The microstructure of di-alkyl chain cationic/nonionic surfactant mixtures: observation of coexisting lamellar and micellar phases and depletion induced phase separation

The evolution of the microstructure and composition occurring in the aqueous solutions of di-alkyl chain cationic/nonionic surfactant mixtures has been studied in detail using small angle neutron scattering, SANS. For all the systems studied we observe an evolution from a predominantly lamellar phase, for solutions rich in di-alkyl chain cationic surfactant, to mixed cationic/nonionic micelles, for solutions rich in the nonionic surfactant. At intermediate solution compositions there is a region of coexistence of lamellar and micellar phases, where the relative amounts change with solution composition. A number of different di-alkyl chain cationic surfactants, DHDAB, 2HT, DHTAC, DHTA methyl sulfate, and DISDA methyl sulfate, and nonionic surfactants, C12E12 and C12E23, are investigated. For these systems the differences in phase behavior is discussed, and for the mixture DHDAB/C12E12 a direct comparison with theoretical predictions of phase behavior is made. It is shown that the phase separation that can occur in these mixed systems is induced by a depletion force arising from the micellar component, and that the size and volume fraction of the micelles are critical factors.     

Self-assembly in mixed dialkyl chain cationic-nonionic surfactant mixtures: dihexadecyldimethyl ammonium bromide-monododecyl hexaethylene glycol (monododecyl dodecaethylene glycol) mixtures

The self-assembly of dialkyl chain cationic surfactant dihexadecyldimethyl ammonium bromide, DHDAB, and nonionic surfactants monododecyl hexaethylene glycol, C(12)E(6), and monododecyl dodecaethylene glycol, C(12)E(12), mixtures has been studied using predominantly small-angle neutron scattering, SANS. The scattering data have been used to produce a detailed phase diagram for the two surfactant mixtures and to quantify the microstructure in the different regions of the phase diagram. For cationic-surfactant-rich compositions, the microstructure is in the form of bilamellar, blv, or multilamellar, mlv, vesicles at low surfactant concentrations and is in an L(beta) lamellar phase at higher surfactant concentrations. For nonionic-rich compositions, the microstructure is predominantly in the form of relatively small globular mixed surfactant micelles, L(1). At intermediate compositions, there is an extensive mixed (blv/mlv) L(beta)/L(1) region. Although broadly similar, in detail there are significant differences in the phase behavior of DHDAB/C(12)E(6) and DHDAB/C(12)E(12) as a result of the increasing curvature associated with C(12)E(12) aggregates compared to that of C 12E 6 aggregates. For the DHDAB/C(12)E(12) mixture, the mixed (blv/mlv) L(beta)/L(1) phase region is more extensive. Furthermore, C(12)E(12) has a greater impact upon the rigidity of the bilayer in the blv, mlv, and L(beta) regions than is the case for C(12)E(6). The general features of the phase behavior are also reminiscent of that observed in phospholipid/surfactant mixtures and other related systems.     

Solution self-assembly of the sophorolipid biosurfactant and its mixture with anionic surfactant sodium dodecyl benzene sulfonate

The self-assembly in aqueous solution of the acidic (AS) and lactonic (LS) forms of the sophorolipid biosurfactant, their mixtures, and their mixtures with anionic surfactant sodium dodecyl benzene sulfonate, LAS, has been studied using predominantly small-angle neutron scattering, SANS, at relatively low surfactant concentrations of <30 mM. The more hydrophobic lactonic sophorolipid forms small unilamellar vesicles at low surfactant concentrations, in the concentration range of 0.2 to 3 mM, and transforms via a larger unilamellar vesicle structure at 7 mM to a disordered dilute phase of tubules at higher concentrations, 10 to 30 mM. In marked contrast, the acidic sophorolipid is predominantly in the form of small globular micelles in the concentration range of 0.5 to 30 mM, with a lower concentration of larger, more planar aggregates (lamellar or vesicular) in coexistence. In mixtures of AS and LS, over the same concentration range, the micellar structure associated with the AS sophorolipid dominates the mixed-phase behavior. In mixtures of anionic surfactant LAS with the AS sophorolipid, the globular micellar structure dominates over the entire composition and concentration range studied. In contrast, mixtures of LAS with the LS sophorolipid exhibit a rich evolution in phase behavior with solution composition and concentration. At low surfactant concentrations, the small unilamellar vesicle structure present for LS-rich solution compositions evolves into a globular micelle structure as the solution becomes richer in LAS. At higher surfactant concentrations, the disordered lamellar structure present for LS-rich compositions transforms to small vesicle/lamellar coexistence, to lamellar/micellar coexistence, to micellar/lamellar coexistence, and ultimately to a pure micellar phase as the solution becomes richer in LAS. The AS sophorolipid surfactant exhibits self-assembly properties similar to those of most other weakly ionic or nonionic surfactants that have relatively large headgroups. However, the more hydrophobic nature of the lactonic sophorolipid results in a more complex and unusual evolution in phase behavior with concentration and with concentration and composition when mixed with anionic surfactant LAS.     

The impact of multivalent counterions, Al3+, on the surface adsorption and self-assembly of the anionic surfactant alkyloxyethylene sulfate and anionic/nonionic surfactant mixtures

The impact of multivalent counterions, Al(3+), on the surface adsorption and self-assembly of the anionic surfactant sodium dodecyl dioxyethylene sulfate, SLES, and the anionic/nonionic surfactant mixtures of SLES and monododecyl dodecaethylene glycol, C(12)E(12), has been investigated using neutron reflectivity, NR, and small angle neutron scattering, SANS. The addition of relatively low concentrations of Al(3+) counterions induces a transition from a monolayer to well-defined surface bilayer, trilayer, and multilayer structures in the adsorption of SLES at the air-water interface. The addition of the nonionic cosurfactant, C(12)E(12), partially inhibits the evolution in the surface structure from monolayer to multilayer interfacial structures. This surface phase behavior is strongly dependent upon the surfactant concentration, solution composition, and concentration of Al(3+) counterions. In solution, the addition of relatively low concentrations of Al(3+) ions promotes significant micellar growth in SLES and SLES/C(12)E(12) mixtures. At the higher counterion concentrations, there is a transition to lamellar structures and ultimately precipitation. The presence of the C(12)E(12) nonionic cosurfactant partially suppresses the aggregate growth. The surface and solution behaviors can be explained in terms of the strong binding of the Al(3+) ions to the SLES headgroup to form surfactant-ion complexes (trimers). These results provide direct evidence of the role of the nonionic cosurfactant in manipulating both the surface and solution behavior. The larger EO(12) headgroup of the C(12)E(12) provides a steric hindrance which disrupts and ultimately prevents the formation of the surfactant-ion complexes. The results provide an important insight into how multivalent counterions can be used to manipulate both solution self-assembly and surface properties.     

The surface and solution properties of dihexadecyl dimethylammonium bromide

The surface adsorption behavior and solution aggregate microstructure of the dichain cationic surfactant dihexadecyl dimethylammonium bromide (DHDAB) have been studied using small angle neutron scattering (SANS), light scattering, neutron reflectivity (NR), and surface tension (ST). Using a combination of surface tension and neutron reflectivity, the DHDAB equilibrium surface excess at saturation adsorption has been measured as 2.60 +/- 0.05 x 10 (-10) mol.cm (-2). The values obtained by both methods are in good agreement and are consistent with the values reported for other dialkyl chain surfactants. The critical aggregation concentration (CAC) values obtained from both methods (NR and ST) are also in good agreement, with a mean value for the CAC of 4 +/- 2 x 10 (-5) M. The surface equilibrium is relatively slow, and this is attributed to monomer depletion in the near surface region, as a consequence of the long monomer residence times in the surfactant aggregates. The solution aggregate morphology has been determined using a combination of SANS, dynamic light scattering (DLS), cryogenic transmission electron microscopy (CryoTEM), and ultrasmall angle neutron scattering (USANS). Within the concentration range 1.5-80 mM, the aggregates are in the form of bilamellar vesicles with a lamellar " d-spacing" of the order of 900 A. The vesicles are relatively polydisperse with a particle size in the range 2000-4000 A. Above 80 mM, the bilamellar vesicles coexist with an additional L beta lamellar phase.     

Structural transitions induced by shear flow and temperature variation in a nonionic surfactant/water system

In this study, we investigate structural transitions of tetraethylene glycol monohexadecyl ether (C(16)E(4)) in D(2)O as a function of shear flow and temperature. Via a combination of rheology, rheo-small-angle neutron scattering and rheo-small-angle light scattering, we probe the structural evolution of the system with respect to shear and temperature. Multi-lamellar vesicles, planar lamellae, and a sponge phase were found to compete as a function of shear rate and temperature, with the sponge phase involving the formation of a new transient lamellar phase with a larger spacing, coexisting with the preceding lamellar phase within a narrow temperature-time range. The shear flow behavior of C(16)E(4) is also found to deviate from other nonionic surfactants with shorter alkyl chains (C(10)E(3) and C(12)E(4)), resembling to the C(16)E(7) case, of longer chain.     

Mixing behavior of the biosurfactant, rhamnolipid, with a conventional anionic surfactant, sodium dodecyl benzene sulfonate

The use of small angle neutron scattering, SANS, neutron reflectivity, NR, and surface tension to study the mixing properties of the biosurfactant rhamnolipid with a conventional anionic surfactant, sodium dodecyl 6-benzene sulfonate, LAS, is reported. The monorhamnose rhamnolipid, R1, mixes close to ideally with LAS at the air-water interface, whereas for mixtures of LAS with the dirhamnose rhamnolipid, R2, the LAS strongly partitions to the air-water interface relative to R2, probably because of the steric hindrance of the larger R2 headgroup. These trends in the binary mixtures are also reflected in the ternary R1/R2/LAS mixtures. However, for these ternary mixtures, there is also a pronounced synergy in the total adsorption, which reaches a maximum for a LAS/rhamnolipid mole ratio of about 0.6 and a R1/R2 mol ratio of about 0.5, an effect which is not observed in the binary mixtures. In solution, the R1/LAS mixtures form relatively small globular micelles, L(1), at low surfactant concentrations (<20 mM), more planar structures (lamellar, L(α), unilamellar/multilamellar vesicles, ulv/mlv) are formed at higher surfactant concentrations for R1 and LAS rich compositions, and a large mixed phase (L(α)/L(1) and L(1)/L(α)) region forms at intermediate surfactant compositions. In contrast, for the R2/LAS mixtures, the higher preferred curvature of R2 dominates the phase behavior. The predominant microstructure is in the form of small globular micelles, except for solution compositions rich in LAS (>80 mol % LAS) where more planar structures are formed. For the ternary mixtures, there is an evolution in the resulting phase behavior from one dominated by L(1) (R2 rich) to one dominated by planar structures, L(α), (R1, LAS rich), and which strongly depends upon the LAS/rhamnolipid and R1/R2 mole ratio.     

Self-assembly of mixed anionic and nonionic surfactants in aqueous solution

We present the phase diagram and the microstructure of the binary surfactant mixture of AOT and C(12)E(4) in D(2)O as characterized by surface tension and small angle neutron scattering. The micellar region is considerably extended in composition and concentration compared to that observed for the pure surfactant systems, and two types of aggregates are formed. Spherical micelles are present for AOT-rich composition, whereas cylindrical micelles with a mean length between 80 and 300 ? are present in the nonionic-rich region. The size of the micelles depends on both concentration and molar ratio of the surfactant mixtures. At higher concentration, a swollen lamellar phase is formed, where electrostatic repulsions dominate over the Helfrich interaction in the mixed bilayers. At intermediate concentrations, a mixed micellar/lamellar phase exists.     

Rheological and rheo-SALS investigation of the multi-lamellar vesicle formation in the C12E3/D2O system

Usually in nonionic surfactant aqueous systems of the C(n)E(m) type, a lamellar phase occurs over a wide temperature and concentration range. For some C(n)E(m) surfactants, multi-lamellar vesicle (MLV) formation has been observed when the lamellar phase is subjected to shear flow. This communication reports the shear flow behavior at different shear rate values of a C(n)E(m) (where "n" is 12 and "m" is 3) aqueous system at 34 °C. The typical transient viscosity behavior of the shear-induced MLV formation in C(12)E(3)/D(2)O at 50 wt% of surfactant has been observed. The MLV formation is confirmed by time-resolved rheo-small angle light scattering (SALS) experiments. The experimental data show an intermediate structure that has been attributed to a multi-lamellar cylinders (MLCs).     

Length control in rigid cylindrical nanoassembly by tuning molecular interactions in aqueous solutions

We have studied aqueous micellar solutions of nonionic surfactant (pentaethylene glycol mono-n-dodecyl ether, C12E5) doped by cationic surfactant (dodecyl trimethylamoniumbromide, DTAB) as a function of doping level, using small angle neutron scattering. At a doping level of at least 6 mol %, rigid cylindrical micelles formed and the local cylindrical structure of the doped micelles showed no variation across the range of doping levels covered in this study (0-10 mol %). However, the total micellar length decreased rapidly as doping level increased, following well the prediction of micellar aggregation number based on molecular-thermodynamic theory. There was no synergistic interaction between surfactants, leading to monotonically decreasing the micellar aggregation number (shortening of the micellar length).     

Equilibrium surface adsorption behavior in complex anionic/nonionic surfactant mixtures

Neutron reflectivity (NR) and small angle neutron scattering (SANS) have been used to investigate the equilibrium surface adsorption behavior and the solution microstructure of mixtures of the anionic surfactant sodium 6-dodecyl benzene-4 sulfonate (SDBS) with the nonionic surfactants monododecyl octaethylene glycol (C12EO8) and monododecyl triiscosaethylene glycol (C12EO23). In the SDBS/C12EO8 and SDBS/C12EO23 solutions, small globular mixed micelles are formed. However, the addition of Ca2+ ions to SDBS/C12EO8 results in a transition to a vesicle phase or a mixed vesicle/micellar phase for SDBS rich compositions. In contrast, this transition hardly exists for the SDBS/C12EO23 mixture, and occurs only in a narrow composition region which is rich in SDBS. The adsorption of the SDBS/C12EO8 mixture at the air-solution interface is in the form of a mixed monolayer, with a composition variation that is not consistent with ideal mixing. In water and in the presence of NaCl, the nonideality can be broadly accounted for by regular solution theory (RST). At solution compositions rich in SDBS, the addition of Ca2+ ions results in the formation of multilayer structures at the interface. The composition range over which multilayer formation exists depends upon the Ca2+ concentration added. In comparison, the addition of a simple monovalent electrolyte, NaCl, at the same ionic strength does not have the same impact upon the adsorption, and the surface structure remains as a monolayer. Correspondingly, in solution, the mixed surfactant aggregates remain as relatively small globular micelles. In the presence of Ca2+ counterions, the variation in surface composition with solution composition is not well described by RST over the entire composition range. Furthermore, the mixing behavior is not strongly correlated with variations in the solution microstructure, as observed in other related systems.     

Effect of cholesterol on diffusion in surfactant bilayers

Biological membranes consist of lipid bilayers with liquid-ordered and liquid-disordered phases. It is believed that cholesterol controls the size of the microdomains in the liquid-ordered phase and thereby affects the mobility as well as the permeability of the membrane. We study this process in a model system consisting of the nonionic surfactant C(12)E(5) and water in the lamellar phase. We measure the diffusion of fluorescent probe molecules (rhodamine B) by fluorescence correlation spectroscopy. For different surfactant to water ratios, we measure how the molecular mobility varies with the amount of cholesterol added. We find that a reduction of the diffusion coefficient is already detectable at a molar ratio of 8 mol % cholesterol.     

Phase diagrams and microstructure of aggregates in mixed ionic surfactant/foam booster systems

The phase behavior and microstructure of surfactant systems containing a new alkanolamide-type foam booster, dodecanoyl N-methyl ethanolamide (NMEA-12), were investigated by means of phase study and small angle X-ray scattering. Different from other similar alkanolamides, NMEA-12 possesses a low melting point and forms a lyotropic liquid-crystalline phase (L(alpha) phase) at room temperature. This is attributed to the attached methyl group, which increases the fluidity of the molecule. In the SDS/NMEA-12/water system, hexagonal and lamellar (L(alpha)) liquid-crystalline phases are obtained at significantly low surfactant concentrations. The stability of these phases decreases when SDS is replaced with a nonionic surfactant (C12EO8). However, for both ionic and nonionic surfactants, the effective area per surfactant molecule at the interface shrinks upon addition of NMEA-12, indicating that the surfactant layer is getting more compact. The possible implications of these results on the potential applications of NMEA-12 as foam stabilizer are discussed.     

Shear-induced morphology transition and microphase separation in a lamellar phase doped with clay particles

We report on the influence of shear on a nonionic lamellar phase of tetraethyleneglycol monododecyl ether (C12E4) in D2O containing clay particles (Laponite RD). The system was studied by means of small-angle light scattering (SALS) and small-angle neutron scattering (SANS) under shear. The SANS experiments were conducted using a H2O/D2O mixture of the respective scattering length density to selectively match the clay scattering. The rheological properties show the familiar shear thickening regime associated with the formation of multilamellar vesicles (MLVs) and a shear thinning regime at higher stresses. The variation of viscosity is less pronounced as commonly observed. In the shear thinning regime, depolarized SALS reveals an unexpectedly strong variation of the MLV size. SANS experiments using the samples with lamellar contrast reveal a change in interlamellar spacing of up to 30% at stresses that lead to MLV formation. This change is much more pronounced than the change observed, when shear suppresses thermal bilayer undulations. Microphase separation occurs, and as a consequence, the lamellar spacing decreases drastically. The coincidence of the change in lamellar spacing and the onset of MLV formation is a strong indication for a morphology-driven microphase separation.     

Surface and solution behavior of the mixed dialkyl chain cationic and nonionic surfactants

The surface and solution behavior of the mixed dialkyl chain cationic and nonionic surfactant mixture of dihexadecyldimethylammonium bromide, DHDAB, and hexaethylene monododecyl ether, C12E6, has been investigated, using primarily the scattering techniques of small-angle neutron scattering and neutron reflectivity. Within the time scale of the measurements, the adsorption of the pure component C12E6 at the air-solution interface shows no time dependence. In contrast, the adsorption of the DHDAB/C12E6 mixture and pure DHDAB has a pronounced time dependence. The characteristic time for adsorption varies with surfactant concentration, composition, and temperature. It is approximately 2-3 h for the DHDAB/C12E6 mixture, dependent upon concentration and composition, and approximately 50 min for DHDAB. At the air-solution interface, the equilibrium composition of the adsorbed layer shows a marked departure from ideal mixing, which is dependent upon both the solution concentration and the concentration of added electrolyte. In contrast, the composition of the aggregates in the bulk solution that are in equilibrium with the surface is close to ideal mixing, as expected for solution concentrations well in excess of the critical micellar concentration. The structure of the mixed adsorbed layer has been measured and compared with the structure of the equivalent pure surfactant monolayer, and no substantial changes in structure or conformation are observed. The extreme departure from ideal mixing in the adsorption behavior of the DHDAB/C12E6 mixture is discussed in the context of the structure of the adsorbed layer, changes in the underlying solution structures, and the failure of regular solution theory to predict such behavior.     

Dioctadecyldimethylammonium bromide vesicles prepared by the surfactant removal method

Dioctadecyldimethylammonium bromide (DODAB) is a double chain vesicle-forming cationic surfactant, whereas octa-ethyleneglycol mono-n-dodecyl ether (C12E8) is a single chain micelle-forming nonionic surfactant. At room temperature (ca. 22 degrees C) C12E8 molecules self-assemble in water as micelles while DODAB is insoluble. A mixture of DODAB and C12E8, however, can be soluble in water at room temperature depending on the relative amount of the compounds. We report the formation of small unilamellar vesicles (SUVs) by dialyzing at room temperature a mixture of 1.0 mM DODAB with 10 mM C12E8 in water. Extended bilayers are formed as well in equilibrium with vesicles. Such structures are viewed by a cryogenic transmission electron microscopy (cryo-TEM) image.     

Charge-induced unilamellar vesicle formation and phase separation in solutions of Di-n-decylmethylamine oxide

A double-tail amine oxide surfactant, di-n-decylmethylamine oxide (2C10MAO), was prepared, and the effects of protonation on aggregate structure were examined by small-angle neutron scattering (SANS), cryo-transmission electron microscopy (cryo-TEM), turbidity, electric conductivity, and solubilization of an oil-soluble dye at various degrees of neutralization, X, defined as the mole ratio of HCl/2C10MAO. The surfactant makes an L(2) phase in the nonprotonated state (X = 0) in water. The L(2) phase is in equilibrium with an aqueous L(1) phase. On protonation, unilamellar vesicles (ULVs) are formed over a wide range of compositions (0.05 < X< 0.4-0.5 at C = 10 mM) as observed by cryo-TEM. At X = 0.2, the ULV is stable over a wide concentration range (3 mM < or = C < 0.1 M), but an L(alpha) phase replaces the vesicle phase at C > 0.1 M. SANS results show that the mean radius of the ULV is about 25 nm and the bilayer thickness is about 2 nm, consistent with the extended configuration of the alkyl chains of the surfactant. An important contribution to the enhanced stability of the bilayer structures over the L(2) phase is suggested to be the translational entropy of the counterions. The enhanced stability of the bilayers diminishes as the counterion concentration increases either by an increase of X or by the addition of a salt. When the counterion concentration exceeds a critical value, the ULV solutions transform into the L(2) phase (or L(2)/L(1) two-phase system at low surfactant concentrations). The critical composition X is about 0.4-0.5 in water, but it is below 0.4 in D(2)O. The critical NaCl concentration is below 5 mM at X = 0.2. The stability of ULVs against multilamellar vesicles is ascribed partly to undulation forces and partly to the adjustable nature of the spontaneous curvature of amine oxide monolayers. The characteristics of the ULV of the surfactant remain the same within a temperature range 25-50 degrees C at X = 0.2. An iridescent lamellar phase and possibly an L(3) phase were observed in a very narrow X range (0 < X < 0.02) prior to the vesicle phase.     

Control of phase behavior and properties of vesicle gels by admixing ionic surfactants to the nonionic surfactant Brij 30

The effect of the addition of two cationic surfactants of different chain length (decyl and dodecyl trimethylammonium bromide, DeTMABr and DTMABr, respectively) and one anionic surfactant of identical chain length (sodium dodecyl sulfate, SDS) on phase behavior, structure, and macroscopic properties of a bilayer forming nonionic surfactant (Brij 30) has been investigated by means of phase studies, rheology, turbidity measurements, dynamic light scattering, and freeze-fracture transmission electron microscopy. We concentrated on DTMABr because of the generically similar behavior for the other ionic surfactants. It is found that already very small amounts of added ionic surfactant have a very pronounced effect on the phase behavior of these systems. The pure nonionic surfactant forms bilayers and has a tendency for the formation of vesicles which becomes enhanced by charging the bilayer through the incorporation of the ionic surfactant. The presence of the ionic surfactant leads to much more viscous systems, which already at a total surfactant concentration of 150 mM become gel-like. For a given surfactant concentration, the elastic properties of the gels increase largely upon the addition of ionic surfactant. This effect is strongly synergistic, requiring only very small amounts of added ionic surfactant, and the elastic properties pass through a maximum for a content of ionic surfactant of about 3-5 mol %. This behavior can be explained in a self-consistent way by a simple rheological model and by combining it with light scattering data. For the addition of larger amounts, the elastic properties decrease again and the formed vesicles become structurally less defined as one is leaving the range of conditions for forming well-defined vesicles, which are required for forming elastic vesicle gels.     

Intercalation of a nonionic surfactant (C10E3) bilayer into a Na-montmorillonite clay

A nonionic surfactant, triethylene glycol mono-n-decyl ether (C(10)E(3)), characterized by its lamellar phase state, was introduced in the interlayer of a Na-montmorillonite clay at several concentrations. The synthesized organoclays were characterized by small-angle X-ray scattering in conjunction with Fourier transform infrared spectroscopy and adsorption isotherms. Experiments showed that a bilayer of C(10)E(3) was intercalated into the interlayer space of the naturally exchanged Na-montmorillonite, resulting in the aggregation of the lyotropic liquid crystal state in the lamellar phase. This behavior strongly differs from previous observations of confinement of nonionic surfactants in clays where the expansion of the interlayer space was limited to two monolayers parallel to the silicate surface and cationic surfactants in clays where the intercalation of organic compounds is introduced into the clay galleries through ion exchange. The confinement of a bilayer of C(10)E(3) nonionic surfactant in clays offers new perspectives for the realization of hybrid nanomaterials, since the synthesized organoclays preserve the electrostatic characteristics of the clays, thus allowing further ion exchange while presenting at the same time a hydrophobic surface and a maximum opening of the interlayer space for the adsorption of neutral organic molecules of important size with functional properties.     

Microstructure and stability of a lamellar liquid crystalline and gel phase formed by a polyglycerol ester mixture in dilute aqueous solution

The self-assembly behavior of a commercial mixture of polyglycerol fatty acid esters (PGE) and water is investigated as a function of temperature and surfactant content. The phase diagram of this pseudo-binary mixture was characterized using a combination of cross-polarized light and freeze-fracture electron microscopy (cryo-SEM), X-ray diffraction (XRD), small-angle neutron scattering (SANS), and differential scanning calorimetry (DSC). Our experiments show that the morphology of the supramolecular aggregates is lamellar and present in the form of a continuous or dispersed phase (multilamellar vesicles) depending on the water content of the system. Under the effect of temperature, the short- and long-range order of the bimolecular layers successively changes from a biphasic surfactant dispersion to a lamellar liquid-crystalline (Lalpha) and a stable lamellar gel phase (Lbeta) upon cooling; this transition is found to be irreversible. Formation of the lamellar aggregates can be related to the average molecular structure and shape factor of PGE. The stability of the resulting gel phase (Lbeta) appears to be due to the presence of small amounts of unreacted ionic co-surfactant, namely, fatty acid soaps, in this per se nonionic commercial mixture.