Volumetric behavior and micelle formation of aqueous surfactant mixtures

A thermodynamic treatment of the volumetric behavior of surfactant mixtures in water have been developed on the basis of the thermodynamic treatment of mixed micelle by Motomura et al. Densities of aqueous solutions of mixtures of decyltrimethylammonium bromide (DeTAB) and dodecyltrimethylammonium bromide (DTAB) have been measured as a function of total molality at constant compositions. The apparent molar volumes of the mixtures have been derived from the density data and the mean partial molar volume of monomeric surfactant mixture V _t ^w , the molar volume of mixed micelle V^M/N _t ^M , the voluem of formation of mixed micelle _W ^M V, and the composition of surfactant in the mixed micelle have been evaluated. The V _t ^W , V^M/N _t ^M , and _W ^M V have been observed to depend on the composition. The linear dependence of V _t ^W and V^M/N _t ^M on the composition indicates that the mixing of DeTAB and DTAB is ideal both in the monomeric and micellar states. This has been confirmed further by the shape of the critical micelle concentration vs. composition curves.     

Mechanism of surfactant micelle formation

The mechanism of micelle formation of surfactants sodium dodecyl sulfate (SDS), n-hexyldecyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) in heavy water solutions was studied by 1H NMR (chemical shift and line shape) and NMR self-diffusion experiments. 1H NMR and self-diffusion experiments of these three surfactants show that their chemical shifts (delta) begin to change and resonance peaks begins to broaden with the increase in concentration significantly below their critical micelle concentrations (cmc's). At the same time, self-diffusion coefficients ( D) of the surfactant molecules decrease simultaneously as their concentrations increase. These indicate that when the concentrations are near and lower than their cmc's, there are oligomers (premicelles) formed in these three surfactant systems. Carefully examining the dependence of chemical shift and self-diffusion coefficient on concentration in the region just slightly above their cmc's, one finds that the pseudophase transition model is not applicable to the variation of physical properties (chemical shift and self-diffusion coefficient) with concentration of these systems. This indicates that premicelles still exist in this concentration region along with the formation of micelles. The curved dependence of chemical shift and self-diffusion coefficient on the increase in concentration suggests that the premicelles grow as the concentration increases until a definite value when the size of the premicelle reaches that of the micelle, i.e., the system is likely dominated by the monomers and micelles. Additionally, the approximate values of premicelle coming forth concentration (pmc) and cmc were obtained by again fitting chemical shifts to reciprocals of concentrations at a different perspective, and are in good accordant with experimental results and literature values and prove the former conclusion.     

Influence of alkoxyethanols on the mixed micelle formation by hexadecyltrimethylammonium bromide and tetradecyltrimethylammonium bromide surfactant mixtures

 The conductances of hexadecyltrimethylammonium bromide (HTAB) and tetradecyltrimethylammonium bromide (TTAB) mixtures over the entire mole fraction range of HTAB were measured in aqueous binary mixtures of ethylene glycol monomethyl ether, monoethyl ether, and monobutyl ether, and of diethylene glycol monomethyl ether and monoethyl ether containing 10–30 wt% additive in their respective binary mixtures at 30 °C. Each conductivity curve showed a single break over the whole mole fraction range of HTAB–TTAB mixtures. From the break in the conductivity curve, various micellar parameters were calculated and the results were discussed with respect to the alkoxyethanol's additive effect on the mixed micelle formation. The micellar parameters of HTAB, TTAB, and of their mixtures showed a strong dependence both on the amount as well as on the number of repeating units in the presence of ethylene glycol derivatives, whereas a significant dependence only on the amount of additive was observed in aqueous diethylene glycol derivatives. The results in the former case were attributed to the hydrophobic hydration of the mixed micelles by the ethylene glycol derivatives, which showed a large dependence on the increase in the alkyl chain length of the additive. The hydrophobic hydration was considerably reduced in the case of diethylene glycol derivatives owing to the presence of an extra ether oxygen. An evaluation of the nonideality in the HTAB–TTAB mixtures revealed that in spite of the strong hydrophobic hydration of the HTAB–TTAB mixtures by the alkoxyethanols, the mixed micelles remain almost free from the additive molecules. Received: 11 January 2000/Accepted: 14 April 2000     

氧杂氟表面活性剂及其与同电性碳氢表面活性剂混合溶液的表面吸附和胶团形成

研究了四种氧杂氟表面活性及其与同电性直链碳氢表面活性剂混合体系的表面活性;考察了混合体系中的表面吸附和胶团形成现象.在吸附层中分子间有明显的互疏作用,在溶液中倾向于各自形成胶团.还讨论了反离子结合度不同对理想混合胶团的组成CMC的计算的影响,提出了一般的计算式,实验测得这些氧杂氟表面活性剂有较低的胶团反离子结合度.     

聚醚型表面活性剂水溶液中胶团的生成

属于ABA型嵌段共聚物(A为聚氧乙烯,B为聚氧丙烯)的聚醚型表面活性剂分子在水中是否生成胶团,文献报道的结果迥异,临界胶团浓度值随测定方法不同出入很大.某些AB型或ABA型嵌段共聚物在选择性有机溶剂中表现出异常胶团化行为,但对于水体系迄今未见报道.本文以多种实验手段研究了典型的聚醚型表面活性剂Pluronic L-64水溶液的胶体与表面性质.结果表明,与通常的表面活性剂不同,随着温度或浓度的变化,L-64溶液中生成单分子胶团或者缔合胶团.在两者的转变间,首次观察到了水体系中的异常胶团化现象.     

Effects of alkyl chain length on synergetic adsorption and micelle formation in homologous cationic surfactant mixtures

The surface tensions (gamma) of the aqueous solutions of tetradecyltrimethylammonium bromide (TTAB) and dodecyltrimethylammonium bromide (DTAB) were measured as a function of the total molality of surfactants (m) and the relative proportion (composition) of DTAB (X(2)) at 298.15 +/- 0.05 K under atmospheric pressure. The effect of the difference in the hydrophobic chain length between hexadecyltrimethylammonium bromide (HTAB) and DTAB on the synergism was examined. This synergism was observed in the miscibility at the surface of a mixture of these two compounds. The excess Gibbs energy of adsorption of the TTAB-DTAB system was positive in contrast to the HTAB-DTAB system. This indicates that there are certain restrictions on the difference in the hydrophobic chain length for the synergism to be brought about in homologous cationic surfactant mixtures. This mechanism was explained by the theory of a staggered structure formation at the air/water interface. A similar argument successfully applied to the hexadecyltrimethylammonium chloride (HTAC)-dodecyltrimethylammonium chloride (DTAC) and tetradecyltrimethylammonium chloride (TTAC)-DTAC mixtures also.     

Markov chain model for the critical micelle concentration of surfactant mixtures

An extension of the Markov chain model (MC) for micellization is proposed, which allows the distribution of the surfactants between the monomer solution and the micelles in a mixed surfactant system to be predicted. The dependence of the critical micelle concentration (cmc) on the composition of the solution is investigated. The equilibrium thermodynamic relation between cmc and micelle composition is discussed. The case of ternary mixtures is analyzed, and theoretical triangular diagram is constructed according to MC. Available experimental data for binary and ternary mixtures agree well with the new MC theory. The dependence of MC parameters on the structure of the surfactants is discussed. Comparison of MC with the simple mixture (“regular solution”) model is presented. The parameters of the MC theory are related to the interaction parameter β _SM of the simple mixture model.     

Critical micelle concentrations and interaction parameters of aqueous binary surfactant:ionic surfactant mixtures

A relationship between the critical micelle concentration (CMC) and the surfactant's composition in the bulk phase that supercedes Rubingh's method is derived for aqueous mixtures of ionic surfactants by considering the interaction between a micellar ionic aggregate and the diffusion layer around it. To test this approach we measured the CMCs of solutions of cationic surfactant mixtures and also of alkylammonium dodecanesulfonate mixtures. In the absence of controlled concentration of the counterion, the CMCs do not fit Clint's equation, but CMCs measured at a constant counterion concentration fit it approximately. The interaction parameter in the theory of regular solutions is obtained from the relationship between the micellar and bulk compositions. The values of the interaction parameter and the concentration exponent change with the hydrophobicity of the counterion in mixtures of alkylammonium dodecanesulfonates. The micellar composition of dodecylammonium chloride and dodecyltrimethylammonium chloride mixtures depends very little on the counterion concentration. The interaction energy between the ammonium and trimethylammonium groups of the cationic surfactants is about -0.05kT on average and depends on the concentration of the counterion.     

Mixed micelle formation and solubilization behavior toward polycyclic aromatic hydrocarbons of binary and ternary cationic-nonionic surfactant mixtures

Water solubility enhancements of polycyclic aromatic hydrocarbons (PAHs), viz., naphthalene, anthracene and pyrene, by micellar solutions at 25 degrees C using two series of surfactants, each involving two cationic and one nonionic surfactant in their single as well as equimolar binary and ternary mixed states, were measured and compared. The first series was composed of three surfactants, benzylhexadecyldimethylammonium chloride (C16BzCl), hexadecyltrimethylammonium bromide (C16Br), and polyoxyethylene(20)mono-n-hexadecyl ether (Brij-58) with a 16-carbon (C16) hydrophobic chain; the second series consisted of dodecyltrimethylammonium bromide (C12Br), dodecylethyldimethylammonium bromide (C12EBr), and polyoxyethylene(4)mono-n-dodecyl ether (Brij-30) with a 12-carbon (C12) chain. Solubilization capacity has been quantified in terms of the molar solubilization ratio, the micelle-water partition coefficient, the first stepwise association constant between solubilizate monomer and vacant micelle, and the average number of solubilizate molecules per micelle, determined employing spectrophoto-, tensio-, and flourimetric techniques. Cationic surfactants exhibited lesser solubilization capacity than nonionics in each series of surfactants with higher efficiency in the C16 series compared to the C12 series. Increase in hydrophobicity of head groups of cationics by incorporation of ethyl or benzyl groups enhanced their solubilization capacity. The mixing effect of surfactants on mixed micelle formation and solubilization efficiency has been discussed in light of the regular solution approximation (RSA). Cationic-nonionic binary combinations showed better solubilization capacity than pure cationics, nonionics, or cationic-cationic mixtures, which, in general, showed increase with increased hydrophobicity of PAHs. Equimolar cationic-cationic-nonionic ternary surfactant systems showed lower solubilization efficiency than their binary cationic-nonionic counterparts but higher than cationic-cationic ones. In addition, use of RSA has been extended, with fair success, to predict partition coefficients of ternary surfactant systems using data of binary surfactants systems. Mixed surfactants may improve the performance of surfactant-enhanced remediation of soils and sediments by decreasing the applied surfactant level and thus remediation cost.     

Adsorption and micelle formation of alkylammonium chloride-alkyltrimethylammonium chloride mixtures

The surface tension of the aqueous solutions of binary cationic surfactant mixtures of (1) dodecylammnonium chloride (DAC)-tetradecyltrimethylammonium chloride (TTAC), (2) decylammonium chloride (DeAC)-dodecyltrimethylammonium chloride (DTAC), and (3) DAC-DTAC was measured as a function of the total molality and composition of surfactants at 298.15 K. The compositions of surfactants in the adsorbed film and micelle were evaluated and the phase diagram of adsorption and that of micelle formation were constructed. Furthermore the excess Gibbs energies of adsorption and micelle formation were calculated to estimate the deviation from the corresponding ideal mixing. It was found that the surface and micelle are enriched in trimethylammonium salts in (1) and (2), while in ammonium salt in (3) compared to the bulk solution. On the other hand, the micelle is enriched in trimethylammonium salts compared to the surface at the critical micelle concentration (CMC) in all the systems. The miscibility of the surfactants was clarified from the standpoints of the structure of the head group and of the matching between the size of polar head group of surfactants and the difference in hydrocarbon chain length.     

Effect of double quaternary ammonium groups on micelle formation of partially fluorinated surfactant

Water-in-oil microemulsions (w/o μEs) stabilized by the cationic surfactant cetyltrimethylammonium chloride (CTACl) have been used as reaction media to generate Au nanoparticles (Au-NPs). In addition the pure μEs have been used as media to disperse Au and Pd-NPs, which have been pre-synthesised in aqueous phases and stabilized by sodium 2-mercaptoethanesulfonate (MES) ligands, and also commercially available SiO(2)-NPs. A general method for recovery and separation of the nanoparticles from these mixed NP-μE systems has been demonstrated by tuning phase behavior of the background microemulsions. Addition of appropriate aliquots of water drives a clean liquid-liquid phase transition, resulting in two macroscopic layers, the NPs preferentially partition into an upper oil-rich phase and are separated from excess surfactant which resides in a lower aqueous portion. UV-vis and (1)H NMR spectroscopy have been used to follow these separation processes and quantify the recovery and recycle efficiencies for the different NPs. For example, ～90% of the microemulsion-prepared Au-NPs can be recovered; with even greater separation efficiencies attainable for pre-synthesised MES-stabilized Au-MES-NPs (～98%) and Pd-MES-NPs (92%). For the silica NP-μE dispersions gravimetry indicates ～84% recovery of the NPs. TEM images of all systems showed that NP shapes and size distributions were generally preserved after these phase transfer processes. This low-energy and cost-effective purification route appears to be a quite general approach for processing different inorganic NPs, having advantages of being isothermal, using only commercially available inexpensive components and requiring no additional organic solvents.     

The effect of counterions on the surface adsorption and micelle formation in mixed surfactant systems of dodecyl sulfates

 The surface tension of the aqueous solutions of sodium dodecyl sulfate (SDS) and tetramethylammonium dodecyl sulfate (TMADS) was measured as a function of total molality of the surfactants at fixed composition of TMADS at 298.15 K under atmospheric pressure. The phase diagrams of adsorption and of micelle formation, the activity coefficients, and the excess Gibbs energy were calculated to estimate the deviation from the ideal mixing quantitatively. The preferential adsorption and the micelle formation for TMA⁺ to Na⁺ is attributable to some extent to the hydrophobicity of the methyl groups of TMA⁺. The composition of TMA⁺ in the micelle is larger than that in the adsorbed film at equilibrium. That is, a larger hydrated counterion is more likely to exist in the micelle than in the adsorbed film owing to geometrical benefit. The negative values of the excess Gibbs energy of the adsorbed film and of the micelle arise from the positive ones of the excess entropy greater than that of excess enthalpy. The counterions of very similar size are mixed ideally in the micelle and the size effect appears sensitively in the adsorbed film. Received: 23 May 2001 Accepted: 16 July 2001     

Aggregate formation of binary nonionic surfactant mixtures on hydrophilic surfaces

Adsorption of surfactant mixtures on hydrophilic solid surfaces is of considerable theoretical and practical importance. Cooperative adsorption of nonionic surfactant mixtures of nonyl phenol ethoxylated decyl ether (NP-10) and n-dodecyl-beta-d-maltoside (DM) on silica and alumina was investigated in this study with a view to elucidate the nanostructures of their aggregates. In the mixed system, DM is identified to be the "active" component and NP-10 is the "passive" one for the process of adsorption on alumina, while their roles are reversed for silica. The difference in the adsorptive interactions of the surfactants with the above minerals is attributed to the differences in the molecular structures of the surfactants. To better understand the interaction between surfactants at solid/solution interface from a molecular structure point of view, the nanostructures of mixed surface aggregates have been quantitatively predicted for the first time using a modified packing parameter: the structures are spherical or cylindrical on silica and those on alumina undergo a spherical-to-cylindrical-to-bilayer transition with the addition of the active component. This work offers a new way for developing of structure-performance relationships.     

The influence of surfactant mixing ratio on nano-emulsion formation by the pit method

The formation of O/W nano-emulsions by the PIT emulsification method in water/mixed nonionic surfactant/oil systems has been studied. The hydrophilic-lipophilic properties of the surfactant were varied by mixing polyoxyethylene 4-lauryl ether (C12E4) and polyoxyethylene 6-lauryl ether (C12E6). Emulsification was performed in samples with constant oil concentration (20 wt%) by fast cooling from the corresponding HLB temperature to 25 degrees C. Nano-emulsions with droplet radius 60-70 nm and 25-30 nm were obtained at total surfactant concentrations of 4 and 8 wt%, respectively. Moreover, droplet size remained practically unchanged, independent of the surfactant mixing ratio, X(C12E6). At 4 wt% surfactant concentration, the polydispersity and instability of nano-emulsions increased with the increase in X(C12E6). However, at 8 wt% surfactant concentration, nano-emulsions with low polydispersity and high stability were obtained in a wide range of surfactant mixing ratios. Phase behavior studies showed that at 4 wt% surfactant concentration, three-liquid phases (W+D+O) coexist at the starting emulsification temperature. Furthermore, the excess oil phase with respect to the microemulsion D-phase increases with the increase in X(C12E6), which could explain the increase in instability. At 8 wt% surfactant concentration, a microemulsion D-phase is present when emulsification starts. The low droplet size and polydispersity and higher stability of these nano-emulsions have been attributed, in addition to the increase in the surface or interfacial activity, to the spontaneous emulsification produced in the microemulsion D-phase.     

Thermodynamics of micelle formation in water, hydrophobic processes and surfactant self-assemblies

The critical micelle concentration (c.m.c.) for four cationic surfactants, alkyl-trimethyl-ammonium bromides, was determined as a function of temperature by conductivity measurements. The values of the standard free energy of micellisation DeltaG degrees(mic) at different temperatures were calculated by using a pseudo-phase transition model. Then, from the diagram (-DeltaG degrees(mic)/T)=f(1/T), the thermodynamic functions DeltaH(app) and DeltaS(app) were calculated. From the plots DeltaH(app)=f(T) and DeltaS(app) = f(ln T) the slopes DeltaC(p) = n(w(H))C(p,w) and DeltaC(p)=n(w(S))C(p,w) were calculated, with the numbers n(w(H)) and n(w(S)) negative and equal and therefore defined simply as n(w). The number n(w)<0, indicating condensed water molecules, depends on the reduction of cavity that takes place as a consequence of the coalescence of the cavities previously surrounding the separate aliphatic or aromatic moieties. The analysis, based on a molecular model consisting of three forms of water, namely W(I), W(II), and W(III), respectively, was extended to several other types of surfactants for which c.m.c. data had been published by other authors. The results of this analysis form a coherent scheme consistent with the proposed molecular model. The enthalpy for all the types of surfactant is described by DeltaH(app)= -3.6 + 23.1xi(w)-xi(w)C(p,w)T and the entropy by DeltaS(app)= +10.2+428xi(w)-xi(w)C(p,w) ln T where xi(w)= |n(w)| represents the number of molecules W(III) involved in the reaction. The term Deltah(w)= +23.1 kJ mol(-1) xi(w)(-1) indicates an unfavourable endothermic contribution to enthalpy for reduction of the cavity whereas the term Deltas(w)= +428 J K(-1) mol(-1) xi(w)(-1) represents a positive entropy contribution for reduction of the cavity, what is the driving force of hydrophobic association. The processes of non polar gas dissolution in water and of micelle formation were found to be strictly related: they are, however, exactly the opposite of one another. In micelle formation no intermolecular electronic short bond is formed. We propose, therefore, to substitute the term "hydrophobic bond" with that of "hydrophobic association".     

The influence of an electrolyte on micelle formation in aqueous solutions of sodium monoalkyl sulfosuccinates

Critical micelle concentrations were determined by conductometry for the homologous series of sodium monoalkyl sulfosuccinates ROOCCH₂CH(SO₃Na)COONa (R is an alkyl radical, C₁₀–C₁₅) in the presence of sodium chloride. Coefficients of the Corrin-Harkins equation were calculated. It was shown that the formation of micelles began when a certain value of the mean ionic activity of the surface active substance was reached.     

SANS investigations of oxide gel formation in inverse micelle and lamellar surfactant systems

The mechanisms of oxide gel formation in inverse micelle and lamellar surfactant systems have been investigated by Small Angle Neutron Scattering (SANS). In the first of these processes colloidal particles and gels are formed by the controlled hydrolysis and condensation of metal alkoxides in a reversed microemulsion system (water in oil), where the water is confined in the microemulsion core. With this route the rate of formation and structure of the oxide gel can be controlled by appropriate choice of the surfactant molecule (e.g. chain length) and the volume fraction of the micelles dispersed in the continuous organic phase. Investigations have been made with the system cyclohexane/water/C₈E _x , where C₈E _x is the non-ionic surfactant octylphenyl polyoxyethylene. The influence of the size and structure of the microemulsion has been studied by contrast variation (using deuterated solvents) before and during the reaction to form zirconia gels, and the mechanism of gelation is analysed in terms of percolation of fractal cluster aggregates. The structure of gels formed in surfactant/water lamellar phase systems, using surfactants with greater chain length, has also been investigated by SANS. The application of contrast variation to study such anisotropic bilayer systems, in which oriented gel films can be formed, is illustrated.     

芳香反离子与离子表面活性剂胶团的相互作用

用紫外吸收光谱的方法研究了多种芳香反离子与离子表面活性剂胶团之间的相互作用。发现阳离子表面活性剂和阴离子表面活性剂胶团对芳香反离子的吸收光谱有着显著不同的影响,芳香反离子结构的细微变化可导致光谱特性显著不同。这被解释为阳离子表面活性剂胶团与芳香环之间的阳离子-π相互作用。阳离子-π相互作用需要阳离子表面活性剂分子与芳香反离子具有合适的相对位置与距离。通过测定各混合体系的吸附量证明,不同的芳香反离子在胶团表面有不同的排列方式。NMR的实验结果支持了上述解释。     

Charge number effect on the miscibility of inorganic salt and surfactant in adsorbed film and micelle: Inorganic salt-dodecylammonium chloride mixtures

The effect of inorganic salts with different charge numbers of cations on the adsorption and micelle formation of dodecylammonium chloride (DAC) was clarified by applying the thermodynamic treatment of surfactant mixtures to mixtures of DAC with calcium and lanthanum chlorides and comparing the results with those of the sodium chloride-DAC mixture in the previous study. Surface tension of aqueous solutions of the salt-DAC mixture was measured as a function of the total molality of the mixture and the mole fraction of DAC in the mixture at 298.15 K under atmospheric pressure. Judging from the phase diagrams of adsorption and micelle formation obtained from the surface tension measurement, dodecylammonium cations expel inorganic cations from the adsorbed film and micelle and the repulsive interaction between dodecylammonium and inorganic cations increases with increasing charge number of the inorganic cation.     

Dynamics of spontaneous vesicle formation in fluorocarbon and hydrocarbon surfactant mixtures

The spontaneous self-assembly of unilamellar vesicles was investigated by means of time-resolved synchrotron small-angle X-ray scattering. The self-assembly process was initiated by rapid mixing of anionic surfactant micelles with either zwitterionic or cationic surfactant micelles in equimolar ratio using a stopped-flow device. For the zwitteranionic systems, transient disklike mixed micelles are observed as structural intermediates prior to the onset of vesiculation. These disklike micelles display an exponential growth law, and above a critical size they close to form unilamellar vesicles. In the catanionic system, the earliest observable structures within the mixing time of 4 ms are unilamellar vesicles. Nevertheless, in both systems a narrow distribution of the vesicle size was observed at the initial stages of their formation. The subsequent evolution of the vesicle size distribution depends on the subtle differences in the bilayer composition and properties.