原油乳状液稳定性和破乳研究进展

本文从控制乳状液稳定性的一些因素－界面膜、界面张力、双电层、空间位阻、固体粒子、液晶、油相溶解度、连续相粘度等方面综述了有关乳状液稳定性的一些研究进展。对国内外有关原油乳状液的破乳研究也做了综述。同时，介绍了应用于乳状液稳定性研究的新的实验技术和仪器。     

Study of the State of Water and Oil in Frozen Emulsions Using Time Domain NMR

Here T(1) and T(2)(*) relaxation time measurements by low-field NMR have been used to quantify the state of oil and water in frozen emulsions. Water-in-oil and oil-in-water emulsions have been studied. A discrete method (NLREG program) and a continuous method (CONTIN program) have been used to analyze the FID and inversion-recovery relaxation curves. The FID signal (T(2)(*)) analysis allowed us to calculate the global solid-intermediate-liquid ratio, and the state of the solid and liquid phases was determined by the T(1) values. Thus we have been able to show that the major part of water ( approximately 99%) is in a solid state in such emulsions (average droplet diameter of about 1.5 &mgr;m). This result was confirmed by the study of a solid paraffin-Span 80-water emulsion and a heavy water-caseinate-triolein emulsion. These first results have shown the interest of this new method for the study of the state of water and oil in frozen emulsions. Copyright 2000 Academic Press.     

Comparison of Pickering and network stabilization in water-in-oil emulsions

We compared the efficacy of Pickering crystals, a continuous phase crystal network, and a combination thereof against sedimentation and dispersed phase coalescence in water-in-oil (W/O) emulsions. Using 20 wt % water-in-canola oil emulsions as our model, glycerol monostearate (GMS) permitted Pickering-type stabilization, whereas simultaneous usage of hydrogenated canola oil (HCO) and glycerol monooleate (GMO) primarily led to network-stabilized emulsions. A minimum of 4 wt % GMS or 10 wt % HCO was required for long-term sedimentation stability. Although there were no significant differences between the two in mean droplet size with time, the free water content of the network-stabilized emulsions was higher than Pickering-stabilized emulsions, suggesting higher instability. Microscopy revealed the presence of crystal shells around the dispersed phase in the GMS-stabilized emulsions, whereas in the HCO-stabilized emulsion, spherulitic growth in the continuous phase and on the droplet surface occurred. The displacement energy (E(disp)) to detach crystals from the oil-water interface was ～10(4) kT, and was highest for GMS crystals. Thermal cycling to induce dispersed phase coalescence of the emulsions resulted in desorption of both GMS and GMO from the interface, which we ascribed to solute-solvent hydrogen bonding between the emulsifier molecules and the solvent oil, based on IR spectra. Overall, Pickering crystals were more effective than network crystals for emulsion stabilization. However, the thermal stability of all emulsions was hampered by the diffusion of the molten emulsifiers from the interface.     

Impact of oil composition on formation and stability of emulsions produced by spontaneous emulsification

In this study, triglycerides of different chain lengths were mixed with paraffin oil, and their effectiveness in forming emulsions produced by spontaneous emulsification upon the addition of water was investigated. The emulsion droplet size exhibited a similar trend as a function of the triglyceride/paraffin oil composition for medium-chain (MCTs) (C8–C10) and long-chain (C18) triglycerides (LCTs). However, emulsions formulated with MCTs and LCTs have a much smaller droplet size (about 50?nm) than emulsions based upon short-chain (C4) triglycerides (SCTs). The addition of SCTs resulted in droplet sizes around 800?nm and the emulsions formed were very unstable. The droplet size, polydispersity index, zeta potential, and emulsion stability of these systems will be described as a function of the oil phase composition.     

Simple, reversible emulsion system switched by pH on the basis of chitosan without any hydrophobic modification

Chitosan without hydrophobic modification is not a good emulsifier itself. However, it has a pH-tunable sol-gel transition due to free amino groups along its backbone. In the present work, a simple reversible Pickering emulsion system based on the pH-tunable sol-gel transition of chitosan was developed. At pH > 6.0, as adjusted by NaOH, chitosan was insoluble in water. Chitosan nanoparticles or micrometer-sized floccular precipitates were formed in situ. These chitosan aggregates could adsorb at the interface of oil and water to stabilize the o/w emulsions, so-called Pickering emulsions. At pH < 6.0, as adjusted by HCl, chitosan was soluble in water. Demulsification happened. Four organic solvents (liquid paraffin, n-hexane, toluene, and dichloromethane) were chosen as the oil phase. Reversible emulsions were formed for all four oils. Chitosan-based Pickering emulsions could undergo five cycles of emulsification-demulsification with only a slight increase in the emulsion droplet size. They also had good long-term stability for more than 2 months. Herein, we give an example of chitosan without any hydrophobic modification to act as an effective emulsifier for various oil-water systems. From the results, we have determined that natural polymers with a stimulus-responsive sol-gel transition should be a good particulate emulsifier. The method for in situ formation of pH-responsive Pickering emulsions based on chitosan will open up a new route to the preparation of a wide range of reversible emulsions.     

Ostwald ripening of oil-in-water emulsions stabilized by phenoxy-substituted dextrans

The stability of oil-in-water emulsions prepared using dextran, a natural polysaccharide, hydrophobically substituted with phenoxy groups, was studied. The evolution of the emulsion droplet size was investigated as a function of polymer concentration (Cp=0.2 to 1% w/w in a water phase) and the degree of phenoxy substitution (tau=4.2 to 15.7%). For the highest tau values, emulsions, which presented submicrometer droplets, were stable over more than 4 months at room temperature. The most substituted polymers clearly showed a better efficiency to lower the surface tension at the oil/water interface. DexP did not induce real viscosification of the continuous phase. The linearity of the particle volume variation with time, and the invariability of the volume distribution function, proved that Ostwald ripening was the main destabilization mechanism of the phenoxy dextran emulsions. The nature of the oil dispersed phase drastically affected the behavior of emulsions. While the emulsions prepared with n-dodecane presented a particle growth with time, only few size variations occurred when n-hexadecane was used. Furthermore, small ratios of n-hexadecane in n-dodecane phase reduced the particle growth due to the lower solubility and lower diffusion coefficient in water of n-hexadecane, which acted as a ripening inhibitor.     

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.     

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.     

Demulsification of water-in-oil emulsions via filtration through a hydrophilic polymer membrane

It is known that hydrophobic microfiltration membranes can be used for demulsification of oil-in-water (o/w) emulsion due to coalescence of oil droplets in membrane pores. This study demonstrates that a hydrophilic polymer membrane can be used for the demulsification of surfactant-stabilized water-in-oil (w/o) emulsions. The success of demulsification is dependent on the type of emulsions and membrane used. Membrane pore size and transmembrane pressure were found to affect demulsification efficiency (DM), while other factors, such as membrane thickness and initial water content have slight or almost no effect. A coalescence mechanism of the demulsification phenomenon is also discussed. The separation process is not based on sieving effects due to a difference in membrane pore size, but is determined by droplet interactions with membrane surface.     

Emulsifying potency of new amino acid-type surfactant (II): stable water-in-oil (W/O) emulsions containing 85 wt% inner water phase

The ternary phase diagram for N-[3-lauryloxy-2-hydroxypropyl]-L-arginine L-glutamate (C12HEA-Glu), a new amino acid-type surfactant, /oleic acid (OA)/water system was established. The liquid crystal and gel complex formations between C12HEA-Glu and OA were applied to a preparation of water-in-oil (W/O) emulsions. Stable W/O emulsions containing liquid paraffin (LP) as the oil and a mixture of C12HEA-Glu and OA as the emulsifier were formed. The preparation of stable W/O emulsions containing 85 wt% water phase was also possible, in which water droplets would be polygonally transformed and closely packed, since the maximum percentage of inner phase is 74% assuming uniformly spherical droplets. Water droplets would be taken into the liquid crystalline phase (or the gel complex) and the immovable water droplets would stabilize the W/O emulsion system. The viscosity of emulsions abruptly increased above the 75 wt% water phase (dispersed phase). The stability of W/O emulsions with a lower weight ratio of OA to C12HEA-Glu and a higher ratio of water phase was greater. This unusual phenomenon may be related to the formation of a liquid crystalline phase between C12HEA-Glu and OA, and the stability of the liquid crystal at a lower ratio of oil (continuous phase). W/O and oil-in-water (O/W) emulsions containing LP were selectively prepared using a mixture of C12HEA-Glu and OA since the desirable hydrophile-lipophile balance (HLB) number for the emulsification was obtainable by mixing the two emulsifiers.     

An NMR study of the freezing of emulsion-containing drops

Various nuclear magnetic resonance (NMR) techniques were used to monitor the freezing behaviour of suspended 2-mm-diameter drops. The drops were composed of hydrocarbon oils emulsified in either water or water/sucrose mixtures. As such they were good model systems for the study of spray freezing, sharing structural similarities with potential products such as ice cream. In particular, simple 1H NMR spectroscopy was used to monitor and individually quantify the freezing or solidification behaviour of the various constituent species of the drops. In addition, the effect of freezing on the emulsion droplet size distribution (and hence emulsion stability) was also measured based on NMR self-diffusion measurements. The effect of freeze/thaw cycling was also similarly studied. The nucleation temperature of the emulsion droplets was found to depend on the emulsion droplet size distribution: the smaller the droplets, the lower the nucleation temperature. Emulsion droplet sizing indicated that oil-in-sucrose-solution emulsions were more stable, showing minimal coalescence, whereas oil-in-water emulsions showed significant coalescence during freezing and freeze/thaw cycling.     

Particle self-assembly in oil-in-ionic liquid Pickering emulsions

We have studied polydimethylsiloxane (PDMS)-in-1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) Pickering emulsions stabilized by polystyrene microparticles with different surface chemistry. Surprisingly, in contrast to the consensus originating from oil/water Pickering emulsions in which the solid particles equilibrate at the oil-water droplet interfaces and provide effective stabilization, here the polystyrene microparticles treated with sulfate, aldehyde sulfate, or carboxylate dissociable groups mostly formed monolayer bridges among the oil droplets rather than residing at the oil-ionic liquid interfaces. The bridge formation inhibited individual droplet-droplet coalescence; however, due to low density and large volume (thus the buoyant effect), the aggregated oil droplets actually promoted oil/ionic liquid phase separation and distressed emulsion stability. Systems with binary heterogeneous polystyrene microparticles exhibited similar, even enhanced (in terms of surface chemistry dependence), bridging phenomenon in the PDMS-in-[BMIM][PF(6)] Pickering emulsions.     

Demulsification of water-in-oil emulsions by permeation through Shirasu-porous-glass (SPG) membranes

To investigate the effect of the droplet/pore size ratio on membrane demulsification, water-in-oil (W/O) emulsions with uniform-sized droplets was demulsified by permeation through Shirasu-porous-glass (SPG) membranes with a narrow pore size distribution at mean droplet/pore diameter ratios of 0.52–5.75. At transmembrane pressures above a critical pressure, the water droplets larger than the membrane pore size were demulsified, where the SPG membrane acted as a coalescer because the hydrophilic membrane surface had a high affinity for the water droplets. By contrast, at transmembrane pressures below the critical pressure, the larger water droplets were all retained by the membrane due to the sieving effect of the uniform-sized pores. When a W/O emulsion with a mean droplet diameter of 2.30 μm was allowed to permeate through a membrane with a mean pore diameter of 0.86 μm, the demulsification efficiency increased with increasing transmembrane pressure, to a maximum value of 91% at a transmembrane pressure of 392 kPa, and then decreased, while the transmembrane flux increased almost linearly with increasing transmembrane pressure. The demulsification efficiency was higher for higher water phase content and lower concentration of the surfactant, tetraglycerin condensed ricinoleic acid ester, in the emulsions due to the reduction of the emulsion stability.     

Interface composition of multiple emulsions: rheology as a probe

We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W1/O/W2) consist of water droplets (W1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W1 in oil globules) and the inverse emulsion (oil globules in W2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.     

Further Investigation into the Stability of Water-in-Crude Oil Emulsions Formed in Burgan Oilfield: Effect of Toluene,Resins to Asphaltenes Ratio,and Surfactant

Factors controlling the formation and stabilization of water-in-crude oil (w/o) emulsions in oil fields are of great concern to the petroleum industry for the economic development of underground oil reservoirs. Controlling and minimizing the formation of w/o emulsions and demulsification of water from emulsions are also important for environmental development. Because of its importance, the mechanisms, formation, and stability of w/o emulsions have received considerable attention. This article deals with some of the factors responsible for the formation and stabilization of w/o emulsions formed in Burgan oil field in Kuwait. Some of the factors investigated in this study are the naturally occurred surface active components of crude oils such as asphaltenes and resins. Stability of emulsion samples with resins to asphaltenes ratio (R/A) contents of 3, 5, 9, 12, and 20 has been studied. It was found that Emulsion tightness is correlated with resins to asphaltene content of the sample. As the R/content increases the emulsion becomes unstable. The effect of additives such as toluene and dodecyle benzene sulfonic acid (DBSA) on the stability of various emulsion samples collected from oil field are also reported. A 2 wt% of DBSA was found to resolve all the water from emulsion samples collected from Burgan oilfield.     

Effect of Emulsifier Type on the Characterization of O/W Emulsions Using a Spectroscopy Technique

The droplet size distribution (DSD) of emulsions is the result of two competitive effects that take place during emulsification process, i.e., drop breakup and drop coalescence, and it is influenced by the formulation and composition variables, i.e., nature and amount of emulsifier, mixing characteristics, and emulsion preparation, all of which affect the emulsion stability. The aim of this study is to characterize oil-in-water (O/W) emulsions (droplet size and stability) in terms of surfactant concentration and surfactant composition (sodium dodecyl benzene sulphonate (SDBS)/Tween 80 mixture). Ultraviolet-visible (UV-vis) transmission spectroscopy has been applied to obtain droplet size and stability of the emulsions and the verification of emulsion stability with the relative cleared volume technique (time required for a certain amount of emulsion to separate as a cleared phase). It is demonstrated that the DSD of the emulsions is a function of the oil concentration and the surfactant composition with higher stability for emulsions prepared with higher SDBS ratio and lower relative cleared volume with the time. Results also show that smaller oil droplets are generated with increasing Tween 80 ratio and emulsifier concentration.     

Fat crystals and water-in-oil emulsion stability

Products such as cosmetics, pharmaceuticals, and crude oil often exist as water-in-oil (W/O) emulsions during their processing or in final form. In many cases, their dispersed aqueous phase is encased in a crystal network and/or by interfacially-adsorbed (‘Pickering’) particles [paraffins, triacylglycerols, polymers, etc.] that promote emulsion kinetic stability by hindering droplet–droplet contact, coalescence and macroscopic phase separation. In processed foods, important questions remain regarding whether a continuous phase fat crystal network or Pickering crystal provides better stabilization. This review explores the following factors related to crystal-stabilized W/O emulsions: i) the key properties dictating fat crystal spatial distribution (at the interface or in the continuous phase); ii) how temperature and freeze–thaw emulsion destabilization are intimately linked with fat crystal spatial distribution, and; iii) why oil-soluble surfactant interactions with the continuous oil phase influence fat crystal wettability and emulsifier efficacy. It is shown that these parameters strongly govern W/O emulsion formation and stability.     

Silicone-protein surfactants; stability of water-in-silicone oil emulsions

Small scale water-in-silicone oil emulsions were readily prepared using high speed mixers. Two surfactant systems were studied: a comb-type silicone-polyether surfactant, and a surfactant system employing a mixture of the surface active protein human serum albumin (HSA, in the internal phase) and an alkoxysilane-modified silicone TES-PDMS in the silicone oil (continuous phase). Little difference in particle sizes was noted between the two surfactant types for a given mixing protocol, but dual-blade turbulent mixing led to relatively monodisperse particles of approximately 2–5 m in diameter while high speed Dremel mixers led to bimodal particle distributions. Prior to spontaneous demulsification of the latter emulsions stabilized by HSA/TES-PDMS (the 3225C emulsions remain stable), they proved very difficult to break. The addition of dibutyltin dilaurate to the HSA/TES-PDMS-stabilized emulsions led to catastrophic collapse of the emulsion and formation of a silicone elastomer at the bulk water/oil interface. This makes unlikely the possibility that silicone elastomers, formed by protein-catalyzed crosslinking of the alkoxysilane in albumin/TES-PDMS-stabilized emulsions, are involved in stabilizing the emulsion. The nature of the stabilization of the interface is discussed.     

Hydroxyapatite nanoparticles as stimulus-responsive particulate emulsifiers and building block for porous materials

Hydroxyapatite (HAp) nanoparticles with spherical, rod-shaped or fiber-shaped morphologies were synthesized by wet chemical method in aqueous media. Scanning electron microscopy, dynamic light scattering, helium pycnometry, and aqueous electrophoresis techniques were used to characterize the nanoparticles in terms of their particle size and morphology, density and zeta potential, respectively. Stable "Pickering-type" emulsions were prepared using the HAp nanoparticles as a particulate emulsifier and methyl myristate as an oil phase above pH 7.7, but not below pH 6.1. These emulsions were characterized in terms of their emulsion type, mean droplet diameter and morphology using electrical conductivity, light diffraction and optical microscopy. Rapid demulsification could be induced by lowering the solution pH: addition of acid led to dissolution of the HAp nanoparticles attached on oil-water interface and the emulsion was destabilized. HAp nanoparticles precipitated by addition of base to the aqueous phase after demulsification and the HAp particles precipitated worked as an effective particulate emulsifier. This emulsification-demulsification cycle was reversible. Sintering of methyl myristate-in-water emulsion stabilized with the HAp nanoparticles led to a porous HAp material.     

Role of liquid crystal in the emulsification of a gel emulsion with high internal phase fraction

A gel emulsion with high internal oil phase volume fraction was formed via an inversion process induced by a water–oil ratio change. The process involved the formation of intermediate multiple emulsions prior to inversion. The multiple emulsions contain a liquid crystal formed by the surfactant with water; this was both predicted by the equilibrium phase diagram as well as observed using polarization microscopy. These multiple emulsions were more stable compared to alternative multiple emulsions prepared in the same way with a surfactant that does not form liquid crystals. While the formation of a stable intermediate multiple emulsion may not be a necessary condition for the inversion to occur, the transitional presence of a liquid crystal proved to be a significant factor in the stabilization of the intermediate multiple emulsions. The resulting gel emulsion contained a small fraction of the liquid crystal according to the phase diagram, and it exhibited excellent stability.