Studying surfactant mass transport through dynamic interfacial tension measurements: A review of the models, experiments, and the contribution of microfluidics.

Surfactant mass transport towards an interface plays a critical role during formation of emulsions, foams and in industrial processes where two immiscible phases coexist. The understanding of these mechanisms as experimentally observed by dynamic interfacial tension measurements, is crucial. In this review, theoretical models describing both equilibrated systems and surfactant kinetics are covered. Experimental results from the literature are analysed based on the nature of surfactants and the tensiometry methods used. The innovative microfluidic techniques that have become available to study both diffusion and adsorption mechanisms during surfactant mass transport are discussed and compared with classical methods. This review focuses on surfactant transport during formation of droplets or bubbles; stabilisation of dispersed systems is not discussed here.

Comparison of Methods Used to Investigate Coalescence in Emulsions.

We present a study of moderately stable dilute emulsions. These emulsions are models for water contaminated by traces of oil encountered in many water treatment situations. The purification of water and the elimination of oil rely on the emulsion stability. Despite actively being studied, the topic of emulsion stability is still far from being fully understood. In particular, it is still unclear whether experimental methods accessing different length scales lead to the same conclusions. In the study presented in this paper, we have used different methods to characterize the emulsions, such as centrifugation and simple bottle tests, as well as investigations of the collision of single macroscopic oil drops at an oil-water interface. We studied different emulsions containing added polymer or surfactant. In the case of added polymer, centrifugation and single drop experiments led to opposite trends in stability when the polymer concentration is varied. In the case of added surfactant, both centrifugation and single drop experiments show a maximum stability when the surfactant concentration is increased, whereas bottle tests show a monotonous increase in stability. We propose tentative interpretations of these unexpected observations. The apparent contradictions are due to the fact that different methods require different drop sizes or different drop concentrations. The puzzling decrease in emulsion stability at a higher surfactant concentration observed with some methods, however, remains unclear. This coalescence study illustrates the fact that different results can be obtained when different experimental methods are used. It is therefore advisable not to rely on a single method, especially in the case of emulsions of limited stability for reasons explained in the paper.

Monitoring the formation kinetics of a bicontinuous microemulsion.

HYPOTHESES: The performance of bicontinuous microemulsions is usually assessed on the characteristics of the middle phase at equilibrium. However, applied to Enhanced Oil Recovery, such an evaluation would not be representative of the structure and composition of fluids in reservoir rocks. Studies on the properties of non-equilibrated microemulsions are still needed to better understand the formation of such complex systems, in particular to optimize input parameters of process simulation tools. EXPERIMENTS: For this purpose, we monitored the formation of a microemulsion from contact with the oil to equilibrium when no mixing or convection is provided. Non-destructive methods such as Nuclear Magnetic Resonance, Micro-Computed Tomography, Dynamic Light Scattering and Small Angle X-ray scattering were used to extract the compositions, phase thicknesses, dynamics and structures of the system over time. FINDING: We found that the system gets structured into several layers over time that include the transient presence of an oriented semi-crystalline phase. The growth of the bicontinuous middle phase results from a progressive reorganization of the liquid crystal. The compositional and structural gradients, observed along the sample height, are correlated and linked to the corresponding structures of the phase diagram of the quaternary system. Equilibrium is reached after the total transfer of the liquid crystal into the bicontinuous phase.

Quantification of microemulsion systems using low-field T1-weighted imaging.

Applied to Enhanced Oil Recovery, microemulsions are valuable systems for extracting the crude oil trapped by capillary forces in the porous reservoir rocks. The performances of the injected formulations are often assessed by quantifying oil composition in model systems that contain relatively high amount of surfactant/co-surfactant. Recently, the question of representativity of such systems was raised because kinetics aspects and complexity of crude were neglected in model systems and are likely to impact the process efficiency. The current quantification techniques limit the characterization of representative model systems as they are destructive, time consuming and not often applicable to dark or opaque systems. In the original aim to provide a quantitative kinetic study of such microemulsions, we propose a high resolution T1-weighted imaging technique to have access to 1D-composition profiles of co-surfactant, oil and brine in Winsor I, Winsor III and Winsor II microemulsions. The analysis is carried out on model systems at equilibrium for proof of concept. Results are correlated with X-Ray Micro-CT experiments to provide better interpretations and assess the method accuracy. We provide conditions of validity of the developed NMR method and discuss its potential limitations. To a larger extent, the method could be of interest to other applications that use similar systems.

Can unmixed complex forming polymer surfactant formulations be injected into oil reservoirs or aquifers without clogging them?

In the context of enhanced oil recovery or soil remediation, we study the role of interactions between polymers and surfactants on the injectivity of formulations containing mixtures of polymers and surfactants. We show that contrary to the first intuition, the formation of aggregates in polymers surfactants formulations is not necessarily a hindrance to the injection of these formulations into pores. It is important above all to compare the size of aggregates according to the applied shear rate and the pore size to find the formulations that may induce clogging. We highlight a new positive and unexpected phenomenon. The small aggregates that do not lead to clogging ensure the transport of the surfactant vesicles in the porous medium and limit the adsorption of the latter.

Insight into Kinetics and Mechanisms of AOT Vesicle Adsorption on Silica in Unfavorable Conditions.

The structure of adsorbed surfactant layers at the equilibrium state has already been investigated using various experimental techniques. However, the comprehension of the formation of structural intermediates in nonequilibrium states and the resulting adsorption kinetics still remain a challenging task. The temporal characterization of these intermediate structures provides further understanding of the layer structure at equilibrium and of the main interactions involved in the adsorption process. In this article, we studied the adsorption kinetics of AOT vesicles on silica at different pHs at ambient temperature. The AOT vesicles were formed in a brine solution. Quartz crystal microbalance with dissipation monitoring (QCM-D) was used to obtain information on the kinetics of surfactant adsorption and on the structure of the adsorbed layer at the equilibrium state. Additionally, neutron reflectivity experiments were performed to provide a detailed description of the mean surfactant concentration profile normal to the surface at equilibrium. Results suggest that vesicles in the bulk influence the adsorption mechanisms. In acidic conditions, after a time-dependent structural rearrangement step, followed by the rupture of initially adsorbed vesicles, the formation of a bilayer was observed. At an intermediate and basic pH, in spite of the electrostatic repulsion between the negatively charged surfactants and silica, results demonstrated the existence of an adsorbed layer composed of AOT vesicles. Vesicles are more or less closely packed depending on the pH of the solution. Results show a non-negligible influence of NaCl addition at pH values where adsorption is initially inhibited. Vesicle adsorption at the intermediate and basic pH is probably due to the combination of attractive van der Waals interactions promoted in high ionic strength systems and the formation of hydrogen bonds. Interpretation of adsorption kinetics gave insight into adsorption mechanisms in an electrostatic repulsion environment.

Interfacial Dynamics and Rheology of a Crude-Oil Droplet Oscillating in Water at a High Frequency.

We report investigations of a pendant diluted crude-oil droplet in water that is forced to oscillate at a frequency ω. The droplet interface contains a significant amount of surface-active agents and displays a marked viscoelastic rheology with elastic moduli larger than viscous ones. At a low frequency, fluid viscosity and inertia are negligible, which allows a direct determination of the dilatational interface rheology. At a large frequency, eigenmodes of inertial shape oscillations are excited. By decomposing the interface shape into spherical harmonics, the resonance curves of the inertial modes of the interface are determined, as well as the frequency and damping rate of each mode. These two parameters are of major importance for the prediction of the deformation and breakup of a droplet in any unsteady flow without any prior knowledge of either the chemical composition or the detailed rheological properties of the interface. Then, interfacial rheology is related to interface dynamics by solving the coupled dynamic equations for the two fluids and the interface. It turns out that the rheology of the interface is well described by an equivalent two-dimensional viscoelastic material, the elasticities and viscosities of which depend upon the frequency. A first significant result is that shear and dilatational elasticities are closely connected, as are shear and dilatational viscosities. This implies that intrinsic rheology plays a major role and that compositional rheology is either negligible or strongly coupled to the intrinsic one. A second major result is that, for moderately aged droplets (≤5000 s), the elasticity and viscosity at a high frequency (10-80 Hz) can be extrapolated from low-frequency measurements (≤1 Hz) by a simple power law of the frequency, ωz. The exponent z is related to the loss angle θloss by a relation found in many previous low-frequency investigations of crude-oil interfaces: z = θloss/2π. The present work thus extends classic observations obtained at a low frequency to a higher frequency range corresponding to the natural frequency of the droplets, where the droplet shape results from the balance between dynamic pressure and surface stresses and the interface involves simultaneous shear and dilatation. These results bring about serious constraints regarding the modeling of physicochemical underlying mechanisms and provide some insights for the understanding of the structure of crude-oil interfaces.

A new way to measure viscosity in droplet-based microfluidics for high throughput analysis.

In this work, we propose a new way to measure the viscosity of samples in a microfluidic device. By analysing the shape of droplets after an expansion, we can measure the viscosity of the phase inside the droplet knowing the surface tension between the two liquids, the flow rate, the geometry of the channel and the viscosity of the continuous phase. This work paves the way for future high throughput studies in the framework of digital microfluidics.

Ultralow Interfacial Tension Measurement through Jetting/Dripping Transition.

In this paper, we present a dynamic microfluidic tensiometer able to perform measurements over more than four decades and which is suitable for high throughput experimentations. This tensiometer is able to withstand hard conditions such as high pressure, high temperature, high salinity, and crude oil. It is made of two coaxial capillaries in which two immiscible fluids are injected. Depending on the flow rate of each phase, either droplets or jetting will be obtained. The transition between these two regimes relies on the Rayleigh-Plateau instability. This transition can be theoretically computed thanks to a linear analysis based on the convective and absolute instabilities theory. From this model, the interfacial tension between the two phases can be calculated.