Expanded Salinity Window of Middle-Phase Microemulsions and Reduced Surfactant Adsorption by Hydrotrope.

Using surfactant blends to mobilize residual oil offers a promising technique for enhanced oil recovery (EOR) and surfactant-enhanced aquifer remediation (SEAR). A major financial setback for broader application of this method is the loss of surfactants, as they get absorbed onto reservoir mineral surfaces. This loss becomes even more costly in oil fields with high-salinity formation water. Our research delved into the use of hydrotropes to minimize the surfactant absorption. The impacts of surfactant adsorption with hydrotrope additives were quantified and compared to three representative porous media. Initial tests studied the ideal salinity range influenced by hydrotropes with the observations of Winsor Type III microemulsions with selected surfactants, and four specific hydrocarbons were confirmed through interfacial tension measurements. When tested on three types of porous media, the presence of hydrotropes reduced the adsorption rates: up to 65% on Indiana limestone, 21% on Ottawa sand, and 53% on activated carbon. Notably, our study revealed urea's role in reducing surfactant retention in porous media. This discovery can help modify the salinity range of middle-phase microemulsions, which is crucial for EOR by easing salinity constraints of target reservoirs. The large middle-phase microemulsion window is also very advantageous for other potential applications. Moreover, urea proves to be more effective than typical sacrificial agents for reservoirs, as it binds the surfactant to the liquid rather than acting as a mere sacrificial component. Our research underscores the potential of improving surfactant flooding results by integrating hydrotropes, offering substantial cost savings in surfactant consumption and enhancing the overall efficiency of EOR and SEAR projects.

Oil-Induced Viscoelasticity in Micellar Solutions of Alkoxy Sulfate.

Rheological properties of the solution of an extended surfactant, sodium alkoxy sulfate (C8-(PO)4-(EO)1-SO4Na), are investigated as a function of the presence of various paraffinic oils over a range of salt conditions in the Winsor III microemulsion region at oil fractions where the microemulsion is "oil-starved". The addition of as small as 3 vol % alkane to 2 wt % surfactant solutions at salt concentrations where the oil-water interfacial tension is minimized induces a sudden shift in the rheological behavior. The solution viscosity increases by 5 orders of magnitude, with solid-like behaviors (G' > G″) being observed in the entire frequency region investigated (0.01-100 rad/s). Commonly, in the cases where wormlike micelles are present in the solution, alkanes are believed to be solubilized in the core of micelles, leading to a radial growth of the cylindrical part of the wormlike micelle, resulting in a drop of end-cap energy (EC) and micelle length and a reduction in viscosity. In this study, however, the addition of oil causes the formation of wormlike micelles. The viscosity of solubilized-oil samples does, however, decrease with an increase in incorporated oil volume. We hypothesize that this "abnormal oleo-responsive" viscoelastic behavior is related to a spacer of intermediate hydrophilicity, that is, polypropylene oxide (PO) segment of the alkoxy sulfate, being inserted between the hydrophobic tail and hydrophilic head (the ethoxylated sulfate segment) of the extended surfactant. The addition of a small amount of oil likely extends the PO moiety and increases the tail length of the surfactant in the aggregates as well as reducing the headgroup size, driving the formation of wormlike micelles from a solution that initially had a viscosity consistent with the absence of such structures.

Counterion binding on coacervation of dioctyl sulfosuccinate in aqueous sodium chloride.

A simple coacervate-forming system consisting of sodium dioctyl sulfosuccinate (DOSS) in aqueous NaCl solution was investigated by turbidity measurement, electromotive force measurement (EMF), dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryo-TEM) to reveal the role of counterion binding in the microstructural changes behind the evolution of the coacervate phase. Coacervation phase boundaries of DOSS against different NaCl concentrations were obtained; the pseudo-coacervation constant, Ksp,co = [DOSS-][Na+], was determined to be 1.35 ± 0.15 × 10-4 M2 at 25 °C. Sodium ion activity from EMF measurements confirmed a drastic rise in counterion binding to DOSS aggregates near the coacervate phase boundary. For DOSS/NaCl solution concentrations near the coacervate phase boundary, the turbidity changed, starting from a clear, isotropic solution far from the phase boundary, transitioning to a turbid solution near the phase boundary, and exhibiting a distinct growth of the hydrodynamic diameter of DOSS aggregates as detected by DLS. Cryo-TEM evidenced the presence of vesicles at concentrations close to the coacervate phase boundary; both unilamellar and multilamellar vesicles were observed. Increased counterion binding on the aggregates led to fusion of the larger vesicles and eventually to formation of a coacervate phase; the DOSS aggregates in the clear supernatant phase were predominately small vesicles of approximately 100 nm diameter. This study suggests that the mechanism for coacervate formation in DOSS solutions is an increase in counterion binding coincident with formation of multilamellar vesicles near the phase boundary, followed by flocculation of the multilamellar vesicles beyond the phase boundary to form the coacervate phase.

Rheological characterization of yield stress gels formed via electrostatic heteroaggregation of metal oxide nanoparticles.

Mixtures of fumed fractal metal oxide nanoparticles (np's) dispersed in water, at a solution pH where one species is positively charged and the other is negatively charged, form yield stress gels at volume fractions as low as 1.5%, due to electrostatic heteroaggregation into networks as confirmed by small-angle neutron scattering. These gels exhibit a measurable yield stress and an apparent viscosity that follows a power law relationship with shear rate. Rotational and oscillatory shear rheology is presented for binary mixtures of fumed silica, fumed alumina, and fumed titania in aqueous dispersions. Gels were characterized at various particle concentrations, solution pHs, mixture ratios, and salt concentrations. The strength of the gel network, as evaluated by the storage modulus and yield stress, is maximized when the mixture contains a mixture of particles with an approximately equal, but opposite, number of charged groups.

Adsorption of anionic and non-ionic surfactants on carbon nanotubes in water with dissipative particle dynamics simulation.

The morphology of surfactants physically adsorbed on the surface of carbon nanotubes (CNTs) has a significant impact on the dispersion of CNTs in the solution. The adsorption of the surfactants alfoterra 123-8s (AF) and tergitol 15-s-40 (TG) on CNTs was investigated with dissipative particle dynamics (DPD) simulations, as well as the behavior of the binary surfactant system with CNTs. Properties of surfactants (i.e., critical micelle concentration, aggregation number, shape and size of micelle, and diffusivity) in water were determined to validate the simulation model. Results indicated that the assembly of surfactants (AF and TG) on CNTs depends on the interaction of the surfactant tail and the CNT surface, where surfactants formed mainly hemimicellar structures. For surfactants in solution, most micelles had spherical shape. The particles formed by the CNT and the adsorbed surfactant became hydrophilic, due to the outward orientation of the head groups of the surfactants that formed monolayer adsorption. In the binary surfactant system, the presence of TG on the CNT surface provided a considerable hydrophilic steric effect, due to the EO groups of TG molecules. It was also seen that the adsorption of AF was more favorable than TG on the CNT surface. Diffusion coefficients for the surfactants in the bulk and surface diffusion on the CNT were calculated. These results are applicable, in a qualitative sense, to the more general case of adsorption of surfactants on the hydrophobic surface of cylindrically shaped nanoscale objects.

Multiwalled Carbon Nanotubes at the Interface of Pickering Emulsions.

Carbon nanotubes exhibit very unique properties in biphasic systems. Their interparticle attraction leads to reduced droplet coalescence rates and corresponding improvements in emulsion stability. Here we use covalent and noncovalent techniques to modify the hydrophilicity of multiwalled carbon nanotubes (MWCNTs) and study their resulting behavior at an oil-water interface. By using both paraffin wax/water and dodecane/water systems, the thickness of the layer of MWNTs at the interface and resulting emulsion stability are shown to vary significantly with the approach used to modify the MWNTs. Increased hydrophilicity of the MWNTs shifts the emulsions from water-in-oil to oil-in-water. The stability of the emulsion is found to correlate with the thickness of nanotubes populating the oil-water interface and relative strength of the carbon nanotube network. The addition of a surfactant decreases the thickness of nanotubes at the interface and enhances the overall interfacial area stabilized at the expense of increased droplet coalescence rates. To the best of our knowledge, this is the first time the interfacial thickness of modified carbon nanotubes has been quantified and correlated to emulsion stability.

Disrupting admicelle formation and preventing surfactant adsorption on metal oxide surfaces using sacrificial polyelectrolytes.

The adsorption of anionic, cationic, and nonionic surfactants was measured on high-surface area silica and alumina nanoparticles when in the presence of the proposed polyelectrolyte sacrificial agents. Surfactant adsorption was characterized using two types of adsorption isotherms: one with constant polymer concentration and varying surfactant concentration, and another with a varying polymer concentration and constant surfactant concentration. Polystyrenesulfonate and Polydiallyl dimethylammonium chloride were tested as potential sacrificial agents on alumina and silica, respectively. Each surfactant/polymer system was allowed to reach equilibrium and supernatant surfactant concentrations were measured. This information was then plotted in order to determine what, if any, effect the proposed sacrificial agent had on the equilibrium adsorption. Results indicate that both of these polymers can have a large effect on total surfactant adsorption at a variety of surfactant concentrations.

Development and evaluation of a biomedical search engine using a predicate-based vector space model.

Although biomedical information available in articles and patents is increasing exponentially, we continue to rely on the same information retrieval methods and use very few keywords to search millions of documents. We are developing a fundamentally different approach for finding much more precise and complete information with a single query using predicates instead of keywords for both query and document representation. Predicates are triples that are more complex datastructures than keywords and contain more structured information. To make optimal use of them, we developed a new predicate-based vector space model and query-document similarity function with adjusted tf-idf and boost function. Using a test bed of 107,367 PubMed abstracts, we evaluated the first essential function: retrieving information. Cancer researchers provided 20 realistic queries, for which the top 15 abstracts were retrieved using a predicate-based (new) and keyword-based (baseline) approach. Each abstract was evaluated, double-blind, by cancer researchers on a 0-5 point scale to calculate precision (0 versus higher) and relevance (0-5 score). Precision was significantly higher (p<.001) for the predicate-based (80%) than for the keyword-based (71%) approach. Relevance was almost doubled with the predicate-based approach-2.1 versus 1.6 without rank order adjustment (p<.001) and 1.34 versus 0.98 with rank order adjustment (p<.001) for predicate--versus keyword-based approach respectively. Predicates can support more precise searching than keywords, laying the foundation for rich and sophisticated information search.

Remediation of NAPL source zones: lessons learned from field studies at Hill and Dover AFB.

Innovative remediation studies were conducted between 1994 and 2004 at sites contaminated by nonaqueous phase liquids (NAPLs) at Hill and Dover AFB, and included technologies that mobilize, solubilize, and volatilize NAPL: air sparging (AS), surfactant flushing, cosolvent flooding, and flushing with a complexing-sugar solution. The experiments proved that aggressive remedial efforts tailored to the contaminant can remove more than 90% of the NAPL-phase contaminant mass. Site-characterization methods were tested as part of these field efforts, including partitioning tracer tests, biotracer tests, and mass-flux measurements. A significant reduction in the groundwater contaminant mass flux was achieved despite incomplete removal of the source. The effectiveness of soil, groundwater, and tracer based characterization methods may be site and technology specific. Employing multiple methods can improve characterization. The studies elucidated the importance of small-scale heterogeneities on remediation effectiveness, and fomented research on enhanced-delivery methods. Most contaminant removal occurs in hydraulically accessible zones, and complete removal is limited by contaminant mass stored in inaccessible zones. These studies illustrated the importance of understanding the fluid dynamics and interfacial behavior of injected fluids on remediation design and implementation. The importance of understanding the dynamics of NAPL-mixture dissolution and removal was highlighted. The results from these studies helped researchers better understand what processes and scales are most important to include in mathematical models used for design and data analysis. Finally, the work at these sites emphasized the importance and feasibility of recycling and reusing chemical agents, and enabled the implementation and success of follow-on full-scale efforts.

Thermodynamics of mixed anionic/nonionic surfactant adsorption on alumina.

The adsorption of sodium dodecyl sulfate and a polyethoxylated nonylphenol, and well defined mixtures thereof, was measured on gamma-alumina. A pseudo-phase separation model to describe mixed anionic/nonionic admicelle (adsorbed surfactant aggregate) formation was developed, analogous to the pseudo-phase separation model frequently used to describe mixed micelle formation. In this model, regular solution theory was used to describe the anionic/nonionic surfactant interactions in the mixed admicelle and a patch-wise adsorption model was used to describe surfactant adsorption on a heterogeneous solid surface. The formation of mixed anionic/nonionic admicelles in the absence of micelles was accurately described by regular solution theory; mixed admicelle formation exhibited stronger negative deviations from ideality than mixed micelle formation. An adequate description of mixed anionic/nonionic admicelle formation in the presence of mixed micelles was obtained through a simultaneous solution of the pseudo-phase separation models for mixed admicelle and mixed micelle formation, and the appropriate mass balance equations. Anionic/nonionic mixed adsorption in the presence of mixed micelles was shown to correspond to an admicelle composition of approximately a 1:1 anionic/nonionic mole ratio throughout Regions II and III of the adsorption isotherm.

Field demonstration of surfactant-enhanced solubilization of DNAPL at Dover Air Force Base, Delaware.

This study reports on a surfactant-based flood for tetrachloroethylene (PCE) removal from a control test cell at the Dover National Test Site. The surfactant formulation (sodium dihexyl sulfosuccinate (Aerosol-MA or AMA), isopropanol and calcium chloride) was able to achieve a high concentration of PCE in swollen micelles (supersolubilization) without vertical PCE migration. The hydraulic system included eight screened wells that were operated in both vertical circulation and line drive configurations. After 10 pore volumes of flushing, the overall PCE removal was 68% (65% of which corresponded to the surfactant flooding alone). In addition, the residual PCE saturation was reduced from 0.7% to 0.2%, and the concentration of PCE in the groundwater was reduced from 37-190 mg/L before the flushing to 7.3 mg/L after flooding. Recycling the surfactant solution reduced the required surfactant mass (and thus cost, and waste) by 90%. Close to 80% of the total PCE removal was obtained during the first five pore volumes which were operated in an upward vertical circulation flow scheme. No free oil phase was observed during the test. Further analysis of multilevel sampler data suggests that most of the trapped oil remaining in the cell was likely localized in secluded regions of the aquifer, which helps explain the lower PCE groundwater concentration after remedial activities. In summary, this field study demonstrated the feasibility of surfactant-enhanced remediation to reduce the mass in the source zone and significantly reduce the PCE aqueous concentration and therefore the risk associated with the contaminant plume.

Modeling solubilization of oil mixtures in anionic microemulsions II. Mixtures of polar and non-polar oils.

Polar/amphiphilic oils, called lipophilic linkers, are sometimes added to oil-water-ionic surfactant microemulsions in order to increase the solubilization of hydrophobic oils. The solubilization increase has been well documented for a number of systems. However, mathematical models to calculate the solubilization increase have been proposed only for optimum microemulsions (i.e., middle phase microemulsions solubilizing equal volumes of oil and water). In this paper we propose a model, which predicts solubilization enhancement for non-optimum microemulsion systems as well. The model is an extension of the net-average curvature model of microemulsion. The net-average curvature model is combined with a surface activity model to account for the increased palisade layer solubilization due to the presence of the polar/amphiphilic oil component. New non-linear mixing rules are also incorporated to account for the optimum salinity and the characteristic length variation of the anionic surfactant microemulsion as a function of the lipophilic linker concentration. The model predicts the effect of the lipophilic linker and the electrolyte concentration on the oil solubilization in accordance with the experimental results.

Preferential solubilization of dodecanol from dodecanol-limonene binary oil mixture in sodium dihexyl sulfosuccinate microemulsions: effect on optimum salinity and oil solubilization capacity.

Solubilization of dodecanol-limonene binary oil mixtures has been studied in saturated Winsor type I and III sodium dihexyl sulfosuccinate microemulsions. The systems showed different oil solubilization behavior below and above dodecanol volume fraction 0.2. Below 0.2 dodecanol volume fraction regular Winsor type microemulsions formed. The oil solubilization was characterized in this concentration range by the optimum salinity and the maximum characteristic length. Dodecanol showed Langmuirian-type surface excess adsorption at the vicinity of the surfactant layer. Variation of the optimum salinity and middle phase characteristic length with increasing dodecanol concentration could be linked to changes in the dodecanol surface excess. These relationships were used to develop new mathematical models for the optimum salinity and characteristic length as a function of oil phase composition. Both models yield excellent agreement with the data. Above dodecanol volume fraction 0.2 regular Winsor type III microemulsions are not formed. Therefore our new models are not applicable in this concentration range.

Linker-based bio-compatible microemulsions.

In this work we have studied the formulation of biocompatible microemulsions using lecithin as the main surfactant and bio-compatible linker molecules (hexyl polyglucoside asthe hydrophilic linker and sorbitan monoleate as the lipophilic linker). These bio-compatible systems are discussed as potential substitutes for chlorinated solvents in dry-cleaning applications and as solvent delivery systems for pharmaceutical applications. Formulation parameters and conditions were evaluated using isopropyl myristate (IPM) as the model oil. It was found that the proposed linker-based formulations were able to form alcohol-free microemulsions while achieving higher solubilization capacity than similar systems reported in the literature. In addition, these lecithin/linker formulations were able to form microemulsions with a wide range of oils, from polar chlorinated hydrocarbons to hydrophobic oils such as squalene. These microemulsions were achieved under isotonic conditions (0.9% NaCl) by only varying the relative proportions of the linkers. The "solvency" power of these bio-compatible formulations was tested for the removal of hexadecane (used as model oil) from cotton fabrics and compared to the solvency power of a typical dry cleaning solvent tetrachloroethylene (PCE). While PCE and the linker-based lecithin formulation removed the same amount of hexadecane at low loading ratios (less than 1% oil volume fraction), at higher loading ratios the linker-based lecithin formulation retained its oil removal capacity while the efficiency of the PCE system declined rapidly. These initial results thus demonstrate the remarkable oil solubilization capacity of these bio-compatible linker-based lecithin formulations and illustrate their potential as environmentally friendly replacements for organic solvents.

A two-state model for selective solubilization of benzene-limonene mixtures in sodium dihexyl sulfosuccinate microemulsions.

When surfactants are used to solubilize oil, the oil to be solubilized is often a mixture of components with differing properties, for example, solubilization of drug molecules in microemulsion formulations, remediation of organic polluted aquifers using surfactants, and so forth. Previous research has demonstrated that selective solubilization of one organic component over the other may occur if the organic components are dissimilar. In this research, we investigated selective solubilization from benzene-limonene mixtures in Winsor type I and III microemulsion systems containing water, sodium di-n-hexyl sulfosuccinate, and NaCl. The effect of the oil phase composition and the electrolyte concentration on the selectivity was studied. It was found that the selectivity toward benzene was highest at low electrolyte and benzene concentrations, decreasing as the electrolyte or benzene concentration increased. The results are discussed on the basis of the two-state solubilization theory and by correlating the curvature of the surfactant film in the microemulsion with changes of the electrolyte concentration and the oil phase composition. A simple mathematical model is developed for the selectivity, which combines the two-state solubilization theory and the net-average curvature model of microemulsion solubilization to yield close agreement with the experimental data.

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems.

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.

Self-assembly in linker-modified microemulsions.

Linker molecules are added to microemulsion systems to enhance the interaction between the surfactant and oil (lipophilic linkers) or water (hydrophilic linkers) phases. Previous results suggest that when lipophilic and hydrophilic linkers are combined they behave as a self-assembled surfactant at the oil/water interface. In this work we investigate this self-assembly phenomenon as a function of surfactant, linker and electrolyte concentration. We find that middle phase microemulsion appears at a specific concentration higher than the critical micelle concentration (CMC), which we denote as the critical middle phase microemulsion concentration (CmicroC). When the lipophilic linker dodecanol is added in equimolar ratio to the hydrophilic linker sodium mono- and dimethyl naphthalene sulfonate (SMDNS), the middle phase microemulsion did not appear until the surfactant sodium dihexyl sulfosuccinate (SDHS) concentration was larger than the CmicroC of the SDHS-alone system. Dodecanol is shown to segregate near the surfactant tails following a Langmuir-type adsorption process. This segregation is not affected by the electrolyte concentration but is significantly reduced when the surfactant (SDHS) concentration approaches the CmicroC. The data suggest that the self-assembly between hydrophilic and lipophilic linkers to form middle phase microemulsions is only possible if a minimum amount of surfactant is present.

Formulating chlorinated hydrocarbon microemulsions using linker molecules.

Previously we reported on the use of lipophilic, hydrophilic, and combined linkers for formulating microemulsions of trichloroethylene and tetrachloroethylene. These linker molecules augment the interaction between the surfactant and oil phase (lipophilic linkers) or between the surfactant and water phase (hydrophilic linkers). Combining both linkers can increase the solubilization capacity several-fold. This formulation technique shows potential advantage in reducing surfactant costs and remedial times, as well as allowing the use of more environmentally friendly additives when designing surfactant-enhanced remediation systems. In this paper, we evaluate the relative importance of the surfactant and each linker in increasing the system's solubilization capacity. This interpretation is based on solubilization curves, partitioning studies, and formulation studies. The solubilization curves show that optimum linker performance is reached at an equimolar ratio of dodecanol, used as a lipophilic linker, and sodium mono and dimethyl naphthalene sulfonate, used as a hydrophilic linker. Furthermore, this equimolar combination was able to replace the anionic surfactant sodium dihexylsulfosuccinate. Dodecanol partitioning at optimum formulation shows that the poor performance of lipophilic linkers alone is due to their low partitioning into the middle phase. Adding hydrophilic linkers into this system increases the fraction of dodecanol in the middle phase, thereby further enhancing the solubilization capacity of the system. A variation of the combined linker approach is introduced by changing a lipophilic linker, oleic acid, into a surfactant (soap), with further increases in the solubilization capacity by 4- to 5-fold.