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.     

Drainage and critical thickness of foam films from aqueous solutions of mixed nonionic surfactants

The thinning and the critical thickness (of rupture or “black spots” formation) of foam films from aqueous solutions of mixed nonionic surfactants are studied under varied experimental conditions, as a function of film radius (0.05–0.15 mm), surfactant concentration (0.01–1.0 CMC) and ionic strength (0.001–0.1 M NaCl). The experimental values of the drainage coefficient (), determined from the film thickness versus time dependences, were used to calculate the theoretical values of the film critical thickness.

The real velocity of film thinning is a major factor in the process of reaching the state of kinetic instability when approaching the critical thickness (Scheludko's criterion). The classical equation used to describe the film thinning rate, proposed and named by Scheludko (1955) “Reynolds Law”, is applicable for small film radii (r < 0.05 mm). At larger radii the velocity of thinning follows the equation of Manev et al. [E.D. Manev, R. Tsekov, B. Radoev, J. Colloid Interf. Sci. 18 (1997) 769], which takes into account the effect of the film thickness local non-homogeneity.

The studied stabilizing surfactants include n-dodecyl-β-d-maltoside (β-C12G2) and hexaethyleneglycol monododecyl ether (C12E6). Along with confirming the dependences following from the theories of the critical thickness [B. Radoev, A. Scheludko, E.D. Manev, J. Colloid Interf. Sci. 95 (1983) 254] and film thinning [E.D. Manev, R. Tsekov, B. Radoev, J. Colloid Interf. Sci. 18 (1997) 769], the results of the present investigation established also certain deviations for films stabilized with mixed surfactants (β-C12G2 + C12E6). The effectiveness of the empirical equation, employing the drainage coefficient () to describe the film thinning, is emphatically proven here.     

Electrolyte effect on mixed micelle and interfacial properties of binary mixtures of cationic and nonionic surfactants

In the present work, the adsorption behavior at the liquid-air interface and micellization characteristics of mixtures of cetyltrimethylammonium bromide (CTAB) and p-(1,1,3,3-tetramethylbutyl) polyoxyethylene (TritonX-100) in aqueous media containing different concentrations of NaBr were investigated by surface tension and potentiometry measurements. From plots of surface tension (gamma) as a function of solution composition and total surfactant concentration, we determined the critical micelle concentration (CMC), minimum surface tension at the CMC (gamma(CMC)), surface excess (Gamma(max)), and mean molecular surface area (A(min)). On the basis of regular solution theory, the compositions of the adsorbed film (Z) and micelles (X(M)) were estimated, and then the interaction parameters in the micelles (beta(M)) and in the adsorbed film phase (beta(sigma)) were calculated. For all mole fraction ratios, the results showed synergistically enhanced ability to form mixed micelles as well as surface tension reduction. Furthermore beta was calculated by considering nonrandom mixing and head group size effects. It was observed that, for both the planar air/aqueous interface and micellar systems, the nonideality decreased as the amount of electrolyte in the aqueous medium was increased. This was attributed to a decrease of the surface charge density caused by increasing the concentration of bromide ions.     

Mixtures of branched non-ionic oligo-oxyethylene surfactants in aqueous solutions — the effect of molecular geometry on LC phase behaviour 4

The LC phase behavior of ternary mixtures of the two corresponding branched non-ionic surfactants 1,3-bis-(methoxy-tetraoxyethylene)-2-propoxy-tetradecane (Y-surfactant) and 1,3-bis-(heptyloxy)-2-propoxyoctaoxyethylene mono-methyl ether (V-surfactant) and water were studied by polarizing microscopy. The two branched surfactants, which have different molecular geometries but nearly the same hydrophilic-lipophilic volume ratio, exhibit extremely different phase behavior in binary surfactant/water systems. For the ternary mixtures of Y- and V-surfactant and water we found-according to established packing models-a continuous stabilization of the cubic and hexagonal phases and a destabilization of the lamellar phase with increasing amount of Y-surfactant. On the other hand, we observed a thermal stabilization of the lamellar phase. The maximal transition temperatures of the lamellar phase pass a maximum with increasing amount of Y-surfactant.     

Interactions between nonpolar surfaces in mixed solutions of cationic and nonionic surfactants

The interaction energy between hydrophobic SiO₂ particles in aqueous solutions of a cationic surfactant (dodecylpyridinium bromide, DDPB), a nonionic surfactant (Triton X-100, TX-100), and their mixed solutions was measured as a function of concentration. Synergism has been observed in mixed surfactant solutions: the surfactant concentration required for achieving the set interaction energy in the mixed solutions was lower than in the solutions of the individual surfactants. The molecular interaction parameters in surfactant mixtures were calculated using the Rosen model. Chain-chain interactions between nonionic and cationic surfactants were suggested as the main reason for the synergism.     

Striking differences between alkyl sulfate and alkyl sulfonate when mixed with cationic surfactants

The properties of alkyl sulfate and alkyl sulfonate are similar except for their Krafft points. However, alkyl sulfate and alkyl sulfonate behave quite differently when they are mixed with cationic surfactants and show some totally unexpected results. In this work sodium alkyl sulfate (C_nH_2n+1SO₄Na,C_nSO₄)–alkyl quaternary ammonium bromide [C_nH_2n+1N(C_mH_2m+1)₃Br, C_nN, m=1–4] mixtures and sodium alkyl sulfonate (C_nH_2n+1SO₃Na, C_nSO₃)–C_nN mixtures were studied. It was found that, in contrast to the single surfactants, C_nSO₃–C_nN mixtures were much more soluble than C_nSO₄–C_nN mixtures. Besides, the two kinds of catanionic surfactant mixtures were quite different in their phase behavior and aggregate properties. The results were interpreted in terms of the interactions between surfactant molecules, which were very different in the two kinds of mixed systems owing to the distinction between alkyl sulfate and alkyl sulfonate in the molecular charge distribution.     

Interactions in mixed cationic surfactants and dextran sulfate aqueous solutions

The interactions between a hydrophilic anionic polysaccharide, dextran sulfate, and oppositely charged surfactants, n-alkylammonium chlorides (the number of carbon atoms per chain being 10, 12, and 14), were investigated by optical microscopy, X-ray diffraction, microelectrophoretic mobility, conductivity, surface tension, and light-scattering measurements at 303 K. The increase of surfactant alkyl chain length shifts both the critical aggregation (cac) and the critical micelle concentrations (cmc) toward lower surfactant concentration. Light-scattering and microelectrophoretic data revealed the coexistence of differently structured complexes beyond the cac. The presence of giant vesicles indicates that at least one type of species is ordered in bilayers. X-ray analysis of dry n-alkylammonium dextran sulfates exhibited mesomorphous ordering and interplanar spacings typical for lamellar structures; i.e., n-alkylammonium molecules form more or less disordered bilayers interconnected with dextran sulfate chains, thus forming multilamellar stacks. The average basic lamellar thickness increased linearly with the increase of surfactant chain length, whereas the average number of lamellar bilayers in the stack of lamellae decreases.     

Wetting of surfactant solutions by alkanes.

Ellipsometry, surface tensiometry, and contact-angle measurement have been used to study the transition between partial wetting and pseudo-partial wetting of surfactant solutions by alkanes. In the partial wetting regime, the air-water surface tension is the same with and without alkane. In the pseudo-partial wetting regime, the air-water surface tension is lowered by the presence of alkane, showing that oil is solubilised into the surfactant monolayer. A discontinuous change in the coefficient of ellipticity with increasing surfactant concentration provides unequivocal evidence for the first-order nature of the wetting transitions. Ellipsometry has been used to explore the generality of wetting transitions of alkanes (dodecane, hexadecane, and squalane) on surfactant solutions [dodecyltrimethylammonium bromide, tetredecyltrimethylammonium bromide, dibucaine hydrochloride, and Aerosol OT (AOT)]. Of the systems studied, only hexadecane on AOT solutions did not show a wetting transition. Excess alkane remains as a lens on the surface of the surfactant solutions at all concentrations, but the contact angle is a minimum at the wetting transition. A semiquantitative model for the variation of the contact angle with surfactant concentration is provided.     

Surface and bulk properties of aqueous binary mixtures of Pluronic F68 and low-molecular-weight cationic surfactants: 2. Wetting and modifying effects of mixed solutions

Wetting and adsorption modification of polystyrene surface with aqueous solutions of F68-cationic surfactant mixtures are studied. The synergism of wetting is revealed. It is established that the degree of synergism upon wetting is determined by the synergism of surfactant adsorption on a solid surface and peculiarities of the formation of mixed adsorption layers of surfactants. It is shown that low-molecular-weight cationic surfactants can be used to increase the efficiency of the modification of polymer surfaces with Pluronics.     

Interaction between anionic and cationic gemini surfactants at air/water interface and in aqueous bulk solution

The mixture of the anionic O,O′-bis(sodium 2-lauricate)-p-benzenediol (C₁₁pPHCNa) and cationic (oligoona)alkanediyl-α, ω-bis(dimethyldodecylammonium bromide) (C₁₂-2-E_x-C₁₂·2Br) gemini surfactants has been investigated by surface tension and pyrene fluorescence. The results show that the surface tension γ drops faster with total surfactant concentration C_T for α₁ = 0.1 or 0.3 than for α₁ = 0.7 or 0.9, where α₁ is the mole fraction of C₁₁pPHCNa in the bulk solution on a surfactant-only basis. The fast drop in γ for α₁ < 0.5 indicates strong adsorption at the air/water interface owing to the interaction between oppositely charged components, resulting in the formation of the adsorption double layers in the subsurface. The slow descent in γ for α₁ > 0.5 is attributed to the pre-aggregation in the solution before the critical micelle concentration cmc. A possible mechanism is proposed.     

Temperature-dependent vesicle formation of aqueous solutions of mixed cationic and anionic surfactants

The phase behavior of aqueous solutions of mixed cetyltrimethylammonium bromide (CTAB) and sodium octyl sulfate (SOS) was examined at different temperatures (20, 30, 40, and 50 degrees C). While stable vesicles were formed in a narrow composition range on the SOS-rich side at 20 degrees C, the range widened remarkably when the temperature was raised to 30 degrees C. Thus, the vesicle region extended to cover almost the entire composition range, CTAB:SOS = 0.5:9.5-5.0:5.0, at the total surfactant concentrations of 50-70 mM on the SOS-rich side. To analyze the temperature dependence of this phase behavior of the mixed surfactant system, DSC and fluorescence polarization measurements were performed on the system. The experimental findings obtained revealed that pseudo-double-tailed CTAB/SOS complex, the major component of the bimolecular membrane formed by the surfactant mixture, undergoes a gel (Lbeta)-liquid crystal (Lalpha) phase transition at about 26 degrees C. This phenomenon was interpreted as showing that the bimolecular membrane has no curvature and is rigid and easy to precipitate at temperatures below the phase transition point, whereas it has a curvature and is loose enough to disperse in the solution as vesicles at temperatures above the phase transition point. Vesicles formed by the anionic/cationic surfactant complex were then stable at temperatures above the phase transition temperature of the complex.     

Steady-state fluorescence investigations of aqueous binary mixtures of myristyl alcohol based bis-sulfosuccinate anionic gemini surfactant and effect of different conventional surfactants therein

The present research work is associated with the fluorescence investigations of binary aqueous mixed surfactants solutions of anionic bis-sulfosuccinate gemini surfactant (BSGSMA_1,8) and three different conventional surfactants—anionic viz. sodium dodecyl sulfate (SDS), cationic viz. cetyl trimethyl ammonium bromide (CTAB), and nonionic surfactant viz. Triton X 100. Steady-state fluorescence spectroscopy technique has been utilized to examine the micellization behavior of aqueous solution of pure myristyl alcohol-based BSGSMA_1,8 having flexible methylene chain [(CH₂)₈] as spacer group. Critical micelle concentration (CMC), aggregation number (N), and micropolarity of pure and mixed surfactants systems were explored during the investigations. The results revealed the best synergism behavior of prepared gemini BSGSMA_1,8 with SDS as compared to CTAB and Triton X 100. The maximum reduction in the value of pyrene intensity ratio (I₁/I₃) was observed for gemini and SDS mixed surfactant solution. On the other hand, the increased I₁/I₃ value of mixed gemini with Triton X 100 exhibited that mixed surfactant system of anionic gemini BSGSMA_1,8 with non-ionic Triton X 100 is not as compact as other mixed surfactant systems. Aggregation number increased and micropolarity decreased with increased concentration of gemini surfactants.     

Interaction of cationic surfactant and anionic polyelectrolytes in mixed aqueous solutions

Surfactant–polymer interactions in aqueous solutions have been studied using dynamic surface tension, polyelectrolyte titration, nephelometric turbidity, and dynamic light scattering. For the preparation of complexes, a technical cationic surfactant was used in combination with two poly(maleic acid-co-polymers) of similar structure but different hydrophobicity. The dynamic surface tensions of mixed solutions as functions of surfactant concentration at constant polyelectrolyte content, as well as changes in the surface activity due to the influence of polyanion at constant surfactant concentration are discussed in terms of a complex or aggregate formation in the bulk phase. The interaction of the surfactant with poly(maleic acid-alt-propene) (P-MS-P) and poly(maleic acid-alt--methylstyrene) (P-MS-MeSty), respectively, is strong in both cases and results in the formation of nanoparticles with properties depending on the composition of the corresponding mixture.     

Simultaneous potentiometric determination of cationic and ethoxylated nonionic surfactants in liquid cleaners and disinfectants

A sensitive potentiometric surfactant sensor based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate (TPB) antagonist ion was used as the end-point detector in ion-pair potentiometric surfactant titrations using sodium TPB as a titrant. Several analytical and technical grade cationic and ethoxylated nonionic surfactants (EONS) and mixtures of both were potentiometrically titrated.The sensor showed satisfactory analytical performances within a pH range of 3-10 and exhibited satisfactory selectivity for all CS and EONS investigated. Ionic strength did not influence the titration except at 0.1 M NaCl, in which a slight distortion of the second inflexion corresponded with the nonionic surfactant.Two-component combinations of four CS and three EONS were potentiometrically titrated using the sensor previously mentioned as the end-point detector. The quantities of the surfactants varied between 2 and 6 μmol for CS and 2.50 and 7.50 μmol for EONS. The known addition methodology was used for determination of the surfactant with considerably lower concentration in the mixture.Three commercial products containing cationic surfactants as disinfectants and nonionic surfactants were potentiometrically titrated, and the results for both type of surfactants were compared with those obtained with standard conventional methods.     

Semi-quantitative determination of cationic surfactants in aqueous solutions using gold nanoparticles as reporter probes

Concentrations of cationic surfactants in aqueous solutions have been estimated on the basis of changes in the color of gold nanoparticles, used as reporter probes. We have shown that the colors of gold nanoparticles with anionic protective groups on their surfaces shift from red to indigo/purple and then back to red in a range of cationic surfactant solutions in which concentrations vary from very low to above the theoretical CMCs. The color changes occur near the theoretical CMCs, presumably because the presence of surfactant micelles in the solution prevents the gold nanoparticles from aggregating. We have used gold nanoparticles as reporter probes to determine the concentrations of cationic surfactants in products such as hair conditioners, which often contain large amounts of alkyltrimethylammonium halides. Although this approach can only provide an estimate, it can be performed simply by addition of a given amount of gold nanoparticles to a series of diluted solutions, without the need for instruments or labor-intensive procedures. Figure Photographs of a series of diluted hair conditioner solutions with added gold nanoparticles

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Silicon‐modified surfactants and wetting: III. The spreading behaviour of equimolar mixtures of nonionic trisiloxane surfactants on a low‐energy solid surface

The spreading behaviour of binary and ternary equimolar mixtures of siloxane surfactants of general formula [(CH₃)₃SiO]₂CH₃Si(CH₂)₃ (OCH₂CH₂) _nOCH₃, n = 3–9, has been investigated. The mixtures show a pronounced temperature dependence on the initial spreading rate. Mixtures imitating the average oligoethylene glycol chain length n = 5 are the fastest spreaders at 15 °C. At 23 °C and 40 °C these mixtures spread fastest sucking n = 6 and n = 8, respectively. For a given average chain length an increasing length difference between the components of the binary mixtures reduces the initial spreading rate. Nevertheless, substantial differences between the phase transition temperature T_c from the lamellar phase (L_α) into the two‐phase state (2Φ) and the actual spreading temperature are tolerated. A clear relation between phase transition temperature T_c and initial spreading rate does not exist. Copyright © 1999 John Wiley & Sons, Ltd.     

Self-assembly of mixed anionic and nonionic surfactants in aqueous solution

We present the phase diagram and the microstructure of the binary surfactant mixture of AOT and C(12)E(4) in D(2)O as characterized by surface tension and small angle neutron scattering. The micellar region is considerably extended in composition and concentration compared to that observed for the pure surfactant systems, and two types of aggregates are formed. Spherical micelles are present for AOT-rich composition, whereas cylindrical micelles with a mean length between 80 and 300 ? are present in the nonionic-rich region. The size of the micelles depends on both concentration and molar ratio of the surfactant mixtures. At higher concentration, a swollen lamellar phase is formed, where electrostatic repulsions dominate over the Helfrich interaction in the mixed bilayers. At intermediate concentrations, a mixed micellar/lamellar phase exists.     

芳香族小分子物质在表面活性剂溶液中的状态

阴、阳离子表面活性剂在水溶液中混合后很容易形成沉淀,因而以往在应用上将这两种表面活性剂视为配伍禁忌。但是最近几年,混合阴、阳离子表面活性剂水溶液理论性质的研究受到了一种程度的重视。研究发现,该混合体系具有与单纯的离子型表面活性剂或离子与非离子型表面活性剂混合物十分不同的性质,     

Micellization and interfacial behavior of binary and ternary mixtures of model cationic and nonionic surfactants in aqueous NaCl medium

Mixed micelle formation and interfacial properties of aqueous binary and ternary combinations of hexadecyltrimethylammonium bromide (C(16)Br), hexadecylbenzyldimethylammonium chloride (C(16)BzCl) and polyoxyethylene (20) cetyl ether (Brij58) at 25 degrees C in 30 mM aqueous NaCl have been studied in detail employing tensiometric and fluorimetric techniques. The micellar and adsorption characteristics like composition, activity coefficients, mutual interaction parameters and free energy of micellization have been estimated using the theoretical approaches of Clint, Rosen, Rubingh, Blankschtein et al., Rubingh-Holland and Maeda. A comprehensive account of the comparative performance of these models on the selected cationic-cationic-nonionic surfactant mixtures at constant ionic strength has been presented. The Blankschtein model predicted lower synergism than from Rubingh's method because it neglects the contribution due to steric interaction between surfactant head groups of different sizes and charges. Free energy of micellization calculated using Maeda's approach, which employs interaction parameter and micellar mole fraction from Rubingh's model as inputs, shows good correlation with that calculated from commonly used phase separation model. The present study also reveals that the modified Rubingh-Holland method along with the Rosen's model can be applied to analyze the interfacial characteristics of ternary surfactant mixtures with a fair degree of success thereby widening the domain of applicability of this model.