Quantification of unadsorbed protein and surfactant emulsifiers in oil-in-water emulsions

Unadsorbed emulsifiers affect the physical and chemical behaviour of oil-in-water (O/W) emulsions. A simple methodology to quantify unadsorbed emulsifiers in the aqueous phase of O/W emulsions has been developed. Emulsions were centrifuged and filtered to separate the aqueous phase from the oil droplets and the concentration of unadsorbed emulsifiers in the aqueous phase determined. The quantification of unadsorbed surfactants based on the direct transesterification of their fatty acids was validated for Tween 20, Tween 80, citric acid ester (Citrem), Span 20 and monolauroyl glycerol. To determine unadsorbed proteins, results obtained with Folin-Ciocalteu reagent or UV-spectrophotometry were compared on emulsions stabilized by β-lactoglobulin (BLG), β-casein (BCN) or bovine serum albumin (BSA). The first method gave more accurate results especially during aging of emulsions in oxidative conditions. The whole methodology was applied to emulsions stabilized with single or mixed emulsifiers. This approach enables optimization of emulsion formulations and could be useful to follow changes in the levels of unadsorbed emulsifiers during physical or chemical aging processes.     

Salting-out surfactant extraction of porphyrins and metalloporphyrin from aqueous non-ionic surfactant solutions

A number of cloud point temperature-depressing electrolytes have been investigated for the separation of a non-ionic surfactant (Triton X-100) from aqueous solutions and the corresponding extraction of the organic solutes into the smaller volume surfactant-rich phase using the salting-out method. High extraction efficiencies and preconcentration factors were obtained at room temperature for the extraction of several hydrophilic and hydrophobic metal-free porphyrins (uroporphyrin, coproporphyrin, protoporphyrin and hematoporphyrin) and one metalloporphyrin (iron-protoporphyrin) that were dissolved in the aqueous non-ionic surfactant solutions. Possible mechanisms responsible for the efficient extraction of these important biological molecules into the surfactant-rich layer are discussed.     

The microwave absorption of emulsions containing aqueous micro- and nanodroplets: a means to optimize microwave heating

The microwave absorption at frequencies between 10 MHz and 4 GHz is measured for aqueous brine droplets dispersed in a dielectric medium (epsilon(')=2.0). By varying the size of the droplets, ion type and ion concentration, it is found that the microwave absorption goes through a maximum which depends on the type of ions and their concentration. The absorption process is attributed to the polarization of the microdroplets through surface charges. Means to optimize microwave heating in emulsions is discussed.     

Behaviour of formula emulsions containing hydrolysed whey protein and various lecithins

Formula emulsion systems are used as enteral, sports and health products. In some formulas addition of hydrolysed protein is necessary to guarantee ease of digestion and hypoallergenicity. In the low fat emulsion model an increase in the content of lecithin (phospholipid mixture) was required, in consideration of the advice of the Food and Nutrition Board (USA) for choline supplementation. The individual and interactive effects of whey protein isolate (WPI) or hydrolysate (WPH) (3.7 and 4.9% w/w), unmodified deoiled or hydrolysed lecithin (0.48 or 0.7% w/w) and carbohydrate in the form of maltodextrin with dextrose equivalent (DE) 18.5 or glucose syrup with DE 34 (11% w/w) on the properties of formula emulsions with 4% v/w sunflower oil, were investigated using a full factorial design. The emulsions were characterised by particle size distribution, coalescence stability, creaming rate, and also surface protein and lecithin concentration. WPI-containing emulsions proved to be stable against coalescence and showed only little creaming after 1 and 7 days standing. There was a significant increase in the mean droplet size and a significant deterioration of coalescence and creaming stability when WPH instead of WPI was used as the protein source, due to the lower number of large peptides and lower surface activity of the WPH. Increasing the WPH concentration led to an increase in oil droplet size and further deterioration of the stability of the emulsions. The starch hydrolysate and lecithin also significantly influenced the emulsion properties. Their influence was less strong when the emulsion contained WPI. Under the conditions used WPH-based emulsions were more stable, in terms of creaming and coalescence, when a low level of protein was used in conjunction with hydrolysed lecithin and glucose syrup. Oil droplets in emulsions containing unmodified lecithin in either the continuous or disperse phase and WPH in the continuous phase were very sensitive to coalescence. The addition of starch hydrolysates (DE 18.5) induced intensive flocculation and phase separation in these emulsions.     

Electrokinetic characterization of polystyrene–non-ionic surfactant complexes

An experimental study on the electrophoretic mobility (μ_e) of polystyrene particles after the adsorption of non-ionic surfactants with different chain lengths is described. Two sulphate latexes with relatively low surface charge densities (3.2 and 4.8 μC cm⁻²) were used as solid substrate for the adsorption of four non-ionic surfactants, Triton X-100, Triton X-165, Triton X-305 and Triton X-405, each one with 9–10, 16, 30 and 40 molecules of ethylene oxide (EO), respectively. The electrophoretic mobility of the polystyrene–non-ionic surfactant complexes was studied versus the amount of adsorbed surfactant (Γ). The presence of non-ionic surfactant onto particles surface seems to produce a slight shifting of the slipping plane because the mobilities of the different complexes display a very small decreasing. The increase in the number of EO chains in the surfactant molecule seems to operate as a steric impediment which decreases the number of adsorbed large surfactant molecules. The electrophoretic mobilities of the latex–surfactant complexes with maximum adsorption were measured versus the pH and ionic strength of the dispersion. While the different complexes showed a similar qualitative behaviour compared with that of the bare latex against the pH, the adsorption of the surfactant reduces the typical maximum in the μ_e−log[electrolyte].     

Thermodynamics of weak interactions: excess enthalpies and excess Gibbs free energies of mixing

Excess enthalpies of chloroform + n-hexane, bromoform + n-hexane, bromoform + pyridine and bromoform + benzene and excess Gibbs free energies of mixing for bromoform + pyridine, chloroform + pyridine, bromoform + n-hexane, chloroform + n-hexane and bromoform + benzene have been determined at 308.15 K and the same factors have been examined for Barker's theory to understand the magnitude and nature of various interactions between the components of these mixtures.     

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.     

Interaction of cationic chlorin photosensitizers with non-ionic surfactant Tween 80

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Effect of added surfactant on temperature-induced gelation of emulsions

This paper involves an investigation of the effect of added ionic surfactant on the temperature-induced gelation of oil-in-water (O/W) emulsions stabilized by a responsive copolymer. The oil phase used in this study is 1-bromohexadecane. The copolymer is poly(NIPAM-co-PEGMa) (NIPAM and PEGMa are N-isopropylacrylamide and poly(ethylene glycol) methacrylate, respectively). The lower critical solution temperature for the copolymer was 39.5 degrees C. The ionic surfactant used in this work was sodium dodecylbenzenesulfonate (NaDBS). The critical association concentration for NaDBS and poly(NIPAM-co-PEGMa) was measured at 0.30 mM using fluorescence measurements (pyrene was the probe molecule). Gelation temperatures were measured for the O/W emulsions to establish the effect of added NaDBS and copolymer concentration (Cp) on the gelation temperature (Tgel). The strength of the gels was measured using dynamic oscillatory measurements. These measurements allowed the shear modulus of the gel at Tgel to be estimated as 100 Pa. A theoretical model based on transient network theory was developed that predicts the dependence of Tgel on Cp. The study revealed that NaDBS has two effects on the overall cross-link density of the emulsion gels: it contributes a source of cross-linking via micellar cross-links and also decreases the proportion of transient cross-links due to electrostatic repulsion.     

Thinning of wetting films formed from aqueous solutions of non-ionic surfactant

We investigated the thinning of wetting films formed from aqueous solution of non-ionic triblock copolymer Pluronic F127 on the surface of silica using a home-made thin film balance and time-resolved ellipsometry. Imaging ellipsometry was used to visualize the film structures at subsequent stages of their development. The results unambiguously show that the time required for the formation of steady films strongly depends on the electrolyte concentration. When increasing the latter from 10(-4) to 0.1 M, this time typically increases with several orders of magnitude, from a few minutes to several hours. Moreover, for sufficiently large amounts of salt, two characteristic relaxation regimes can be clearly identified. After initial quick thinning, further thinning slows down enormously. These typical kinetic regimes are thought to result from the coupled dependencies of the bulk and interfacial properties of F127 on salt concentration. Possible explanations of the phenomenon are discussed.     

Physicochemical behavior of oil-in-water emulsions: influence of milk protein mixtures, glycerol ester mixtures and fat characteristics

Different emulsions based on two protein mixtures (skim milk powder (SMP) and functional dairy proteins (FDP)), two mono-di-glyceride mixtures (MDG) (saturated and partially unsaturated), three fats (hydrogenated and refined coconut oils and refined palm oil) were studied to investigate the interactions occurring between the oil phase, low molecular weight emulsifiers and proteins. Immediately following the emulsification process, high diameters of fat globules were obtained in FDP-based systems, relevant of an aggregation phenomenon. At this stage, the fat globule size characteristics were dependent on the emulsifier and fat types present in the formulation. In contrast, SMP-based emulsions were characterized by low proportions of aggregated particles regardless the formulations. Ageing (24 h at 4 °C) promoted disaggregation in FDP formulations, while SMP emulsions were well stabilized. Just after the homogenization step, less proteins were required to stabilize the globule interface in FDP systems as compared to SMP ones. Only with SMP, the amount of protein load at the fat globule surface was influenced by the oil nature and/or by the emulsifier type. A competitive adsorption of caseins, over whey proteins, was demonstrated in the case of FDP. The ageing period promoted a displacement of the proteins adsorbed at the oil droplet interface, suggesting a disruption of the interfacial protein interactions. This disruption was more marked with SMP than with FDP and, in both cases, was more or less influenced by the emulsifier and oil phase natures. The variations of the viscosity and rheological parameters (elastic and viscous moduli) were not dependent on one specific component of the formulation.     

Fluorometric determination of uranium and tungsten with o-hydroxyhydroquinonephthalein in the presence of non-ionic surfactant

Complex formation between uranium or tungsten and o-hydroxyhydroquinonephthalein (Qnph) in various micellar surfactant media has been investigated fluorometrically, and determination of uranium and tungsten based on the difference between the relative fluorescence intensities of Qnph and the metal complex at 535 nm, with excitation at 400 nm in the presence of poly(vinyl) alcohol as a non-ionic surfactant. The calibration curves were linear up to 1.0 mu/ml uranium and 0.9, mu/ml tungsten. The relative standard deviations (5 replicates) were 2.6% for tungsten and 3.0% for uranium, and recovery tests gave relatively good results (97-104%).     

Preparation and characteristics of multiple emulsions containing liquid crystals

In this paper, multiple emulsions containing liquid crystals were prepared successfully and the influence of formulation parameters on the formation mechanism was studied. Moreover, differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) spectra analysis and stability analysis were used to characterise the property of them. The results showed that the chemical structure of water-in-oil (W/O) emulsifiers directly impacted on the formation of multiple structure, but the effect on the formation of liquid crystal structure was negligible. With the gap of the polarity between inner and outer liquid oils decreased, both multiple structure and liquid crystal structure were harder to form. The content of sodium chloride in internal aqueous phase, which should be neither too high nor too low, has great impact on the formulation of multiple structure. It was easier to form two structures simultaneously when the carbon chain length of fatty alcohols was closer to that of emulsifier C₂₂ alkyl polyglucoside (202). DSC elucidated the phase transitions of water in the liquid crystal layer and the W/O emulsions. SAXS indicated that the liquid crystal orientation was lamellar. The stability analysis showed that the presence of liquid crystal structure had a significant contribution to the stability of the multiple emulsions.