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.     

Breakup of a Multiple Emulsion Drop in a Uniform Electric Field

The steady deformation and breakup of emulsion drops in a uniform electric field are considered experimentally. Due to the low volume fraction of inner drops, the emulsions can be effectively assumed as Newtonian fluids with spatial nonuniformity. The measurements of the electrical properties show that the oil-in-water (o/w) emulsion drop behaves like a conducting drop. On the other hand, the water-in-oil (w/o) emulsion drops can be regarded as inhomogeneous leaky dielectric drops. It is found that the viscosity ratio is not an important parameter within the small deformation limit and breakup mode of the o/w emulsion drops. In the case of w/o emulsion drops, however, the breakup mode depends on the viscosity ratio. Inherent nonuniformity of the emulsion drops makes drop more deformable and unstable. The tip-streaming is the dominant breakup mode of o/w emulsion drops when the nonuniformity of drop phase is appreciable. Copyright 1999 Academic Press.     

Physicochemical parameters influencing the emulsion drop size

The stirring-mixing energy is the most obvious factor in the drop size reduction process, but it is not necessarily the most important one. Both the physicochemical formulation and the composition variables are shown to play a determinant role, at constant stirring condition.The generalized formulation versus water/oil ratio diagram allows to map emulsion properties such as emulsion type, stability and viscosity. It is used to discuss the combined effect of the formulation and composition upon the emulsion drop size, through their influences on the interfacial tension, and the emulsion viscosity and stability.     

Characterization of Optical Properties in Water-in-Oil Emulsion

There have been few studies on the factors that determine the overall appearance of emulsions. Optical properties are quite important in determining the perceived quality of emulsion-based products. The overall appearance of an emulsion is determined by the way that it interacts with electromagnetic radiation in the visible region of the spectrum, for example, reflection, transmission, adsorption, and scattering. These interactions are principally determined by the characteristics of emulsion droplets (size, concentration, and refractive index). The present study aims at characterizing the optical properties and rheological behaviors of water-in-oil emulsions, especially macroemulsions. There is a decrease in the absorbance spectra as increasing glycerin ratio in aqueous phase because the difference of refractive index between oil phase and aqueous phase decreased, which improved the transparency of water-in-oil emulsion. The absorbance of linear and branched surfactant emulsions were smaller than that of alkyl modified branched surfactant emulsion. Moreover the transparency of emulsions prepared with linear and branched surfactants was much clearer than that of alkyl modified branched surfactant emulsion. The absorbance spectra also showed that low polar oil attributed to the more transparent emulsion, compared with high polar or nonpolar oil. However, these kinds of oils were not helpful to prepare transparent emulsion because the appearance of these emulsions was translucent or opaque, even if polyols in aqueous phase was 30 wt%.     

High internal phase emulsions: catastrophic phase inversion, stability, and triggered destabilization

We have investigated the formation, drop sizes, and stability of emulsions prepared by hand shaking in a closed vessel in which the emulsion is in contact with a single type of surface during its formation. The emulsions undergo catastrophic phase inversion from oil-in-water (o/w) to water-in-oil (w/o) as the oil volume fraction is increased. We find that the oil volume fraction required for catastrophic inversion exhibits a linear correlation with the oil-water-solid surface contact angle. W/o high internal phase emulsions (HIPEs) prepared in this way contain water drops of diameters in the range 10-100 μm; emulsion drop size depends on the surfactant concentration and method of preparation. W/o HIPEs with large water drops show water separation but w/o HIPEs with small water drops are stable with respect to water separation for more than 100 days. The destabilization of the w/o HIPEs can be triggered by either evaporation of the oil continuous phase or by contact the emulsion with a solid surface of the "wrong" wettability.     

Water pH and surfactant addition effects on the stability of an Algerian crude oil emulsion

In many oil production sites water injection is used as a piston to push the crude out of the well. As the age of the field progresses, the ratio of water to oil produced increases. Agitation of a water and crude oil mixture may give stable water-in-oil emulsion in which the water remains dispersed for a long period of time. These emulsions can cause severe problems in production and transport processes since they normally possess high stability and viscosity. The most important water properties which may contribute to the emulsion stability include pH and additive content. In this study, we report on the effect of both, water pH and the presence of surfactant molecules (anionic, cationic or non-ionic) on the stability of an Algerian crude oil (Haoudh el Hamra well) aqueous emulsion prepared by a mechanical agitation procedure. The stability was followed by the test-bottle method to measure the resolved water separated from the emulsion, and optical microscopy to visualize the dispersed water droplets in the oil phase. The results of the effects of varying the aqueous-phase pH suggest that the neutral medium is more efficient than acidic or basic environment for stabilizing the emulsions. The addition of non-ionic surfactants has a better potential to improve crude oil emulsion stability with respect to both cationic and anionic surfactants which do not show any improvement in the oil/water phase compatibility.     

Nanoemulsion formation by phase inversion emulsification: on the nature of inversion

Emulsification processes are usually characterized by the way they allow the surfactants, as well as the dispersed phase, to be incorporated into emulsions. A model cyclohexane-in-water emulsion using a pair of polyoxyethylene nonylphenyl ether surfactants, one oil-soluble and one water-soluble, was considered. Two surfactant mixing approaches consisting of mixed surfactants (agent-in-oil and agent-in-water) and segregated surfactants (agent in corresponding oil and water phases) were used to produce the model emulsion. Formation of oil-in-water nanodroplets could be only achieved if emulsification was associated with the formation of a three-phase microemulsion structure (transitional phase inversion) across the path. This occurred only if segregated surfactants were used in a process in which water was added to oil. With decreasing surfactant concentration, a point was reached below which the inversion mechanism transformed from transitional to catastrophic, leading to the formation of large droplets. The transformation was also accompanied by a shift in the evolution of the drop size. Drop size variations showed a minimum at the inversion point for the transitional phase inversion, whereas they showed a maximum for the catastrophic phase inversion. The agent-in-oil technique followed a catastrophic phase inversion mechanism and ranked second in terms of drop size.     

Emulsification properties of a star-shaped anionic surfactant in oil-based drilling fluid

A novel star-shaped sulfonate surfactant, synthesized with triethanolamine, was identified as a hydrophilic emulsifier which could form a stable water-in-oil emulsion. The interfacial film strength was measured by suspension drop method. The emulsification properties of emulsions were obtained by the emulsification rate experiment and demulsification voltage measurement. The emulsion shows an excellent emulsification effect when the addition of star-shaped anionic surfactant into oil-based drilling fluid was 2.0?wt%. In addition, the properties of surfactant in drilling fluid with different adding amounts were studied by rheological properties, thermal stability analysis and filtration experiments. The results show that star-shaped anionic surfactant used as emulsifier can improve the performance in oil-based drilling fluid, which maybe provides a new idea for this type of surfactant.     

Monodisperse titania microspheres via controlled nanoparticle aggregation

This paper describes the fabrication of highly monodisperse TiO(2) nanoparticle aggregates (NPAs) by controlled aggregation of nanoparticles in a water-in-oil emulsion. Equally sized drops containing a titanium dioxide nanoparticle suspension are produced in a T-channel device. This procedure has a high tuning potential. Increasing the velocity of the titania suspension phase leads to an enlargement of the droplets, while raising the velocity of the oil phase reduces the drop diameter. The technique enables the preparation of monodisperse (<2%) drops between 150 and 400 μm in diameter. Evaporation of the suspension medium leads to nanoparticle aggregates. There is no significant change in dispersity from emulsion drops to NPAs, if the drying is carried out slowly.     

Phase inversion of UV-curable anionic polyurethane in the presence of acetone solvent

UV-curable self-emulsified polyurethane acrylates were synthesized in acetone and then dispersed in water. The effect of acetone’s ratio on the emulsification of the polyurethane acrylate was investigated. With a proper amount of acetone as a solvent, stable emulsion with small particle size and narrow particle size distribution was successfully produced and the viscosity during the process of emulsification was greatly reduced. However, stable emulsion could not be obtained when the acetone level was larger than a critical value. A ternary phase diagram was mapped. It was found that only those systems experiencing a phase inversion process lead to a stable emulsion. The carboxylic content is another important factor influencing the properties of emulsion and the process of emulsification. The effect of the carboxylic content on the emulsification was also studied in the experiment. There was another critical carboxylic content for stability. Stable emulsions with small drop sizes less than 50 nm were produced.     

Generation of Water-In-Oil-In-Water (W/O/W) Double Emulsions by Microfluidics

Novel compartment microparticles prepared with double emulsion droplets as templates provide a protected internal space for material encapsulation. The effect of three-phase flow rate on the micro-droplet generation of double emulsion mechanism is available for reference to produce precise size and highly monodisperse particles. The influence of three-phase flow rate on the formation mode and size of the emulsion droplets is investigated by combination of experiment and numerical simulation. The size of compound droplets decreases and frequency increases with the increasing outer fluid flow rate. The monodispersity of the double emulsion reduces due to transition from dripping to narrowing jetting regime. Outer droplet size increases with the increasing flow rate of the middle fluid, whereas inner droplet size is the opposite. The frequency increases and then stabilizes, which leads to a widening regime. When Q₂/Q₁ > 6, the multi-core type double emulsion droplets are produced. Droplet coalescence occurs when surfactants is not involved. As Q₁ increases, there is an increasing tendency for inner drop size. The outer drop size is proportional to the sum of the inner and middle flow rate, and that is irrelevant to Q₁/Q₂. For drop size, the ratio of core-shell and internal structure is precisely controlled by adjusting three-phase flow rate respectively.     

Sustainable stabilization of oil in water emulsions by cellulose nanocrystals synthesized from deep eutectic solvents

There is an urgent global need to develop novel types of environmentally safe dispersing chemicals from renewable resources in order to reduce the environmental impact of oil spills. For this goal, cellulose, the most abundant natural polymeric source, is a promising green, nontoxic alternative that could replace the current synthetic surfactants. In this study, cellulose nanocrystals (CNC) synthesized using a deep eutectic solvent (DES) and two commercially available cellulose nanocrystals were used as marine diesel oil–water Pickering emulsion stabilizers. In particular, oil in water (o/w) emulsion formation and stability of emulsified oil during storing were addressed using a laser diffraction particle size analyzer, image analysis, and oil emulsion volume examination. The particle size of the o/w reference without CNCs after dispersing was over 50 µm and coalescence occurred only a few minutes after the emulsifying mixing procedure. All three investigated CNCs were effective stabilizers for the o/w system (oil droplets size under 10 µm) by preventing the oil droplet coalescence over time (6 weeks) and resulting in a stable creaming layer. The CNCs prepared using green DES systems boasted performance comparable to that of commercial CNCs, and they showed effectiveness at 0.1% dispersant dosage.     

One-step formation of w/o/w multiple emulsions stabilized by single amphiphilic block copolymers

Multiple emulsions are complex polydispersed systems in which both oil-in-water (O/W) and water-in-oil (W/O) emulsion exists simultaneously. They are often prepared accroding to a two-step process and commonly stabilized using a combination of hydrophilic and hydrophobic surfactants. Recently, some reports have shown that multiple emulsions can also be produced through one-step method with simultaneous occurrence of catastrophic and transitional phase inversions. However, these reported multiple emulsions need surfactant blends and are usually described as transitory or temporary systems. Herein, we report a one-step phase inversion process to produce water-in-oil-in-water (W/O/W) multiple emulsions stabilized solely by a synthetic diblock copolymer. Unlike the use of small molecule surfactant combinations, block copolymer stabilized multiple emulsions are remarkably stable and show the ability to separately encapsulate both polar and nonpolar cargos. The importance of the conformation of the copolymer surfactant at the interfaces with regards to the stability of the multiple emulsions using the one-step method is discussed.     

MINIEMULSION FORMATION BY TRANSITIONAL INVERSION

Very fine emulsions with droplet size in the sub-micron range, often called miniemulsions, are prepared by the moderate (magnetic) stirring of a system undergoing a dynamic transitional inversion driven by a continuous change in physicochemical formulation (here temperature). Near optimum formulation for three-phase systems, the ultralow interfacial tension favors the drop breaking rate, and fine emulsions can be made. However, this region is also known for its rapid coalescence rate. Thus, a high enough stability can be attained only by shifting the formulation away from optimum as soon as the emulsion is made. Moreover, a rapid change in formulation through the three-phase region also results in a separation phenomenon that can be harnessed to produce ultra fine droplets.

The phase behavior of surfactant-oil-water systems and emulsion properties (type, droplet size and stability) are studied as a function of surfactant concentration (2 wt.% and 6 wt.%), for two different nonionic surfactants (polyoxyethylene tri-terbutyl ethers and sorbitan derivatives) with HLB ranging from 4 to 16. Kerosene and paraffin oil are used as oil phases. The transitional inversion form W/O to O/W is induced by a rapid cooling of the stirred systems from above to below the optimum temperature for three-phase behavior.

Miniemulsions are attained when the surfactant concentration is high enough, and when the temperature quenching span covers an appropriate range related to phase behavior.     

Role of surfactants in the behavior of emulsion liquid membranes — development of new surfactants

Surfactants play an important role in the emulsion liquid membrane (henceforth ELM) process. However, only two commercial surfactants have been used so far, Span 80 and polyamine. Relatively little attention has been spent in searching for other suitable surfactants. In order to develop new surfactants for the ELM process, in this study a series of derivatives of glutamic acid dialkyl esters and dialkyl-type quaternary ammonium salts were synthesized. Copper extraction by ELM was carried out in a stirred cell using these surfactants. It was found that glutamic acid dioleyl ester was a more suitable surfactant for the ELM process than Span 80 and polyamine as regards break-up, swelling and demulsification of the W/O emulsion, and enrichment of copper.     

DETERMINATION OF LONG-TERM STABILITY OF VITAMIN E EMULSION AND FORMATION OF MICROEMULSIONS BY USING LASER LIGHT SCATTERING AND UV ABSORPTION MEASUREMENTS

This paper presents methods of determining the long-term stability of vitamin E emulsion and formation of microemulsions. Several emulsion systems formed by using anionic, zwitterionic and cationic surfactants have been studied in the presence and absence of NaCI. Several conclusions can be drawn: (1) by using UV absorption and particle size measurements, one may be able to predict the long-term stability of an emulsion or the possibility of forming a microemulsion by measuring the initial properties of an emulsion, (2) in order to form a stable vitamin E emulsion or microemulsion, the initial properties of the emulsion should have the following features : (a) the particle size is ≤ 200 nm, (b) the surfactant system has a saturation value ≥ 1 and (c) the surfactant system can dissolve a substantial amount of vitamin E without causing an increase of the emulsion droplet size and (3) the saturation value and the stability of many vitamin E emulsion systems can be increased by adding an optimum amount of NaCI.     

Stability studies of high-stable water-in-oil model emulsions

Different compositions and emulsification protocols were used to prepare stable water-in-oil (w/o) emulsions. Water, mineral oil, and a mixture of Span 80 and Tween 80 surfactants were combined to form emulsions that can be used as reference for electrolyte-free systems. Here, we have proposed emulsions wherein different properties were evaluated. Electrical conductivity measurements indicated that conductivity increases linearly with increasing surfactant content. The emulsions’ flow curves and viscoelastic behaviors were delineated by rheological measurements. Stability studies by centrifugal testing have shown that smaller the surfactant content, lower the stability, for any used stirring speeds. Furthermore, higher the applied mixing rate to make the emulsion, higher the stability, regardless of the amount of surfactant. Electrical field stability analysis showed, for all systems, that critical electric field (CEF) values were dependent on either surfactant amount and emulsion elastic modulus.     

Molecular thermodynamic modeling of droplet-type microemulsions

Microemulsions are nanoheterogeneous, thermodynamically stable, spontaneously forming mixtures of oil and water by means of surfactants, with or without cosurfactants. The pledge to use small volumes of amphiphile molecules compared to large amounts of bulk phase modifiers in a variety of chemical and industrial processes, from enhanced oil recovery to biotechnology, fosters continuous investigation and an improved understanding of these systems. In this work, we develop a molecular thermodynamic theory for droplet-type microemulsions, both water-in-oil and oil-in-water, and provide the theoretical formulation for three-component microemulsions. Our thermodynamic model, which is based on a direct minimization of the Gibbs free energy of the total system, predicts the structural and compositional features of microemulsions. The predictions are compared with experimental data for droplet size in water-alkane-didodecyl dimethylammonium bromide systems.     

熔融纺丝-拉伸法制备PVDF中空纤维膜及其油-水分离性能

以聚偏氟乙烯(PVDF)为成膜聚合物, 聚全氟乙丙烯(FEP)为添加剂, 聚乙二醇(PEG)和氯化钙(CaCl₂)为复合成孔剂, 采用熔融纺丝-拉伸法制备了PVDF中空纤维膜. 在制膜过程中未使用其它溶剂和稀释剂, 实现了制膜过程的相对绿色化. 分析和讨论了拉伸比对PVDF中空纤维膜结构与性能的影响, 测试了纤维膜的孔径分布、 力学性能和油-水分离性能等. 结果表明, 进行拉伸后处理的膜的孔径分布较窄, 在油包水乳液分离测试中, 分离效率均在97%以上, 表现出良好的油-水分离效果.     

HYDRODYNAMIC AND THERMODYNAMIC EFFECTS IN PHASE INVERSION EMULSIFICATION PROCESS OF EPOXY RESIN IN WATER

The mechanism of phase inversion emulsification process （PIE） was studied for waterborne dispersion of highly viscous epoxy resin using non-ionic polymeric surfactants. Drop deformation and breakup, rheological properties, conductivity, and particle size measurements reveal the micro-structural transition amid emulsification. It is revealed that strong flow causes water drop to burst with the formation of droplets and huge interface. Phase inversion corresponds to an abrupt rheological transition from a type of viscous melt with weak elasticity to a highly elastic type of aqueous gel. This implies that the phase inversion equivalent to a curvature inversion. Based on this, a geometric model is postulated to correlate process variables to the particle size. The coverage and conformation of the surfactant plays key role for the particle size of the final emulsion. The interactions of thermodynamic and hydrodynamic effects are also discussed. It is concluded that the thermodynamics control the PIE while the hydrodynamics drives the creation of interface and involves every step of PIE.