Investigations into the electrical and coalescence behaviour of water-in-crude oil emulsions in high voltage gradients

The stability of water-in-crude oil emulsions when subjected to high voltage electric fields depends on the nature of the crude oil and the presence of chemical additives. Optical microscopy, conductivity and coalescence measurements have revealed two distinct types of behaviour, designated type I and type II. These are shown to be related to the crude oil/water interfacial rheological properties. For incompressible crude oil/water films, droplet—droplet coalescence is hindered and chains of water droplets are established. These increase the electrical conductivity of the emulsion (type I behaviour). On the other hand, efficient droplet—droplet coalescence accompanied by minimal conduction occurs in electric fields if the interfacial film is compressible (type II).     

Stability of various silicone oil/water emulsion films as a function of surfactant and salt concentration

There have been reports, originally by the Bristol group, and subsequently by others, of the preparation and properties of emulsions of stable, nearly monodisperse droplets of poly(dimethylsiloxane) (PDMS) in water, where no added surfactant is used. It has been assumed that their stability is due to the high density of surface-ionized hydroxyl groups, similar in fact to the closely related St?ber silica particles. In this study we confirm, from droplet lifetime studies, that droplets, prepared from such synthesized PDMS, are significantly more stable to coalescence than similar-sized droplets prepared from three types of commercially available PDMS, containing HO-, MeO-, or Me3-terminated chains, respectively. It is shown, however, that the zeta potentials of the synthesized PDMS and of the various commercial oils are all very similar (as indeed are their Hamaker constants). So some other explanation must be inferred for the enhanced stability to coalescence of the synthesized PDMS droplets compared to the commercial PDMS droplets. It is shown, for droplets formed from n-hexane and the synthesized oil, that stability to coalescence is conferred at PDMS volume fractions (phiPDMS) around 0.2 in the mixture. The synthesized PDMS is known to consist of mixtures of cyclic PDMS and short-chain linear species, with terminal -OH groups. There is some (indirect) evidence that in the interval 0.25 < phiPDMS < 0.35, the linear PDMS chains may be adsorbed close to a monolayer at the mixed oil/water interface, possibly conferring some enhanced Gibbs elasticity to the interface. This underpins the possibility that, in the synthesized oil droplets themselves, there is also preferential adsorption of the linear chains at the PDMS/water interface, and this leads to a value of the Gibbs elasticity, sufficient to significantly reduce coalescence. Unfortunately, the Gibbs elasticity could not be measured in this case. However, such preferential adsorption is unlikely to occur with the commercial PDMS oils, which are not so heterogeneous. Finally, it is shown that droplets of the three commercial PDMS oils could be stabilized against coalescence, if a sufficient, minimum amount of sodium dodecyl sulfate (SDS) is added. Gibbs elasticity values have been estimated in these cases, from plots of interfacial tension against ln(SDS concentration).     

Influence of pH on the stability of oil-in-water emulsions stabilized by a splittable surfactant

A laboratory study was conducted to evaluate the effect of pH on the stability of oil-in-water emulsions stabilized by a commercial splittable surfactant Triton SP-190 by comparison with the results obtained by a common surfactant Triton X-100. The emulsion stability was explored by measuring the volume of oil phase separated and the size of the dispersed droplets. It was found that the addition of inorganic acids did not significantly affect the stability of emulsions stabilized by Triton X-100, but had a profound influence on the stability of emulsions stabilized by Triton SP-190. Moreover, the droplet size of a Triton X-100-stabilized emulsion and its dynamic interfacial activity were insensitive to acids. However, at lower pH the droplet size of the emulsions stabilized by Triton SP-190 was considerably increased. From the dynamic interfacial tension measurements the dynamic interfacial activity of Triton SP-190 at the oil/water interface was found to be strongly inhibited by the addition of acids, resulting in a slower decreasing rate of dynamic interfacial tension. The results demonstrate that the dramatic destabilization of Triton SP-190-stabilized emulsions could be realized by the use of acids, which evidently changed the interfacial properties of the surfactant and resulted in a higher coalescence rate of oil droplets.     

Novel Oil‐in‐Water Emulsions Stabilised by Ionic Surfactant and Similarly Charged Nanoparticles at Very Low Concentrations

Novel oil‐in‐water (O/W) emulsions are prepared which are stabilised by a cationic surfactant in combination with similarly charged alumina nanoparticles at concentrations as low as 10^?5 m and 10^?4 wt %, respectively. The surfactant molecules adsorb at the oil‐water interface to reduce the interfacial tension and endow droplets with charge ensuring electrical repulsion between them, whereas the charged particles are dispersed in the aqueous films between droplets retaining thick lamellae, reducing water drainage and hindering flocculation and coalescence of droplets. This stabilization mechanism is universal as it occurs with different oils (alkanes, aromatic hydrocarbons and triglycerides) and in mixtures of anionic surfactant and negatively charged nanoparticles. Further, such emulsions can be switched between stable and unstable by addition of an equimolar amount of oppositely charged surfactant which forms ion pairs with the original surfactant destroying the repulsion between droplets.     

Influence of oil polarity on droplet growth in oil-in-water emulsions stabilized by a weakly adsorbing biopolymer or a nonionic surfactant

The influence of oil type (n-hexadecane, 1-decanol, n-decane), droplet composition (hexadecane:decanol), and emulsifier type (Tween 20, gum arabic) on droplet growth in oil-in-water emulsions was studied. Droplet size distributions of emulsions were measured over time (0-120 h) by laser diffraction and ultrasonic spectroscopy. Emulsions containing oil molecules of low polarity and low water solubility (hexadecane) were stable to droplet growth, irrespective of the emulsifier used to stabilize the droplets. Emulsions containing oil molecules of low polarity and relatively high water solubility (decane) were stable to coalescence, but unstable to Ostwald ripening, irrespective of emulsifier. Droplet growth in emulsions containing oil molecules of relatively high polarity and high water solubility (decanol) depended on emulsifier type. Decanol droplets stabilized by Tween 20 were stable to droplet growth in concentrated emulsions but unstable when the emulsions were diluted. Decanol droplets stabilized by gum arabic exhibited rapid and extensive droplet growth, probably due to a combination of Ostwald ripening and coalescence. We proposed that coalescence was caused by the relatively low interfacial tension at the decanol-water boundary, which meant that the gum arabic did not absorb strongly to the droplet surfaces and therefore did not prevent the droplets from coming into close proximity.     

Forces between two oil drops in aqueous solution measured by AFM

The surface and hydrodynamic forces between individual oil droplets in solution can provide insight into both emulsion stability and processes such as drop coalescence in liquid-liquid extraction. We present the first measurements of the interaction forces between alkane droplets in aqueous solution using atomic force microscopy. The radii of the droplets were well below the capillary lengths for the system, thus gravity effects are negligible, and interfacial tension and interaction forces governed the system behavior. The effects of modulating electrostatic double-layer interactions and interfacial tension through the presence of an anionic surfactant are demonstrated. Challenges in interpretation of the force data due to drop deformation are also discussed. A range of drop approach and retract speeds was used to determine the regime where hydrodynamic drainage effects had significant impact on the measurement.     

Stability of Water/Crude Oil Systems Correlated to the Physicochemical Properties of the Oil Phase

A characterization of 30 crude oils has been performed to determine the relative level of influence that individual parameters have over the overall stability of w/o emulsions. The crude oils have been analyzed with respect to bulk and interfacial properties and the characteristics of their w/o emulsions. The parameters include compositional properties, acidity, spectroscopic signatures in the infrared and near‐infrared region, density, viscosity, molecular weight, interfacial tension, dilational relaxation, droplet size distribution, and stability to gravitationally and electrically induced separation. As expected, a strong covariance between several physicochemical properties was found. Near‐infrared spectroscopy proved to be an effective tool for crude oil analysis. In particular, we have showed the importance of the hydrodynamic resistance to electrically‐induced separation (static) in heavy crude oil‐water emulsions. A rough estimate of the drag forces and dielectrophoretic forces seemed to capture the difference between the 30 crude oils. Given enough time, water‐in‐heavy oil emulsions could be destabilized even at very low electric field magnitude (d.c.). When droplets approach each other in an inhomogeneous electric field, strong dielectrophoretic forces disintegrate the films and result in coalescence. The relative contribution from film stability to the overall emulsion stability may therefore be very different in a gravitational field compared to that in an electrical field.     

The dispersion of natural oils in de-gassed water

Recent studies have demonstrated that pure hydrocarbon oils can be dispersed in water as fine droplets without the use of additives. The high interfacial tension between hydrocarbons and water is expected to cause cavitation between oil droplets during separation. This cavitation is aided by dissolved atmospheric gases present in both the oil and water. Their removal allows oil droplets to be readily dispersed in water. In this paper we report on the effect of the de-gassing process on the dispersion of several natural, water immiscible oils. These natural, mixed oils are eucalyptus, lavender and tea tree oil. Although these oils are mixtures and in some cases not as hydrophobic as those used in the earlier studies, the effect of de-gassing substantially enhances their dispersion, producing micron-sized droplets without the need for additives. Dispersions of these natural oils in pure water have a wide range of uses where purity is an advantage, for example, in skin cleaning products and oral sprays.     

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.     

Study of Winsor I to Winsor II transitions in a lattice model

Experiments show that with increasing temperature, microemulsion systems undergo Winsor transitions. The transitions occur from Winsor I (oil droplets in water media) to Winsor II (water droplets in oil media) via Winsor III (bicontinuous phase) with an increase in the temperature. In this paper, it has been shown, for the first time, how one can study the qualitative effects of temperature, head, tail, and oil chain lengths, on these transitions. Simple cubic lattice with excluded volume and periodic boundary conditions is used to mimic the box of the simulation as a bulk of solution. The simulations have been done using the standard traditional Metropolis algorithm in the canonical ensemble (N, V, T). Configurational bias Monte Carlo and reptation moves are used with an equal probability to relax the systems. A very simple interaction model, i.e., the repulsions of water (or heads of surfactants) with oil (or tails of surfactants), is used due to the main characteristic of oil-water mixtures or amphiphilic molecule that is the hydrophobicity. The interfacial tension between oil and water (gammaow) is related to the averaged total energy of the lattice. The model shows that the Winsor III has a minimum interfacial tension (gammaow) similar to experimental results. Changing the phase structure from Winsor III to Winsor I (or Winsor II), increases the interfacial tension which is in agreement with experiments. To relate interfacial tension with the interaction parameter, the simple theory of Bragg-Williams has been used. All of the results such as the effects of oil chain length, head and tail beads number are all similar to the experimental results. Using the Davies method for calculating hydrophilic-lypophilic Balance (HLB), similar to the experimental results, Winsor III phase is formed at HLB value nearly to 10.     

Numerical simulation of droplet coalescence behavior in gas phase under the coupling of electric field and flow field

The coalescence behavior of droplets in an electric field belongs to the important research contents of electrohydrodynamics. Based on the phase field method of the Cahn–Hilliard equation, the electric field and the flow field are coupled to establish the numerical model of twin droplet coalescence in a coupled field. The effects of flow rate, electric field strength, droplet diameter, and interfacial tension on the coalescence behavior of droplets during the coalescence process were investigated. The results show that the dynamic behavior of the droplets is divided into coalescence, after coalescence rupture, and no coalescence under the coupling of electric field and flow field. The proper increase of the electric field strength will accelerate the coalescence of the droplets, and the high electric field strength causes the droplets to burst after coalescence. Excessive flow rates make droplets less prone to coalescence. Under the coupling field, the larger the droplet interface tension, the smaller the droplet diameter, the smaller the flow rate, and the shorter the droplet coalescence time. The results provide a theoretical basis for the application of electrostatic coalescence in gas–liquid separation technology.     

Detergency in spontaneously formed emulsions

We report a microemulsion system with commercial nonionic surfactants, which produces kinetically stable o/w emulsions with sub-micron sized oil droplets, when added to water/brine. These emulsions have shown to be promising for fabric detergency. It is hypothesized that superior detergency could be due to (i) a low value of oil-emulsion interfacial tension (0.01-7 mN/m) even at a low (1 g/l) surfactant concentration, thus effecting rapid emulsification and solubilisation of oily matrix/film present in dirt and (ii) extremely tiny emulsion oil droplets (50-100 nm), which can have easy access to dirt entrapped in the inter-yarn voids. The aim of this work was to investigate the above factors in a model system (cellulose-coated glass slides with attached oil droplets) with a view to detergency. Further, an attempt was made to study changes in contact angles of oil droplets attached to cellulose-coated glass slides immersed in the emulsion system as a function of brine concentration. Correlations were drawn between equilibrium contact angle, interfacial tension and detergency at different brine concentrations through arguments of work of adhesion and showed an excellent match with detergency trends on commercial fabric test monitors. These correlations also provide insights into possible underlying mechanisms that account for detergency at each level of brine concentrations. An important consequence of the work is that superior detergency is achieved when the oil, present in the microemulsion, is physico-chemically similar to those oils which are to be removed from contaminated surfaces.     

受限空间内油水界面动态特性及粘附行为的荧光原位观测

水污染作为润滑油污染的常见形式,对润滑油本身以及机械系统都有巨大的危害。为了模拟实际非均匀多相系统中的界面行为,本文搭建了高精度点接触实验台来研究传统的不溶相替换问题。将目前静态平行受限空间内油水界面行为的研究推广到动态点接触楔形受限空间内,探究了游离水滴穿过点接触狭缝间毛细油池过程中的界面特性。重点关注固壁润湿性以及固壁的分离运动对整个侵入过程中液滴动态行为的影响。实验发现了铺展系数是决定油水界面融合和分离特性的关键因素,揭示了固壁润湿性和球盘间的相对分离运动会影响游离水滴穿过毛细油池之后的粘附行为。表面张力和液体与壁面之间的粘附功能够解释观测的实验现象。     

Physical properties of diglycerol esters in relation to rheology and stability of protein-stabilised emulsions

The surface activity and lyotropic phase behaviour of concentrated diglycerol-esters of fatty acids with chain length of C14, C16, C18 and C18:1 (cis-oleic acid) are investigated. Diglycerol-esters show a much stronger reduction in the interfacial tension at a low concentration (0.01–0.1%) than corresponding monoglycerides. The diglycerol-esters form lamellar mesophases above their Krafft point, and no other types of mesophases are found in the temperature region examined (0–80°C). The lamellar phases show a limited swelling capacity, corresponding to a water layer thickness of ≈24 Å, which is found when the ratio of diglycerol-ester to water is 60:40, or lower. At high water concentrations (>90%) multi-lamellar liposomes are formed. The diglycerol-monooleate form lamellar phases in water in the temperature region from zero to 80°C. This is in strong contrast to the corresponding glycerol-monooleate, which forms cubic and reversed hexagonal mesophases in water. Oil in water emulsions are stabilised by diglycerol-esters by formation of liquid crystalline interfacial films around the oil droplets, which can be seen in polarised light microscopy. In presence of milk proteins in the aqueous phase the emulsion stability is depending on the protein to emulsifier ratio. At 40°C a mixed interfacial film of diglycerol-monooleate (DIGMO) and protein is present at the oil–water interface, but when cooled to 5°C, the proteins are displaced by DIGMO. This behaviour affects the stability and rheological properties of emulsions stored at low temperatures.     

Kinetics of flow‐induced coalescence and form relaxation in polymer blends as studied by rheo small angle light scattering

The kinetics of flow‐induced coalescence in PS/PMMA (polystyrene/polymethylmethacrylate) blends containing 1 wt% and 5 wt% PMMA was measured by rheo small angle light scattering under conditions of non‐deformed droplets. The results are in agreement with a coalescence model which includes binary hydrodynamic interactions. Under conditions where droplet deformation occurs, coalescence is suppressed and the interfacial tension was determined from the form relaxation time on the basis of the Palierne model.     

Modeling oil droplets in plateau borders

It is widely known that oil droplets can decrease the stability of aqueous films and foams. While less widely recognized, it has also been observed that oil droplets can, under certain circumstances, increase the stability of foams, especially if they are caught in the Plateau borders. In this paper, how the oil droplet deforms and is, in turn, deformed by the Plateau border is modeled using Surface Evolver. The two dimensionless parameters that affect these shapes are the size of the oil droplet relative to the Plateau border and the ratio of the oil-water interfacial tension to the air-water interfacial tension. The calculated pressures in all the phases were used to obtain the pressure exerted on the oil-water-air pseudoemulsion film, which allows the factors that influence the stability of these droplets in the Plateau border to be investigated. The final section of the paper demonstrates that the presence of an oil droplet in a Plateau border can have a major influence on the drainage of the aqueous phase along the Plateau border. This retardation of the flow would result in the oil droplets in the Plateau borders increasing the stability of foams in which they are found.     

Dynamic stability of liquid—liquid dispersions containing polymeric suspension stabilizers

In this paper we present an experimental study on the dynamic stability of suspended oil droplets such as those found in suspension polymerization processes. The system used in the present study was a mixture of ethylbenzene and 1,2-dichloroethane as a substitute for vinyl chloride monomer. The suspending agents included hydroxylpropyl methylcellulose and polyvinyl alcohol and their blends. We have measured the interfacial tension and the dynamic interfacial properties, such as shear viscosity and shear modulus or ridigity at the oil-water interfaces containing suspending agents in order to examine their effects on the droplet dynamic stability. It is concluded that the dynamic interfacial properties, and not the equilibrium interfacial tension, are the controlling parameters in droplet dynamic stability.     

Triton X-100/甲苯/水三元体系界面张力的耗散颗粒动力学模拟

采用耗散颗粒动力学方法在介观层次上模拟了非离子表面活性剂Triton X-100 在油/水界面上的分布行为, 并把用于油/水二元体系界面张力的计算方法拓展到含表面活性剂的三元体系. 利用该方法可以得到与实验数值吻合的界面张力数据. 另外, 模拟结果直观展示了表面活性剂界面张力与界面密度的关系, 为表面活性剂复配增效理论提供了依据. 该模拟方法给出的微观信息可以为驱油体系配方筛选和表面活性剂有效应用提供指导.     

The influence of partial emulsification on coalescence suppression and interfacial tension reduction in PP/PET blends

This study examines how the relative role of coalescence suppression and interfacial tension reduction influence the particle size at various levels of in situ compatibilization. The polymers studied are polyethylene terephthalate (PET) as matrix and a polypropylene (PP) as dispersed phase compatibilized by a triblock copolymer of poly(styrene–hydrogenated butadiene–styrene) (SEBS) grafted with maleic anhydride. The interfacial tension was studied by the breaking‐thread method, and it was used along with the morphology to characterize the emulsification efficacy of the copolymers. By modifying the concentration of MA grafted on the SEBS, different levels of emulsification of the blends were obtained. A comparison of 1/99 and 10/90 PP/PET blends compatibilized by SEBS‐g‐MA allows one to distinguish the relative role of interfacial tension and coalescence suppression in diminishing particle size. It is shown that varying degrees of residual coalescence remain, depending on the level of %MA in the copolymer. A detailed study of the 2%MA system below interfacial saturation was carried out to shed further light on the dependence of coalescence suppression on emulsification level and interfacial coverage. After separating out the contribution of interfacial tension on particle size reduction, it is shown that coalescence suppression for this system increases gradually with areal density of modifier at the interface right up to the region of interfacial saturation. Finally, the interfacial and morphological data were used to test the ability of the Lee and Park model to describe coalescence in polymer blends. Reasonable agreement was found between the parameter c₁, describing the coalescence in that model, and the trends related to residual coalescence from this study. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 939–951, 1999