Phase behavior of an extended surfactant in water and a detailed characterization of the concentrated phases

The formation of microemulsions with triglycerides at ambient conditions can be improved by increasing the surfactant-water and surfactant-oil interactions. Therefore, extended surfactants were developed, which contain hydrophilic/lipophilic linkers. They have the ability to stretch further into the oil and water phase and enhance the solubility of oil in water. In this work, the phase behavior of a chosen extended surfactant (C(12-14)-PO(16)-EO(2)-SO(4)Na, X-AES) in H(2)O/D(2)O at high surfactant concentrations (30-100 wt %) and at temperatures between 0 and 90 °C is studied for the first time. The lyotropic liquid crystals formed were determined by optical microscopy, small-angle X-ray scattering (SAXS), and (2)H and (23)Na NMR, and a detailed phase diagram of the concentrated area is given. The obtained mesophases are a hexagonal phase (H(1)), at low temperatures and small concentrations, a lamellar phase (L(α)) at high temperatures or concentrations, a bicontinuous cubic phase (V(2)) as well as a reverse hexagonal phase (H(2)). To our knowledge, this is the first surfactant that forms both H(1) and H(2) phases without the addition of a third compound. From the (2)H NMR quadrupole splittings of D(2)O, we have examined water binding in the L(α) and the H(2) phases. There is no marked difference in the bound water between the two phases. Where sufficient water is present, the number of bound water molecules per X-AES is estimated to be ca. 18 with only small changes at different temperatures. Similar results were obtained from the (23)Na NMR data, which again showed little difference in the ion binding between the L(α) and the H(2) phases. The X-ray diffraction data show that X-AES has a much smaller average length in the L(α) phase compared to the all-trans length than in the case for conventional surfactants. At very high surfactant concentrations an inverse isotropic solution (L(2)), containing a small fraction of solid particles, is formed. This isotropic solution is clearly identified and the size of the reversed micelles was determined using (1)H NMR measurements. Furthermore, the solid particles within the L(2) phase and the neat surfactant were analyzed. The observed results were compared to common conventional surfactants (e.g., sodium dodecyl sulfate, sodium lauryl ether sulfate, and sodium dodecyl-p-benzene sulfonate), and the influence of the hydrophilic/lipophilic linkers on the phase behavior was discussed.     

Phase behavior of 1-alkylpyridinium octane-1-sulfonates. effect of the 1-alkylpyridinium counterion size

The temperature-versus-composition phase diagrams of eight different 1-alkylpyridinium octane-1-sulfonates (APOSs) in water were studied by 1H NMR, 2H NMR, pulsed gradient spin-echo NMR, small-angle X-ray diffraction, differential scanning calorimetry, surface tension and conductivity measurements, and polarizing microscopy. The number of carbons (n(c)) in the hydrocarbon chain of the pyridinium counterions was varied from n(c) = 1 to n(c) = 8 to study how the phase behavior of the APOS/2H2O systems was affected by a change in the chain length of the counterion. The sodium octane-1-sulfonate (NaOS)/water system was used as a reference. This system formed an isotropic micellar solution (L1) phase and a normal hexagonal (H(I)) phase. All APOSs were readily soluble in water and formed L1 phases. The surface tension above the critical micelle concentration for n(c) between 1 and 3 was higher than that for NaOS, and it decreased steadily for the different APOSs with increasing chain length. The area per molecule at the air/solution interfaces was rather constant at 68 A2 for n(c) between 1 and 7. For 1-octylpyridinium octane-1-sulfonate (OPOS), it was about 5 A2 smaller, which was just outside the estimated error. However, the smallest area was obtained for NaOS. At higher surfactant concentrations, liquid crystalline phases formed. Both cubic and H(I) phases were found for n(c) = 1 and 2, while for n(c) between 3 and 5 only an H(I) phase was observed. H(I) and lamellar liquid crystalline (Lalpha) phases formed for n(c) = 6 and 7. The only liquid crystalline phase found in the OPOS system was a Lalpha phase. The NaOS H(I) phase was the only liquid crystalline phase that showed a linear relation between the 2H2O NMR quadrupolar splitting (deltaW) and Xsurf/X(W), where Xsurf and X(W) are the mole fractions of surfactant and water. The OPOS lamellae were found to be much thinner than expected, indicating a defect lamellar structure. This was further supported by the behavior of the quadrupolar splitting ofdeuterated OPOS. The anomalous behaviors of the 2H2O NMR quadrupolar splitting observed in the Lalpha phases of 1-heptylpyridinium octane-1-sulfonate and OPOS were interpreted in terms of changes in the population of the water molecules residing in different sites combined with a continuous rearrangement of the lamellae surface with the possible development of holes. The appearances of the phase diagrams were discussed in terms of surfactant molecular geometry and the packing of the amphiphiles in the aggregates formed.     

Effect of shear on vesicle and lamellar phases of DDAB/lecithin ternary systems

The influence of shear flow on bilayer structures (vesicle and planar lamellar phases, L(α)), formed in DDAB/lecithin ternary systems, is studied by means of conventional rheology, Rheo NMR, and optical microscopy. The vesicles in the diluted (Lam(1)) phase are polydisperse multilamellae which turn into smaller monodisperse vesicles under shear. The concentrated (Lam(2)) phase is formed by non-oriented lamellae that do not surprisingly exhibit any pronounced shear-induced alignment prior to the transition into giant multilamellar vesicles. The biphasic region (Lam(1)+Lam(2)) shows a mosaic texture with a powder pattern indicating the prevalence of lamellae that transform into onions under shear.     

Use of the ternary phase diagram of a mixed cationic/glucopyranoside surfactant system to predict mesostructured silica synthesis

Mixed surfactant systems have the potential to impart controlled combinations of functionality and pore structure to mesoporous metal oxides. Here, we combine a functional glucopyranoside surfactant with a cationic surfactant that readily forms liquid crystalline mesophases. The phase diagram for the ternary system CTAB/H(2)O/n-octyl-beta-D-glucopyranoside (C(8)G(1)) at 50 degrees C is measured using polarized optical microscopy. At this temperature, the binary C(8)G(1)/H(2)O system forms disordered micellar solutions up to 72 wt% C(8)G(1), and there is no hexagonal phase. With the addition of CTAB, we identify a large area of hexagonal phase, as well as cubic, lamellar and solid surfactant phases. The ternary phase diagram is used to predict the synthesis of thick mesoporous silica films via a direct liquid crystal templating technique. By changing the relative concentration of mixed surfactants as well as inorganic precursor species, surfactant/silica mesostructured thick films can be synthesized with variable glucopyranoside content, and with 2D hexagonal, cubic and lamellar structures. The domains over which different mesophases are prepared correspond well with those of the ternary phase diagram if the hydrophilic inorganic species is assumed to act as an equivalent volume of water.     

Effect of sodium diclofenac loads on mesophase components and structure

We studied the effect of a model electrolytic drug on intermolecular interactions, conformational changes, and phase transitions in structured discontinuous cubic QL lyotropic liquid crystals. These changes were due to competition with hydration of the lipid headgroups. Structural changes of the phase induced by solubilization loads of sodium diclofenac (Na-DFC) were investigated by directly observing the water, ethanol, and Na-DFC components of the resulting phases using 2H and 23Na NMR. Na-DFC interacted with the surfactant glycerol monoolein (GMO) at the interface while interfering with the mesophase curvature and also competed with hydration of the surfactant headgroups. Increasing quantities of solubilized Na-DFC promoted phase transitions from cubic phase (discontinuous (QL) and bicontinuous (Q)) into lamellar structures and subsequently into a disordered lamellar phase. Quadrupolar coupling of deuterated ethanol by 2H NMR showed that it is located near the headgroups of the lipid and apparently is hydrogen bonded to the GMO headgroups. A phase transition between two lamellar phases (L alpha to L alpha*) was seen by 23Na NMR of Na-DFC at a concentration where the characteristics of the drug change from kosmotropic to chaotropic. These findings show that loads of solubilized drug may affect the structure of its vehicle and, as a result, its transport across skin-blood barriers. The structural changes of the mesophase may also aid controlled drug delivery.     

Structural evolution in the isotropic channel of a water-nonionic surfactant system that has a disconnected lamellar phase: a 1H NMR self-diffusion study

We showed in a previous study that a water-nonionic surfactant system, where the surfactant is a 9:1 mixture of tetraethylene glycol monodecyl ether (C(10)E(4)) and pentaethylene glycol monodecyl ether (C(10)E(5)), forms a disconnected lamellar (L(α)) phase. Thus, the isotropic phase spans the whole concentration range from the water-rich L(1) region to the surfactant-rich L(2) region of the phase diagram. The L(1) and L(2) regions are connected via an isotropic channel that separates the two regions of the L(α) phase. In this letter, we monitored the structural evolution of the isotropic phase along a path through this isotropic channel via (1)H NMR self-diffusion measurements. We used this technique because it enables us to distinguish between discrete and bicontinuous structures by comparing the relative self-diffusion coefficients (obstruction factors) D/D(0) of the solvents (i.e. of water and surfactant in the present case). We found that the obstruction factor of water decreases whereas the obstruction factor of the surfactant increases with increasing surfactant concentration and increasing temperature. This trend is interpreted as the transition from a water-continuous L(1) region, which contains discrete micelles, to a bicontinuous structure, which may extend to very high surfactant concentrations. Although there is good evidence of bicontinuity over a broad concentration range, there is no evidence of inverse micelles or any other microstructure at the highest concentration studied in the surfactant-rich L(2) phase.     

Fragmentation of the lamellae and fractionation of polymer coils upon mixing poly(dimethylacrylamide) with the lamellar phase of aerosol OT in water

The lamellar mesophase formed by surfactant 1,4-bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in deuterated water is mixed with poly(dimethylacrylamide) (PDMAA) polymers of low molecular weight (Mn= (2-20) x 10(3)). The mixtures separate into microphases (lamellar plus isotropic polymer solution). Their microstructures are studied by microscopy, small-angle X-ray scattering (SAXS), and deuterium NMR (2H NMR). According to SAXS, the lamellar phase fractionates the molecular weight distribution of the polymer, by dissolving only chains with coil sizes smaller than the thickness of the water layers between lamellae, and keeping larger chains segregated from the lamellar phase. The fraction of polymer that is segregated from the lamellar phase grows with Mn of the polymer. In 2H NMR, there are two signals, a quadrupolar doublet (water molecules hydrating the anisotropic lamellar phase contribute to this doublet) and a singlet (water molecules in the isotropic polymer solution contribute to this singlet). These two signals are deconvoluted to analyze the phases. Mixing with the polymer produces the partial dispersion of the lamellar phase into small fragments (microcrystallites). The structure of these microcrystallites is such that they conserve the regular long period spacing of the macrophase, and are thus identified in SAXS, but they are smaller than the minimum size required to produce quadrupolar splitting (about 4 microm), and therefore, in 2H NMR, they contribute to the singlet. 2H NMR can thus not distinguish between small microcrystallites and an isotropic polymer solution segregated from the lamellar phase; instead small microcrystallites are detected as an apparent increase of the isotropic solution. The degree of dispersion produced by the polymer in the lamellar phase is correlated with the degree of segregation that the polymer suffers. Thus, much greater dispersion into microcrystallites is produced by the higher Mn polymers than by the lower Mn polymers (in the range covered by the present samples, although with a much higher molecular weight sample (3 x 10(6)) that is totally segregated no such microcrystallites were detected).     

Effect of L64 on the Phase Behavior of 1-Dodecyl-3-methylimidazolium Chloride/Water System

Phase behavior of ternary system involving surfactant‐like ionic liquid 1‐dodecyl‐3‐methylimidazolium chloride ([C₁₂mim]Cl), water, and nonionic surfactant PEO‐PPO‐PEO block copolymer (Pluronic L64) is investigated at 25°C. Hexagonal (H₁) and lamellar liquid crystal phase (Lα) are found in [C₁₂mim]Cl/H₂O/L64 system by using polarized optical microscopy (POM), small‐angle X‐ray scattering (SAXS) techniques and ²H NMR spectra. The phase structure (H₁ phase), which is formed in [C₁₂mim]Cl/H₂O binary system, is not changed when L64 with a low concentration is added. However, phase transitions will occur from hexagonal to multiphases of H₁ and cubic phases (C), then to Lα+C phases with constant [C₁₂mim]Cl/H₂O ratio and increasing L64 concentration. Moreover, at given L64 (5%, 20%) concentration, the lattice parameter of H₁ or Lα phase decreases with increasing [C₁₂mim]Cl/H₂O ratio. Fourier transform infrared (FTIR) spectra indicate that the H‐bonded network comprising an imidazolium ring, chloride ion and water formed in [C₁₂mim]Cl/H₂O binary system is disrupted upon addition of L64. This is helpful to the phase transition, due to the decreasing of interfacial curvature induced by dehydration of hydrated layer after the addition of PEO block of L64.     

Formation of Cubic-Phase Microemulsions with Anionic and Cationic Surfactants at Equal Amounts of Oil and Water

The formation and microstructure of cubic phases were investigated in anionic and cationic surfactant-containing systems at 25 degrees C. In the system sodium dodecyl sulfate(SDS)-dodecyltrimethylammonium bromide(DTAB)-water, mixing of two surfactants shows the phase transition hexagonal phase (H(1))-->surfactant precipitate, accompanied by an obvious decrease in the cross-sectional area per surfactant in the rod micelles of the hexagonal liquid crystal. In the mixed systems brine(A)-dodecane(B)-SDS(C)-DTAB(D)-hexanol(E), the isotropic discontinuous cubic phase is formed from the H(1) phase at a low cationic surfactant weight fraction, Y=D/(C+D), and from the lamellar phase at high Y upon dilution with equal amounts of oil and brine, respectively. The minimum surfactant concentration to form the cubic phase decreases with increases both in cationic surfactant weight fraction Y from 0 to 0.30 and in hexanol weight fraction, W(1)=E/(C+D+E), accordingly. The maximum solubilization for oil of the cubic phase reaches 43 wt% at 14 wt% of mixed surfactants and alcohol. Copyright 2000 Academic Press.     

Phase behavior of a DNA-based surfactant mixed with water and n-alcohols

The self-assembly behavior of a cationic surfactant (dodecyltrimethylammonium, DTA) with DNA as counterion in mixtures of water and n-alcohols (decanol, octanol, hexanol, butanol, and ethanol) was investigated. The phase diagrams were established and the different regions of the phase diagram characterized with respect to microstructure by (2)H NMR, small-angle X-ray scattering (SAXS), and other techniques. The DNA-DTA surfactant is soluble in all of the studied alcohols, showing increased solubility from decanol down to ethanol. All of the phase diagrams are analogous with respect to the occurrence of liquid crystalline (LC) regions, but the area of the LC region increases as one goes from decanol to ethanol. In all phase diagrams, hexagonal phases (of the reversed type) for the alcohol-rich side and lamellar phases for the other side were detected. For balanced proportions of the components, there is a coexistence of the lamellar and the hexagonal phase, here detected with a double quadrupole splitting in the (2)H NMR spectra. The correctness of the phase diagrams is confirmed by the fact that along the tie-lines the splitting magnitude remains nearly constant. All of the alcohols except for ethanol act as cosurfactants penetrating the DNA-DTA film. Adding salt to the ternary mixtures causes an increase in the unit cell dimension of the lamellar and the hexagonal phases. The phase diagram becomes more complicated when butanol is used for the alcohol phase. Here, there is the occurrence of a new isotropic phase with some properties analogous to those of the disordered sponge (L3) phase obtained for simple surfactant systems.     

Evidence of formation of ammonium perfluorononanoate/2H2O multilamellar vesicles: morphological analysis by rheology and rheo-2H NMR experiments

Rheology and rheo-(2)H NMR measurements are presented for 30 wt % ammonium perfluorononanoate (APFN)/(2)H(2)O mixture in the temperature range 20-70 °C. A first-order lamellar-to-nematic transition occurs at 42 °C, and a first-order nematic-to-isotropic transition occurs at 49 °C. Different rheological behaviors of the lamellar phase were observed with increasing the temperature. The lamellar structure at low temperature (Lα(-)) has a clear gel-like viscoelasticity, while at high temperature the lamellar structure (Lα(+)) has a liquid-like response. In this study we have observed for the first time, along with the lamellar phase of a surfactant containing fluorinated fatty acid, the formation of multilamellar vesicles (MLVs) ("onions") induced by shear. With the aid of nonlinear rheology and rheo-NMR techniques, onion formation was found to occur in both temperature regimes of the lamellar phase, but at different strain units. It is suggested that the lamellar phase consists of smectic structures in both Lα(-) and Lα(+), but with different percentages of defect density.     

31P and 1h NMR as probes of domain alignment in a rigid crystalline surfactant mesophase

A viscous reverse hexagonal surfactant mesophase containing bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and alpha-phosphatidylcholine (lecithin), with comparable volume fractions of isooctane and water, was characterized by Fourier transform (31)P and (1)H NMR spectroscopy. Shear alignment was reflected through both (31)P NMR and (1)H NMR spectra. A complicated (31)P spectrum was observed as a result of superposition of chemical shifts according to the distribution of crystalline domains prior to shear. The initially disordered samples with polydomain structures become macroscopically aligned after Couette shear. (31)P NMR chemical shift anisotropy characteristics are used to elucidate orientation of the hexagonal phase. Interestingly, (1)H NMR spectra exhibit spectral changes upon shear alignment closely corresponding with that of (31)P NMR spectra. These observations complement the findings of mesophase alignment obtained using SANS and imply that (31)P and (1)H NMR spectroscopy can be used as probes to define microstructure and monitor orientation changes in this binary surfactant system. This is especially beneficial if these mesophases are used as templates for materials synthesis.     

Magnesium and calcium surfactants Ternary phase diagrams of magnesium and calcium dodecylsulphate with decanol and water

The isothermal ternary phase diagrams for the systems magnesium dodecylsulphate-decanol-water at 40 °C and calcium dodecylsulphate-decanol-water at 50 °C are determined by water deuteron NMR and polarizing microscopic studies. In the magnesium system, three liquid crystalline phases (lamellar and normal and reverse hexagonal) and two isotropic (normal and reverse) solution phases are characterized and their ranges of existence are obtained. The calcium system yields the same liquid crystalline phases, but only the lamellar liquid crystalline phase is investigated in detail. The important observations made are: (i) The lamellar liquid crystalline phase for the magnesium and calcium systems can incorporate, respectively, a maximum of 22.5 and 14.3 mole water per mole surfactant ion against 139 mole water for the corresponding sodium system. (ii) The reverse hexagonal liquid crystalline phase is formed for both the magnesium and calcium systems while no such liquid crystalline phase exists for the corresponding sodium system. (iii) The²H NMR quadrupole splittings obtained in the liquid crystalline phases for C₈SO ₄ ^– and C₁₂SO ₄ ^– surfactant systems with different counterions (Ca²⁺,Mg²⁺,Be²⁺,Na⁺) reveal that surfactant hydration is almost independent of alkyl chain length and counterions.     

Structure of mesh phases in a cationic surfactant system with strongly bound counterions

We report the observation of an intermediate mesh phase with rhombohedral symmetry, corresponding to the space group Rm, in a mixed surfactant system formed by the cationic surfactant cetyltrimethylammonium bromide (CTAB) and the organic salt 3-sodium-2-hydroxy naphthoate (SHN). It occurs between a random mesh phase (L(alpha)(D)) and a lamellar phase (L(alpha)) at low temperatures; at higher temperatures, the (L(alpha)(D)) phase transforms continuously into the (L(alpha)) phase with an increasing surfactant concentration (phi(s)). To separate the effects of salt and phi(s) on the phase behavior, the ternary system consisting of cetyltrimethylammonium 3-hydroxy-naphthalene-2-carboxylate (CTAHN), sodium bromide (NaBr), and water was studied. The intermediate mesh phase is found in this system at high NaBr concentrations. The micellar aggregates, both in the intermediate and random mesh phases, are found to be made up of a two-dimensional network of rod-like segments, with three rods meeting at each node. The average mesh size increases with phi(s), and the transition from the random mesh phase to the intermediate phase is found to occur when it is approximately 1.5 times the lamellar periodicity. The intermediate mesh phase is absent in the equimolar dodecyltrimethylammonium bromide (DTAB)-SHN system, indicating the role of the surfactant chain length in the formation of this phase. This system exhibits a random mesh phase over a very wide range of water content, with the average mesh size decreasing upon an increasing phi(s), contrary to the trend seen in the CTAB-SHN system.     

Phase behavior and preparation of mesoporous silica in aqueous mixtures of fluorinated surfactant and hydrophobic fluorinated polymer

The phase behavior and formation of self-assemblies in the ternary water/fluorinated surfactant (C(8)F(17)EO(10))/hydrophobic fluorinated polymer (C(3)F(6)O)(n)COOH system and the application of those assemblies in the preparation of mesostructured silica have been investigated by means of phase study, small angle X-ray scattering, and rheology. Hexagonal (H(1)), bicontinuous cubic (V(1)) with Ia3d symmetry, and polymer rich lamellar (L(alpha)(')) are observed in the ternary diagram. C(8)F(17)EO(10) molecules are dissolved in polymer rich aggregates, whereas (C(3)F(6)O)(n)COOH molecules are practically insoluble in the surfactant lamellar phase due to packing restrictions. Hence, two types of lamellar phases exist: one with surfactant rich (L(alpha)) and the other with polymer rich (L(alpha)(')) in the water/C(8)F(17)EO(10)/(C(3)F(6)O)(n)COOH system. As suggested by rheological measurements, worm-like micelles are present in C(8)F(17)EO(10) aqueous solutions but a rod-sphere transition takes place by solubilization of (C(3)F(6)O)(n)COOH. C(8)F(17)EO(10) acts as a structure directing agent for the preparation of hexagonal mesoporous silica by the precipitation method. The addition of (C(3)F(6)O)(n)COOH induces the formation of larger but disordered pores.     

X-ray diffraction study of the structure of carboxymethylcellulose-cationic surfactant complexes.

We have investigated dilute aqueous solutions of an anionic polymer (carboxymethylcellulose) mixed with cationic surfactants of different chain lengths (dodecyl to octadecyl trimethylammonium bromides: DTAB, TTAB, CTAB and OTAB). The structures of the concentrated phases formed above the precipitation threshold were studied by X-ray diffraction. Different body-centred cubic structures with space groups Pm3n were observed in the presence of surfactant with a short aliphatic chain (DTAB), despite the fact that the polymer persistence length is comparable to the repeat distance of the structure (5 nm). For larger surfactant chain lengths (TTAB and CTAB), the structure of the precipitates can be either cubic (Pm3n) or 2D hexagonal depending on the initial surfactant and polymer concentrations. For still larger chain length (OTAB), the structure becomes lamellar. This structural evolution from micellar cubic towards 2D hexagonal and lamellar is attributed to the decrease of the local curvature of the surfactant aggregates, as observed for flexible synthetic polymers and short DNA fragments under similar conditions. Furthermore, the structure of the bulk complexes formed just below the precipitation threshold anticipates the structure seen in the precipitated phases.     

Elongated silica nanoparticles with a mesh phase mesopore structure by fluorosurfactant templating

Mesoporous silica materials with pore structures such as 2D hexagonal close packed, bicontinuous cubic, lamellar, sponge, wormhole-like, and rectangular have been made by using surfactant templating sol-gel processes. However, there are still some "intermediate" phases, in particular mesh phases, that are formed by surfactants but which have not been made into analogous silica pore structures. Here, we describe the one-step synthesis of mesoporous silica with a mesh phase pore structure. The cationic fluorinated surfactant 1,1,2,2-tetrahydroperfluorodecylpyridinium chloride (HFDePC) is used as the template. Like many fluorinated surfactants, HFDePC forms intermediate phases in water (including a mesh phase) over a wider range of compositions than do hydrocarbon surfactants. The materials produced by this technique are novel elongated particles in which the layers of the mesh phase are oriented orthogonal to the main axis of the particles.     

Lamellar miscibility gap in a binary catanionic surfactant-water system

The coexistence of two lamellar liquid-crystalline phases in equilibrium for binary surfactant-water systems is a rare and still puzzling phenomenon. In the few binary systems where it has been demonstrated experimentally, the surfactant is invariably ionic and the miscibility gap is thought to stem from a subtle balance between attractive and repulsive interbilayer forces. In this paper, we report for the first time a miscibility gap for a catanionic lamellar phase formed by the surfactant hexadecyltrimethylammonium octylsulfonate (TASo) in water. Synchrotron small-angle X-ray scattering, polarizing light microscopy, and 2H NMR unequivocally show the coexistence of a dilute (or swollen) lamellar phase, Lalpha', and a concentrated (or collapsed) lamellar phase, Lalpha' '. Furthermore, linear swelling is observed for each of the phases, with the immiscibility region occurring for 15-54 wt % surfactant. In the dilute region, the swollen lamellar phase is in equilibrium with an isotropic micellar region. Vesicles can be observed in this two-phase region as a dispersion of Lalpha' in the solution phase. A theoretical cell model based on combined DLVO and short-range repulsive potentials is presented in order to provide physical insight into the miscibility gap. The surfactant TASo is net uncharged, but it undergoes partial dissociation owing to the higher aqueous solubility of the short octylsulfonate chain. Thus, a residual positive charge in the bilayer is originated and, consequently, an electrostatic repulsive force, whose magnitude is dependent on surfactant concentration. For physically reasonable values of the solubility of the octyl chain, assumed to be constant with surfactant volume fraction, a fairly good agreement is observed between the experimental miscibility gap and the theoretical one.     

An NMR study of translational diffusion and structural anisotropy in magnetically alignable nonionic surfactant mesophases

The diffusion of both water and surfactant components in aqueous solutions of the nonionic surfactant "C12E6"--which includes hexagonal, cubic, lamellar, and micellar mesophases--has been studied by pulsed-field-gradient NMR. Diffusion coefficients were measured in unaligned samples in all of these phases. They were also obtained in the hexagonal and lamellar phases in oriented monodomain samples that were aligned by slow cooling from the micellar phase in an 11.7 T magnet. Measured water and soap diffusion coefficients in the NMR-isotropic cubic and (high-water-content) micellar phases as well as diffusion anisotropy measurements in the magnetically aligned hexagonal phase were quantitatively consistent with the constituent structures of these phases being identical surfactant cylinders, with only the fraction of surface-associated water varying with the water-soap molar ratio. The values of the water and soap diffusion coefficients in the oriented lamellar phase suggest an increase in defects and obstructions to soap diffusion as a function of increasing water content, while those in the low-water-content micellar phase rule out the presence of inverse micelles.     

Unravelling micellar structure and dynamics in an unusually extensive DDAB/bile salt catanionic solution by rheology and NMR-diffusometry

The mixed didodecyldimethylammonium bromide (DDAB)-sodium taurodeoxycholate (STDC)-(2)H(2)O catanionic system forms a large isotropic (L(1)) phase at 25 degrees C. The evolution of microstructure along different dilution lines has been followed by means of rheology and NMR diffusometry. In general, the L(1) phase is characterised by a weak viscoelasticity and Newtonian response. In the STDC-rich regime (W(s)=[DDAB]/[STDC]=0.2), 5 wt% is an overlapping concentration at which the discrete-to-rodlike micellar transition occurs as indicated from the total surfactant concentration (C(s)) dependency of both zero-shear viscosity (eta(0) approximately C(s)(3.7)) and surfactant self-diffusion (D(s) approximately C(s)(-3.0)). As the surfactant molar ratio (W(s)1) increases, i.e., DDAB concentration increases, and at constant C(s), eta(0) decreases and D(s) increases, indicating the formation of a multiconnected micellar network.