The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

Ionic Mixed Interactions in Macromolecules

Purely ionic interactions in natural and synthetic macromolecules involve the mutual interaction of fixed charges and their interaction with mobile ions. Such charge‐dependent interactions lead to well‐documented effects, including chain expansion of polyelectrolytes, globularization of polyampholytes, distributions of mobile ions according to charge screening, or ion condensation models. A variety of structural features, functions, and applications of these systems is amplified by the superimposition of charge‐independent effects associated with the occurrence of less polar or hydrophobic groups, special salts, surfactants, or complementary protein assemblies. For instance, ionic and hydrophobic attractive interactions stabilize pearls (or rings)‐on‐a‐string conformations, possibly a model for the formation of the chromatin assembly. The attractive interactions due to hydrophobic fatty acid groups attached to polysaccharides promote the formation of vesicles that entrap and slowly release water‐soluble drugs. Intra‐ and intermolecular associations based on ion‐pairing mixed interactions also control the formation of host–guest compounds, protein conformation, and the assembly of layered polyelectrolytes. Metallo‐supramolecular polymers and networks are formed due to the coordination of multivalent cations with bi‐ and trifunctional organic ligands. The association of lithium salts to polymers in the absence of water allows the formation of highly efficient energy sources. It also allows the identification of the ionic species that control charge‐independent contributions to Hofmeister effects. This critical review presents a synthetic classification of systems displaying ionic mixed interactions, and a discussion of underlying molecular mechanisms.     

Interactions in Calcium Oxalate Hydrate/Surfactant Systems

Phase transformation of calcium oxalate dihydrate (COD) into the thermodynamically stable monohydrate (COM) in anionic (sodium dodecyl sulfate (SDS)) and cationic (dodecylammonium chloride) surfactant solutions has been studied. Both surfactants inhibit, but do not stop transformation from COD to COM due to their preferential adsorption at different crystal faces. SDS acts as a stronger transformation inhibitor. The general shape of adsorption isotherms of both surfactants at the solid/liquid interface is of two-plateau-type, but differences in the adsorption behavior exist. They originate from different ionic and molecular structures of crystal surfaces and interactions between surfactant headgroups and solid surface. Copyright 1999 Academic Press.     

Micellar Aggregation Behavior and Electrochemically Reversible Solubilization of a Redox-Active Nonionic Surfactant

For the purpose of studying the potential of a novel nonionic switchable surfactant, 11-ferrocenylundecyl polyoxyethylene ether (FPEG), applied to surfactant-enhanced remediation (SER), the surface properties and micelle solubilization behavior of FPEG were investigated with different inorganic salts. With the addition of inorganic salts (NaCl and CaCl₂), the critical micelle concentration (CMC) of FPEG dropped from 15 to 12 and 8 mg·L^?1, respectively, due to the salting-out effect on the alkyl chain. Thermodynamic parameters based on the CMCs indicated that micelle formation was an entropy-driven process. Dynamic light scattering measurements verified that these inorganic salts can decrease the hydrodynamic diameters (D _h) of the micelles. Solubilization experiments with three typical polycyclic aromatic hydrocarbons (PAHs) demonstrated that the system of FPEG with NaCl shows the highest solubilization ability, and the molar solubilization ratio and micelle–water partition coefficient (K _m ) values follow the order pyrene > phenanthrene > acenaphthene. After oxidation, PAHs can be released from the micelles through breaking up of the micelles, and the cumulative release efficiency of pyrene, phenanthrene and acenaphthene are 31.2, 42.8 and 44.6 %; the order of release efficiency is opposite to that of the reduced form for solubilization abilities. All the results suggest that the ferrocene-containing, redox-active surfactant FPEG has the potential to be recycled in SER technology through electrochemistry approaches.     

Micellar Extraction of Carboxylic Acids with Phases of OP-10 Nonionic Surfactant on Heating

Extraction of carboxylic acids from aqueous solutions with phases of OP-10 nonionic surfactant on heating was studied in relation to the concentration and hydrophobicity of the acids. A multiple linear regression equation describing the process was suggested.     

Micellar Behavior of n-Alkyl Sulfates in Binary Mixed Systems

The micellar behavior of the binary mixed systems of sodium n-hexylsulfate with sodium n-decyl-, n-dodecyl-, and n-tetradecylsulfate has been studied. The critical micelle concentration of the mixtures was quantitatively estimated by conductance methods. The micellar composition in the micelles was determined by the Motomura model and the mutual interactions were estimated from Holland and Rubingh's theory. The surfactant mixtures were found to be nonideal. The influence of the alkyl chain length in these parameters was studied. Copyright 2000 Academic Press.     

核磁共振波谱技术应用在表面活性剂混合胶束体系中的研究进展

由于表面活性剂混合体系具有协同效应,又称协同作用或增效作用,使得混合体系通常较单一体系在性能上更具优势.当前,核磁共振技术(NMR)在表面活性剂混合体系研究中应用十分活跃,扩散、弛豫、二维等多种现代核磁共振技术被成功用于表面活性剂混合体系的胶束形成动力学过程、胶束表征以及胶束物理/化学特性等研究工作中.该文对近年来国内外有关工作进行分析和归纳,展望了核磁共振在表面活性剂混合体系研究中的潜力.     

Toward a Theory of Diffusion of a Nonionic Surfactant with Variable Aggregation Number in a Micellar System

Since the aggregation number of micelles always grows with concentration, and, in some cases this dependence is noticeable even for spherical micelles, there is a need to revise the theory of micellization, in which the aggregation number is assumed to be constant. This work reformulates the theory of diffusion of nonionic surfactants in micellar solutions with regard to the variability of the aggregation number. A new formula, which expresses the diffusion coefficient of a surfactant via the diffusion coefficients of monomers and micelles, contains an additional factor capable of increasing the diffusion coefficient with the surfactant concentration. However, this factor is not overly strong, and the “old” part of the formula acts in the opposite direction; as a result, the conventional decrease in the diffusion coefficient of a nonionic surfactant remains prevailing. The analytical consideration has been supplemented with numerical calculations, the results of which are presented in the tables.     

Activity Coefficients of Aqueous Mixed Ionic Surfactant Solutions from Osmometry

Osmotic techniques for measuring thermodynamic activities, such as isopiestic equilibration, are well established for multicomponent solutions, especially mixed salt solutions. Surprisingly, these techniques have not yet been applied to mixed ionic surfactants, despite the numerous practical applications of these systems and the importance of the Gibbs free energy for micelle stability. In this study, mass-action equations are developed for the osmotic coefficients of solutions of ionic surfactant CA + ionic surfactant CB, with common counterion C. Extended Debye–Hückel equations are used for the ionic activity coefficients. The equilibrium constants for mixed micelle formation are evaluated by Gibbs–Duhem integration of critical micelle concentrations. Fitting the derived equations to the osmotic coefficients of aqueous sodium decanoate + sodium dodecylsulfate solutions measured by freezing-point osmometry is used to evaluate the activities of the total surfactant components. Very large departures from ideal solution behavior are indicated, including stoichiometric surfactant activity coefficients and micelle activity coefficients that drop below 0.05 and 10^?8, respectively, relative to unity for ideal solutions. Osmometry offers many interesting and unexplored possibilities for studies of mixed surfactant thermodynamics.     

Viscosity of Nonionic Polymer/Anionic Surfactant Complexes in Water

The polymer-micelle model, formerly established by Cabane, is revised to develop a new viscosity equation to describe the dependence of dilute solution viscosity on polymer concentration in PEG/SDS aqueous solutions. Two parameters inthe new equation were proposed to characterize the influence of the polymer solution viscosity on the added surfactant. The viscosity data of polyethylene glycol (PEG) solutions containing sodium dodecyl sulfate (SDS) were measured by the Ubbelohde dilution viscometer and the new equation proved to be in good agreement with the experimental data. Copyright 2000 Academic Press.     

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.     

Partitioning of Amino Acids in Surfactant Based Aqueous Two-Phase Systems Containing the Nonionic Surfactant (Triton X-100) and Salts

The partitioning of three amino acids, L-phenylalanine, L-tryptophan and L-tyrosine, has been studied in surfactant-based aqueous two-phase systems (ATPS) of Triton X-100 + salts + H₂O at 298.15 K. Sodium citrate as an organic salt and magnesium sulfate as an inorganic salt were used to prepare the ATP systems. The effects of tie-line length and salt type on the partitioning of amino acids have been discussed. The results show that the partitioning behavior of the amino acids in the systems containing MgSO₄ and Na₃C₆H₅O₇ are significantly different, because increasing the tie-line length in MgSO₄ solutions leads to a decrease of the partition coefficient, whereas the opposite trend is found in Na₃C₆H₅O₇ solutions.     

Kinetic Effects in non Ionic Micellar Solutions

The elimination reaction between 2-(p-nitrophenyl)ethyl bromide and OH^- ions was studied in nonionic aqueous micellar solutions of two esters of long chain fatty acids and sorbitan polyethylene glycol, Tween 20 (monolaurate) and Tween 80 (monooleate). The equilibrium binding constants of the 2-(p-nitrophenyl)ethyl bromide molecules to the nonionic micellar aggregates were obtained by spectroscopic measurements. The experimental kinetic data were quantitatively rationalized by the treatment of first-order reactions based on the pseudophase model. Results from this work and from previous studies show that, whereas the presence of cationic and sulfobetaine micelles accelerates the reaction, the presence of nonionic micelles inhibits the reaction.     

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.

     

非离子表面活性剂在气液界面的分子动力学模拟

采用分子动力学方法研究了十二烷基醇聚氧乙烯醚系列非离子表面活性剂单分子层在气液界面的微观结构,并通过表面张力的计算考察了表面活性剂分子结构与性能的关系.研究结果表明,随着表面活性剂分子乙氧基基团个数的增加,模拟所得的表面张力的变化趋势与实验一致,所有分子的计算误差在5 mN·m-1以内.同时,随着乙氧基基团数目的增加,...     

Mixed Cationic-Nonionic Surfactants Route to MCM-48: Effect of the Nonionic Surfactant on the Structural Properties

Structurally ordered MCM-48 silicas were facilely synthesized using the mixtures of cetyltrimethylammonium bromide (CTAB) and p-Octyl polyethylene glycol phenyl ether (OP-10) as co-templates with low molar ratio of CTAB to silica (0.139:1) and low concentration of mixed surfactants (ca. 5%) and within a wide range of OP-10/CTAB ratio (0.08–0.25). For comparison purpose, the cubic material was also prepared with only CTAB as the structure-directing agent under the same preparation conditions. The products obtained by different templating method were thoroughly characterized by XRD, N₂ sorption, TEM, TG-DSC and ²⁹Si MAS NMR. Measurement results from these techniques indicated that the introduction of nonionic OP-10 had significant effect on the structural properties of MCM-48 and the mixed surfactants' route allowed an efficient synthesis and a more condensed product compared to the only cationic CTAB templating protocol. Finally, our preliminary explanation for that why cubic MCM-48 materials could be obtained in this system and structural properties were sensitive to the OP-10/CTAB ratios was discussed in detail.     

微量热法研究非离子型表面活性剂微乳液

用微量热法研究了由正十六烷／正己醇／水／烷基聚氧乙烯醚组成的微乳液中水的状态，对微乳液中水的模式对热效应的影响进行了解释。在微乳液具有异常流变性的水油比范围内，测定了体系在负触变性状态恢复期间的热效应。     

Kinetics of Aggregation and Relaxation in Micellar Surfactant Solutions

Theoretical results published in the last 17 years on the kinetics of aggregation and relaxation in micellar surfactant solutions have been reviewed. The results obtained by the analytical and direct numerical solution of the Becker–Döring kinetic equations and the Smoluchowski generalized equations, which describe different possible mechanisms of aggregation and relaxation on all time scales from ultrafast relaxation while reaching the quasi-equilibrium in the region of subcritical molecular aggregates to the last stage of slow relaxation of micelles to the final aggregated state, have been considered in detail. The droplet model and the model linear with respect to aggregation numbers have been used for the work of aggregation to describe the dynamics of the rearrangement of micellar systems consisting of only spherical, only cylindrical, and coexisting spherical and cylindrical aggregates, with the dynamics being both linear and nonlinear with respect to deviations from equilibrium. The results of molecular simulation of the rearrangement kinetics of micellar systems subjected to initial disturbance have been reviewed.