离心系数表征丙烯酰胺反相乳液的稳定性

用丙烯酰胺反相乳液经离心处理后保留的乳液体积与原乳液体积之比（离心系数Vr）考察了丙烯酰胺及其衍生物反相乳液的稳定性。 结果表明,离心系数Vr越大,其乳液的稳定性越好。 在高速离心条件下,由Span80/Span85和Tween80构成的丙烯酰胺及其衍生物反相乳液的Vr与油相质量分数存在正相关的关系。 在油相质量分数确定的情况下,离心系数Vr不仅与3种表面活性剂构成的亲水亲油平衡值（HLB）有关,而且与丙烯酰胺及其衍生物的浓度和类型有关。 HLB值在4.20左右时,乳液是稳定的;随丙烯酸氧乙基三甲基氯化铵（DAC）在水相中质量分数的提高,反相乳液稳定性增强,w(DAC)＞24%时可得到稳定乳液。 在15000 r/min离心3 min,Vr=0.95以上的丙烯酰胺及其衍生物反相乳液很稳定,静置半年仍未出现分层现象。     

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.     

A Three-Step Model for Submicron W/O Emulsion Formation in a Transitional-Phase Inversion Process

A three-step model of the transitional phase inversion (TPI) process for the formation of water-in-oil (W/O) emulsions is presented. Three types of emulsions exist in an emulsification process at different oil–water ratios and hydrophilic–lipophilic balance (HLB). A stable W/O emulsion was obtained using Sorbitan oleate (Span 80) and polyoxyethylenesorbitan monooleate (Tween 80) with a specified HLB and oil volume fraction. Oil was added into water, which contained the water-soluble surfactant, to dissolve the oil-soluble surfactant. This route allowed TPI to occur, and an interesting emulsification process was observed by varying the HLB, which corresponded to the change in the oil–water ratio. Two types of emulsions in the emulsification process were found: transition emulsion 1 (W/O/W high internal phase emulsion) and target emulsion 2 (W/O emulsion with low viscosity). This study describes the changes that occurred in the emulsification process.     

Acrylamide as cosurfactant and hydrotrope in the pseudoternary Span 80-Tween 85/isopar M/water emulsion/microemulsion forming system

The aim of this study was to investigate the effects of acrylamide on emulsification of the pseudoternary Span 80-Tween 85/isopar M/water system at 40 °C. It was revealed that acrylamide could act as a surface-active agent to decrease the isopar M/water interfacial tension, and as a hydrotrope to increase the aqueous solubility of Tween 85, and further remarkably influence the emulsification of the investigated pseudoternary Span 80-Tween 85/isopar M/water system. The surface-active role of acrylamide could reduce the minimal weight fraction of the mixture of Span 80 and Tween 85 in pseudoternary systems (X_ST) to form stable water-in-oil (W/O) emulsions when the weight fraction of acrylamide in the aqueous domain (X_AM) is below 0.1; while its hydrotropic role at high X_AM levels (>0.1) could drive more Tween 85 molecules to transfer into aqueous phase and slightly improved the minimal X_ST to form stable W/O emulsions, as compared to that of X_AM at 0.1. Moreover, under a given X_ST, the mean diameter of the droplet size distribution of the W/O emulsion remarkably decreased with the increase in X_AM; while the smaller droplets in the W/O emulsion systems at higher level of X_AM still coalesced rapidly when the compositions of the emulsion was slightly above the visually determined boundary between non-emulsion and stable emulsion regions.     

Silica particle-stabilized emulsions of silicone oil and water: aspects of emulsification

A study of the emulsification of silicone oil and water in the presence of partially hydrophobic, monodisperse silica nanoparticles is described. Emulsification involves the fragmentation of bulk liquids and the resulting large drops and the coalescence of some of those drops. The influence of particle concentration, oil/water ratio, and emulsification time on the relative extents of fragmentation and coalescence during the formation of emulsions, prepared using either batch or continuous methods, has been investigated. For batch emulsions, the average drop diameter decreases with increasing particle concentration as the extent of limited coalescence is reduced. Increasing the oil volume fraction in the emulsion at fixed aqueous particle concentration results in an increase in the average drop diameter together with a dramatic lowering of the uniformity of the drop size distribution as coalescence becomes increasingly significant until catastrophic phase inversion occurs. For low oil volume fractions (phi(o)), fragmentation dominates during emulsification since the mean drop size decreases with emulsification time. For higher phi(o) close to conditions of phase inversion, coalescence becomes more prevalent and the drop size increases with time with stable multiple emulsions forming as a result.     

FORMATION OF O/W EMULSIONS BY SURFACTANT PHASE EMULSIFICATION AND THE SOLUTION BEHAVIOR OF NONIONIC SURFACTANT SYSTEM IN THE EMULSIFICATION PROCESS

Surfactant-Phase Emulsification is a very useful method to produce oil-in-water emulsions having fine and uniform droplets. The mechanism of this emulsification method and the effect of hydrophile-lipophile balance (HLB) of the surfactants on the process of this emuisification were investigated by using phase diagrams of nonionic surfactant/hexadecane/water/1,3-butanediol four component systems.

It was shown that the process of this emulsification begins with the formation of isotropic surfactant solution, followed by formation of oil-in-surfactant clear gel emulsion, and finally by formation of oil-in-water emulsion. By using this emulsification technique, fine oil-in-water emulsions were formed without a need for adjusting of HLB.     

Oil Base Mud. Part I: Synthesis of Some Local Surfactants Used as Primary Emulsifiers for Oil Base Mud and Evaluation of Their Rheology Properties

Six oil soluble nonionic surfactants with different HLBs have been prepared. Their HLBs situate between 3.9 and 6.7. Transesterification was carried out for glycerol and triethanol amine with oleic acid at different moles to obtain six emusilifiers. They named glycerol momooleate (I), glycerol diooleate (II), glycerol trioleate (III), triethanol amine mono-, di- and tri-oleate (IV), (V,) and (VI). The chemical structure was confirmed using; the elemental analysis, FTIR and ¹HNMR. They were evaluated as a primary emulsifiers (PE) for thdrilling fluids (oil base mud) comparing with a currently used primary emulsifier (Fc). The water in oil base mud (w/o emulsions) was prepared. The concentration of emulsifiers and their HLB exhibited interesting rheology properties including shear-thinning behavior, yield value, viscoelastic effects, thixtropy, gel strength, and filtration loss. The rheology properties of such emulsions strongly depended on the average size distribution of the dispersed droplets that could be varied both with the bulk concentration and HLB value of the emulsifiers. The interfacial and surface properties of these emulsifiers suggest that the droplet size of the dispersed phase and bulk concentration are strongly related to the HLB value of emulsifiers. The w/o emulsion (mud formulation) stability is sensitive to the droplet size of the dispersed phase and HLB value of the used emulsifier. The results were discussed on the light the chemical structure of the primary emulsifiers and the emulsion ingredients.     

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.     

Effect of Aqueous Phase Composition on the Properties of a Silica-Stabilized W/O Emulsion

A high volume fraction silica stabilized w/o emulsion with small droplet size ( approximately 3 μm) has been prepared using a commercially available hydrophobic silica. Addition of hydroxypropyl cellulose to the dispersed aqueous phase was found to improve the monodispersity of the emulsion by suppressing the production of larger droplets. The droplet size distribution showed complex behavior as the silica concentration was varied, which was explained using a simple kinetic argument. The effect of varying the acidity and ionic strength of the internal water phase was investigated. It was found that the presence of strong acid or strong alkali in the internal aqueous phase increased the gelation of the emulsions by promoting flocculation. This could be explained by acid- and alkali-catalyzed cleavage of surface siloxane groups increasing the number of surface silanol groups. If emulsions of strong acid and strong alkali were mixed, substantial additional gelation (again caused by flocculation) occurred. A possible explanation, preferred by the author, was an electrostatic one involving the interaction of dipoles in close proximity in the flocculated emulsion. Copyright 1999 Academic Press.     

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.     

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.     

Emulsion liquid membranes: Role of internal droplet size distribution on toluene/n-heptane separation

Using oil/water/oil-type emulsion liquid membranes, batch wise extraction experiments are carried out to separate toluene from a mixture of toluene and n-heptane. In the separation process using emulsion liquid membranes, the internal phase polydispersity affects mass transport of a solute because under steady operating conditions, internal droplet size and size distribution are proportional to the interfacial area. The present study aims to assess the polydispersity character of the internal droplets of emulsion globules. In this paper, the important variables affecting dispersed drop sizes as well as internal droplets mean diameter and size distribution of the emulsion globule, including impeller speed during emulsification, surfactant concentration, volume ratio of surfactant solution, carrier concentration and composition of feed phase are systematically investigated.     

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.     

Extraction of Cr (VI) by pickering emulsion liquid membrane using amphiphilic silica nanowires (ASNWs) as a surfactant

Pickering emulsion is the replacement of surfactants with solid, often nano-sized particles. The particle-stabilized emulsions have good thermodynamic and kinetic stability. Pickering emulsion liquid membrane (PELM) was prepared using mahua oil as a diluent, aliquat 336 (Trioctyl methylammonium chloride) as a carrier and amphiphilic silica nanowires (ASNWs) (10–40?ml ethanol addition) as a surfactant. Sodium hydroxide (NaOH) was used as stripping phase in the concentration range from 0.1 to 0.5?M for the extraction of hexavalent chromium [Cr (VI)] from aqueous solution. The variety of edible and non-edible oils was investigated for the stability of water in oil emulsion. Factors that influence silica-stabilized Pickering emulsions are pH, agitation speed, stripping phase concentration, the volume ratio of membrane to stripping phase (M/S), initial feed concentration, treat ratio(feed to emulsion volume ratio) and surfactant concentration for better PELM stability. And also, the extraction efficiency of Cr (VI) was investigated using aliquat as a carrier. The physicochemical properties of ASNWs were studied using Scanning Electron Microscopy (SEM), Fourier Transforms Infrared Spectroscopy (FTIR) and Dynamic Light Scattering (DLS) techniques. At an optimum condition, 99.69% of Cr (VI) removal from aqueous solution was obtained.     

Thickening properties and emulsification mechanisms of new derivatives of polysaccharides in aqueous solution

The thickening properties of aqueous solutions of HHM-HEC (hydrophobically-hydrophilically modified hydroxyethylcellulose) and the emulsification mechanisms of HHM-HEC/water/oil systems were investigated. A dramatic increase in viscosity was observed with increased HHM-HEC concentration in water, caused by aggregation of hydrophobic alkyl chains. At higher concentrations of HHM-HEC (above 0.6 wt%) in water, it forms an elastic gel, which has good thixotropic properties and a high yield value. O/W (oil-in-water) type emulsions were obtained using HHM-HEC, which can emulsify various kinds of oil, including hydrocarbon, silicone, and perfluoropolymethylisopropyl ether. The viscosity of these emulsions depends only upon the oil volume fraction, not on the kind of oil. In addition, the oil particle size in the emulsions remained constant after a certain period because HHM-HEC formed a strong gel network structure and a protective layer, which prevented the emulsion from coalescing. Measurements of interfacial tension revealed that the alkyl chains in HHM-HEC did not significantly lower the interfacial tension at the water/oil interface when 0.5 wt% of HHM-HEC was added to water. Steady flow and oscillatory experimental results show that the rheological behavior of HHM-HEC/water/oil emulsions was similar to that of aqueous solutions of HHM-HEC. In the HHM-HEC/water/oil emulsion system, oil droplets were dispersed and kept stable in the strong gel structure of HHM-HEC. The aqueous solution of HHM-HEC showed salt resistance. It is thought to be due to sulfonic acid groups in HHM-HEC. The stability of the emulsion using HHM-HEC is based on both protective colloidal effects and associative thickening caused by alkyl chains in HHM-HEC.     

Effect of silica particles on stability of highly concentrated water-in-oil emulsions with non-ionic surfactant

Water-in-oil, high internal phase emulsion made of super-cooled aqueous solution containing a mixture of inorganic salts and stabilized with non-ionic surfactant (sorbitan monooleate) alone was investigated. It was not possible to produce a highly concentrated emulsion (with aqueous phase fraction = 94 wt %), stabilized with surface-treated silica, solely: we were able to form an emulsion with a maximal aqueous phase mass fraction of 85 wt % (emulsion inverts/breaks above this concentration). The inversion point is dependent on the silica particle concentration, presence of salt in the aqueous phase, and does not depend on the pH of the dispersed phase. All emulsions stabilized by the nanoparticles solely were unstable to shear. So, the rheological properties and stability of the emulsions containing super-cooled dispersed phase, with regards to crystallization, were determined for an emulsion stabilized by non-ionic surfactant only. The results were compared to the properties obtained for emulsions stabilized by surface treated (relatively hydrophobic) silica nanoparticles as a co-surfactant to sorbitan monooleate. The influence of the particle concentration, type of silica surface treatment, particle/surfactant ratio on emulsification and emulsion rheological properties was studied. The presence of the particles as a co-stabilizer increases the stability of all emulsions. Also, it was found that the particle/surfactant ratio is important since the most stable emulsions are those where particles dominate over the surfactant, when the surfactant’s role is to create bridging flocculation of the particles. The combination of the two types of hydrophobic silica particles as co-surfactants is: one that resides at the water/oil interface and provides a steric boundary and another that remains in the oil phase creating a 3D-network throughout the oil phase, which is even more beneficiary in terms of the emulsion stability.     

Stabilization of Water‐Soluble Antioxidant in Water‐in‐Oil‐in‐Water Double Emulsions

Abstract

In this study, we are introducing a method that can effectively stabilize antioxidants in water‐in‐oil‐in‐water (W/O/W) double emulsions. Preliminarily, stable W/O/W double emulsions were produced by manipulating the characteristics of internal aqueous phase via two‐stage emulsification, resulting consequently in the formation of fine internal water droplets in the dispersed oil droplets. From conductivity measurements that can determine the elution amount of internal aqueous phase, it was confirmed that the double emulsion stability could be improved by treating the internal aqueous phase with a hydroxypropyl‐beta‐cyclodextrin. In this study, kojic acid, 5‐hydroxy‐2‐(hydroxymethyl)‐4‐pyrone was selected as a model antioxidant. The stabilization of kojic acid was attempted by locating it in the internal water droplets of the stable W/O/W double emulsions. The stability of kojic acid in the double emulsion system could be maintained at 90% for 10 weeks at high temperature. We believe that these stable W/O/W double emulsions could be used meaningfully as a carrier for many unstable antioxidants.     

Rapid Evaluation of Water-in-Oil (w/o) Emulsion Stability by Turbidity Ratio Measurements

In this Note, we investigated the turbidity ratio method for the evaluation of water-in-oil emulsion stability. The slope of turbidity ratio of water-in-oil emulsions with time was taken as an index of stability; the higher the slope, the less stable the system. Various factors affecting the stability of emulsion such as HLB of emulsifier, amount of emulsifiers, and water were tested using this technique. The results of the turbidity ratio technique for the evaluation of emulsion stability were well consistent with those obtained by the measurement of phase separation when incubated for 30 days at room temperature. Copyright 2000 Academic Press.     

Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization

Poly(styrene-co-methacrylic acid) (PS-co-MAA) particles were synthesized via surfactant-free emulsion polymerization and then used as particulate emulsifiers for preparation of Pickering emulsions. Our results showed that adjusting the solution pH can tune the wettability of PS-co-MAA particles to stabilize either water-in-oil (W/O) or oil-in-water (O/W) Pickering emulsions. Stable W/O emulsions were obtained with PS-co-MAA particles at low pH values due to their better affinity to the dispersed oil phase. In contrast, increasing the pH value significantly changed the stabilizing behavior of the PS-co-MAA particles, leading to the phase inversion and formation of stable O/W emulsions. We found that the oil/water ratio had a significant influence on pH value of the phase inversion. It decreased with decreasing the oil/water ratio, and no phase inversion occurred when the styrene volume fraction reduced to 10 %. Additionally, macroporous polystyrene (PS) foam and PS microspheres were obtained via polymerization of Pickering high internal phase emulsion (Pickering HIPE) and O/W Pickering emulsion, respectively.     

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%.