Phase behavior in mixtures of cationic and anionic surfactants in aqueous solutions

Phase behavior of cationic/anionic surfactant mixtures of the same chain length (n=10, 12 or 14) strongly depends on the molar ratio and actual concentration of the surfactants. Precipitation of catanionic surfactant and mixed micelles formation are observed over the concentration range investigated. Coacervate and liquid crystals are found to coexist in the transition region from crystalline catanionic surfactant to mixed micelles.The addition of oppositely charged surfactant diminishes the surface charge density at the mixed micelle/solution interface and enhances the apparent degree of counterion dissociation from mixed micelles. Cationic surfactants have a greater tendency to be incorporated in mixed micelles than anionic ones.     

Nonideal mixing of dodecyltrimethylammonium halides and nonionic surfactant in adsorbed films and micelles

The ion–dipole interaction between dodecyltrimethylammonium cations and nonionic surfactant molecules in adsorbed films and micelles was investigated by concentrating on the difference in the degree of counterion binding by employing dodecyltrimethylammonium chloride (DTAC)–octyl methyl sulfoxide (OMS) and dodecyltrimethylammonium bromide (DTAB)–OMS mixtures. The phase diagrams of adsorption and micelle formation were constructed and then the nonideal mixing of different species of surfactants was demonstrated in terms of the excess Gibbs free energies of adsorption and micelle formation, and the surface excess areas. Furthermore the dependence of them on the counterion was clearly shown. All these results were found to support our previous view that the direct interaction between surfactant cation and the dipole of the hydrophilic part of a nonionic surfactant is essential in cationic-nonionic surfactant mixtures, i.e., the DTAC system with a lower counterion biding has more negative excess thermodynamic quantities than the DTAB system with a higher one.     

Volume behavior of mixed micelles of dodecyltrimethylammonium chloride and bromide

Densities of aqueous solutions of mixtures of dodecyltrimethylammonium chloride (DTAC) and dodecyltrimethylammonium bromide (DTAB) have been measured as a function of total molality at constant composition and the apparent molar volumes of the mixtures were derived from the density data. The partial molar volumes of monomeric surfactant mixtures, the molar volumes of mixed micelles, and the volumes of formation of mixed micelles were evaluated and are compared with those for decyltrimethylammonium bromide (DeTAB) and DTAB mixtures. The partial molar volumes of monomeric surfactant mixtures and the molar volumes of mixed micelles are observed to depend linearly on the monomer and micelle compositions, respectively. Although the volume of formation of mixed micelles of the DeTAB-DTAB mixture depends on the micellar composition, that of the DTAC-DTAB mixture is observed to be almost independent of the micellar composition. This suggests that the volumes of the counter ions in the micellar solutions are almost equal to those in the monomeric solutions.     

Spectroscopic studies of interaction of Safranine T with nonionic micelles and mixed micelles

The visible spectra of Safranine T (ST) in micellar solution of Brij 58, Tween 20 and Tween 40 and mixed micellar solution of Brij 58/Tween 20 and Brij 58/Tween 40 indicate formation of 1:1 charge transfer (CT) complex between acceptor ST and donor nonionic micelles and mixed micelles. The experimental CT transition energies are well correlated (through Mulliken's equation) with the vertical ionization potential of the donors. The solvent parameters, i.e. the intramolecular charge transfer energy ET(30) have been determined from the Stokes spectral shift. Variations of ionization potential and micropolarity in the mixed micellar region have been investigated as a function of surfactant composition and the obtained results in mixed micellar medium has been compared to the normal micelles. The critical micelle concentration (CMC) values determined at various surfactant compositions are lower than the ideal values indicating a synergistic interaction. The interaction parameter (beta) and micellar stability has been calculated using regular solution theory.     

Micellar solutions of ionic surfactants and their mixtures with nonionic surfactants: Theoretical modeling vs. Experiment

Here, we review two recent theoretical models in the field of ionic surfactant micelles and discuss the comparison of their predictions with experimental data. The first approach is based on the analysis of the stepwise thinning (stratification) of liquid films formed from micellar solutions. From the experimental step-wise dependence of the film thickness on time, it is possible to determine the micelle aggregation number and charge. The second approach is based on a complete system of equations (a generalized phase separation model), which describes the chemical and mechanical equilibrium of ionic micelles, including the effects of electrostatic and non-electrostatic interactions, and counterion binding. The parameters of this model can be determined by fitting a given set of experimental data, for example, the dependence of the critical micellization concentration on the salt concentration. The model is generalized to mixed solutions of ionic and nonionic surfactants. It quantitatively describes the dependencies of the critical micellization concentration on the composition of the surfactant mixture and on the electrolyte concentration, and predicts the concentrations of the monomers that are in equilibrium with the micelles, as well as the solution’s electrolytic conductivity; the micelle composition, aggregation number, ionization degree and surface electric potential. These predictions are in very good agreement with experimental data, including data from stratifying films. The model can find applications for the analysis and quantitative interpretation of the properties of various micellar solutions of ionic surfactants and mixed solutions of ionic and nonionic surfactants.     

混合胶束中Gemini阳离子表面活性剂14-s-14与常规表面活性剂的协同作用:连接臂及反离子效应(英文)

The mixed micelle formation of binary cationic 14-s-14 gemini with conventional single chain surfactants was studied by conductivity measurements.The critical micelle concentration(cmc) and the degree of counterion binding values(g) of the binary systems were determined.The results were analyzed by applying regular solution theory(RST) to calculate micellar compositions(X),activity coefficients(f1,f2),and the interaction parameters(β).The synergistic interactions of all the investigated cationic gemini+conventional surfactant combinations were found to be dependent upon the length of hydrophobic spacer of the gemini surfactant.The excess Gibbs free energy of mixing was evaluated,and it indicated relatively more stable mixed micelles for the binary combinations.     

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.     

Mixed micellization of a nonionic-cationic surfactant system constituted by n-octyl-beta-D-glucopyranoside/dodecyltrimethylammonium bromide/H2O. An electrochemical, thermodynamic, and spectroscopic study

The mixed micelles constituted by a nonionic surfactant widely used in the biochemical field, n-octyl-beta-D-glucopyranoside, and a cationic surfactant with 12 carbon atoms on the hydrophobic tail, dodecyltrimethylammonium bromide, have been studied in aqueous solution, at 298.15 K, by means of conductivity, speed of sound, density, and fluorescence spectroscopy experiments. From these data, the monomeric and micellar phases of the mixed aggregates were fully analyzed through the determination of the total and partial critical micellar concentrations, the dissociation degree of the mixed micelle, the total and partial aggregation numbers, the apparent molar volumes and isentropic compressibilities, the hydration numbers, and the corresponding changes in these thermodynamic properties due to the mixed aggregation process. The experimental findings have been compared with those obtained with several theoretical models, some of them modified in this work to take into account the specific characteristics of the aggregates studied herein.     

Kinetics of micellization: its significance to technological processes

The association of many classes of surface active molecules into micellar aggregates is a well-known phenomenon. Micelles are often drawn as static structures of spherical aggregates of oriented molecules. However, micelles are in dynamic equilibrium with surfactant monomers in the bulk solution constantly being exchanged with the surfactant molecules in the micelles. Additionally, the micelles themselves are continuously disintegrating and reforming. The first process is a fast relaxation process typically referred to as τ₁. The latter is a slow relaxation process with relaxation time τ₂. Thus, τ₂ represents the entire process of the formation or disintegration of a micelle. The slow relaxation time is directly correlated with the average lifetime of a micelle, and hence the molecular packing in the micelle, which in turn relates to the stability of a micelle. It was shown earlier by Shah and coworkers that the stability of sodium dodecyl sulfate (SDS) micelles plays an important role in various technological processes involving an increase in interfacial area, such as foaming, wetting, emulsification, solubilization and detergency. The slow relaxation time of SDS micelles, as measured by pressure-jump and temperature-jump techniques was in the range of 10⁻⁴–10¹ s depending on the surfactant concentration. A maximum relaxation time and thus a maximum micellar stability was found at 200 mM SDS, corresponding to the least foaming, largest bubble size, longest wetting time of textile, largest emulsion droplet size and the most rapid solubilization of oil. These results are explained in terms of the flux of surfactant monomers from the bulk to the interface, which determines the dynamic surface tension. The more stable micelles lead to less monomer flux and hence to a higher dynamic surface tension. As the SDS concentration increases, the micelles become more rigid and stable as a result of the decrease in intermicellar distance. The smaller the intermicellar distance, the larger the Coulombic repulsive forces between the micelles leading to enhanced stability of micelles (presumably by increased counterion binding to the micelles). The Center for Surface Science & Engineering at the University of Florida has developed methods using stopped-flow and pressure-jump with optical detection to determine the slow relaxation time of micelles of nonionic surfactants. The results show relaxation times τ₂ in the range of seconds for Triton X-100 to minutes for polyoxyethylene alkyl ethers. The slow relaxation times are much longer for nonionic surfactants than for ionic surfactants, because of the absence of ionic repulsion between the head groups. The observed relaxation time τ₂ was related to dynamic surface tension and foaming experiments. A slow break-up of micelles, (i.e. a long relaxation time τ₂) corresponds to a high dynamic surface tension and low foamability, whereas a fast break-up of micelles, leads to a lower dynamic surface tension and higher foamability. In conclusion, micellar stability and thus the micellar break-up time is a key factor in controlling technological processes involving a rapid increase in interfacial area, such as foaming, wetting, emulsification and oil solubilization. First, the available monomers adsorb onto the freshly created interface. Then, additional monomers must be provided by the break-up of micelles. Especially when the free monomer concentration is low, as indicated by a low CMC, the micellar break-up time is a rate limiting step in the supply of monomers, which is the case for many nonionic surfactant solutions. Therefore, relaxation time data of surfactant solutions enables us to predict the performance of a given surfactant solution. Moreover, the results suggest that one can design appropriate micelles with specific stability or τ₂ by controlling the surfactant structure, concentration and physico-chemical conditions, as well as by mixing anionic/cationic or ionic/nonionic surfactants for a desired technological application.     

Counterion condensation and release in micellar solutions

Counterion condensation and release in micellar solutions are investigated by direct measurement of counterion concentration with ion-selective electrode. Monte Carlo simulations based on the cell model are also performed to analyze the experimental results. The degree of counterion condensation is indicated by the concentration ratio of counterions in the bulk to the total ionic surfactant added, alpha< or =1. The ionic surfactant is completely dissociated below the critical micelle concentration (cmc). However, as cmc is exceeded, the free counterion ratio alpha declines with increasing the surfactant concentration and approaches an asymptotic value owing to counterion condensation to the surface of the highly charged micelles. Micelle formation leads to much stronger electrostatic attraction between the counterion and the highly charged sphere in comparison to the attraction of single surfactant ion with its counterion. A simple model is developed to obtain the true degree of ionization, which agrees with our Monte Carlo results. Upon addition of neutral polymer or monovalent salts, some of the surfactant counterions are released to the bulk. The former is due to the decrease of the intrinsic charge (smaller aggregation number) and the degree of ionization is increased. The latter is attributed to competitive counterion condensation, which follows the Hefmeister series. This consequence indicates that the specific ion effect plays an important role next to the electrostatic attraction.     

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.     

Small-angle neutron scattering of mixed ionic perfluoropolyether micellar solutions

Aqueous mixed micellar solutions of perfluoropolyether carboxylic salts with ammonium counterions have been studied by small-angle neutron scattering. Two surfactants differing in the tail length were mixed in proportions n2/n3 = 60/40 w/w, where n2 and n3 are the surfactants with two and three perfluoroisopropoxy units in the tail, respectively. The tails are chlorine-terminated. The mixed micellar solutions, in the concentration range 0.1-0.2 M and thermal interval 20-40 degrees C, show structural characteristics of the interfacial shell that are very similar to ammonium n2 micellar solutions previously investigated; thus, the physics of the interfacial region is dominated by the polar head and counterion. The shape and dimensions of the micelles are influenced by the presence of the n3 surfactant, whose chain length in the micelle is 2 A longer than that of the n2 surfactant. The n3 surfactant favors the ellipsoidal shape in the concentration range 0.1-0.2 M with a 1/2 ionization degree of n2 micelles. The very low surface charge of the mixed micelles is attributed to the increase in hydrophobic interactions between the surfactant tails, due to the longer n3 surfactant molecules in micelles. The closer packing of the tails decreases the micellar curvature and the repulsions between the polar heads, by surface charge neutralization of counterions migrating from the Gouy-Chapman diffuse layer, leading to micellar growth in ellipsoids with greater axial ratios.     

Removal of cadmium ions using micellar-enhanced ultrafiltration with mixed anionic-nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF) was used to remove cadmium ions from wastewater efficiently. In this study the nonionic surfactants polyoxyethyleneglycol dodecyl ether (Brij35) and polyoxyethylene octyl phenyl ether (TritonX-100) were for micellar-enhanced ultrafiltration to lower the dosage of the anionic surfactant sodium dodecyl sulfate (SDS). The surfactant critical micelle concentration (CMC) and the degree of micelle counterion binding were investigated. The effects of nonionic surfactant addition on the efficiency of cadmium removal, the residual quantities of surfactant, the permeate flux and the secondary membrane resistance were investigated. A comparison between MEUF with SDS and MEUF with mixed anionic–nonionic surfactants was undertaken. The results show that the addition of Brij35 or TritonX-100 reduced the CMC of SDS and the degree of counterion binding for the micelles. Due to these variations the Cd²⁺ rejection efficiency was at a maximum when the Brij35:SDS and the TritonX-100:SDS molar ratio was 0.5. The Cd²⁺ rejection efficiency in MEUF with SDS is higher than for MEUF with mixed surfactants when the total dose of surfactant is constant. The permeate flux of MEUF with SDS is higher than that for MEUF with mixed surfactants while the secondary resistance of MEUF with SDS is less than that of MEUF with mixed surfactants.     

The interaction of isomeric hexanediols with sodium dodecyl sulfate and dodecyltrimethylammonium bromide micelles

The micelle formation process for a typical anionic surfactant, sodium dodecyl sulfate, and a typical cationic surfactant, dodecyltrimethylammonium bromide, has been investigated in a series of mixed solvents consisting of different concentrations of isomeric hexanediols (1,2-hexanediol and 1,6-hexanediol) in water. The critical micelle concentrations and the degrees of counterion dissociation of the mixed micelles were obtained from conductance experiments. Luminescence probing experiments have been used to determine the concentration of micelles in solution and, hence, the micellar aggregation numbers of the surfactants in the mixed solvent systems. The alcohol aggregation numbers were determined by combining the partition coefficients (obtained using NMR paramagnetic relaxation enhancement experiments) with the micellar concentrations from the luminescence probing experiments. All these results are interpreted in terms of the difference in the interaction of the isomeric hexanediols with the surfactant as a function of the position of the hydroxyl groups on the six-carbon chain of the alcohol. Received: 28 June 2000/Accepted: 5 July 2000     

混合反胶束的电导与微结构研究

反胶束是两亲分子在非极性溶剂中形成的一种有序组合体，在医药、化工、采油、胶束催化及酶催化等领域中有重要应用．与胶束溶液相比，人们对反胶束的形成与结构的了解至今仍不充分．特别是对于由混合表面活性剂形成的反胶束的研究几乎无人涉及．本文采用动态光散射、电导及荧光光谱等手段对阴离子表面活性剂AOT与非离子表面活性剂形成的混合反胶束进行了研究，旨在探讨利用表面活性剂的复配来调节和控制反胶束的结构和性能．亚实验部分二异辛基磺化琉璃酸钠（AOT，Sigma公司）；Brij30为含4个氧乙烯基（EO基）的十二碳醇（AcrosOrgani…     

SDS对SB3-12胶束表面电荷密度的调控作用及对药物增溶的影响

两性离子甜菜碱表面活性剂(SB3-12)胶束具有较好的生物相容性,由于相反电荷的极性头之间具有静电中和作用,胶束表面具有小的负电荷密度。当加入阴离子的十二烷基硫酸钠(SDS)以后,负离子SD-与SB3-12胶束极性区内层季铵正电荷的静电中和作用,能连续地调节胶束表面磺酸基的负电荷密度,这有利于对药物分子的选择性增溶和调节在生理条件下的药物的输送。等温滴定量热(ITC)研究发现SB3-12和SDS有强的协同效应,混合临界胶束浓度(CMC)和胶束化焓明显降低,并得到两者协同效应的弱静电作用机理。当模型药物分子芦丁(Rutin)与SB3-12/SDS混合胶束作用时,芦丁7位羟基的氢解离后的阴离子与SDS共同作用于SB3-12形成混合胶束。UV-Vis吸收光谱和~1H NMR谱研究发现,在SB3-12胶束中,芦丁分子的A环位于季铵阳离子附近,B环位于两个相反电荷之间的弱极性区域。在SDS胶束中,B环位于栅栏层,而A环和二糖暴露于水相侧。在混合胶束中,随着SDS摩尔分数增加,对A环的静电吸引变弱。离子表面活性剂对两性离子表面活性剂胶束表面电荷密度的调节作用,本质上是对胶束极性区域的物理及化学性质的微调,进而实现对药物的可控增溶。     

Micellar medium effects on the hydrolysis of phenyl chloroformate in ionic,zwitterionic, nonionic,and mixed micellar solutions

The spontaneous hydrolysis of phenyl chloroformate was studied in various anionic, nonionic, zwitterionic, and cationic aqueous micellar solutions, as well as in mixed anionic–nonionic micellar solutions. In all cases, an increase in the surfactant concentration results in a decrease in the reaction rate and micellar effects were quantitatively explained in terms of distribution of the substrate between water and micelles and the first‐order rate constants in the aqueous and micellar pseudophases. A comparison of the kinetic data in nonionic micellar solutions to those in anionic and zwiterionic micellar solutions makes clear that charge effects of micelles is not the only factor responsible for the variations in the reaction rate. Depletion of water in the interfacial region and its different characteristics as compared to bulk water, the presence of high ionic concentration in the Stern layer of ionic micelles, and differences in the stabilization of the initial state and the transition state by hydrophobic interactions with surfactant tails can also influence reactivity. The different deceleration of the reaction observed in the various micellar solutions studied was discussed by considering these factors. Synergism in mixed‐micellar solutions is shown through the kinetic data obtained in these media. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 445–451, 2002     

Mixed micelle behavior of Pluronic L64 and Triton X-100 with conventional and dimeric cationic surfactants

The mixed micellar properties of a triblock copolymer, Pluronic L64, (EO)13(PO)30(EO)13, and a nonionic surfactant, Triton X-100, in aqueous solution with conventional alkyl ammonium bromides and their dimeric homologues were investigated with the help of fluorescence and cloud point measurements. The composition of mixed micelles and the interaction parameter, beta, evaluated from the critical micelle concentration (cmc) data for different mixtures using Rubingh's and Motomura's theories are discussed. It has been observed that the mixed micelle formation between monomeric/dimeric alkyl ammonium bromides and L64 was due to synergistic interactions which increase with the increase in hydrophobicity of the cationic component. On the other hand, synergistic mixing was observed in the mixed micelles of Triton X-100 and monomeric cationic surfactants, the magnitude of which decreases slightly with the increase in hydrophobicity of the cationic component. Antagonistic interactions were observed in the case of Triton X-100 and dimeric cationic surfactants.     

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.