Formulating middle-phase microemulsions using mixed anionic and cationic surfactant systems

Although mixtures of anionic and cationic surfactants can show great synergism, their potential to precipitate and form liquid crystals has limited their use. Previous studies have shown that alcohol addition can prevent liquid crystal formation, thereby allowing formation of middle-phase microemulsions with mixed anionic-cationic systems. This research investigates the role of surfactant selection in designing alcohol-free anionic-cationic microemulsions. Microemulsion phase behavior was studied for three anionic-cationic surfactant systems and three oils of widely varying hydrophobicity [trichloroethylene (TCE), hexane, and n-hexadecane]. Consistent with our hypothesis, using a branched surfactant and surfactants with varying tail length allowed us to form alcohol-free middle-phase microemulsion using mixed anionic-cationic systems (i.e., liquid crystals did not form). The anionic to cationic molar ratio required to form middle-phase microemulsions approached 1∶1 for univalent surfactants as oil hydrophobicity increased (i.e., TCE to hexane to n-hexadecane); even for these equimolar systems, liquid crystal formation was avoided. To test the use of these anionic-cationic surfactant mixtures in surfactant-enhanced subsurface remediation, we performed soil column studies: Greater than 95% of the oil was extracted in 2.5 pore volumes using an anionic-rich surfactant system. By contrast, cationic-rich systems performed very poorly (<1% oil removal), reflecting significant losses of the cationic-rich surfactant system in the porous media. The results thus suggest that, when properly designed, anionic-rich mixtures of anionic and cationic surfactants can be efficient for environmental remediation. By corollary, other industrial applications and consumer products should also find these mixtures advantageous.     

Microemulsion phase behavior of anionic-cationic surfactant mixtures: Effect of tail branching

This research evaluated middle-phase microemulsion formation by varying the mole ratio of anionic and cationic surfactants in mixtures with four different oils (trichloroethylene, n-hexane, limonene, and n-hexadecane). Mixtures of a double-tailed anionic surfactant (sodium dihexyl sulfosuccinate, SDHS) and an unbalanced-tail (i.e., doubletailed with tails of different length) cationic surfactant (benzethonium chloride, BCl) were able to form microemulsions without alcohol addition. The amount of NaCl required to form the middle-phase microemulsion decreased dramatically as an equimolar anionic-cationic surfactant mixture was approached. Although the mixture of anionic and cationic surfactants demonstrated a higher critical microemulsion concentration (cμc) compared to the anionic surfactant alone, the Winsor Type IV single-phase microemulsion started at lower surfactant concentrations for the anionic-cationic mixture than for the anionic surfactant alone. Under optimum middlephase microemulsion conditions, mixed anionic-cationic surfactant systems solubilized more oil than the anionic surfactant alone. Pretreatment detergency studies were conducted to test the capacity of these mixed surfactant systems to remove oil form fabrics. It was found that anionic-rich mixed surfactant formulations yielded the largest oil removal, followed by cationic-rich systems.     

Microemulsion formation and detergency with oily soils: I. Phase behavior and interfacial tension

The ultimate objective of the project was to investigate the relationship between microemulsion phase behavior and detergency for oily soils. In this study, surfactant phase behavior was evaluated for hexadecane and motor oil as model oily soils. Producing microemulsions with these oils is particularly challenging because of their large hydrophobic character. To produce the desired phase behavior we included three surfactants with a wide range of hydrophilic/lipophilic character: alkyl diphenyl oxide disulfonate (highly hydrophilic), dioctyl sodium sulfosuccinate (intermediate character), and sorbitan monooleate (highly hydrophobic). This mixed surfactant was able to bridge the hydrophilic/lipophilic gap between the water and the oil phases, producing microemulsions with substantial solubilization and ultralow interfacial tension. The effects of surfactant composition, temperature, and salinity on system performance were investigated. The transition of microemulsion phases could be observed for both systems with hexadecane and motor oil. In addition, the use of surfactant mixtures containing both anionic and nonionic surfactants leads to systems that are robust with respect to temperature compared to single-surfactant systems. Under conditions corresponding to “supersolubilization”, the solubilization parameters and oil/microemulsion interfacial tensions are not substantially worse than at optimal condition for a middle-phase system, so a middle-phase microemulsion is not necessary to attain quite low interfacial tensions. A potential drawback of the formulations developed here is the fairly high salinity (e.g., 5 wt% NaCl) needed to attain optimal middle-phase systems. The correlation between interfacial tension and solubilization follows the trend predicted by the Chun-Huh equation.     

Adsorption, Desorption and Adsolubilization Properties of Mixed Anionic Extended Surfactants and a Cationic Surfactant

Anionic and cationic surfactant mixtures exhibit desirable synergism, but are limited by their tendency to form precipitates. This research evaluates the adsorption, adsolubilization and desorption of mixtures of carboxylate-based anionic extended surfactants and a pyridinium-based cationic surfactant. The mixture of cetylpyridinium chloride (CPC), selected as the cationic surfactant, with four anionic extended surfactants were studied. The anionic surfactants studied were alkyl propoxylated ethoxylated carboxylate with average number of carbon chain length of 16 and 17 or 16 and 18 with 4?mol of propylene oxide groups and either 2 or 5?mol of ethylene oxide groups. The adsorption of anionic extended and cationic surfactant mixtures onto a negatively charged metal oxide surface (silica dioxide) was evaluated. The adsolubilization of phenylethanol, styrene and ethylcyclohexane were evaluated for these mixed surfactant systems. The desorption potential of individual and mixed surfactant systems was also evaluated by varying the number of washing (desorption) steps. It was found that the plateau adsorption of mixed anionic extended surfactant and cationic surfactant occurred at lower surfactant concentration than that of the CPC alone, although the maximum adsorption capacity of CPC was not enhanced in our mixed surfactant systems. Adsolubilization capacities of these mixed surfactant systems are higher than that of the individual surfactant system. For desorption studies, these mixed surfactant systems showed lower stability than the individual surfactant system.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Solubilization and adsolubilization of styrene and ethylcyclohexane

Mixtures of anionic and cationic surfactants with single and twin head groups were used to solubilized styrene and ethylcyclohexane into mixed micelles and adsolubilize them into mixed admicelles on silica and alumina surfaces. Two combinations of anionic and cationic surfactants were studied: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), with a single-head cationic surfactant, dodecylpyridinium chloride (DPCl). Mixtures of SDS/PODD showed solubilization synergism (increased oil solubilization capacity) when mixed at a molar ratio of 1∶3; however, the SHD-PDS/DPCl mixture at a ratio of 3∶1 did not show solubilization enhancement over SHDPDS alone. Adsolubilization studies of SDS/PODD (enriched in PODD) adsorbed on negatively charged silica and SHDPDS/DPCl adsorbed on positively charged alumina showed that while mixtures of anionic and cationic surfactants had little effect on the adsolubilization of styrene, the adsolubilization of ethylcyclohexane was greater in mixed SHPDS/DPCl systems than for SHDPDS alone. Finally, it was concluded that whereas mixing anionic and cationic surfactants with single and double head groups can improve the solubilization capacity of micelles or admicelles, the magnitude of the solubilization enhancement depends on the molecular structure of the surfactant and the ratio of anionic surfactant to cationic surfactant in the micelle or admicelle.     

New Interfacial Rheology Characteristics Measured Using a Spinning Drop Rheometer at the Optimum Formulation. Part 2. Surfactant–Oil–Water Systems with a High Volume of Middle-Phase Microemulsion

This article is a continuation of our first study on dilational interfacial rheology properties at optimum formulation for surfactant-oil–water systems at low surfactant concentration just above the cμc. Here, we have investigated a high content of middle-phase microemulsion with an optimum WIII phase behavior for a system containing sodium dodecyl sulfate, n-pentanol, and kerosene. A new oscillating spinning drop interfacial rheometer was used to measure the interfacial properties. The very low dilational elasticity moduli and phase angle found at or near hydrophilic–lipophilic deviation (HLD) = 0 are related to the presence of the bicontinuous phase microemulsion and to the fast surfactant exchanges between the bulk and the interface, regardless of the phases involved in the measurement using the spinning drop apparatus, i.e., the two-phase excess oil and excess water (O-W) or the bicontinuous microemulsion and excess water (M-W). We show that at or near optimum formulation, the interfacial tension and the dilational modulus for the M-W case almost instantly reach equilibrium, because of the high surfactant content in the microemulsion and the fast exchanges between the bulk and the interface. In contrast, when both excess phases (O-W) are measured, the changes in these properties are slower, due to the scarce presence of surfactants in both phases. The possibility of having almost all the surfactants trapped in the middle-phase bicontinuous microemulsion could explain the emulsion instability in all the WIII range. This is behaving as if there were no surfactant available in the oil and water phases to stabilize the oil or water droplets thus formed.     

Synergism and Performance for Systems Containing Binary Mixtures of Anionic/Cationic Surfactants for Enhanced Oil Recovery

The surfactant structure–performance relationship and application properties in enhanced oil recovery (EOR) for binary mixtures of anionic and cationic surfactants are presented and discussed. A polyoxyethylene ether carboxylate anionic surfactant was blended with a quaternary ammonium chloride cationic surfactant and tested for a high-temperature, low-salinity, and high-hardness condition as found in an oil reservoir. These mixtures were tailored by phase behavior tests to form optimal microemulsions with normal octane (n-C8) and crude oil having an API gravity of 48.05°. The ethoxy number of the polyoxyethylene carboxylate anionic surfactant and the chain length of the cationic surfactant were tuned to find an optimal surfactant blend. Interfacial tensions with n-C8 and with crude oil were measured. Synergism between anionic and cationic surfactants was indicated by surface tension measurement, CMC determination, calculation of surface excess concentrations and area per molecule of individual surfactants and their mixtures. Molecular interactions of anionic and cationic surfactants in mixed monolayers and aggregates were calculated by using regular solution theory to find molecular interaction parameters β ^σ and β ^M . Morphologies of surfactant solutions were studied by cryogenic TEM. The use of binary mixtures of anionic/cationic surfactants significantly broadens the scope of application for conventional chemical EOR methods.     

不同因素对CTAB/TX-100微乳液相图的影响

用ε-β"鱼状"相图法研究了阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)与非离子表面活性剂辛基苯酚聚氧乙烯(10)醚(TX-100)以不同摩尔比复配形成的CTAB/TX-100/醇/油/NaCl水溶液微乳液体系的相行为和增溶性能.结果表明,随着醇浓度的增加,体系由水包油型(O/W)(winsor Ⅰ or (2-)...     

Cleaning properties of single-phase hydrocarbon-based microemulsion systems

Single-phase hydrocarbon-based microemulsions with low volatile organic carbon levels can help deliver solvent-like cleaning properties while allowing formulators to meet regulatory requirements. The rheology and petroleum jelly solubilization properties of model microemulsion systems that contained equal volumes of hydrocarbon solvent and water were evaluated as a function of microemulsion structure and composition. Single-phase microemulsions with low surfactant contents and broad formulation flexibility were obtained through the use of efficient anionic surfactants and low electrolyte levels. The microemulsion structure was advanced from solvent-continuous to water-continuous by varying the solvent alkane carbon number or the electrolyte content, whereas the liquid crystal content was controlled via cosurfactant concentration. Both microemulsion structure and viscosity influenced solubilization rates. Low-viscosity, solvent-continuous microemulsions showed solubilization rates comparable to those found with solvent-based systems, while water-continuous microemulsions showed relatively poor solubilization rates. Microemulsions containing dispersed liquid crystals exhibited high viscosity and low solubilization rates.     

Selective nitration of phenol to ortho-nitrophenol using dilute nitric acid by microemulsion of cetytrimethylammonium bromide (CTAB) in isooctane

The paper reports near-selective nitration of phenol to ortho-nitrophenol using CTAB microemulsion solution in the presence of dilute nitric acid. The difference betweem the selective nitration of different kinds of surfactants such as AOT (anionic surfactant) and CTAB (cationic surfactant) has been investigated. All these experimental results indicate that microemulsions can be selective to give the ortho-phenol.     

Effect of Alkyl Sulfate on the Phase Behavior of Microemulsions Stabilized with Monoacylglycerols

In this study the effect of an anionic surfactant (sodium dodecyl sulfate SDS) and oils (hydrocarbons: C12–C16) on the formation and phase behavior of the systems of oil/monoacylglycerols (MAG):SDS/propylene glycol/water has been investigated. The effects of the surfactant mixture on the phase behavior and the concentration of water or oil in the systems were studied at three temperatures (50, 55, 60 °C). Electrical conductivity measurement, FT-IR spectroscopy and differential scanning calorimetry methods were applied to determine the structure and type of the microemulsions formed. The dimension of microemulsion droplets was characterized by dynamic light scattering. It has been stated that the concentration of SDS has a strong influence on the shape and extent of the microemulsion areas. Addition of an ionic surfactant to the mixture with MAG promotes an increase in the area of microemulsion formation in the phase diagrams, and these areas of the isotropic region change with the temperature. It was shown that the presence in the systems of a surfactant more hydrophilic than MAG caused an increase in water content in the microemulsions. It was found that, depending on temperature and concentration of the surfactant mixture, it was possible to obtain a W/O type microemulsion with a dispersed particles size distribution ranging from 20 to 50 nm and containing about 17–38% water in the system. Among different alkanes (from C12 to C16), hexadecane embedded microemulsions showed a maximum water solubilization capacity.     

Effect of Branched Alcohols on Phase Behavior and Physicochemical Properties of Winsor IV Microemulsions

The microemulsion phase behavior and physicochemical properties of surfactant–water–alcohol–oil systems are the pioneer laboratory study as a function of alcohol, water content and temperature to develop an experimental investigation for a better understanding of the microstructure of a single phase microemulsion and its stability under reservoir condition during hydraulic fracturing to recover the residual trapped oil. Viscosified surfactants are used as an efficient proppant conducting medium in hydraulic fracturing applications. The physicochemical properties of microemulsions are very helpful for characterization of microemulsions to justify their abilities and screening of surfactants. In the study, two branched alcohols, 2-methyl butan-2-ol, 3-methyl butan-1-ol selected as the cosurfactant in the proposed microemulsion system and their effect in tailoring the viscosity of microemulsions were studied. Microemulsion regions elucidated from Winsor’s pseudophase model of an oleate surfactant show a signatory distribution pattern of components between different domains with non-polar and asymmetric geometry of cosurfactant directs macromolecular alignments; their alignment contributes to a viscous microemulsions (gel) regime. The effect of surfactant and alkali, and the experimental temperature on the rheological properties of the lamellar mesophase were investigated. Phase transit regions and exact microemulsion and viscous microemulsion magnitudes were elucidated with the help of conductivity and viscosity studies of the ternary system as a function of the aqueous fraction and were in good agreement with Winsor’s pseudophase model. Dynamic and steady shear rheological studies showed that the gel is viscoelastic in nature, sustain viscosity and elastic modulus values appropriate for proppant suspension under high shear conditions. The proppant suspension and thermal behavior of ideal gel composition was found to be suitable for Coal Bed Methane and soft rock, clay reservoir stimulation.     

Synthesis of porous hydrogel structures by polymerizing the continuous phase of a microemulsion

A series of microemulsions have been formulated, with 2-hydroxyethyl methacrylate (HEMA) or HEMA/water/propanol mixtures as the continuous phase and methylcyclohexane as the discontinuous phase. The effect of surfactant type was investigated with the utilization of both anionic and nonionic surfactants. The microemulsion continuous phase was polymerized by UV radiation and a thermal post-cure. The resultant polymers were extracted to remove the discontinuous phase and the surfactant. On swelling, the majority of the polymers became opaque, although transparent PHEMA hydrogels were synthesized with an improved equilibrium water content (EWC). The cause of opacity was shown by field emission scanning electron microscopy (FESEM). The breakdown in the microemulsion on polymerization is caused by unfavourable interactions between the PHEMA and the stabilizing surfactants causing agglomerization of the discontinuous phase. All the hydrogels were found to have higher water retention than PHEMA, with EWCs of up to 70%. The modified polymers also demonstrated an increased rate of water diffusion into the matrix. A preliminary study of oxygen permability revealed that a significant improvement had been made over standard PHEMA membranes. The porous structure of the PHEMA gels has been shown to be dependent on the type of surfactant used during synthesis.     

Microemulsion formation and detergency with oily soils: II. Detergency formulation and performance

In part I of this series (J. Surfact. Deterg. 6, 191–203, 2003), the mixed surfactant system of sodium dioctyl sulfosuccinate (AOT), alkyl diphenyl oxide disulfonate (ADPODS) and sorbitan monooleate (Span 80) was shown to form Winsor type I and type III microemulsions with hexadecane and motor oil. In addition, high solubilization and low interfacial tension were obtained between the oils and surfactant solutions both in the supersolubilization region (Winsor type I system close to type III system) and at optimal conditions in a type III system. In the present study, this mixed surfactant system was applied to remove oily soil from fabric (a polyester/cotton blend), and detergency results were correlated to phase behavior. Dynamic interfacial tensions were also measured between the oils and washing solutions. In the supersolubilization and in the middle-phase regions (type III), much better detergency performance was found for both hexadecane and motor oil removal than that with a commercial liquid detergent product. In addition, the detergency performance of our system at low temperature (25°C) was close to that obtained at high temperature (55°C), consistent with the temperature robustness of the microemulsion phase behavior of this system.     

Precipitation and Micellar Properties of Novel Mixed Anionic Extended Surfactants and a Cationic Surfactant

Surfactant-modified mineral surfaces can provide both a hydrophobic coating for adsorbing organic contaminants and, in the case of ionic surfactants, a charged exterior for adsorbing oppositely charged species. This research evaluates the precipitation phase boundaries and synergistic behavior of the mixtures of carboxylate-based anionic extended surfactants with a pyridinium-based cationic surfactant. One cationic surfactant (cetylpyridinium chloride) and four anionic extended surfactants were studied. The anionic surfactants studied were ethoxy carboxylate extended surfactants with average carbon chain lengths of either 16 and 17 or 16 and 18 with 4 mol of a propylene oxide group and a different number of moles of an ethylene oxide group (2 and 5 mol). Precipitation phase boundaries of mixed anionic extended surfactants and cationic surfactant were evaluated to ensure that the surface tension studies are in regions without precipitate. Surface tension measurements were conducted to evaluate the critical micelle concentration of individual and mixed surfactant systems. Precipitation phase boundaries of these novel mixed surfactant systems showed greatly reduced precipitation areas as compared to a conventional mixed surfactant system which is attributed to the presence of the ethylene oxide and propylene oxide groups and resulting steric hindrances to precipitation. Moreover, it was demonstrated that the CMC of mixed surfactant systems were much lower than that of individual surfactant systems. Synergism was evaluated in the four systems studied by the β parameter which found that all systems studied exhibited synergism. From these results, these novel mixed surfactant systems can greatly increase formulation space (reduce the precipitation region) while maintaining synergism, although slightly reduced from conventional anionic-cationic mixtures reported previously.     

Phase stability,fuel properties,and diesel engine performance of palm-oil-based microemulsion biofuels

Microemulsification and blending are two viscosity-modifying techniques of vegetable oils for direct use with diesel engine. In this study, alcohol blends are mixtures of ethanol, diesel, and palm-oil biodiesel while microemulsion biofuels are thermodynamically stable, clear, and single-phase mixtures of diesel, palm oil, and ethanol stabilized by surfactants and cosurfactants. Although there are many studies on biofuels lately, there is limited research on using biodiesel as a surfactant in microemulsion formulations and applied on engine performance at different engine loads. Therefore, the objectives are to investigate phase stability and fuel properties of formulated biofuels (various blends and microemulsions), to determine the engine performance at different engine loads (no load, and from 0.5 to 2.0 kW), and to estimate laboratory-scale cost of the selected biofuels compared to diesel and biodiesel. The results showed that phase stability and fuel properties of selected microemulsion biofuels are comparable to diesel and biodiesel. These microemulsion biofuels can be applied to the diesel engine at different loads while diesel-ethanol blends and palm-oil-biodiesel-ethanol blends cannot be. It was found that the energy efficiencies of the system using microemulsion biofuels were slightly lower than the average energy efficiency of diesel engine. From this study, it can be summarized that microemulsion biofuels can be formulated using palm-oil biodiesel (palm-oil methyl ester) as a bio-based surfactant and they can be considered as environmentally-friendly alternatives to diesel and biodiesel. However, cost considerations showed that the raw materials should be locally available to reduce additional costs of microemulsion biofuels.     

Increasing the stability of vegetable oil solutions with the aid of monoglycerides and a cosurfactant

The conditions for an enhanced mutual miscibility of water and Canola oil, with the aid of one or two surface active components, were investigated at 25 C. First, the ability of short chain alcohols to increase the mutual solubility was charted. Such systems frequently are denoted detergentless microemulsions. Second, normal microemulsion systems were formed by using surface active monoglycerides of foodstuff grade. Third, the synergism was monitored when both the surfactant and the cosurfactant (the alcohols) were mixed either with water or oil. Finally, the combined effect was determined when all four components were mixed together into a microemulsion system. It is shown that the extension of the ternary solution phase is dependent primarily on the surfactant used. Some improvement of the mutual solubility of water and oil, however, also was produced by the alcohols. The solubilization capacity of water in the quaternary systems is easily understood when the solution phase is compared with the microemulsion phases of the ternary systems included. Although no dramatic composition dependency was found, an enhanced solubility of water was observed for the oil rich microemulsions of roughly equal weight fractions of the surfactant components. Presented in part at the 8th Scandinavian Symposium on Surface Chemistry, Lund, Sweden, 1984.     

Experimental Conditions for HPLC Analysis of Ethoxylated Alkyl Phenol Surfactants in Microemulsion Systems. Part I. Isocratic Mode with Mixed Solvents

Abstract

In surfactant–oil–water phase behavior studies, especially those related to enhanced oil recovery, each of the oligomers of commercial polyethoxylated non-ionic surfactants partitions in a different pattern into the two or three phases in equilibrium, and a simple, fast, and accurate method is required to analyze all phases. Up to now, only oil-phase GC was relied upon to determine the partitioning without closing the surfactant inventory. Isocratic normal phase HPLC with a ternary mobile phase (n-heptane–chloroform–methanol 70–10–20) is shown to comply with these requirements to analyze the oligomer distribution in microemulsion, excess oil, and excess water phases of an optimum formulation system.     

Effect of Ethylene Oxide Group in the Anionic–Nonionic Mixed Surfactant System on Microemulsion Phase Behavior

The phase behavior of microemulsions stabilized by a binary anionic–nonionic surfactant mixture of sodium dihexyl sulfosuccinate (SDHS) and C12-14 alcohol ethoxylate (C_{12 − 14}E_j) that contains an ethylene oxide (E_j) group number, j, of either 1, 5, or 9 was investigated for oil remediation. The oil–water interfacial tension (IFT) and optimal salinity of the microemulsion systems with different equivalent alkane carbon numbers (EACN) were examined. The anionic–nonionic surfactant ratio was found to play a pivotal role in the phase transition, IFT, and optimal salinity. The minimum IFT of mixed SDHS − C_{12 − 14}E_j systems were about three times lower than those of neat SDHS systems. A hydrophilic–lipophilic deviation (HLD) empirical model for the mixed anionic–nonionic surfactant system with the characteristic parameter was proposed, as represented in the excess free energy term . The results suggested that the mixed system of SDHS − C_{12 − 14}E₁ was more lipophilic, while SDHS − C_{12 − 14}E₉ was more hydrophilic than the ideal mixture (no excess free energy during the microemulsion formation), and the SDHS − C_{12 − 14}E₅ system was close to the ideal mixture. The findings from this work provide an understanding of how to formulate mixed anionic–nonionic microemulsion systems using the HLD model for oils that possess a wide range of EACN.     

十二烷基苯磺酸钠微乳液体系中无机盐的作用规律

通过改变无机盐的种类,研究无机盐及其混合盐对十二烷基苯磺酸钠（SDBS）/正丁醇/正辛烷/水微乳液体系的影响。微乳体系随着各种盐类浓度的增加,均发生WinsorⅠ Winsor Ⅲ Winsor Ⅱ的相变,但对不同的无机盐其最佳盐度不同。通过对6组混合无机盐体系的研究,表明混合无机盐的效率参数与混合盐组成之间存在线性关系,可以用单一无机盐的效率参数预测出混合盐的情况。以效率参数为桥梁推导出了单一无机盐与混合无机盐之间最佳盐度的关系式,可用于预测混合盐效应,发现预测结果与实验结果吻合良好。