Use of Micellar-Enhanced Ultrafiltration at Low Surfactant Concentrations and with Anionic-Nonionic Surfactant Mixtures

Micellar-enhanced ultrafiltration is a separation technique which can be used to remove metal ions or dissolved organics from water. Metal ions bind to the surface of negatively charged micelles of an anionic surfactant while organic solutes tend to dissolve or solubilized within the micelles. The mixture is then forced through an ultrafiltration membrane with pore sizes small enough to block passage of the micelles and associated metal ions and/or dissolved organics. Monomeric or unassociated surfactant passes through the membrane and does not contribute to the separation. This paper considers advantages of addition of small concentrations of nonionic surfactant to an anionic surfactant; the resulting anionic-nonionic mixed micelles exhibit negative deviation from ideality of mixing which leads to a smaller fraction of the surfactant being present as monomer and a subsequently larger fraction present in the micellar form. The addition of nonionic surfactant improved the separation of divalent zinc substantially at total concentrations above the critical micelle concentration (cmc) of the anionic surfactant. Both zinc and tert-butylphenol (a nonionic organic solute) show unexpected rejection at surfactant concentrations moderately below the cmc, where micelles are absent. This is considered as due to a higher surfactant concentration in the gel layer adjacent to the membrane where micelles are present. Reduction of this rejection at lower transmembrane pressure drops supports this mechanism. Some rejection of zinc was observed in the absence of surfactant but not of tert-butylphenol, indicating an additional effect of membrane charge for ionic solutes. Copyright 1999 Academic Press.     

Microstructure of un-neutralized hydrophobically modified alkali-soluble emulsion latex in different surfactant solutions

At low pH conditions and in the presence of anionic, cationic, and nonionic surfactants, hydrophobically modified alkali-soluble emulsions (HASE) exhibit pronounced interaction that results in the solubilization of the latex. The interaction between HASE latex and surfactant was studied using various techniques, such as light transmittance, isothermal titration calorimetry, laser light scattering, and electrophoresis. For anionic surfactant, noncooperative hydrophobic binding dominates the interaction at concentrations lower than the critical aggregation concentration (CAC) (C < CAC). However, cooperative hydrophobic binding controls the formation of mixed micelles at high surfactant concentrations (C > or = CAC), where the cloudy solution becomes clear. For cross-linked HASE latex, anionic surfactant binds only noncooperatively to the latex and causes it to swell. For cationic surfactant, electrostatic interaction occurs at very low surfactant concentrations, resulting in phase separation. With further increase in surfactant concentration, noncooperative hydrophobic and cooperative hydrophobic interactions dominate the binding at low and high surfactant concentrations, respectively. For anionic and cationic surfactant systems, the CAC is lower than the critical micelle concentration (CMC) of surfactants in water. In addition, counterion condensation plays an important role during the binding interaction between HASE latex and ionic surfactants. In the case of nonionic surfactants, free surfactant micelles are formed in solution due to their relatively low CMC values, and HASE latexes are directly solubilized into the micellar core of nonionic surfactants.     

Electrophoretic behaviour and viscosities of metal oxides in mixed surfactant systems

 The electrokinetic behavior and viscosity of anatase and alumina in mixed-surfactant solutions were investigated. Sodium dodecylsulfate and nonionic polyoxyethylene ethers were investigated as model surfactants. Pure nonionic surfactants adsorbed on anatase and coated the particles, so that the zeta potential was nearly zero near the critical micelle concentration of surfactant. At higher surfactant concentrations, an increase in the zeta potentials was observed, suggesting a change in the microstructure of the adsorbed layer. Addition of nonionic surfactant to positively charged anatase and alumina with some preadsorbed sodium dodecylsulfate reversed the surface charge of the oxide to negative, indicating enhanced coadsorption of the anionic surfactant. At higher concentrations of the nonionic surfactant, the charge reversed back to positive. Nonionic surfactants did not reverse the surface charge of these oxides in the absence of the anionic surfactant. Coenhanced adsorption of nonionic and anionic surfactants was used to stabilize alumina at the isoelectric point, where neither surfactant adsorbed appreciably on its own. These results suggest a dramatic change in conformation of the surfactant chains in mixed systems. Further explanation and justification of the proposed changes in adsorbed surfactant conformation require spectroscopic evidence. Received: 12 March 1997 Accepted: 22 July 1997     

Photoluminescence of ZnO nanoparticles prepared by laser ablation in different surfactant solutions

ZnO nanoparticles were prepared by laser ablation of a zinc metal plate in a liquid environment using different surfactant (cationic, anionic, amphoteric, and nonionic) solutions. The nanoparticles were obtained in deionized water and in all surfactant solutions except the anionic surfactant solution. The average particle size and the standard deviation of particle size decreased with increasing amphoteric and nonionic surfactant concentrations. With the increase of the amphoteric surfactant concentration, the intensity of the defect emission caused by oxygen vacancies of ZnO rapidly decreased, while the exciton emission intensity increased. This indicates that anionic oxygen in the amphoteric surfactant molecules effectively occupied the oxygen vacancy sites at the ZnO nanoparticle surface due to charge matching with the positively charged ZnO nanoparticles.     

Effect of Surfactants on the Formation,Morphology, and Surface Property of Synthesized SiO2 Nanoparticles

Abstract

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10^?3–1 × 10^?6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10^?3 M), cationic and anionic surfactants both induced colloid aggregation, while the nonionic surfactant showed no effect on particle size. Raman spectroscopic analysis suggests that molecules of cationic surfactants adsorb on silica surfaces via head groups, aided by favorable electrostatic attraction, while molecules of anionic and nonionic surfactants adsorb via their hydrophobic tails.     

Characterizing the distribution of nonylphenol ethoxylate surfactants in water-based pressure-sensitive adhesive films using atomic-force and confocal Raman microscopy

Surfactant distributions in model pressure-sensitive adhesive (PSA) films were investigated using atomic force microscopy (AFM) and confocal Raman microscopy (CRM). The PSAs are water-based acrylics synthesized with n-butyl acrylate, vinyl acetate, and methacrylic acid and two commercially available surfactants, disodium (nonylphenoxypolyethoxy)ethyl sulfosuccinate (anionic) and nonylphenoxypoly(ethyleneoxy) ethanol (nonionic). The ratio of these surfactants was varied, while the total surfactant content was held constant. AFM images demonstrate the tendency of anionic surfactant to accumulate at the film surfaces and retard latex particle coalescence. CRM, which was introduced here as a means of providing quantitative depth profiling of surfactant concentration in latex adhesive films, confirms that the anionic surfactant tends to migrate to the film interfaces. This is consistent with its greater water solubility, which causes it to be transported by convective flow during the film coalescence process. The behavior of the nonionic surfactant is consistent with its greater compatibility with the polymer, showing little enrichment at film interfaces and little lateral variability in concentration measurements made via CRM. Surfactant distributions near film interfaces determined via CRM are well fit by an exponential decay model, in which concentrations drop from their highs at interfaces to plateau values in the film bulk. It was observed that decay constants are larger at the film-air interface compared with those obtained at the film-substrate side indicating differences in the mechanism involved. In general, it is shown here that CRM acts as a powerful compliment to AFM in characterizing the distribution of surfactant species in PSA film formation.     

Adsorptive bubble separation of zinc and cadmium cations in presence of ferric and aluminum hydroxides

The adsorptive bubble separation of zinc and cadmium cations from solution in the presence of ferric and aluminum hydroxides was carried out by means of Tween 80 (nonionic surfactant), and sodium laurate and stearate (anionic surfactants). The mechanism of metal removal is different depending on the nature of the surfactant used. The removal of zinc cations by adsorbing colloid flotation is higher than that of cadmium cations. It increases with increases in the amount of hydroxide precipitate and the concentration of Tween 80. The removal of zinc cations by ion flotation is lower than that of cadmium cations. It does not change with increases in the hydroxide amount. It increases, however, with increased sodium laurate or stearate concentration. Both separation methods turned out to be helpful for studying both the solution's structure and the interactions at the solution-solid interface.     

Role of the Surfactant Structure in the Behavior of Hydrophobic Ionic Liquids within Aqueous Micellar Solutions

The behavior of an ionic liquid (IL) within aqueous micellar solutions is governed by its unique property to act as both an electrolyte and a cosolvent. The influence of the surfactant structure on the properties of aqueous micellar solutions of zwitterionic SB‐12, nonionic Brij‐35 and TX‐100, and anionic sodium dodecyl sulfate (SDS) in the presence of the “hydrophobic” IL 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]) is assessed along with the possibility of forming oil‐in‐water microemulsions in which the IL acts as the “oil” phase. The solubility of [bmim][PF₆] within aqueous micellar solutions increases with increasing surfactant concentration. In contrast to anionic SDS, the zwitterionic and nonionic surfactant solutions solubilize more [bmim][PF₆] at higher concentrations and the average aggregate size remains almost unchanged. The formation of IL‐in‐water microemulsions when the concentration of [bmim][PF₆] is above its aqueous solubility is suggested for nonionic Brij‐35 and TX‐100 aqueous surfactant solutions.     

Experimental study on methane solubilization by organic surfactant aggregates

Seeking to enhance coal mine safety, an experimental study of a kind of water-based explosion suppression medium for the absorption of mine gas was carried out. Using methane as the model gas, solubilizing experiments with different concentrations of anionic and nonionic surfactants were carried out using headspace gas chromatography for surfactants consisting of sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), fatty acid methyl ester sulfonate (MES), fatty methyl ester ethoxylate (FMEE), hexyl d-glucoside (APG06), octyl beta-d-glucopyranoside (APG08) and n-decyl glucoside (APG10). By selecting individual surfactants, the study investigated the methane solubilization performance of water mist with binary anionic–nonionic surfactants. Furthermore, the release of methane in solution was also examined. The results show that the apparent solubility of methane in solution is linearly and positively correlated with the surfactant concentration. The methane solubilization is significantly improved by the addition of anionic–nonionic surfactants. The optimal solubilizing ratio of the anionic–nonionic surfactant varies with the solution compositions. For a fixed ratio, surfactant compositions exhibit the most distinct synergistic effect and the best performance for methane solubilization. The release of methane from mixed micelles composed of the compound solution is superior to that of a single surfactant. Through the analysis of the solubilization effect and the stability of different absorbents, it is concluded that the anionic–nonionic surfactant system shows much better capability than the other selected surfactants.     

Synergism and Physicochemical Properties of Anionic/Amphoteric Surfactant Mixtures with Nonionic Surfactant of Amine Oxide Type

The physicochemical properties of initial formulation, that is anionic/amphoteric surfactants mixture SLES/AOS/CAB (sodium lauryl ether sulfate (SLES), α-olefin sulfonates (AOS) and cocamidopropyl betaine (CAB) at ratio 80 : 15 : 5) with nonionic surfactant of amine oxide type (lauramine oxide (AO)) in various concentration (1–5%) were studied. To characterize the surfactants mixture, the critical micelle concentration (CMC), surface tension (γ), foam volume, biodegradability and irritability were determined. This study showed that adding of AO in those mixtures lowered both γ and CMC as well as enhanced SLES/AOS/CAB foaming properties, but did not significantly affect biodegradability and irritability of initial formulation. Moreover, an increase in AO concentration has a meaningful synergistic effect on the initial formulation properties. All those results indicates that a nonionic surfactant of amine oxide type significantly improves the performance of anionic/amphoteric mixed micelle systems, and because of that anionic/amphoteric/nonionic mixture can be used in considerably lower concentrations as a cleaning formulation.

     

The influence of ionic and nonionic surfactants on aggregative stability and electrical surface properties of aqueous suspensions of titanium dioxide

The influence of concentration of nonionic TRITON X-100 and anionic ATLAS G-3300 surfactants, and pH of medium on the size and zeta-potential of TiO2 particles in the water suspensions has been studied. Suspensions have been prepared by mixing of the titanium dioxide in the suitable mediums at 10 min and 6 h correspondingly. It was established, that the duration of mixing of the suspensions has an essential influence on the dependence of zeta-potential and size of particles versus concentration of surfactant. However, the duration of mixing does not influence the dependence of electrical conductivity and pH of the suspensions on concentration of surfactant. It is shown that anionic ATLAS G-3300 surfactant is more effective stabilizator of aqueous suspensions of titanium dioxide, than nonionic surfactants of TRITON X-100. It is found that hydrophobic interaction has important role in the processes of stabilization of suspensions for nonionic surfactant, and for anionic surfactant--moving of psi(delta)-planes into solution's depth.     

Study of the reaction Fe(CN)5(4‐CNpy)3− + S2O82− in aqueous salt and micellar solutions

The reaction Fe(CN)₅(4‐CNpy)³⁻ + S₂O₈²⁻ (4‐CNpy=4‐cyanopyridine) was studied in aqueous salt solutions in the presence of several electrolytes as well as in anionic, cationic, and nonionic surfactant solutions. In aqueous salt solutions the noncoulombic interactions seem to be important in determining the positive salt effects observed. The salting effects are influencing the activity coefficients of any participant in the reaction, including those ion pairs which can be formed between the anionic reagents and the cations which come from the added salts. The changes in surfactant concentration in anionic and nonionic surfactant solutions do not affect the reaction rate, which is similar to that in pure water at the same ionic strength. In cationic micellar solutions an increase in the rate constant compared to that in pure water is found; the reaction rate decreasing when the surfactant concentration increases. The kinetic trends can be explained assuming that the reagents are totally bound to the micelles and, therefore, an increase in the surfactant concentration results in a decrease in the reagent concentrations at the micellar phase and thus in a decrease in the observed rate constant. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet: 31: 229–235, 1999     

Shape and Structure Formation of Mixed Nonionic–Anionic Surfactant Micelles

Aqueous solutions of a nonionic surfactant (either Tween20 or BrijL23) and an anionic surfactant (sodium dodecyl sulfate, SDS) are investigated, using small-angle neutron scattering (SANS). SANS spectra are analysed by using a core-shell model to describe the form factor of self-assembled surfactant micelles; the intermicellar interactions are modelled by using a hard-sphere Percus–Yevick (HS-PY) or a rescaled mean spherical approximation (RMSA) structure factor. Choosing these specific nonionic surfactants allows for comparison of the effect of branched (Tween20) and linear (BrijL23) surfactant headgroups, both constituted of poly-ethylene oxide (PEO) groups. The nonionic–anionic surfactant mixtures are studied at various concentrations up to highly concentrated samples (ϕ ≲ 0.45) and various mixing ratios, from pure nonionic to pure anionic surfactant solutions. The scattering data reveal the formation of mixed micelles already at concentrations below the critical micelle concentration of SDS. At higher volume fractions, excluded volume effects dominate the intermicellar structuring, even for charged micelles. In consequence, at high volume fractions, the intermicellar structuring is the same for charged and uncharged micelles. At all mixing ratios, almost spherical mixed micelles form. This offers the opportunity to create a system of colloidal particles with a variable surface charge. This excludes only roughly equimolar mixing ratios (X≈ 0.4–0.6) at which the micelles significantly increase in size and ellipticity due to specific sulfate–EO interactions.     

Atmospheric and electrochemical oxidation of ascorbic acid in anionic,nonionic and cationic surfactant systems

It is well known that the antioxidant activity of some species in homogenous solutions may not be the same as that in heterogeneous media. This environment dependence is the reason for investigating ascorbic acid antioxidant activity in surfactant solutions. In our study we have investigated the kinetics of atmospheric oxidation and electrochemical oxidation of ascorbic acid in aqueous solutions of the four surfactants: SDS, AOT (anionic), TRITON-100 (nonionic), and CTAB (cationic). For each surfactant the concentrations below and above CMC were investigated. As expected, a general trend in the atmospheric oxidation rate changes in the following manner: the micellar solution of nonionic surfactant shows a faster oxidation rate than that of the anionic surfactant, and the cationic surfactant an even higher one. The more subtle effects were observed with each surfactant concentration change. The influence of the surfactants on the electrochemical behavior of ascorbic acid was also studied. A general conclusion emerging from our investigation is that surfactants shift the ascorbic acid oxidation potential and change the peak current value. This phenomenon is due mainly to the surfactant film formed at the electrode/solution interface.     

Adsorbing colloid flotation separation and polarographic determination of Mo(VI) in water

A method is described for the flotation and determination of Mo(VI) in water at ng/ml levels. Mo(VI) is preconcentrated and separated by adsorbing colloid flotation employing aluminium(III) hydroxide as collector and sodium lauryl sulphate as surfactant at pH 5.3 ± 0.1. The molybdenum content in the froth is estimated by using the catalytic wave of Mo(VI) in the presence of nitrate by charging current compensated d.c. polarography (CCCDCP) or differential pulse polarography (DPP). The effect of variables such as pH, ionic strength, concentration of collector and surfactant, time of stirring and gas flow-rate on the recovery of Mo by flotation is reported. The effects of various cations and anions on the flotation and determination of Mo are studied. This method is employed for the determination of molybdenum in natural fresh water samples.     

Stabilization of Paraffin Emulsions Used in the Manufacture of Chipboard Panels by Liquid Crystalline Phases

Paraffin emulsions are commonly used in the manufacture of chipboard panels to provide resistance to water and humidity. The quality and performance of chipboards are improved with the use of paraffin emulsions stabilized by mixed surfactant systems, although little is known about the basic colloidal chemistry of such systems and their implications in the manufacturing and processing of the chipboard panels. In the present work, the stability and the phase behavior of paraffin emulsions stabilized by a mixture of anionic and nonionic surfactants, are described. Stability is studied by applying thermal and ultracentrifugation cycles, and also by rheology (steady state and dynamic determinations). A significant increase of stability is observed at high {anionic surfactant/(anionic surfactant+nonionic surfactant)} ratios. Phase behavior studies have demonstrated the presence of hexagonal liquid crystalline structures at high ionic surfactant/nonionic surfactant ratios and the presence of lamellar structures at low ratios. The stability of emulsions could be related to phase behavior, and, thus, providing a qualitative tool to predict stability.     

Micellar-enhanced ultrafiltration of cadmium ions with anionic–nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF), a surfactant-based separation process, is promising in removing multivalent metal ions from aqueous solutions. The micellar-enhanced ultrafiltration of cadmium from aqueous solution was studied in systems of anionic surfactant and mixed anionic/nonionic surfactants. The micelle sizes and zeta potentials were investigated by dynamic light scattering measurements. The effects of feed surfactant concentration, cadmium concentration and the molar ratio of nonionic surfactants to sodium dodecyl sulfate (SDS) on the cadmium removal efficiency, the rejection of SDS and nonionic surfactants and the permeate flux were investigated. The rejection efficiencies of cadmium in the MEUF operation were enhanced with higher SDS concentration and moderate Cd concentration. When SDS concentration was fixed at 3 mM, the optimal ranges of the molar ratios of nonionic surfactants to SDS for the removal of cadmium were 0.4–0.7 for Brij 35 and 0.5–0.7 for Triton X-100, respectively. With the addition of nonionic surfactants, the SDS dosage and the SDS concentration in the permeate were reduced efficiently.     

The impact of multivalent counterions, Al3+, on the surface adsorption and self-assembly of the anionic surfactant alkyloxyethylene sulfate and anionic/nonionic surfactant mixtures

The impact of multivalent counterions, Al(3+), on the surface adsorption and self-assembly of the anionic surfactant sodium dodecyl dioxyethylene sulfate, SLES, and the anionic/nonionic surfactant mixtures of SLES and monododecyl dodecaethylene glycol, C(12)E(12), has been investigated using neutron reflectivity, NR, and small angle neutron scattering, SANS. The addition of relatively low concentrations of Al(3+) counterions induces a transition from a monolayer to well-defined surface bilayer, trilayer, and multilayer structures in the adsorption of SLES at the air-water interface. The addition of the nonionic cosurfactant, C(12)E(12), partially inhibits the evolution in the surface structure from monolayer to multilayer interfacial structures. This surface phase behavior is strongly dependent upon the surfactant concentration, solution composition, and concentration of Al(3+) counterions. In solution, the addition of relatively low concentrations of Al(3+) ions promotes significant micellar growth in SLES and SLES/C(12)E(12) mixtures. At the higher counterion concentrations, there is a transition to lamellar structures and ultimately precipitation. The presence of the C(12)E(12) nonionic cosurfactant partially suppresses the aggregate growth. The surface and solution behaviors can be explained in terms of the strong binding of the Al(3+) ions to the SLES headgroup to form surfactant-ion complexes (trimers). These results provide direct evidence of the role of the nonionic cosurfactant in manipulating both the surface and solution behavior. The larger EO(12) headgroup of the C(12)E(12) provides a steric hindrance which disrupts and ultimately prevents the formation of the surfactant-ion complexes. The results provide an important insight into how multivalent counterions can be used to manipulate both solution self-assembly and surface properties.     

Studies on the Interaction of Surfactants with Cationic Dye by Absorption Spectroscopy

The interaction of methyl violet, a cationic dye, with various surfactants, viz. anionic (SDS), nonionic (Triton X-100), and cationic (CTAB), has been investigated spectrophotometrically in submicellar and micellar concentration range. While in the submicellar concentration region of SDS the higher aggregates of the dye are found, in the micellar concentration region the monomer of the dye predominates. With nonionic surfactant the dye is solubilized primarily as the monomer. CTAB produces no perturbation to the visible spectra of the dye. In the presence of strong electrolytes such as NaNO(3) and NaCl the dye aggregates are formed at a much lower SDS concentrations. Copyright 2000 Academic Press.     

Calorimetric study on the temperature dependence of the formation of mixed ionic/nonionic micelles

The differential excess enthalpy of mixed micelle formation was measured at different temperatures by mixing nonionic hexa(ethylene glycol) mono n-dodecyl ether with anionic sodium dodecyl sulfate or cationic dodecylpyridinium chloride. The experimental data were obtained calorimetrically by titrating a concentrated surfactant solution into a micellar solution of nonionic surfactant. The composition and the size of the mixed nonionic/ionic micelles at different surfactant concentrations were also determined. Pronounced differences in both composition and excess enthalpy were found between the anionic and the cationic mixed system. For both systems, the excess enthalpies become more exothermic with increasing temperature, but for the anionic mixed system an additional exothermic contribution was found which was much less temperature dependent. Temperature dependence of the excess enthalpy was attributed to the effect of the ionic headgroup on the hydration of the ethylene oxide (EO) groups in the mixed corona. Ionic headgroups located in the ethylene oxide layer cause the dehydration of the EO chains resulting in an additional hydrophobic contribution to the enthalpy of mixing. A high affinity of sodium dodecyl sulfate for nonionic micelles and an extra exothermic and less temperature dependent contribution to the excess enthalpy found for the SDS-C(12)E(6) system might be attributed to specific interactions (hydrogen bonds) between the sulfate headgroup and the partly dehydrated EO chain.