Effect of the type of the oil phase on stability of highly concentrated water-in-oil emulsions

The water-in-oil high internal phase emulsions were the subject of the study. The emulsions consisted of a super-cooled aqueous solution of inorganic salt as a dispersed phase and industrial grade oil as a continuous phase. The influence of the industrial grade oil type on a water-in-oil high internal phase emulsion stability was investigated. The stability of emulsions was considered in terms of the crystallization of the dispersed phase droplets (that are super-cooled aqueous salt solution) during ageing. The oils were divided into groups: one that highlighted the effect of oil/aqueous phase interfacial tension and another that investigated the effect of oil viscosity on the emulsion rheological properties and shelf-life. For a given set of experimental conditions the influence of oil viscosity for the emulsion stability as well as the oil/aqueous interfacial tension plays an important role. Within the frames of our experiment it was found that there are oil types characterized by optimal parameters: oil/aqueous phase interfacial tension being in the region of 19–24 mN/m and viscosity close to 3 mPa s; such oils produced the most stable high internal phase emulsions. It was assumed that the oil with optimal parameters kept the critical micelle concentration and surfactant diffusion rate at optimal levels allowing the formation of a strong emulsifier layer at the interface and at the same time creating enough emulsifier micelles in the inter-droplet layer to prevent the droplet crystallization.     

Instability of highly concentrated emulsions with oversaturated dispersed phase. Role of a surfactant

Instability of highly concentrated emulsions of the water-in-oil type which were investigated in this work is related to the existence of the internal phase as an oversaturated salt solution in water. The principal features of crystallization of these systems were studied by as earlier. This study is devoted to the development of this investigation and based on involving different surfactants and various concentrations of surfactants. It was shown that the originally proposed mechanism of crystallization, which suggested that growing crystals break through interfacial layers, was valid for all highly concentrated emulsions under investigation. Moreover, the Kholmogorov-Avrami kinetic equation with an unusually high exponent value equal to 6 is also applicable to different systems. It was proven that the general relationship between the growth of the yield stress and the degree of crystallization can be formulated for all surfactants studied in the work. The role of a surfactant consists in varying the characteristic time constant for the rate of crystallization. This time constant is much lower for a low-molecular-weight surfactant compared to oligomeric surfactants. This constant noticeably increases with an increase of concentration and the decrease of the average droplet size.     

Diffusion in highly concentrated emulsions

High internal phase ratio emulsions (HIPREs) are a kind of emulsions characterized by a dispersed phase volume fraction higher than 0.74. In the last years much attention has been paid to their rheological properties and to their use for the preparation of low-density porous materials. However, in spite of their advantageous features concerning compartmentalization at different scale lengths with hydrophilic and hydrophobic domains and high internal phase ratio, little attention has been given to diffusion, an issue which can have a striking influence in many properties and applications of HIPREs. This review gives an overview on the work carried out in the last years concerning diffusion in highly concentrated emulsions from theoretical and practical points of view.     

Effect of calcium salts and surfactant concentration on the stability of water-in-oil (w/o) emulsions prepared with polyglycerol polyricinoleate

The objective of this work was to obtain water-in-oil (w/o) emulsions with polyglycerol polyricinoleate (PGPR) as emulsifier and to study the effect of the addition of calcium in the dispersed aqueous phase on the stability of these systems. Emulsions were formulated with 0.2, 0.5 and 1.0% w/w PGPR and 10% w/w water containing calcium chloride at varied concentrations or other salts (calcium lactate or carbonate; sodium, magnesium or potassium chloride). The stability of these systems was studied with a vertical scan analyzer during 15 days; coalescence and sedimentation were observed as simultaneous destabilization processes. The increase of PGPR concentration and/or calcium chloride content gave more stable emulsions. The stabilizing effect of calcium salt was attributed to the diminution of the water droplets size, the decrease of the attractive force between water droplets and the increase of the adsorption density of the emulsifier. The viscoelastic parameters of the interfacial film were decreased with increasing calcium and PGPR concentrations. Calcium chloride produced a higher increase of stability than calcium salts with lower dissociation degree. The presence of any assayed salt in the aqueous phase also allowed the stabilization of w/o emulsions with higher water contents.     

Freeze–thaw stability of water-in-oil emulsions

Factors influencing water-in-oil emulsion stability during freeze/thaw-cycling, namely interfacial crystallization vs. network crystallization and the sequence of crystallization events (i.e., dispersed vs. continuous phase or vice versa), are assessed. We show that destabilization is most apparent with a liquid-state emulsifier and a continuous oil phase that solidifies prior to the dispersed phase. Emulsions stable to F/T-cycling are obtained when the emulsifier crystallizes at the oil–water interface or in emulsions where the continuous phase crystallizes after the dispersed aqueous phase. The materials used are two food-grade oil-soluble emulsifiers – polyglycerol polyricinoleate (PGPR) and glycerol monostearin (GMS) and two continuous oil phases with differing crystallization temperatures – canola oil and coconut oil. Emulsion stability is assessed with pulsed field gradient NMR droplet size analysis, sedimentation, microscopy and differential scanning calorimetry. This study demonstrates the sequence of crystallization events and the physical state of the surfactant at the oil–water interface strongly impact the freeze–thaw stability of water-in-oil emulsions.     

Study on the flow of highly concentrated emulsions

An investigation was performed into the flow of highly concentrated water-in-oil emulsions. The viscosity of the low shear rate region in the downward curve was much higher than the viscosity of the upward curve due to the refining effect of the intensive shear. However, this refining effect lasted for just a short time. After that, the structure of highly concentrated emulsion (HCE) can return to its original state. The flow of HCE depends on the shear rate and droplet size of the dispersed phase. The viscosity curve of HCE, which is measured in the initial upward shearing sweep, had two platforms, whereas the region of shear rate was 10^?4?s^?1?～?10³?s^?1. The water-in-oil structure was destroyed by intensive shear and much solid ammonium nitrate (AN) was observed in the image of HCE. The small droplets can enhance the capacity of HCE to prevent the breakage of structure under shearing. The microstructure of HCE was closer to its original situation when the droplet size was small.     

The influence of internal phase viscosity on the viscosity of concentrated water-in-oil emulsions

Summary The influence of the viscosity of the internal phase on the viscosity of concentrated water-in-oil emulsions has been investigated and found to be negligible. It is indicated that thechemical nature of the dispersed medium may be of importance, however, with particular reference to its relationship to the stabilising agent, and an example of this is given. In liquid suspensions the ratio of the viscosities of the two phases is of importance in the transmission of viscous effects from the continuous to the disperse medium. This is not found to be the case for the emulsions examined, and the significance of the rigid structure of the interfacial film in this respect is discussed.

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Zusammenfassung Der Einflu? der Viskosit?t der inneren Phase auf die Viskosit?t von konzentriertem Wasser-in-?lemulsion wurde untersucht. Er ist vernachl?ssigbar. Dagegen ist die chemische Struktur des dispergierten Mediums wichtig, besonders im Zusammenhang mit dem Stabilisator, wie ein Beispiel zeigt. Da in flüssigen Suspensionen das Verh?ltnis der Viskosit?ten der beiden Phasen für die Berechnung der Viskosit?t der Dispersion aus denen der beiden Medien eine Rolle spielen sollte und dies bei den untersuchten Emulsionen nicht der Fall war, wird eine Wirkung von festen Grenzfl?chenfilmen für eine Erkl?rung diskutiert.

     

Effect of adding anionic surfactant on the stability of Pickering emulsions

We investigated the structure and stability of dodecane-in-water emulsions stabilised by partially hydrophobised silica particles after dilution of the emulsions in solutions of sodium dodecyl sulfate and sodium chloride. The emulsions were stable to coalescence on dilution in salt solutions, but did cream over time. The rate and extent of creaming gradually decreased as the salt concentration in the diluted emulsion increased. Dilution in low concentrations of the anionic surfactant did not affect the emulsion stability to coalescence or alter the creaming behaviour of the emulsion. At surfactant concentrations above the critical micelle concentration, however, the rate and extent of creaming and flocculation of the drops were enhanced.     

Rheology of foams and highly concentrated emulsions

We review the state of the art in foam and highly concentrated emulsion rheology, with an emphasis on progress made over the last five years. Since the structures and physico-chemical processes relevant for foams and emulsions are closely analogous, comparing the knowledge recently gained in these two neighboring fields brings fresh insight. In this spirit, we review how the macroscopic mechanical response arises from a coupling between interfacial energy and long range molecular interactions, entropic effects, interfacial rheology, and dynamics at the droplet or bubble scale. We present experiments and models concerning elasticity, osmotic pressure, yielding and flow behavior.     

Rheological behavior of water-in-oil emulsions stabilized by hydrophobic bentonite particles

A study of the rheological behavior of water-in-oil emulsions stabilized by hydrophobic bentonite particles is described. Concentrated emulsions were prepared and diluted at constant particle concentration to investigate the effect of drop volume fraction on the viscosity and viscoelastic response of the emulsions. The influence of the structure of the hydrophobic clay particles in the oil has also been studied by using oils in which the clay swells to very different extents. Emulsions prepared from isopropyl myristate, in which the particles do not swell, are increasingly flocculated as the drop volume fraction increases and the viscosity of the emulsions increases accordingly. The concentrated emulsions are viscoelastic and the elastic storage and viscous loss moduli also increase with increasing drop volume fraction. Emulsions prepared from toluene, in which the clay particles swell to form tactoids, are highly structured due to the formation of an integrated network of clay tactoids and drops, and the moduli of the emulsions are significantly larger than those of the emulsions prepared from isopropyl myristate.     

Water-in-carbon dioxide emulsions stabilized with hydrophobic silica particles

W/C emulsions were stabilized using hydrophobic silica particles adsorbed at the interface, resulting in average droplet diameters as low as 7.5 microm. A porous cross-linked shell was formed about a hydrophilic (colloidal and fumed) silica core with a trifunctional silylating agent, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)triethyoxysilane, to render the particles CO(2)-philic. The stability of emulsions comprising equal weights of CO(2) and water was assessed with visual observations of settling fronts and the degree of emulsion coalescence, and the average drop size was measured by optical microscopy. The effect of CO(2) density on both emulsion stability and droplet size was determined quantitatively. The major destabilizing mechanism of the emulsions was settling, whereas Ostwald ripening and coalescence were not visible at any density, even over 7 days. Flocculation of the settling droplets did not occur, although gelation of the emulsions through particle interactions resulted after longer periods of time. CO(2)-philic particles offer a new route to highly stable W/C emulsions, with particle energies of attachment on the order of 10(6)kT, even at CO(2) densities as low as 0.78 g ml(-1). At these low densities, surfactants rarely stabilize emulsions as the result of poor surfactant tail solvation.     

Adsorption of non-ionic surfactants on hydrophobic silica particles and the stability of the corresponding aqueous dispersions

The temperature stability of aqueous dispersions of hydrophobic monodisperse silica particles stabilized with nonionic surfactants has been investigated. Adsorption isotherms in conjunction with surface tension measurements showed that the surfactant formed a monolayer on the surface of the particles, where the adsorbed amount depended on the molecular weight of the ethylene oxide headgroup. The temperature stability of these dispersions has been measured by a standard turbidimetric technique and visual observations in terms of their critical flocculation temperature (CFT). Parameters controlling the CFT of the individual dispersions stabilized with a monolayer of surfactant include the thickness of the steric layer, the particle size, and the volume fraction of the particles. Calculations show that the van der Waals attraction between the particles with adsorbed polymer layers increases as the temperature of the dispersion increases, and this largely accounts for the observed CFT behavior.     

The effect of modifier concentration on the stability of emulsions and foams stabilized with colloidal silica particles

The stability of emulsions and foams stabilized with hexylamine-modified silica particles has been studied as depending on the concentration of the surfactant. Silica modification with short-chain hexylamine leads to a marked increase in the contact angle upon selective wetting and inversion of the phases in the emulsions. The contact angles upon wetting silica surface by aqueous phases are no larger than 60°, while the maximum stability of foams corresponds to contact angles of 38°–50° depending on the concentration of the solid particles.     

Effect of oil soluble surfactant in emulsions stabilised by clay particles

Although surfactants and particles are often mixed together in emulsions, the contribution of each species to the stabilisation of the oil-water interface is poorly understood. We report the results of investigations into the formation of emulsions from solutions of surfactant in oil and aqueous suspensions of laponite. Depending on the salt concentration in the aqueous suspensions, the laponite dispersed as individual disc-shaped particles, 30 nm in diameter, or flocculated into aggregates tens of micrometres in diameter. At the concentrations studied, the flocculated particles alone stabilized oil-in-water emulsions. Synergistic interactions between the particles and octadecylamine at the oil-water interface reduced the average emulsion drop size, while antagonistic interactions with octadecanoic acid enhanced coalescence processes in the emulsions. The state of particle dispersion had dramatic effects on the emulsions formed. Measurements of the oil-water interfacial tension revealed the origins of the interactions between the surfactants and particles.     

Factors affecting the stability of foamed concentrated emulsions

This paper attempts to quantify the stability of three-phase systems generated by aerating concentrated water-in-oil emulsions. In such materials, which we call foamed emulsions, the continuous phase is itself a two-phase system. In this work, we modify and extend the method originally proposed by Iglesias et al. (Colloids and Surfaces A, 98 (1995) 167–174) to viscous three-phase foams. The modified method involves imparting a destabilising force to the sample to make the foam short-lived and measuring the change in height as a function of decay time. The change of height during decay represents the rate at which gas is evolved from the foamed emulsion and is logarithmic with time. The data treatment yields two values, the decay constant and half-life, which are used as a means of measuring and comparing stability. Two distinct decay mechanisms (smooth decay and catastrophic collapse) operate in foamed emulsions that are subjected to oscillations. For a given decay mechanism, the decay constant is an intrinsic property of the foamed emulsion and is independent of the imposed oscillations. Experimental results indicate that different bubble stabilising surfactants and emulsion morphology significantly affect the foam stability, and that the stability is inversely related to the initial expansion. Examination of the gas–emulsion interface shows a segregation of droplets, with smaller droplets found preferentially at the gas–emulsion interface.     

On the flow characteristics of highly concentrated oil-in-water emulsions

The laminar flow characteristics of oil-in-water emulsions with oil concentrations greater than 59% by volume have been investigated experimentally. Up to an oil concentration of 65% by volume, the emulsions exhibited power-law non-newtonian behaviour. At a higher oil concentration, of 72.21% by volume, a dramatic change in the flow behaviour of the emulsion was observed. The flow curve, i.e. shear stress vs. shear rate plot on a log-log scale, clearly exhibited the presence of a yield-stress.The rheological data on the emulsions were used to correlate the laminar pipeline transport data on the same emulsions. For power-law emulsions, values of the drop in pipeline pressure could be accurately predicted from simple rheological measurements. For a yield-stress emulsion, the experimental pipeline data deviated from the predicted values especially at low values of shear stress.     

Effect of electrolyte in silicone oil-in-water emulsions stabilised by fumed silica particles

Partially hydrophobised fumed silica particles are used to make silicone oil-in-water emulsions at natural pH of the aqueous phase. The stability and rheological properties of the emulsions and suspensions are studied at NaCl concentrations in the range 0-100 mM. It is found that all emulsions are very stable to coalescence irrespective of the NaCl concentration. However, a strong effect of electrolyte on the creaming and rheological properties is observed and linked to the particle interactions in aqueous suspensions. The creaming rate and extent are large at low electrolyte concentrations but both abruptly decrease at salt concentrations exceeding the critical flocculation concentration of the suspension (approximately 1 mM NaCl). The drastic improvement of the stability to creaming is attributed to the formation of a visco-elastic three-dimensional network of interconnected particles and emulsion droplets.     

Influence of electrolyte on interfacial and rheological properties and shear stability of highly concentrated W/O emulsions

The effect of the electrolyte concentration on the interfacial interactions, rheological properties and emulsion shear stability was investigated. The increase of the electrolyte concentration leads to the growth of storage modulus and the yield stress of emulsions and enhances the emulsion stability to shearing, while interfacial tension decreases. The observed effects were attributed to the interfacial interaction of a surfactant and an electrolyte that was confirmed by the IR-analysis. The interaction between an electrolyte and a surfactant provides a stable interface.     

Macroporous polymers obtained in highly concentrated emulsions stabilized solely with magnetic nanoparticles

Magnetic macroporous polymers have been successfully prepared using Pickering high internal phase ratio emulsions (HIPEs) as templates. To stabilize the HIPEs, two types of oleic acid-modified iron oxide nanoparticles (NPs) were used as emulsifiers. The results revealed that partially hydrophobic NPs could stabilize W/O HIPEs with an internal phase above 90%. Depending upon the oleic acid content, the nanoparticles showed either an arrangement at the oil-water interface or a partial dispersion into the oil phase. Such different abilities to migrate to the interface had significant effects on the maximum internal phase fraction achievable and the droplet size distribution of the emulsions. Highly macroporous composite polymers were obtained by polymerization in the external phase of these emulsions. The density, porosity, pore morphology and magnetic properties were characterized as a function of the oleic acid content, concentration of NPs, and internal phase volume of the initial HIPEs. SEM imaging indicated that a close-cell structure was obtained. Furthermore, the composite materials showed superparamagnetic behavior and a relatively high magnetic moment.