Emulsion drops in external flow fields — The role of liquid interfaces

We review the flow of emulsion drops, focusing on recent work involving complex interfaces, which may include the presence of surfactants, particles, surface-active polymers, or solid-like membrane layers. En route, important phenomena in multiphase flow associated with emulsion rheology are considered, including drop coalescence and breakup, surfactant transport, or the mechanics of composite interfaces.     

Evaluation of adsorption of nonionic surfactants blend at water/oil interfaces

The inherent biocompatibility of Span and Tween surfactants makes them an important class of nonionic emulsifiers that are employed extensively in emulsion and foam stabilization. The adsorption of Span-Tween blend at water/oil surface of emulsion has been investigated using a population balance model for the first time. Destability of emulsion was modeled by considering sedimentation, coalescence and interfacial coalescence terms in population balance equation (PBE). The terms of coalescence efficiency and interfacial coalescence time were considered as a function of surface coverage of droplets by surfactant molecules. The surface coverage at different surfactant concentrations was determined by minimization of difference between the model predictions and experimental average droplet sizes. After optimization, the surface coverage outputs were fitted with different adsorption isotherms to evaluate the adsorption behavior of Span-Tween surfactants blend at water/oil surface. The results show that Freundlich isotherm can predict the adsorption behavior of closer to the experimental observation. Moreover, fitted parameters imply the favorable adsorption of Span-Tween blend at water/oil interface.     

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.     

Binary Coalescence of Water Drops in Organic Media in Presence of Ionic Surfactants and Salts

Binary coalescence of water drops in o‐xylene and toluene, and ethylene glycol drops in toluene were studied in this work. The effects of cationic and anionic surfactants on coalescence time were studied. Cetyl trimethyl ammonium bromide (CTAB) and cetyl pyridinium bromide (CPyBr) were used as cationic surfactants. Sodium dodecyl benzene sulfonate (SDBS) was used as the anionic surfactant. The effects of salts (NaCl and CaCl₂) containing monovalent and divalent ions on coalescence were investigated. The coalescence time was found to follow distributions in each of these experiments. The minimum and maximum values of the distributions were largely different. The stochastic model developed earlier by us was used to fit the distributions. The effects of the physical properties of the system (such as density, size of the drops, interfacial tension, and surface excess of adsorbed surfactant) on the model parameters were discussed.     

Scintillation phase method: A new approach for studying surfactant behavior at liquid/liquid interface

Radiochemical approach for the investigation of partitioning and adsorption of surfactants at water-oil interfaces has been developed. The so-called “scintillation phase method” is based on the introduction of tritium labeled surfactant in an aqueous phase of the water-oil system followed by measuring radioactivity of the whole system. Partition coefficients and the value of adsorption at water-non-polar liquid interfaces of homologous series of alkyltrimethylammonium bromides (DTAB, TTAB and CTAB) have been experimentally determined by means of scintillation phase method. The influence of non-ionic surfactants on TTAB adsorption has also been studied.     

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.     

Near-Contact Motion of Surfactant-Covered Spherical Drops: Ionic Surfactant

A lubrication analysis is presented for near-contact axisymmetric motion of spherical drops covered with an insoluble nondiffusing surfactant. The surfactant equation of state is arbitrary; detailed results are presented for ionic surfactants. The qualitative behavior of the system is determined by the dimensionless force parameter &Fcirc;, the external force normalized by the maximum resistance force generated by Marangoni stresses. For &Fcirc; > 1 drops coalesce on a time scale commensurate with the coalescence time tau0 for drops with clean interfaces. For &Fcirc; < 1, the system evolves on the time scale tau0 until Marangoni stresses approximately balance the external force; thereafter a slow evolution occurs on the Stokes time scale. In the long-time regime a self-similar surfactant concentration profile is attained that scales with the extent of the near-contact region. The gap width decreases exponentially with time but slower than for rigid particles because of surfactant backflow. For &Fcirc; < 1, drop coalescence does not occur without van der Waals attraction. Quantitative results depend only moderately on the surfactant equation of state. Copyright 1999 Academic Press.     

Effect of Insoluble Surfactants on Drainage and Rupture of a Film between Drops Interacting under a Constant Force

The deformation, drainage, and rupture of an axisymmetrical film between colliding drops in the presence of insoluble surfactants under the influence of van der Waals forces is studied numerically at small capillary and Reynolds numbers and small surfactant concentrations. Constant-force collisions of Newtonian drops in another Newtonian fluid are considered. The mathematical model is based on the lubrication equations in the gap between drops and the creeping flow approximation of Navier–Stokes equations in the drops, coupled with velocity and stress boundary conditions at the interfaces. A nonuniform surfactant concentration on the interfaces, governed by a convection–diffusion equation, leads to a gradient of the interfacial tension which in turn leads to additional tangential stress on the interfaces (Marangoni effects). The mathematical problem is solved by a finite-difference method on a nonuniform mesh at the interfaces and a boundary-integral method in the drops. The whole range of the dispersed to continuous-phase viscosity ratios is investigated for a range of values of the dimensionless surfactant concentration, Peclét number, and dimensionless Hamaker constant (covering both “nose” and “rim” rupture). In the limit of the large Peclét number and the small dimensionless Hamaker constant (characteristic of drops in the millimeter size range) a fair approximation to the results is provided by a simple expression for the critical surfactant concentration, drainage being virtually uninfluenced by the surfactant for concentrations below the critical surfactant concentration and corresponding to that for immobile interfaces for concentrations above it.     

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.     

Flocculation and Coalescence of Oil-in-Water Poly(dimethylsiloxane) Emulsions

The stability of poly(dimethylsiloxane) (PDMS) oil-in-water emulsions has been investigated in the presence of added NaCl as well as in the presence of added surfactant. The emulsions were prepared using a combination of nonionic (C(x)E(y), x and y represent the number of methylene (C) and ethylene oxide (E) groups, respectively) and cationic (quarternary alkylammonium) surfactants. The droplets were observed to exhibit weak flocculation in the presence of high NaCl concentration (1 M). Phase separation and optical microscopic observations revealed that the principal mechanism for emulsion destabilization at high salt concentration was coalescence, which was accelerated at elevated temperature (50 degrees C). The effective coalescence rate for diluted emulsions was investigated using photon correlation spectroscopy. The small effective Hamaker constant for PDMS is the primary reason for the slow rate of coalescence observed for the emulsions at neutral pH in the presence of NaCl. The stability of PDMS emulsions to flocculation is qualitatively similar to that reported for low Hamaker constant dispersions (e.g., microgel particles). Addition of cationic surfactants (cetyltrimethylammonium chloride and dodecyl dimethylbenzylammonium chloride) to the negatively charged droplets after preparation was shown to decrease the emulsion stability once the surfactant concentration exceeded the CMC. Electrophoretic mobility measurements showed that added cationic surfactant changed the sign of the droplet charge from negative to positive at concentrations well below the CMC. Charged micelles of the same sign as the droplets are electrostatically excluded from close approach to the droplet surface within a distance (varepsilon) which results in depletion flocculation. Copyright 2000 Academic Press.     

Characterizing the distribution of nonylphenol ethoxylate surfactants in water-based pressure-sensitive adhesive films using atomic-force and confocal Raman microscopy

Surfactant distributions in model pressure-sensitive adhesive (PSA) films were investigated using atomic force microscopy (AFM) and confocal Raman microscopy (CRM). The PSAs are water-based acrylics synthesized with n-butyl acrylate, vinyl acetate, and methacrylic acid and two commercially available surfactants, disodium (nonylphenoxypolyethoxy)ethyl sulfosuccinate (anionic) and nonylphenoxypoly(ethyleneoxy) ethanol (nonionic). The ratio of these surfactants was varied, while the total surfactant content was held constant. AFM images demonstrate the tendency of anionic surfactant to accumulate at the film surfaces and retard latex particle coalescence. CRM, which was introduced here as a means of providing quantitative depth profiling of surfactant concentration in latex adhesive films, confirms that the anionic surfactant tends to migrate to the film interfaces. This is consistent with its greater water solubility, which causes it to be transported by convective flow during the film coalescence process. The behavior of the nonionic surfactant is consistent with its greater compatibility with the polymer, showing little enrichment at film interfaces and little lateral variability in concentration measurements made via CRM. Surfactant distributions near film interfaces determined via CRM are well fit by an exponential decay model, in which concentrations drop from their highs at interfaces to plateau values in the film bulk. It was observed that decay constants are larger at the film-air interface compared with those obtained at the film-substrate side indicating differences in the mechanism involved. In general, it is shown here that CRM acts as a powerful compliment to AFM in characterizing the distribution of surfactant species in PSA film formation.     

Molecular simulations of surface forces and film rupture in oil/water/surfactant systems

We use dissipative particle dynamics (DPD) and molecular models to simulate interacting oil/water/surfactant interfaces. The system comprises sections of two emulsion droplets separated by a film. The film is in equilibrium with a continuous phase, in analogy with the surface force apparatus. This is achieved by combining DPD with a Monte Carlo scheme to simulate a muVT ensemble. The setup enables the computation of surface forces as a function of the distance between the two interfaces, as well as the detection of film rupture. We studied monolayers of nonionic model surfactants at different densities and compared oil-water-oil and water-oil-water emulsion films. Between surfactant monolayers facing each other tails-on (water-oil-water films), we observed repulsive forces due to the steric interaction between overlapping hydrophobic tails. The repulsion increases with surfactant density. Conversely, no such repulsion is observed between surfactant monolayers facing each other heads-on. Instead, the film ruptures, the monolayers merge, and a channel forms between the two droplet phases. Film rupture can also be induced in the water-oil-water films by forcing the interfaces together. The separation at rupture increases for oil-water-oil films and decreases for water-oil-water films when the surfactant density increases. The results are in qualitative agreement with existing theories of emulsion stability in creams, in particular with the channel nucleation theory based on the natural curvature of surfactants.     

Coalescence during emulsification. 2. Role of small molecule surfactants

An oil-soluble hexadecyl pyrene (HDP) probe is used to monitor coalescence of hexadecane oil-in-water emulsions, during emulsification, in stirred systems and in a high-pressure homogenizer (microfluidizer), when small molecule surfactants are used as emulsifiers. The effect of sodium dodecyl sulfate concentration and salt concentration on the amount of coalescence and final drop size is studied. The behavior of oil-soluble surfactants and mixtures of oil-soluble and water-soluble surfactants on emulsification performance is also discussed. For high-pressure homogenizers, the drop sizes obtained are found to depend mostly on the ability of surfactants to stabilize the drops against coalescence, rather than their ability to reduce the interfacial tension. Increasing oil phase fractions increase the coalescence rate, because of the increase in collision frequency, which, in turn, impacts the drop size of the homogenized emulsion.     

A novel formulation of the pickering emulsion stabilized with silica nanoparticles and its thermal resistance at high temperatures

Stabilization of emulsions with solid particles can be used in several fields of oil and gas industry because of their higher stability. Solid particles should be amphiphilic to be able to make Pickering emulsions. This goal is achieved by using surfactants at low concentrations. Oil-in-water (o/w) emulsions are usually stabilized by surfactant but show poor thermal stability. This problem limits their applications at high-temperature conditions. In this study, a novel formulation for o/w stabilized emulsion by using silica nanoparticles and the nonionic surfactant is investigated for the formulation of thermally stable Pickering emulsion. The experiments performed on this Pickering emulsion formula showed higher thermal stability than conventional emulsions. The optimum wettability was found for DME surfactant and silica nanoparticles, consequently, in that region; Pickering emulsion showed the highest stability. Rheological changes were evaluated versus variation in surfactant concentration, silica concentration and pH. Scanning electron microscopy images approved the existence of a rigid layer of nanoparticle at the oil-water interface. Finally, the results show this type of emulsion remains stable in harsh conditions and allows the system to reach its optimum rheology without adding any further additives.     

Influence of interfacial rheology on foam and emulsion properties

Foams and emulsions are stabilized by surfactant monolayers that adsorb at the air-water and oil-water interfaces, respectively. As a result of monolayer adsorption, the interfaces become viscoelastic. We will describe experiments showing that foaming, emulsification, foam and emulsion stability, are strongly dependent upon the value of compression elasticity and viscosity. This will include excited surface wave devices for the measurement of surface viscoelasticity and thin film videointerferometry for the study of model films between air bubbles and emulsion drops.     

Role of surfactant type and concentration for the mean drop size during emulsification in turbulent flow

A systematic experimental study of the effect of several factors on the mean drop diameter, d32, during emulsification, is performed with soybean oil-in-water emulsions. These factors are (1) type of used emulsifier; (2) emulsifier concentration, CS; and (3) ionic strength of the aqueous solution. Three different types of emulsifier, anionic (sodium dodecyl sulfate, SDS), nonionic (polyoxyethylene-20 cetyl ether, Brij 58), and protein (whey protein concentrate), are studied. For all of the studied systems, two well-defined regions are observed in the dependence of d32 on CS: at low surfactant concentration, d32 increases significantly with the decrease of CS (region 1), whereas d32 does not depend on CS at high surfactant concentration (region 2). The model, proposed by Tcholakova et al. (Langmuir 2003, 19, 5640), is found to describe well the dependence of d32 on CS in region 1 for the nonionic surfactant and for the protein emulsifier at high electrolyte concentration, 150 mM NaCl. According to this model, a well defined minimal surfactant adsorption (close to that of the dense adsorption monolayer) is needed for obtaining an emulsion. On the other hand, this model is found inapplicable to emulsions stabilized by the ionic surfactant, SDS, and by the nonionic surfactant, Brij 58, at low electrolyte concentration. The performed theoretical analysis of drop-drop interactions, in the emulsification equipment, shows that a strong electrostatic repulsion between the colliding drops impedes the drop-drop coalescence in the latter systems, so that smaller emulsion drops are obtained in comparison with the theoretically predicted ones. The results for SDS-stabilized emulsions in region 1 are explained by a quantitative consideration of this electrostatic repulsion. The drop size in region 2 (surfactant-rich regime) is described very well by the Kolmogorov-Hinze theory of turbulent emulsification.     

Properties of Interfacial Layers in Multicomponent Systems Containing Gelatin

The review is devoted to the analysis of the effect of the addition of various surfactants on the composition, structure, and the properties of the interfacial adsorption layers (IALs) formed at equilibrium in the aqueous gelatin solution–hydrocarbon system. Associates of variable compositions that are determined by the component ratio and the concentration of added surfactant are formed due to the interaction between gelatin and surfactant. The formation of associates is equivalent to the modification of gelatin. The properties of the IALs of modified gelatins are discussed on the basis of our own results and published data on the interfacial tension, the mass accumulation of surface-active components at the interfaces during the IAL formation, the IAL rheological properties and the stability of emulsion films varied with the conditions of IAL formation (the nature of low-molecular-weight surfactant, component concentrations, pH of aqueous phase, and temperature). It was concluded that modified gelatins can be considered as new surfactants governing the dynamics of the formation and fracture mechanism of the IALs and the stability of emulsion films. The properties of the IALs of modified gelatins are compared with those of IALs formed by gelatin and low-molecular-weight surfactants under the conditions when associates are formed directly at the interface due to the use of oil-soluble surfactants.     

Naturally occurring spore particles at planar fluid interfaces and in emulsions

We have investigated the potential of utilizing naturally occurring spore particles of Lycopodium clavatum as sole emulsifiers of oil and water mixtures. The preferred emulsions, prepared from either oil-borne or aqueous-borne dispersions of the monodispersed particles of diameter 30 microm, are oil-in-water. The particles act as efficient stabilizers for oils of different polarity. Droplets as large as several millimeters are stable to coalescence indefinitely, despite the low coverage of interfaces by particles observed microscopically. Consistent with the emulsion findings, we discover that particles spontaneously adsorb to bare oil-water interfaces of single drops from oil dispersions, whereas adsorption is less spontaneous and extensive from aqueous dispersions. Monolayers of the spore particles at both air-water and oil-water planar interfaces contain particles in an aggregated state forming clusters and chains. The influence of particle concentration, oil/water ratio, and additives in the aqueous phase is studied.     

Effect of dynamic surfactant adsorption on emulsion stability

The effect of dynamic surfactant adsorption on the stability of concentrated oil in water emulsions is studied. For this purpose, a modification of the standard Brownian dynamics algorithm (Ermak, D.; McCammon, J. A. J. Chem. Phys. 1978, 69, 1352) previously used to study the behavior of bitumen emulsions assuming instantaneous adsorption (Urbina-Villalba, G.; García-Sucre, M. Langmuir 2000, 16, 7975) was employed. In the present case, dynamic adsorption (DA) was accounted for through a time-dependent electrostatic repulsion between the drops, a function of the surfactant surface excess. The surface excess was allowed to evolve with time according to well-established analytical expressions which depend parametrically on the surfactant diffusion constant (Ds) and the total surfactant concentration (C). The investigation required appropriate incorporation of hydrodynamic interactions in concentrated systems. This was achieved through a novel methodology, which expresses the diffusion constant of each particle as a function of its local concentration and the shortest distance of separation between nearest neighbors. In model systems, the variation of the number of drops as a function of time was followed for different magnitudes of the apparent diffusion constant D(app) of the surfactant. For each of these values, the effect of C and the volume fraction of internal phase (phi) was considered. DA was found to influence emulsion stability appreciably at moderately high phi. In this case, the average collision time between drops is comparable to the time required for the occurrence of a substantial surfactant adsorption, but the interdrop separation is sufficiently large to prevent a considerable slowdown of particle movement due to hydrodynamic interactions.     

Preparation of a stable double emulsion (W1/O/W2): role of the interfacial films on the stability of the system

This paper presents new protocols enabling preparation of W1/O/W2 double emulsions: one, using soybean oil as the O phase, that yields edible emulsions with industrial applications, and a second that yields emulsions with a previously unattainable concentration 15% (w/w) of surfactants in the external phase (the 15% target was chosen to meet the typical industry standard). Preparation of a stable W1/O emulsion was found to be critical for the stability of the system as a whole. Of the various low HLB primary surfactants tested, only cethyl dimethicone copolyol (Abil EM90), A-B-A block copolymer (Arlacel P135), and polyglycerol ester of ricinoleic acid (Grinstead PGR-90) yielded a stable W/O emulsion. Investigation of the surface properties of those surfactants using the monolayer technique found two significant similarities: (1) stable, compressible, and reversibly expandable monolayers; and (2) high elasticity and surface potential. The high degree of elasticity of the interfacial film between W1 and O makes it highly resilient under stress; its failure to break contributes to the stability of the emulsion. The high surface potential values observed suggest that the surfactant molecules lie flat at the O/W interfaces. In particular, in the case of PGR-90, the hydroxyl (-OH) groups on the fatty acid chains serve as anchors at the O/W interfaces and are responsible for the high surface potential. The long-term stability of the double emulsion requires a balance between the Laplace and osmotic pressures (between W1 droplets in O and between W1 droplets and the external aqueous phase W2). The presence of a thickener in the outer phase is necessary in order to reach a viscosity ratio (preferably approximately 1) between the W1/O and W2 phases, allowing dispersion of the viscous primary emulsion into the W2 aqueous phase. The thickener, which also serves as a dispersant and consequently prevents phase separation due to its thixotropic properties, must be compatible with the surfactants. Finally, the interactions between the low and high HLB emulsifiers at the O/W2 interface should not destabilize the films. It was observed that such destructive interaction for the system could be prevented by the use of two high HLB surfactants in the outer aqueous phase: an amphoteric surfactant, Betaine, and an anionic surfactant, sodium lauryl ether sulfate. The combination of such pairs of surfactants was found to contribute to the films' stability.