The viscoelasticity of spinnable solutions of alkyltrimethylammonium salicylates

The viscoelasticity has been measured for aqueous solutions of tetradecyl-and hexadecyltrimethylammonium salicylates (C₁₄TASal, C₁₆TASal). The aqueous solutions of C₁₄TASal without salt displayed the gel-like behavior at 10.0×10^–2 g cm^–3, but those more dilute than 3.2×10^–2 g cm^–3 presented the viscoelasticity similar to that of a Maxwell liquid. The Maxwell-like behavior was converted to the polymer-like one on the addition of (0.1–0.2) M NaBr or (0.02–0.2) M NaSal. The gel-like viscoelasticity can be connected with the spinnability of cohesive fracture failure, and the Maxwell-like and polymer-like viscoelasticities are concerned with the spinnability of ductile failure. The gel-like and Maxwell-like viscoelasticities originate in the pseudo-network formed by the pseudo-linkages between rodlike micelles, while the polymer-like viscoelasticity is caused by the entanglement of long rodlike micelles in semidilute and concentrated solutions. The aqueous solutions of C₁₆TASal behaved very similar to those of C₁₄TASal.     

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.     

The influence of surfactants on the structure of transparent gelatin films

The interference image of cold-dried transparent gelatin films containing different surfactants was determined in the conoscopic ray of monochromatic light. From the results obtained the order of the structure of gelatin in the film was characterized. Unlike the ionic surfactants (sodium dodecyl sulfate and hexadecyltrimethyl ammonium bromide), which lead to a reduction of the ordered structure, the addition of nonionic and amphoteric surfactants [ethoxylized octylphenole and a technical C₁₂/C₁₄-dipoly(oxyethylene)ammoniopropane sulfonate] causes an increase of the ordered structure of gelatin. The results quantitatively agree with those found for the influence of surfactants on the secondary structure of gelatin in diluted gelatin solutions. The influence is independent of the gelatin/surfactant ratio and has been explained by gelatin/gelatin interaction competing with the gelatin/surfactant interaction if the gelatin concentration becomes sufficiently high.     

Conformational change of poly(L-lysine) and poly(L-ornithine) and cooperative binding of sodium alkanesulfonate surfactants with different chain length

Conformations of poly(L-lysine) (PLL) and poly(L-ornithine) (PLO) were examined in aqueous solutions of sodium alkanesulfontates (C_nSO₃Na, n=9, 10, 11, 12) in the presence of 0.02 M NaCl by circular dichroism (CD) spectroscopy. These surfactants induce the-structure for PLL and the-helix for PLO. The binding of surfactants on the polypeptides was measured potentiometrically with a surfactant ion electrode and was found to be highly cooperative. The cooperativity increases with increasing chain length of surfactant. The behavior accompanying the surfactant binding and the conformational change indicated that the conformational change requires a certain amount of bound surfactants in the case of C₉SO₃Na and starts immediately on binding of surfactant in the case of C_{1 2}SO₃Na. The clustering of bound surfactants due to the cooperative binding as well as neutralization of polypeptides contributes to their conformational change. A slow conformational change of PLO was found in the time scale of hours, sometimes days, for C₉- and C₁₀SO₃Na at low concentrations, but the binding process reached the equilibrium quickly. This slow mode might occur due to the slow interaction between surfactant/polypeptide complexes.     

Properties of aqueous solution of sodium glycocholate and a nonionic surfactant,and their mixtures

The micellar properties of aqueous binary mixed solutions of sodium glycocholate, NaGC, and octa-oxyethylene glycol mono-n-decyl ether, C₁₀E₈, have been studied on the basis of surface tensions, the mean aggregation number and the polarity of the interior of the micelles. The mean aggregation number, measured by steady state quenching method, decreased with the increase of the mole fraction of NaGC in the mixed system. The polarity of the interior, estimated by the ratio of first and third vibronic peak in a monomeric pyrene fluorescence emission spectrum, suggested that the hydrophobicity of intramicelles increased with the increase of the mole fraction of NaGC in the mixed system. These are considered to be caused by the differences in the chemical structure and the hydrophobic nature between NaGC and C₁₀E₈. The mean aggregation number and the polarity of the interior for each micelle near the CMC in lower total concentration of surfactants showed the tendency approaching those of pure micelle of the nonionic surfactant. This suggests that the ratio of NaGC in the initial micelles in the range of lower total concentration near the CMC is lower than that of the corresponding prepared mole fraction in the mixed system. This lower value was confirmed also from theoretical calculation of the ratio of NaGC at the CMC in the mixed micelle by regular solution treatment of Rubingh in the solution.     

Structure/performance relationships in long chain dimethylamine oxide/sodium dodecylsulfate surfactant mixtures

Dramatic differences in the structure of mixed micelles of long chain amine oxides and sodium dodecylsulfate are noted as a function of composition. In the L₁ micellar pseudophase, a sphere-to-rod transition driven by ion-dipole interactions between the dissimilar headgroups leads to synergisms in aqueous solution thickening, Ross-Miles foaming, and nonpolar oil solubilization. For example, an astounding seven orders of magnitude increase in the zero shear viscosity and viscoelastic properties are observed at a single total surfactant concentration. The sphere-to-rod transition can be viewed in FT-IR by examining both the CH₂ stretching for the methylene tails, and the S-O stretching modes for the sulfate headgroups.     

The flexibility of rodlike micelles in aqueous solutions and the crossover concentrations among dilute,semidilute, and concentrated regimes

A flexibility parameter, the persistence length, has been evaluated from the radii of gyration and the contour lengths for rodlike micelles of heptaoxyethylene alkyl ethers (C _n E₇,n=12, 14, 16) and tetradecyldimethylammonium chloride (C₁₄DAC) and bromide (C₁₄DAB) at the observed crossover concentrations between dilute and semidilute regimes. The persistence length range is 43–73 nm, except for C₁₂E₇, for which it is 32 nm. The crossover concentrations between dilute and semidilute regimes for the semiflexible rodlike micelles calculated according to Ying and Chu as a function of the molecular weight, the contour length, and the persistence length are consistent with the observed values. The crossover concentration between semidilute and concentrated regimes was, on the other hand, calculated by using the same micelle parameters, including the value of thickness of cross-section of the rodlike micelles. The obtained values are at variance with the observed values. This means that rodlike micelles in semidilute and concentrated solutions might differ in size and/or flexibility from those in dilute solution.     

Estimation of the critical micelle concentrations and the aggregation numbers of sodium alkyl sulfates by capillary-type isotachophoresis

The analytical procedure for the separation and quantification of bulk and micellar phases for sodium alkyl sulfates has been investigated by a capillary-type isotachophoresis using a potential gradient detector. Monomer solutions were distinguished from micellar solutions at pH 5.5–6.0; hydrochloric acid — L-Histidine mixture was used as the leading electrolyte and 2-(N-Morpholino) ethanesulfonic acid as the terminating electrolyte.The potential unit value (PU value) due to the monomer solutions was larger than that due to the micellar solutions. The zone length due to monomer solutions increased with increasing concentration of surfactant until a given concentration (CMC); beyond this point the values became constant. On the other hand, the zone length due to micellar solutions increased from this point. We report an applicability of capillary-type isotachophoresis to determination of the CMC's and aggregation number for various sodium alkyl sulfates.     

Interfacial tension of gelatin/sodium dodecylsulphate solutions against air,toluene, and diethylphthalate

The adsorption isotherms between aqueous solutions of sodium dodecylsulphate and gelatin against air, toluene, or diethylphthalate were determined using the spinning drop method. The results qualitatively and quantitatively agreed with those found by surface tension measurements on sodium dodecylsulphate/gelatin solutions using the ring method in the version of Du Noüy. Interaction between gelatin and the surfactant will yield complexes which are more interfacially active than the components by themselves. The saturation of the interfaces occurs at lower concentrations than in solutions of the single components.     

Thermodynamics of surfactant-dye complex formation in aqueous solutions. Sodium alkyl sulfates and azo oil dye systems

Thermodynamics of surfactant-dye complex formation have been studied, in terms of equilibrium coefficient, using a spectrophotometer. The systems are 6 sodium alkyl sulfates, which have different alkyl chain lengths, and 4-phenylazo-1-naphthylamine. A pronounced spectral change in the dye solution occurs on addition of the surfactant; the change has a definite isosbestic point and a new absorption band at 535 nm because of surfactant-dye complex formation, which is caused by hydrophilic-hydrophilic interaction. As the alkyl chain length in the surfactant increases, the values of free energy change (negative) increase, while the value of enthalpy change (negative) increases and the value of entropy change (positive) decreases. The longer the alkyl chain length in surfactant increase, the more stable the surfactant-dye complex becomes.Surfactant-dye complex will form due to hydrophilic-hydrophilic interaction and will become more stable due to hydrophobic-hydrophobic interaction.     

Precipitation of surfactant salts III. Metal perfluoroalkanecarboxylates

Precipitation of perfluorocarboxylic acids (n-C₃H₇OOH, n-C₇H₁₅COOH, and n-C₉F₁₉COOH) in aqueous solutions of different metal nitrates (K⁺, Ag⁺, Ca²⁺, Ba²⁺, Zn²⁺, Al³⁺, La³⁺) was studied by solubility and calorimetric measurements. The free energy of precipitation per single surfactant chain was found to depend on the chain length but not on the charge of the reacting cation. It was shown that the precipitation of perfluorocarboxylates of multivalent cations was governed by positive entropy change and a low enthalpic contribution, whereas the soaps of monovalent cations exhibited the opposite behavior. The entropy of precipitation was not affected by the chain length of the surfactants in the presence of monovalent cations, but it increased for cations of higher charge.Supported by the NSF Grant CHE-8619509.This paper is dedicated to Professor Armin Weiss on the occasion of his 60th birthday. One of the authors (E. M.) particularly appreciates many years of cooperation with Professor Weiss in editing Colloid and Polymer Science, as well as in many other scientific interactions.     

Effect of pH on the binding of alkyl sulfates to gelatin

A surfactant-selective eletrode in which the membrane is an o-nitrotoluene phase containing a dissolved complex of cetyltrimethylammonium-dodecyl sulfate has been applied to investigations of the interaction between gelatin and alkyl sulfates as well as gelatin and alkyltrimethylammoniumions in dilute aqueous solutions.The binding isotherms were obtained by comparing emf-values obtained for surfactant in water to the electrode potentials in gelatin solutions plotted in terms of surfactant concentration.The binding of alkyl sulfates was measured as a function of pH at constant free surfactant concentration. At pH values 7 the degree of binding is indpendent of the pH of the solution. The level of binding of alkyl sulfates to gelatin increases strongly with increasing chain length of the alkyl sulfate. At pH values 6 the extent of binding increases steeply with decreasing pH. Octyl sulfate shows a very low level of binding even at low pH. Cationics show much weaker interactions with gelatin than anionic surfactants of comparable alkyl chain length.     

Influence of sodium sulfate or sodium sulfite on the solubilization of benzylalcohol in cationic micellar solutions

The enthalpy of benzylalcohol (BzOH) solution has been determined as a function of alcohol concentration in aqueous trimethyltetradecylammonium bromide (TTAB) solutions in the presence of sodium sulfite or sodium sulfate up to high salt concentration. The electrolytes studied do not seem to induce TTAB sphere-torod transition at least up to 0.6 mol/kg of salt. Comparison with the enthalpic behavior of BzOH in sodium dodecylsulfate solutions and with that of 1-pentanol in both cationic and anionic micellar solutions suggests that the solubilization of BzOH in TTAB solutions is specifically favored by intramolecular interactions between alcohol molecules within the cationic micelles. The replacement of the bromide counterions by the sulfite or sulfate ions has been studied using potentiometry with an ionselective electrode in the case of trimethylhexadecylammonium bromide (CTAB). No difference could be detected between the effects of either divalent anions on the rate of change of the bromide ion-condensation with the salt/surfactant concentration ratioR. The degree of counter-ion condensation on micellar surface depends not only on theR values, but also on the total surfactant concentration.     

Interactions of mixed surfactant solution with liposome membrane

Interactions of the mixed surfactant solution of dodecylamido propyl dimethyl aminoacetate and sodium dodecyl sulfate with the liposomal membrane were studied. Lytic activities of the surfactants were measured as a function of the concentrations of surfactant and phospholipid and the composition of mixed surfactants. The solubilization limits of phospholipid by surfactants were determined from the change of their aggregation behavior in suspensions at equilibrium by means of quasi-elastic light scattering. The mixed surfactant solutions showed lower lytic activity than single component surfactant solution in spite of the strong adsorption onto the liposome surface. This was attributed to low solubilization power of binary mixture for phospholipid.     

Differential scanning calorimetric study of phase changes in poly(ethylene glycol) dodecyl ether-water systems

Phase changes in binary systems of poly(ethylene glycol) dodecyl ethers, C₁₂H₂₅(OC₂H₄)_xOH (x=5, 6 and 8) with water have been studied between –40 to 100 C by differential scanning calorimetry. A number of transitions, including the liquidliquid phase separation, were seen and the transition temperatures and enthalpy changes were determined. The observed temperatures were generally in good agreement with reported phase diagrams. In the C₁₂E₅ system, three of the four three-phase lines were seen and a more complete phase diagram is suggested for the water-rich part of the system. Most of the phase changes seen above 0 C are accompanied by small endothermic enthalpy changes of 0.7 to 0.9 kJ (mol C₁₂E_x)^–1, independent of system studied, type of transition and transition temperature. Water-rich solutions and liquid crystalline phases separate upon freezing into ice and crystals of hydrated amphiphile. Eutectics are developed at the following temperatures and compositions: C₁₂E₅ –3.0 C and 54 wt % C₁₂E₅; Q₂E₆ –4.5 C and 54 wt % C₁₂E₆, C₁₂E₈ –3.8 C and 49 wt % C₁₂E₈.     

The pH dependence of dispersion of TiO2 particles in aqueous surfactant solutions

The pH dependence of dispersion of titanium dioxide (TiO₂) particles has been examined in the presence of surfactant molecules in water. Whereas particles were dispersed in water at acid and alkaline regions rather than at neutral region, the dispersion was enhanced at neutral region in an aqueous sodium dodecyl sulfate (SDS) solution and at acid and alkaline regions in an aqueous dodecyldimethylamine oxide (C₁₂DAO) solution. Considering the pH dependence of zeta potential, the adsorption models of surfactant molecules on a particle were estimated on the basis of the modes of hemimicelle and double-layer compression. While the particles that adsorbed Al³⁺ were remarkably dispersed around pH 6, their dispersion does not largely depend on pH in the addition of SDS, indicating the adsorption of SDS molecules to form double-layer compression in the whole pH region. Dynamic light-scattering measurement and electron microscopic observation suggested that the particles were dispersed in water as small flocs.     

Role of ionic species and valency on the steady shear behavior of partially hydrolyzed polyacrylamide solutions

Polyacrylamides are anionic polymers with a large number of charges along the polymer chains. The rheological properties of aqueous polyacrylamide solutions can be significantly modified by varying the solvent environment with the addition of salt. The presence of cations substantially reduces the inter- and intra-molecular interactions of the macroions. It was found that the valency of the cation has a strong effect on the rheological behavior of polyacrylamide solutions, but the size and type of salt have a negligible effect.The reduction in the solution viscosity with di-valent salts (e.g., CaCl₂, MgCl₂, BaCl₂, and MgSO₄) can be as high as an order of magnitude compared with mono-valent salt (KI, KC1, NaCl, and NaBr), depending on the salt concentration and shear rate. An identical viscosity function can be obtained for different types of polyacrylamide solutions by varying the salt content in solution. This interesting feature provides a useful means in the development and preparation of certain ideal fluids for simulation studies of complex flow problems.     

Physicochemical properties of α, ω-type bolaform surfactant in aqueous solution. Eicosane-1,20-bis(triethylammonium bromide)

The physicochemical properties of the, - type (bolaform) surfactant, eicosane-1, 20-bis(triethylammonium bromide) (C₂₀Et₆), in aqueous solution have been investigated by means of surface tension, electrical conductivity, dye solubilization, and time-resolved fluorescence quenching (determination of average micelle aggregation number). Using electrical conductivity, the critical micelle concentration of C₂₀Et₆ was found to be 6.0×10^–3 mol dm^–3 and the ionization degree of C²⁰Et₆ micelle was found to be 0.42. From surface tension measurments, the molecular area of C₂₀Et₆ at the air-water interface was about twice that of normal type surfactants such as dodecyltrimethylammonium bromide (DTAB). The solubilizing power of micellar solution of C₂₀Et₆ toward Orange OT was 1.0×10^–2 mole of dye per mole of surfactant, i. e., slightly smaller than that of DTAB. The micelle aggregation number,N, was found to be 17±2 by time-resolved fluorescence quenching. C₂₀Et₆ showed a very small temperature dependence ofN, much less than for normal surfactants.     

Solubilization properties of aqueous solutions of alkyltrimethylammonium halides toward a water-insoluble dye

The solubility of a water-insoluble dye, Sudan Red B, in aqueous sodium halide solutions of tetradecyl-, cetyl-, and stearyltrimethylammonium halides has been measured at different surfactant and salt concentrations, and the dependence of solubilization properties on alkyl chain length has been discussed with reference to the micelle size and shape. At low ionic strengths where only spherical micelles exist, the solubilization power of micellar surfactant slightly increases with increasing the ionic strength, but it sharply increases at high ionic strengths above the threshold value of sphere-rod transition. However, the solubilization power becomes independent of the ionic strength, if their rodlike micelles are sufficiently long. The solubilization capacity increases linearly with increasing the molecular weight, almost independent of counterion species, but the rod-like micelle has a higher solubilization capacity than the spherical micelle. The solubilization capacity is larger for a surfactant with longer alkyl chain, indicating that the dye is solubilized more readily in a larger hydrophobic core. The solubilized dye is situated in a rodlike micelle of alkyltrimethylammonium halides, on average, 4.5–7.5 nm apart from each other.     

Effect of inorganic electrolyte concentration on anionic-cationic adsorption films Part 1. Decylpyridinium chloride + sodium octylsulphonate + sodium chloride

The effect of NaCl on simultaneous adsorption of decylpyridinium chloride (R₁₀PyCl) and sodium octylsulphonate (R₈SO₃Na) on the free surface of their aqueous solutions has been examined. The surface excess of each component was determined on the basis of a suitable form of the Gibbs adsorption equation. The ionic strength effect on the adsorption of particular components of mixtures, as well as on the composition of anionic-cationic films adsorbed from equimolar solutions, is small. This is due to little difference in surface activity of surfactants investigated.