Electrophoretic behaviour and viscosities of metal oxides in mixed surfactant systems

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

Clouding: origin of phase separation in oppositely charged polyelectrolyte/surfactant mixed solutions

The phase behavior in the system of cationic modified poly(vinyl alcohol) (CPVA)-sodium dodecylsulfate (SDS)-water has been investigated. Samples were found phase separated near electroneutral mixing at CPVA concentrations < or =6%, while in a medium CPVA concentration of 7-12%, the phase separation disappeared and the system transformed into bluish homogeneous solution. At > or =13% CPVA concentrations, the mixed systems became colorless homogeneous. Preclouding phenomenon was observed in 5-8% CPVA-SDS mixed systems at an electroneutral mixing ratio. The addition of inorganic salts, such as Na2SO4, NaCl, NaBr, and NaSCN, could exclude the bluish and phase separation phenomenon that was found to be caused by the increase of clouding point in these systems. The clouding phenomenon was proven to be the origin of the phase separation in the CPVA-SDS mixed system. The ability for the inorganic salts to increase the clouding point follows the order of the Hofmeister series.     

Clouding behavior of nonionic–cationic and nonionic–anionic mixed surfactant systems in presence of carboxylic acids and their sodium salts

The study is focused on evaluation of clouding phenomena of the aqueous single nonionic surfactant system Triton X-100 (TX-100) and its mixed systems with anionic aerosol-OT (AOT) and cationic dodecylpyridinium chloride (DPC) in presence of hydrophobic ions furnished by sodium salts of carboxylic acids, viz., sodium ethanoate, sodium propanoate, sodium butanoate, and sodium hexanoate and the respective carboxylic acids [ethanoic acid, propanoic acid, butanoic acid, and hexanoic acid]. The influence of salts on the cloud point (CP) has been explained on the basis of salt effect as well as the solubilization of higher alkyl chain hydrophobic ions furnished by these salts. Moreover, the co- and counterion effect has been taken into account to explain the variation of the CP in the mixed systems. However, the effect of acids on CP has been explained in the light of their aqueous solubility and their partitioning ability between octanol and water as reflected by their K _OW values.     

Investigation of the thermal and structural behaviour of diclofenac sodium-sugar ester surfactant systems

Sugar esters (SEs) have a wide range of hydrophilic-lipophilic balance (HLB) values (1–16) and hence can be applied as surfactants or as solubility or penetration enhancers. They can be used for hot melt technology and solvent method which are frequently applied techniques to preparation of solid dispersions. In this study drug-SE products were prepared by physical mixing, melt technology and solvent methods. The products were investigated by DSC, X-ray powder diffraction and dissolution tests. Diclofenac sodium (DS) as model drug and two SEs, P1670 (HLB=16) and S970 (HLB=9) were used for the preparation of the products. DSC curves revealed considerable melting range and enthalpy decreases for the DS-SE products. The dissolved drug molecules broke down the structures of the SEs but were not built into the crystalline phase of the carrier. The melt technology led to a solid dispersion while in the case of the solvent methods the DS was in molecularly dispersed form which resulted in faster dissolution. The drug release was influenced by the structures resulting from the various treatments, by the HLB and by the gel-forming behaviour of the SEs.     

Temperature-sensitive aqueous surfactant two-phase system formation in cationic-anionic surfactant systems

Temperature-induced aqueous surfactant two-phase system (T-ASTP), which was found to be of generic importance, was investigated in a series of conventional mixed cationic-anionic surfactant systems. On the basis of the investigations of turbidity, dynamic light scattering, transmission electron microscopy, and fluorescence resonance energy transfer, the formation of T-ASTP can be attributed to temperature-induced vesicle aggregation. Aggregated vesicles existed in the upper part, while the separated vesicles existed in the lower part. The phase separation temperature can be regulated by varying the surfactant composition or adding additives, such as d-sorbitol, urea, or NaBr. The hydrophobic interaction and cooperative effect between cationic and anionic surfactants played a significant role in the formation of T-ASTP.     

Clouding of nonionic surfactants

Nonionic surfactants have broad applications such as cleaning and dispersion stabilization, which frequently are hampered by strong temperature sensitivities. As manifested by clouding and decreased solubility with increasing temperature, the interaction between water and the oligo(oxyethylene) head-groups is becoming less favorable. Different aspects of surfactant self-assembly, like the critical micelle concentration, micelle size and shape, intermicellar interactions and phase separation phenomena are reviewed as well as suggested underlying causes of the temperature dependence. Furthermore, the effect of cosolutes on clouding and the behavior of related systems, non-aqueous solutions and nonionic polymers, are examined.     

Second CMC in surfactant micellar systems

Experimental reports of surfactant systems displaying a second critical micelle concentration (second CMC) have been surveyed. It turns out that surfactant micelles usually show a growth behavior with some typical features. (i) Micelles grow weakly at low surfactant concentrations but may switch to a much stronger growth behavior at higher concentrations. The second CMC is defined as the point of transition from weakly to strongly growing micelles. (ii) Micelles are found to be non-spherically shaped below the second CMC. (iii) At the second CMC micelles are found to be much smaller, with aggregation numbers typically 100–200, than expected for flexible micelles. (iv) Micelles of intermediate size are present in a narrow concentration regime close to the second CMC. (v) Micelles grow much stronger above the second CMC than expected from a sphere-to-rod transition. The conventional spherocylindrical micelle model predicts a smooth growth behavior that contradicts the appearance of a second CMC. Modifying the model by means of including swollen end caps neither account for the presence of micelles with intermediate size, nor the strong growth behavior above the second CMC. Taking into account micelle flexibility is not consistent with the rather low micelle aggregation numbers observed at the second CMC. On the other hand, a recently proposed alternative theoretical approach, the general micelle model, have been demonstrated to take into account basically all features that are typical of experimentally observed micellar growth behaviors.     

The behaviour of drag-reducing cationic surfactant solutions

The behaviour of two types of drag reducing surfactant solutions was studied in turbulent flows in pipes of different diameters. Our surfactant systems contained rod-like micelles; they consisted of equimolar mixtures ofn-tetradecyltrimethylammonium bromide,n-hexadecyltrimethylammonium bromide, and sodium salicylate. The structure of the turbulence was studied using a laser-Doppler anemometer in a 50 mm pipe. In the turbulent flow regime both surfactant solutions exhibited characteristic flow regimes. These flow regimes can be influenced by changing the amount of excess salt, the surfactant concentration, or the temperature. Shear viscosity measurements in laminar pipe and Couette flows show the occurrence of the so-called shear-induced state, where the viscosity increases and the surfactant solution becomes viscoelastic. The shape of the turbulent velocity profile depends on the flow regime. In the turbulent flow regime at low Reynolds numbers, velocity profiles similar to those observed for dilute polymer solutions are found, whereas at maximum drag reduction conditions more S-shaped profiles that show deviations from a logarithmic profile occur. An attempt is made to explain the drag reduction by rod-like micelles by combining the results of the rheological and the turbulence structure measurements.     

Kinetics of morphological changes in surfactant systems

Equilibrium structures of surfactants have been studied in much more detail than morphological changes that can occur under non-equilibrium conditions. Recent experiments attempt to analyse pathways of such morphological transitions, in particular for micellar kinetics, solubilisation and formation/break-up of vesicles. Significant progress was made with respect to the achievable time-resolution in such structural investigations, which allows to identify intermediate structures. Understanding and control of the dynamics of surfactant systems is of fundamental importance for many applications of surfactants.     

Synergism and polymorphism in mixed surfactant systems

Mixed surfactant systems have been, for a long time, one of the favorite areas for experimental studies on interfacial and bulk properties of surfactants. Beyond the well-known synergistic properties, with relevance to technical applications, recent studies increasingly focus on the bulk aggregation behavior. As more systematic and detailed experimental data is collected (for example, by use of scattering and direct imaging techniques), increasingly refined theoretical models are developed. Most references reviewed here clearly show both the trends. Topics such as micellar growth, micelle-to-vesicle transition and equilibrium vesicle formation in dilute systems (in particular in catanionic systems) continue to expand and sometimes pose challenges to conventional notions of surfactant self-organization. As the rich polymorphism of mixed aggregates is unraveled, the possibilities of using them for broader goals also increase (e.g. mesoporous materials and polymer-aggregate gels).     

Properties of surfactant monolayers in relation to microemulsion phase behaviour

The relationship between the properties of surfactant monolayers at oil-water interfaces and the phase behaviour in bulk of mixtures of oil + water + surfactant is discussed. Such monolayer properties include the spontaneous curvature, c_o the interfacial tension, I γ, the elasticity K (or rigidity) associated with the mean curvature, and the elasticity K associated with the Gaussian curvature. The model system chosen for investigation is the anionic surfactant AOT + aqueous NaCl + n-alkane at 20°C. In such systems, inversion of microemulsion type from oil-in-water (o/w) to water-in-oil (w/o) is possible with increasing electrolyte concentration. The tension, γ, passes through an ultralow minimum value at conditions corresponding to the formation of three phases. Using small angle neutron scattering, we have determined the structure of surfactant-rich third phases (c_o ~ 0) formed with the different alkanes. Lamellar phases consisting of surfactant monolayers separated alternately by oil and water appear with short alkanes, whereas L₃ and bicontinuous phases form in systems containing longer alkanes. The bending elasticity K has been measured for planar monolayers at the oil-water interface by ellipsometry. K is independent of salt concentration but depends markedly on alkane chain length N, falling from ~ 1 k_BT for N < 11 to ~0.1 k_BT for N = 14. This is discussed in terms of the differing extents of oil penetration into the surfactant chains. Higher rigidities favouring lamellar phases and lower rigidities favouring bicontinuous microemulsions are in line with the theoretical predictions of de Gennes and Taupin. Estimates of the constant K have been obtained in droplet microemulsions (w/o) from a knowledge of their size, K and γ. The sign of the constant is in agreement with the geometry of the phases formed in three phase systems. Finally, the ideas and concepts developed in the oil-water systems described above are used to explain the wetting behaviour by alkanes of AOT monolayers at the air-water surface.     

Recent developments in materials synthesis in surfactant systems

The paper reviews the use of surfactant self-assembly to template the synthesis of polymers, ceramics with extended structures, and nanoparticles. The objective of the review is to highlight newer concepts linking self-assembly to materials nanostructure and to the realization of functional materials.     

Formation of reverse vesicles in silicone surfactant systems

This study deals with the formation of reverse vesicles based on the phase behavior of silicone surfactants. The surfactants, polyoxyethylene–polydimethylsiloxane and polyoxyethylene–polyoxypropylene–polydimethylsiloxane copolymer, were found to form lamellar liquid crystal phases in three different types of silicone oil upon the addition of a certain amount of water. A conventional method in which reverse vesicles are prepared by physically dispersing this lamellar liquid crystal phase in oil was employed in addition to a technique based on a temperature-induced phase transition. The particle sizes and stabilities of the resulting reverse vesicles were evaluated.     

Wetting in oil/water/surfactant systems

The behaviour of oils at aqueous interfaces is ubiquitous to many industrially and biologically relevant processes. In this review we consider modifications to the wetting properties of oils at the air/water, oil/water and solid/liquid interfaces in the presence of surfactants. First-order wetting transitions can be induced in a wide range of oils by varying the aqueous surfactant concentration, leading to the formation of mixed monolayers at the interface. In certain cases, these mixed monolayers display novel surface freezing behaviour, including the formation of unusual bilayer structures, which further modifies the properties of the interface. The effects of surfactant on line tension at the three-phase contact line and differences between the air/liquid and liquid/liquid interfaces are discussed.     

Cubic phases in surfactant and surfactant-like lipid systems

Cubic liquid crystalline phases are common in surfactant and surfactant-like lipid systems at temperatures above the Krafft point. They are optically isotropic and very stiff. Therefore, they are often not recognized as independent phases and separated in pure state. The liquid crystalline nature is evidenced by a low-angle diffraction pattern with sharp reflections having Bragg-values above 20 Å coupled with a diffuse wide-angle reflection at 4.5 Å, proving that the hydrocarbon moiety is in a liquid state. The cubic phases occur in a variety of lipid/water systems (also with liquid organic solvents), such as simple soaps, amphiphilic lipids of biological origin, and extracts from membrane lipids. The location of the cubic phases in a phase diagram varies.The original concept of a cubic structure composed of closed globular aggregates, either of oil-in-water or water-in-oil type in face-centered array seems to be obsolete. The present structure concepts include closed anisotropic aggregates, short rod-like aggregates forming continuous networks or lamellar aggregates with zero curvature forming networks of Infinite Periodic Minimal Surfaces (IPMS). The structure is mostly primitive or body-centered cubic.     

Oil-induced anomalous thermoresponsive viscoelasticity in fluorinated surfactant systems

We have studied the rheology and structure of a mixed nonionic fluorinated surfactant, perfluoroalkyl sulfonamide ethoxylate, C(8)F(17)SO(2)N(C(3)H(7))(CH(2)CH(2)O)(n)H abbreviated as C(8)F(17)EO(10), and perfluorodecalin (C(10)F(18)) or perfluoropolyether oil, (C(3)F(6)O)(n)COOH, in an aqueous system using rheometry and small-angle X-ray scattering (SAXS) techniques. In the absence of oil, the viscosity of surfactant solutions (10 and 15 wt %) first decreases slightly and then more strongly with temperature. Addition of a small amount of fluorinated oil to the wormlike micellar solution disrupts the network structure and decreases the viscosity sharply at lower temperature indicating a rod-sphere transition. The trend of the viscosity curve changes gradually and an anomalous viscosity maximum as a function of temperature appears. It is found that perfluoropolyether oil decreases the viscosity more effectively than perfluorodecalin. The generalized indirect Fourier transformation (GIFT) analysis of the SAXS data confirmed the formation of long rod-like particles in an oil-free, surfactant/water system at 20 degrees C. Addition of a trace amount of fluorinated oils induces modulation in the structure of the micelles and eventually short rods or spherical particles are formed. The decreasing trend in the viscosity with oil concentration is thus attributed to the microstructure changes induced by the added oils.     

Solubilization of phenols in surfactant/polyelectrolyte systems

The properties of the microheterogeneous systems formed by mixtures of cetyltrimethylammonium bromide (CTAB) and an alternating copolymer of maleic acid and styrene, MAS, and their anionic monoesters, MAS-n with n=2, 4, 6, 8, were investigated. The fluorescence of pyrene was used to sense the polarity of the polymer/CTAB aggregates. Measurements of the ratio III/I in pyrene fluorescence spectra indicate that the polymer/CTAB aggregates are more hydrophobic than normal micelles. A series of p-alkyl substituted phenols were employed to probe the solubilization ability of these aggregates. The distribution constant K(S) of phenol, p-methylphenol, p-ethylphenol, and p-propylphenol between water and MAS-n/CTAB aggregates and the corresponding free energy of transfer Deltamicro(0)(t) have been determined using the pseudo-phase model. The results show that the distribution is mainly determined by the phenol structure, and a linear free energy relationship has been found between Deltamicro(0)(t) and the structure of phenols. On the other hand, an increase in the number of methylene groups in the side alkyl chain has no effect on Deltamicro(0)(t). The results are discussed and compared with those obtained for ionic micelles.     

Tetraethanolammonium counterions in surfactant and classical colloidal systems

Interaction forces between mica surfaces as a function of added tetraethanolammonium bromide, (EtOH)₄NBr, were determined using surface forces measurements. Critical micelle concentrations and aggregation numbers were determined for tetraethanolammonium dodecylsulfate, (EtOH)₄NDS, using surface tension and fluorescence probe-quencher measurements. The properties of the large hydrophilic counterion (EtOH)₄N⁺ are compared to those of its hydrophobic analogue Pr₄N⁺.     

Viscoelastic micellar solutions in nonionic fluorinated surfactant systems

The formation and rheological behavior of a viscoelastic wormlike micellar solution in an aqueous solution of a nonionic fluorinated surfactant, perfluoroalkyl sulfonamide ethoxylate, of structure C8F17SO2N(C3H7)(CH2CH2O)10H was studied. Temperature-induced viscosity growth is observed even at low-surfactant concentration (approximately 1 wt %), and viscosity reaches the maximum at a temperature T(eta)-max. Upon successive increases in the temperature, the viscosity decreases, and ultimately a phase separation occurs. Small-angle X-ray scattering (SAXS) measurements confirm the presence of cylindrical aggregates at low temperature, which undergo continuous one-dimensional growth with increasing temperature, and ultimately, an indication of a slight lamellarlike structural pattern is observed, which probably comes from the formation of micellar joints or branching. Such changes in the microstructure result in a decrease in the viscosity and stress-relaxation time, while the network structure is retained; the trends in the evolution of shear modulus (Go) and relaxation time (tauR) with temperature are in agreement with this. With increased surfactant concentration, the temperature corresponding to the viscosity maximum (T eta-max) in the temperature-viscosity curve shifts to lower values, and the viscosity at temperatures below or around T eta-max increases sharply. A viscoelastic solution with Maxwellian-type dynamic rheological behavior at low-shear frequency is formed, which is typical of entangled wormlike micelles. Rheological parameters, eta(o) and Go, show scaling relationships with the surfactant concentrations with exponents slightly greater than the values predicted by the living-polymer model, but the exponent of tauR is in agreement with the theory. Dynamic light-scattering measurements indicate the presence of fast relaxation modes, associated with micelles, and medium and slow modes, associated with transient networks. The disappearance of the slow mode and the predominance of the medium mode as the temperature increases support the conclusions derived from SAXS and rheometry.     

Simulation of phase equilibria in lamellar surfactant systems

The coexistence of two lamellar liquid crystalline phases has been investigated by means of Monte Carlo simulations. The surfaces of the negatively charged bilayers formed by the surfactant molecules are modeled as planar infinite walls with a uniform surface charge density. Water is treated as a dielectric continuum, and only electrostatic interactions are considered. The counterions are mono- and divalent point ions, and their ratio is allowed to vary. Monovalent counterions lead to a repulsive osmotic pressure at all separations, while an attractive region exists when the counterions are divalent. In the latter case, one would expect a phase separation to take place, although it is not observed experimentally due to the limited stability of the lamellar phase at high water content. In a system with mixed counterions, however, the osmotic pressure exhibits a van der Waals loop under such conditions that two phases can coexist. A phase diagram is constructed, and the agreement with experimental data is excellent.